KR102027030B1 - Organic light emitting device - Google Patents

Abstract

The present specification relates to an organic light emitting device.

Description

Organic light emitting device {ORGANIC LIGHT EMITTING DEVICE}

The present specification relates to an organic light emitting device. This specification claims the benefit of the filing date of Korean Patent Application No. 10-2016-0065774 filed with the Korea Intellectual Property Office on May 27, 2016, the entire contents of which are incorporated herein.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from two electrodes are combined in the organic thin film to form a pair, then disappear and emit light. The organic thin film may be composed of a single layer or multiple layers as necessary.

Most of the materials used in the organic light emitting device are pure organic materials or complex compounds in which organic materials and metals are complexed, and depending on the purpose, hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. It can be divided into. Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material which is easily oxidized and has an electrochemically stable state during oxidation, is mainly used. On the other hand, as the electron injecting material or the electron transporting material, an organic material having an n-type property, that is, an organic material which is easily reduced and has an electrochemically stable state at the time of reduction is mainly used. As the light emitting layer material, a material having a p-type property and an n-type property at the same time, that is, a material having a stable form in both oxidation and reduction states, and a material having high luminous efficiency that converts it to light when excitons are formed desirable.

In order to improve the performance, lifespan or efficiency of the organic light emitting device, the development of the material of the organic thin film is continuously required.

International Patent Application Publication No. 2003-012890 Korean Patent Laid-Open Publication No. 2000-0051826

An object of the present specification is to provide an organic light emitting device having high luminous efficiency and / or low driving voltage and long life.

According to an exemplary embodiment in the present specification, the anode; A cathode provided to face the anode; In the organic light emitting device comprising a light emitting layer provided between the anode and the cathode,

Further provided with an organic material layer provided between the cathode and the light emitting layer and comprising a compound represented by the following formula (1),

The light emitting layer provides an organic light emitting device comprising a compound represented by the following formula (2).

[Formula 1]

In Chemical Formula 1,

Ar1 to Ar3 are different from each other,

Ar 1 to Ar 3 each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms,

[Formula 2]

In Chemical Formula 2,

Ar4 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,

At least one of Ar4 and Ar5 is an aryl group having 10 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms,

R 5 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; Substituted or unsubstituted C6-C30 aryl group; Or a substituted or unsubstituted C 2-30 heteroaryl group,

n is an integer of 0-8, and R <5> when n is two or more is mutually same or different.

The organic light emitting diode according to the exemplary embodiment of the present application may have a low driving voltage and may improve lifespan characteristics of the device by thermal stability of the compound. When used in the organic light emitting device described herein it is possible to lower the driving voltage of the device, improve the light efficiency, and improve the life characteristics of the device by the thermal stability of the compound.

The organic light emitting device of the present specification uses a triazine compound in which three nitrogens (3.0) having an electronegativity greater than carbon (2.5) are substituted in a benzene ring in the electron transport layer, so that one or two nitrogens are substituted with pyridine and pyrimidine. It has higher stability to electrons on reduction than compound. In addition, when comparing the electron affinity by functional theory (DFT), the triazine (-0.16 eV) compound is more neutral than the compound of pyrimidine (-0.51 eV) and pyridine (-1.00 eV). The difference in energy between the anion and the anion is small, which is very advantageous in injecting electrons into the light emitting layer.

In addition, when the anthracene compound is used in the light emitting layer, there is an excellent effect in the organic light emitting device, if the number of carbon atoms of the substituents bonded to the anthracene is more than 30, the deposition temperature is increased due to the increase in molecular weight and the breakdown of molecules due to high temperature appears. Therefore, a substituent having 30 or less carbon atoms is preferable, and when at least one of the substituents is an aryl group or heteroaryl group having 10 to 30 carbon atoms, there is an excellent effect in terms of voltage, efficiency, and lifetime.

1 shows an organic light emitting device in which a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7 and a cathode 4 are sequentially stacked. An example is shown.

Hereinafter, this specification is demonstrated in detail.

Examples of substituents herein are described below, but are not limited thereto.

The term "substituted" means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Cyano group; An alkyl group; Cycloalkyl group; Silyl groups; Aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group or substituted with a substituent to which two or more substituents in the above-described substituents are connected, or does not have any substituents. 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 or may be interpreted as a substituent to which two phenyl groups are linked.

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 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, iso Pentyl, 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-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably 3 to 60 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. Do not.

 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, when the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but preferably 6 to 25 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-24. Specifically, the polycyclic aryl group may be naphthyl group, anthracene group, phenanthrene group, pyrenyl group, peryleneyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

,

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

Etc., but is not limited thereto.

), 피리다지닐기, 피라지닐기, 퀴놀리닐기, 퀴나졸리닐기, 퀴녹살리닐기, 프탈라지닐기, 피리도피리미디닐기, 피리도피라지닐기, 피라지노피라지닐기, 이소퀴놀리닐기, 인돌기, 카바졸기, 벤즈옥사졸기, 벤즈이미다졸기, 벤조티아졸기, 벤조카바졸기, 디벤조카바졸기, 벤조티오펜기, 디벤조티오펜닐기, 벤조퓨란기, 디벤조퓨란기, 벤조나프토퓨란기, 벤조실롤기, 디벤조실롤기, 페난트롤리닐기(phenanthrolinyl group), 이소옥사졸릴기, 티아디아졸릴기, 페노티아지닐기, 페노옥사지닐기, 및 이들의 축합구조 등이 있으나, 이들에만 한정되는 것은 아니다. 이외에도 헤테로고리기의 예로서, 술포닐기를 포함하는 헤테로고리 구조, 예컨대,

,

등이 있다.In the present specification, the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number of a heterocyclic group is not specifically limited, It is preferable that it is C2-C60. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, tria Genyl group, acridil group, hydroacridyl group (e.g.,

), Pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, and isoquinolinyl , Indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, dibenzocarbazole group, benzothiophene group, dibenzothiophenyl group, benzofuran group, dibenzofuran group, benzo Naphthofuran group, benzosilol group, dibenzosilol group, phenanthrolinyl group, isoxoxazolyl group, thiadiazolyl group, phenothiazinyl group, phenooxazinyl group, and condensation structures thereof; It is not limited only to these. In addition, examples of heterocyclic groups include heterocyclic structures including a sulfonyl group, for example,

,

Etc.

가 될 수 있다.Carbazole condensed ring herein

Can be

In one embodiment of the present specification, Ar1 to Ar3 are each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted naphthyl group; A substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted fluorene group; Substituted or unsubstituted benzofluorene group; Substituted or unsubstituted anthracene group; Substituted or unsubstituted phenanthrene group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted carbazole group; Substituted or unsubstituted carbazole condensed ring group; Substituted or unsubstituted pyridine group; Substituted or unsubstituted pyrimidine group; Substituted or unsubstituted quinoline group.

In one embodiment of the present specification, the "substituted or unsubstituted" means substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, a phenyl group and a naphthyl group.

In one embodiment of the present specification, Ar3 is represented by the following Chemical Formula 1-1.

[Formula 1-1]

In Chemical Formula 1-1,

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxyl group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms; A substituted or unsubstituted alkylthioxy group having 1 to 20 carbon atoms; Substituted or unsubstituted arylthioxy group having 6 to 30 carbon atoms; Substituted or unsubstituted C1-C20 alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group having 6 to 30 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or combine with an adjacent group to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle, or substituents in the same carbon combine with each other to substitute Or an unsubstituted spiro bond.

L 1 is a direct bond; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted divalent C 2-30 heterocyclic group,

l is an integer from 1 to 5,

m is an integer of 1 to 3,

n is an integer from 1 to 4,

When l, m and n are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other.

In one embodiment of the present specification, R1 and R2 are hydrogen.

In one embodiment of the present specification, R3 and R4 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, R3 and R4 are the same as or different from each other, and each independently a methyl group or a phenyl group.

In one embodiment of the present specification, R3 and R4 are phenyl groups.

In one embodiment of the present specification, L1 is a direct bond.

In one embodiment of the present specification, L1 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L1 is an arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L1 is a phenylene group.

In one embodiment of the present specification, Ar5 is an aryl group having 10 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms.

In one embodiment of the present specification, the Ar4 substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted fluorene group; Substituted or unsubstituted anthracene group; Substituted or unsubstituted phenanthrene group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted carbazole group; Substituted or unsubstituted carbazole condensed ring group; Substituted or unsubstituted benzofluorene group; Or a substituted or unsubstituted benzonaphthofuran group,

Ar5 is a substituted or unsubstituted naphthyl group; Substituted or unsubstituted fluorene group; Substituted or unsubstituted anthracene group; Substituted or unsubstituted phenanthrene group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted carbazole group; Substituted or unsubstituted carbazole condensed ring group; Substituted or unsubstituted benzofluorene group; Or a substituted or unsubstituted benzonaphthofuran group.

In one embodiment of the present specification, Ar4 is a substituted or unsubstituted phenyl group; Substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted dibenzofuran group, Ar5 is a substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted dibenzofuran group.

 In one embodiment of the present specification, Ar4 is a phenyl group unsubstituted or substituted with a naphthyl group; Naphthyl group; Or a dibenzofuran group, wherein Ar5 is a naphthyl group unsubstituted or substituted with a phenyl group; Or a dibenzofuran group.

In one embodiment of the present specification, the "substituted or unsubstituted" means substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, a phenyl group and a naphthyl group.

In one embodiment of the present specification, R5 is hydrogen.

In one embodiment of the present specification, the substituent of the compound represented by Formula 1 is selected from the following table.

Dotted line in the table means a position to combine with formula (1).

In one embodiment of the present specification, the substituent of the compound represented by Formula 2 is selected from the following table.

Dotted line in the table means a position to combine with the formula (2).

In one embodiment of the present specification, Ar4 and Ar5 of the compound represented by Formula 2 are selected from the above table, and R5 is hydrogen.

In this specification, when a member is located "on" another member, this includes not only when a member is in contact with another member but also when another member exists between the two members.

In the present specification, when a part "contains" a certain component, this means that the component may further include other components, except for the case where there is no contrary description.

The organic material layer of the organic light emitting device of the present application may be made of a single layer structure, but may be made of a multilayer structure in which two or more organic material layers are stacked. For example, as a representative example of the organic light emitting device of the present invention, the organic light emitting device may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.

In one embodiment of the present specification, the organic material layer including the compound represented by Formula 1 is an electron transport layer.

In one embodiment of the present specification, the organic material layer including the compound represented by Formula 1 includes an electron transport layer and an electron injection layer, and the electron transport layer includes a compound represented by Formula 1.

In one embodiment of the present specification, the light emitting layer further includes a dopant, and the content ratio of the compound represented by Formula 2 and the dopant is 99: 1 to 90:10.

In an exemplary embodiment of the present application, the organic material layer including the compound represented by Chemical Formula 1 is a single layer or two or more organic material layers.

In an exemplary embodiment of the present application, the two or more organic material layers may be selected from the group consisting of an electron transport layer, an electron injection layer, a layer simultaneously performing electron transport and electron injection, and a hole blocking layer.

In another exemplary embodiment, the organic light emitting diode may be an organic light emitting diode having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

 In another exemplary embodiment, the organic light emitting diode may be an organic light emitting diode having an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

For example, the structure of an organic light emitting device according to an exemplary embodiment of the present application is illustrated in FIG.

1 shows an organic light emitting device in which a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7 and a cathode 4 are sequentially stacked. The structure is illustrated. In this structure, the compound represented by Formula 1 may be included in the electron transport layer (7), the compound represented by Formula 2 may be included in the light emitting layer (3).

The organic light emitting device of the present application may be manufactured by materials and methods known in the art, except that two or more layers of the organic material layers each include the compound of Formula 1 and Formula 2 of the present application.

When the organic light emitting diode 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 of the present application may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, metal or conductive metal oxides or alloys thereof are deposited on the substrate to form an anode. And an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer thereon, and then 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 compounds of Formulas 1 and 2 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. 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.

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 anode materials that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SnO ₂ : Combination of metals and oxides such as 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.

The cathode material is generally a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the cathode materials 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.

The hole injection layer is a layer for injecting holes from the electrode, and has a capability of transporting holes to the hole injection material, has an effect of hole injection at the anode, excellent hole injection effect to the light emitting layer or the light emitting material, and produced in the light emitting layer The compound which prevents the excitons from moving to the electron injection layer or the 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 material 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-based Organic substances, anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer. The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocyclic containing compounds include dibenzofuran derivatives, ladder type furan compounds, and pyrides. Midine derivatives and the like, but is not limited thereto.

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 transporting material is a material that can inject electrons well from the cathode and transfer the electrons to the light emitting layer. Suitable. Specific examples thereof 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.

The electron injection layer is a layer that injects electrons from an electrode, has an ability to transport electrons, has an electron injection effect from a cathode, an electron injection effect with respect to a light emitting layer or a light emitting material, and 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.

The hole blocking layer is a layer for preventing the cathode from reaching the hole, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double-sided emission type according to a material used.

Fabrication of an organic light emitting device including the compound represented by Chemical Formulas 1 and 2 will be described in detail in the following Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

<Production example>

[Synthesis of BH-1]

                                                         [BH-1]

9-bromo-10- (naphthalen-1-yl) anthracene (20 g, 52.2 mmol), naphthalen-2-yl boronic acid (10.8 g, 62.6 mmol), Pd (t-Bu ₃ P) ₂ (0.13 g, 0.02 mmol) was added to a 2M K ₂ CO ₃ aqueous solution (50 mL) and THF (200 mL) and stirred at reflux for about 12 hours. After the reaction, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, distilled under reduced pressure and recrystallized with Tol / EA to obtain BH-1 (12.0 g, 53%): MS [M] = 430

[Synthesis of BH-2]

                                                         [BH-2]

BH-2 was synthesized according to the synthesis method of BH-1. (Yield 55%, MS [M] = 506).

[Synthesis of BH-3]

                                                         [BH-3]

BH-3 was synthesized according to the synthesis method of BH-1. (Yield 64%, MS [M] = 456)

[Synthesis of BH-4]

                                                         [BH-4]

BH-4 was synthesized according to the synthesis method of BH-1. (Yield 51%, MS [M] = 546).

[Synthesis of BH-5]

                                                         [BH-5]

BH-5 was synthesized according to the synthesis method of BH-1. (Yield 60%, MS [M] = 471).

[Synthesis of ET-B]

                                                         [ET-B]

ET-B was synthesized according to the synthesis method of BH-1. (Yield 51%, MS [M] = 702)

 [Synthesis of ET-C]

                                                         [ET-C]

 ET-C was synthesized according to the synthesis method of BH-1. (Yield 48%, MS [M] = 599)

[Synthesis of ET-D]

                                                         [ET-D]

 ET-D was synthesized according to the synthesis method of BH-1. (Yield 50%, MS [M] = 625).

<Example 1>

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) having a thickness of 1,400 kPa was put in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as 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 following compound HI-A and hexanitrile hexaazatriphenylene (HAT) were sequentially vacuum deposited to a thickness of 650 kPa and 50 kPa, respectively, on the prepared ITO transparent electrode to form a hole injection layer.

 The following compound HT-A was vacuum deposited to a thickness of 600 kPa as a hole transport layer, and the following compound HT-B was thermally vacuum deposited to a thickness of 50 kPa as an electron blocking layer. Subsequently, the following host compound BH-1 and 4 wt% of the dopant compound BD were vacuum deposited to a thickness of 200 kPa as a light emitting layer. Subsequently, the following compounds ET-B and Liq were thermally vacuum deposited to a thickness of 360 kPa in a ratio of 1: 1 using an electron transporting layer and an electron injection layer, and then Liq was vacuum deposited to a thickness of 5 kPa. Magnesium and silver were sequentially deposited on the electron injection layer at a thickness of 10 kW in a ratio of 10: 1 and aluminum was deposited at a thickness of 1000 kW to form a cathode, thereby manufacturing an organic light emitting device.

<Example 2>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the ET-C was used instead of the ET-B.

<Example 3>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the ET-D was used instead of the ET-B.

<Example 4>

An organic light emitting device was manufactured in the same manner as in Example 1, except that BH-2 was used instead of BH-1.

Example 5

An organic light-emitting device was manufactured in the same manner as in Example 4, except that the ET-C was used instead of the ET-B.

<Example 6>

An organic light-emitting device was manufactured in the same manner as in Example 4, except that the ET-D was used instead of the ET-B.

<Example 7>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that BH-3 was used instead of BH-1.

<Example 8>

An organic light emitting device was manufactured in the same manner as in Example 7, except that the ET-C was used instead of the ET-B.

Example 9

An organic light emitting device was manufactured in the same manner as in Example 7, except that the ET-D was used instead of the ET-B.

<Example 10>

An organic light emitting device was manufactured in the same manner as in Example 1, except that BH-4 was used instead of BH-1.

<Example 11>

An organic light-emitting device was manufactured in the same manner as in Example 10, except that the ET-C was used instead of the ET-B.

<Example 12>

An organic light emitting device was manufactured in the same manner as in Example 10, except that the ET-D was used instead of the ET-B.

Example 13

An organic light-emitting device was manufactured in the same manner as in Example 1, except that BH-5 was used instead of BH-1.

<Example 14>

An organic light-emitting device was manufactured in the same manner as in Example 13, except that the ET-C was used instead of the ET-B.

<Example 15>

An organic light-emitting device was manufactured in the same manner as in Example 13, except that the ET-D was used instead of the ET-B.

Comparative Example 1

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the ET-A was used instead of the ET-B.

Comparative Example 2

An organic light-emitting device was manufactured in the same manner as in Example 4, except that the ET-A was used instead of the ET-B.

Comparative Example 3

An organic light-emitting device was manufactured in the same manner as in Example 7, except that the ET-A was used instead of the ET-B.

<Comparative Example 4>

An organic light-emitting device was manufactured in the same manner as in Example 10, except that the ET-A was used instead of the ET-B.

Comparative Example 5

An organic light-emitting device was manufactured in the same manner as in Example 13, except that the ET-A was used instead of the ET-B.

Comparative Example 6

An organic light-emitting device was manufactured in the same manner as in Example 4, except that the ET-E was used instead of the ET-B.

Comparative Example 7

An organic light-emitting device was manufactured in the same manner as in Example 4, except that the ET-F was used instead of the ET-B.

<Comparative Example 8>

An organic light-emitting device was manufactured in the same manner as in Example 4, except that the ET-G was used instead of the ET-B.

Comparative Example 9

An organic light-emitting device was manufactured in the same manner as in Example 1, except that BH-6 was used instead of BH-1.

Comparative Example 10

An organic light emitting device was manufactured in the same manner as in Example 2, except that BH-6 was used instead of BH-1.

Comparative Example 11

An organic light emitting device was manufactured in the same manner as in Example 3, except that BH-6 was used instead of BH-1.

Example Host Electron transport layer @ 10 mA / cm ² @ 20 mA / cm ² Voltage (V) Efficiency (cd / A) color Life (hr) Example 1 BH-1 ET-B 3.65 6.87 blue 140 Example 2 BH-1 ET-C 3.67 6.89 blue 150 Example 3 BH-1 ET-D 3.63 6.81 blue 160 Example 4 BH-2 ET-B 3.60 6.37 blue 150 Example 5 BH-2 ET-C 3.58 6.49 blue 150 Example 6 BH-2 ET-D 3.50 6.67 blue 155 Example 7 BH-3 ET-B 3.74 6.34 blue 160 Example 8 BH-3 ET-C 3.72 6.45 blue 155 Example 9 BH-3 ET-D 3.69 6.56 blue 150 Example 10 BH-4 ET-B 3.48 6.76 blue 130 Example 11 BH-4 ET-C 3.44 6.83 blue 130 Example 12 BH-4 ET-D 3.42 6.88 blue 135 Example 13 BH-5 ET-B 3.46 6.84 blue 145 Example 14 BH-5 ET-C 3.45 6.85 blue 145 Example 15 BH-5 ET-D 3.42 6.85 blue 150 Comparative Example 1 BH-1 ET-A 4.15 5.89 blue 115 Comparative Example 2 BH-2 ET-A 4.23 5.54 blue 90 Comparative Example 3 BH-3 ET-A 4.30 5.36 blue 85 Comparative Example 4 BH-4 ET-A 3.93 4.88 blue 102 Comparative Example 5 BH-5 ET-A 3.91 4.71 blue 105 Comparative Example 6 BH-2 ET-E 4.10 4.12 blue 70 Comparative Example 7 BH-2 ET-F 3.81 5.94 blue 120 Comparative Example 8 BH-2 ET-G 4.36 3.66 blue 80 Comparative Example 9 BH-6 ET-B 4.40 4.22 blue 80 Comparative Example 10 BH-6 ET-C 4.38 5.52 blue 70 Comparative Example 11 BH-6 ET-D 4.38 5.64 blue 75

As can be seen in Table 1, when the compound represented by the formula (1) of the present invention as an electron transporting layer, the compound represented by the formula (2) as a host material of the light emitting layer is used in terms of voltage, efficiency and lifetime It was confirmed.

Comparing Examples 4 to 6 and Comparative Examples 6 to 8, when the triazine compound of Formula 1 was used as the electron transport layer, excellent effects in terms of voltage, efficiency and lifespan were confirmed. Examples 1 to 3 and Comparative Examples Comparing 9 to 11, when the compound having at least one of Ar 4 and Ar 5 of the anthracene compound of Formula 2 having 10 or more carbon atoms was used as the light emitting layer, excellent effects in terms of voltage, efficiency and lifetime were confirmed.

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

Claims (8)

Anode; A cathode provided to face the anode; In the organic light emitting device comprising a light emitting layer provided between the anode and the cathode,
Further provided with an organic material layer provided between the cathode and the light emitting layer and comprising a compound represented by the following formula (1),
The light emitting layer is an organic light emitting device comprising a compound represented by the formula (2):
[Formula 1]

In Chemical Formula 1,
Ar1 to Ar3 are different from each other,
Ar1 and Ar2 each independently represent a phenyl group; Naphthyl group; Biphenyl group; Terphenyl group; Anthracene groups; Or phenanthrene groups,
Ar3 is a fluorene group substituted with a cyano group and a phenyl group,
[Formula 2]

In Chemical Formula 2,
Ar4 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,
At least one of Ar4 and Ar5 is an aryl group having 10 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms,
R 5 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; Substituted or unsubstituted C6-C30 aryl group; Or a substituted or unsubstituted C 2-30 heteroaryl group,
n is an integer of 0-8, and R <5> when n is two or more is mutually same or different. delete The organic light emitting device of claim 1, wherein Ar3 is represented by the following Chemical Formula 1-1:
[Formula 1-1]

In Chemical Formula 1-1,
R1 to R4 are the same as or different from each other, and each independently hydrogen; Cyano group; Or a phenyl group,
At least one of R1 to R4 is a phenyl group,
At least one of R1 to R4 is a cyano group,
L1 is a direct bond,
l is 1,
m is an integer of 1 to 3,
n is an integer from 1 to 4,
When m and n are each an integer of 2 or more, the structures in two or more parentheses are the same or different from each other. The method according to claim 1, wherein Ar4 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted fluorene group; Substituted or unsubstituted anthracene group; Substituted or unsubstituted phenanthrene group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted carbazole group; Substituted or unsubstituted carbazole condensed ring group; Substituted or unsubstituted benzofluorene group; Or a substituted or unsubstituted benzonaphthofuran group,
Ar5 is a substituted or unsubstituted naphthyl group; Substituted or unsubstituted fluorene group; Substituted or unsubstituted anthracene group; Substituted or unsubstituted phenanthrene group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted carbazole group; Substituted or unsubstituted carbazole condensed ring group; Substituted or unsubstituted benzofluorene group; Or a substituted or unsubstituted benzonaphthofuran group. The organic light emitting device of claim 1, wherein R5 is hydrogen. The organic light emitting device of claim 1, wherein the substituent of the compound represented by Chemical Formula 1 is selected from the following table:

The organic light emitting device of claim 1, wherein the substituent of the compound represented by Chemical Formula 2 is selected from the following table:

The organic light emitting device of claim 1, wherein the organic material layer is an electron transport layer.

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