KR102134379B1 - Novel phenanthrene compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel phenanthrene compound and organic light emitting device comprising the same}

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

In general, the organic light emitting phenomenon refers to a phenomenon that converts 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, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.

The organic light emitting device generally has a structure including an anode and 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 formed of a multi-layer structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.

The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides a compound represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

L is substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted C _2-60 heteroarylene containing one or more of N, O and S,

Ar ₁ is substituted or unsubstituted C _6-60 aryl or C _2-60 heteroaryl including one or more of substituted or unsubstituted N, O and S,

Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of N, O and S.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and an organic light emitting device is provided. do.

The compound represented by Chemical Formula 1 may be used as a material of an organic material layer of an organic light emitting device, and may improve efficiency, low driving voltage, and/or life characteristics in the organic light emitting device. In particular, the compound represented by Formula 1 may be used as a hole injection and transport, electron suppression, light emission, electron transport, or electron injection material.

FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
2 is a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron suppressing layer (7), a light emitting layer (8), an electron transport layer (9), an electron injection layer (10) And it shows an example of an organic light-emitting device consisting of the cathode (4).

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a linkage to another substituent.

The term "substituted or unsubstituted" in this specification is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; An alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" 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 connected.

In this 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 oxygen of the ester group may be substituted with a straight chain, 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, 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 trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

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

In the present 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 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 are 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 a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. 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, steelbenyl 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 an exemplary 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 is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 25. 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 combine with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be back. However, it 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 heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl 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, thiazolyl group, Isooxazolyl groups, oxadiazolyl groups, thiadiazolyl groups, benzothiazolyl groups, phenothiazinyl groups and dibenzofuranyl groups, and the like, but are not limited thereto.

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

On the other hand, the present invention provides a compound of Formula 1:

[Formula 1]

In Chemical Formula 1,

L is substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted C _2-60 heteroarylene containing one or more of N, O and S,

Ar ₁ is substituted or unsubstituted C _6-60 aryl or C _2-60 heteroaryl including one or more of substituted or unsubstituted N, O and S,

Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of N, O and S.

Specifically, the compound of Formula 1 includes phenanthrene as a central structure, and the phenanthrene is a -N(Ar ₂ )(Ar ₃ ) functional group and an Ar ₁ functional group linked through L at positions 9 and 10 It has an asymmetric structure. Therefore, the functional groups combined around phenanthrene may be more advantageous in terms of voltage, efficiency and life characteristics of the organic light emitting device compared to when the functional groups are symmetrical.

Specifically, in the compound of Formula 1, L is substituted or unsubstituted C _6-24 arylene,

Ar ₁ is substituted or unsubstituted C _6-24 aryl or substituted or unsubstituted C _2-22 heteroaryl including one or more of N, O and S,

Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-25 aryl; Or it may be a substituted or unsubstituted C _2-20 heteroaryl containing one or more of N, O and S.

Preferably, L is any one selected from the group consisting of the following functional groups.

Also preferably, Ar ₁ is any one selected from the group consisting of the following functional groups.

Also preferably, Ar ₂ and Ar ₃ are each independently selected from the group consisting of the following functional groups.

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

0

The compound represented by Chemical Formula 1 may be prepared by the following Reaction Scheme 1.

[Scheme 1]

In Reaction Scheme 1, L, Ar ₁ , Ar ₂ and Ar ₃ are as defined above, X is halogen, and preferably X is bromo.

Reaction Scheme 1 is a Suzuki coupling reaction, in which a compound represented by Chemical Formula 1-1 and a compound represented by Chemical Formula 1-2 are reacted to prepare a compound represented by Chemical Formula 1.

At this time, the compound of Formula 1-1 may be prepared by the same method as in Scheme 2.

[Scheme 2]

In Reaction Scheme 1, Ar ₁ is as defined above, X is halogen, and preferably X is bromo.

The above manufacturing method may be more specific in the manufacturing examples to be described later.

In addition, the present invention provides an organic light emitting device comprising the compound represented by the formula (1). In one example, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and an organic light emitting device is provided. do.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron suppressing layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited to this, and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer simultaneously performing hole injection and transport, and the hole injection layer, a hole transport layer, or a layer simultaneously performing hole injection and transport may be represented by Formula 1 It includes the compound displayed.

In addition, the organic material layer may include an electron suppression layer, and the electron suppression layer includes a compound represented by Chemical Formula 1.

In addition, the organic material layer may include a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1.

Further, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes a compound represented by Chemical Formula 1.

In addition, the electron transport layer, the electron injection layer, or a layer that simultaneously performs electron transport and electron injection includes a compound represented by Chemical Formula 1.

In addition, the organic material layer includes a light emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by Chemical Formula 1.

Further, the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present invention may be an organic light emitting device of 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 the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.

2 is a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron suppressing layer (7), a light emitting layer (8), an electron transport layer (9), an electron injection layer (10) And it shows an example of an organic light-emitting device consisting of the cathode (4). In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron suppressing layer, the light emitting layer, the electron transport layer and the electron injection layer, preferably a hole injection layer, It may be included in one or more of the hole transport layer and the electron suppressing layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Chemical Formula 1. Further, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound represented by Chemical Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

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

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.

The positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth. 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), and indium zinc oxide (IZO); A combination of metal and oxide 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 to facilitate electron injection into an 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; There is a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is produced in the light emitting layer. A compound which prevents migration of the excitons to the electron injection layer or the electron injection material, and has excellent thin film formation ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances. Organic materials, anthraquinones, 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 from the hole injection layer to the light emitting layer. It is a material that transports holes from the anode or the hole injection layer as a hole transport material and transfers them to the light emitting layer. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

The electron suppressing layer is a layer that suppresses electron injection from the hole transport layer and the light emitting layer to the hole transport layer, and can increase the size of an energy barrier that serves to trap electrons in the light emitting layer than when the hole transport layer and the light emitting layer are in direct contact, Therefore, high luminous efficiency can be obtained. Specifically, the hole transporting material may be used as the electron suppressing layer. The electron suppressing layer may be made of only the hole transport material, or may have a structure in which the hole transport material is dispersed in an organic material such as an inorganic material or a polymer.

As the light-emitting material, a material capable of emitting light in the visible region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly(p-phenylenevinylene) (PPV)-based polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes, platinum complexes, and the like.

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 transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer, a material having high mobility for electrons Suitable. Specific examples include the Al complex 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 according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, followed by an aluminum layer or a silver layer in each case.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, an excellent electron injection effect on a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds and nitrogen-containing 5-membered ring derivatives, 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-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type, depending on the material used.

In addition, the compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

The preparation of the compound represented by Formula 1 and the organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the invention, and the scope of the invention is not limited by them.

Manufacturing example A

9,10-dibromophenanthrene (40.0 g, 119.76 mmol), and phenylboronic acid (16.80 g, 137.72 mmol) were dissolved in 380 mL of tetrahydrofuran in a 1000 mL round-bottom flask in a nitrogen atmosphere, followed by 2M. Aqueous potassium carbonate solution (190 mL) was added, tetrakis-(triphenylphosphine)palladium (4.15 g, 3.59 mmol) was added, followed by heating and stirring for 5 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 320 mL of ethyl acetate to prepare Compound A (10.58 g, 74%).

MS[M+H] ⁺ = 650

Manufacturing example B to J

Compounds B to J were prepared in the same manner as in Preparation Example A, except that the compounds shown in the above reaction formulas were used instead of phenylboronic acid as boronic acid.

Manufacturing example One

Compound A (7.26 g, 21.87 mmol), and compound a1 (11.09 g, 25.15 mmol) were completely dissolved in 260 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (130 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.76 g, 0.66 mmol) was added thereto, followed by heating and stirring for 4 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 260 mL of ethyl acetate to prepare Preparation Example 1 (10.58 g, 74%).

MS[M+H] ⁺ = 650

Manufacturing example 2

Compound A (6.34 g, 19.10 mmol) and Compound a2 (10.56 g, 21.96 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M potassium carbonate aqueous solution (120 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.66 g, 0.57 mmol) was added thereto, followed by heating and stirring for 2 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 ethyl acetate to prepare Preparation Example 2 (8.95 g, 68%).

MS[M+H] ⁺ = 689

Manufacturing example 3

Compound A (5.37 g, 16.17 mmol), and compound a3 (9.88 g, 18.60 mmol) were completely dissolved in 260 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (130 mL) was added. After adding tetrakis-(triphenylphosphine)palladium (0.56 g, 0.49 mmol), the mixture was heated and stirred for 7 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 200 mL of tetrahydrofuran to prepare Preparation Example 3 (9.25 g, 77%).

MS[M+H] ⁺ = 740

Manufacturing example 4

Compound A (5.31 g, 15.99 mmol), and Compound a4 (8.11 g, 18.39 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.55 g, 0.48 mmol) was added thereto, followed by heating and stirring for 3 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 mL of ethyl acetate to prepare Preparation Example 4 (6.37 g, 61%).

MS[M+H] ⁺ = 650

Manufacturing example 5

Compound A (4.67 g, 14.07 mmol), and compound a5 (8.36 g, 16.18 mmol) were dissolved in 180 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (90 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.49 g, 0.42 mmol) was added and then heated and stirred for 5 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 mL of ethyl acetate to prepare Preparation Example 5 (10.58 g, 74%).

MS[M+H] ⁺ = 726

Manufacturing example 6

Compound A (5.19 g, 15.63 mmol), and compound a6 (10.55 g, 17.98 mmol) were completely dissolved in 220 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (110 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.54 g, 0.47 mmol) was added thereto, followed by heating and stirring for 6 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 mL of ethyl acetate to prepare Preparation Example 6 (7.78 g, 63%).

MS[M+H] ⁺ = 796

Manufacturing example 7

Compound E (3.64 g, 10.96 mmol) and Compound a1 (6.70 g, 12.61 mmol) were completely dissolved in 120 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (60 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.38 g, 0.33 mmol) was added and then heated and stirred for 3 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate 170 mL to prepare Preparation Example 7 (5.92 g, 73%).

MS[M+H] ⁺ = 740

Manufacturing example 8

Compound B (6.95 g, 18.19 mmol), and compound a1 (11.11 g, 20.92 mmol) were completely dissolved in 220 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (110 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.63 g, 0.55 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 210 mL of ethyl acetate to prepare Preparation Example 8 (7.65 g, 60%).

MS[M+H] ⁺ = 700

Manufacturing example 9

Compound C (5.59 g, 13.70 mmol), and compound a1 (8.37 g, 15.76 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.47 g, 0.41 mmol) was added and then heated and stirred 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 ethyl acetate to prepare Preparation Example 9 (6.12 g, 62%).

MS[M+H] ⁺ = 726

Manufacturing example 10

Compound C (5.37 g, 13.16 mmol), and Compound a2 (7.28 g, 15.14 mmol) were completely dissolved in 200 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (100 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.46 g, 0.39 mmol) was added thereto, followed by heating and stirring for 3 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 ethyl acetate to prepare Preparation Example 10 (7.69 g, 76%).

MS[M+H] ⁺ = 766

Manufacturing example 11

Compound A (6.28 g, 14.02 mmol) and Compound a1 (7.11 g, 16.12 mmol) were completely dissolved in 210 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (105 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.49 g, 0.42 mmol) was added and then heated and stirred 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 ethyl acetate to prepare Preparation Example 11 (6.37 g, 59%).

MS[M+H] ⁺ = 766

Manufacturing example 12

Compound F (3.64 g, 10.96 mmol), and compound a7 (6.70 g, 12.61 mmol) were completely dissolved in 120 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (60 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.38 g, 0.33 mmol) was added and then heated and stirred for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate 170 mL to prepare Preparation Example 12 (5.92 g, 73%).

MS[M+H] ⁺ = 756

Manufacturing example 13

Compound G (5.49 g, 13.01 mmol), and compound a8 (8.78 g, 14.96 mmol) were completely dissolved in 180 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (90 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.45 g, 0.39 mmol) was added thereto, followed by heating and stirring for 5 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 mL of ethyl acetate to prepare Preparation Example 13 (8.16 g, 71%).

MS[M+H] ⁺ = 886

Manufacturing example 14

Compound G (6.14 g, 14.55 mmol), and compound a9 (7.78 g, 16.73 mmol) were completely dissolved in 200 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (100 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.50 g, 0.44 mmol) was added thereto, followed by heating and 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 220 mL of ethyl acetate to prepare Preparation Example 14 (8.16 g, 71%).

MS[M+H] ⁺ =764

Manufacturing example 15

Compound I (5.86 g, 13.89 mmol), and compound a10 (8.22 g, 15.97 mmol) were completely dissolved in 140 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (70 mL) was added. After adding tetrakis-(triphenylphosphine)palladium (0.48 g, 0.42 mmol), the mixture was heated and stirred for 6 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 200 mL of ethyl acetate to prepare Preparation Example 15 (9.14 g, 81%).

MS[M+H] ⁺ = 814

Manufacturing example 16

Compound H (4.75 g, 10.84 mmol) and Compound a11 (5.05 g, 12.47 mmol) were completely dissolved in 160 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (80 mL) was added. , Tetrakis-(triphenylphosphine) palladium (0.38 g, 0.33 mmol) was added and then heated and stirred 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 190 mL of ethyl acetate to prepare Preparation Example 16 (5.06 g, 65%).

MS[M+H] ⁺ = 720

Example 1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 에 was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer (Fischer Co.) was used as the detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeated for 10 minutes by repeating it twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and transporting to a plasma cleaner. In addition, the substrate was washed for 5 minutes using oxygen plasma, and then transferred to a vacuum evaporator.

On the ITO transparent electrode thus prepared, a compound represented by the following chemical formula HAT was thermally vacuum-deposited to a thickness of 100 Pa to form a hole injection layer. A hole transport layer was formed by vacuum-depositing a compound represented by the following Chemical Formula HT1 (1250HT) on the hole injection layer. Subsequently, an electron suppressing layer was formed on the hole transport layer by vacuum-depositing the compound of Preparation Example 1 with a thickness of 150 mm 2. Subsequently, a compound represented by the following Chemical Formula BH and a compound represented by the following Chemical Formula BD with a film thickness of 200 mm 2 were vacuum-deposited at a weight ratio of 25:1 on the electron suppressing layer to form a light emitting layer. A hole blocking layer was formed by vacuum-depositing a compound represented by the following Chemical Formula HB1 with a thickness of 50 mm 2 on the light emitting layer. Subsequently, on the hole blocking layer, a compound represented by the following Chemical Formula ET1 and a compound represented by the following Chemical Formula LiQ were vacuum-deposited at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 310 MPa. On the electron injection and transport layer, lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 1,000 순차적 were sequentially deposited to form a negative electrode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, the degree of vacuum upon deposition 2ⅹ10 ^-7 ~ An organic light-emitting device was manufactured by maintaining 5ⅹ10 ^-6 torr.

Example 1-2 to Example 1-16

An organic light emitting diode was manufactured according to the same method as Example 1-1 except for using the compound described in Table 1 below instead of the compound of Preparation Example 1.

Comparative example 1-1 to 1-5

An organic light emitting diode was manufactured according to the same method as Example 1-1 except for using the compound described in Table 1 below instead of the compound of Preparation Example 1. The compounds of EB1, EB2, EB3, EB4 and EB5 used in Table 1 below are as follows.

Experimental Example One

When current was applied to the organic light-emitting device manufactured in the above Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured and the results are shown in Table 1 below. T95 means the time required for the luminance to decrease from the initial luminance (1600 nit) to 95%.

compound
(Electronic suppression layer) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinate
(x,y) T95
(hr) Example 1-1 Preparation Example 1 4.50 6.41 (0.141, 0.046) 270 Example 1-2 Preparation Example 2 4.33 6.43 (0.141, 0.047) 285 Example 1-3 Preparation Example 3 4.56 6.44 (0.142, 0.04) 280 Example 1-4 Preparation Example 4 4.40 6.45 (0.142, 0.044) 280 Example 1-5 Preparation Example 5 4.53 6.56 (0.140, 0.045) 285 Example 1-6 Preparation Example 6 4.56 6.47 (0.141, 0.046) 285 Example 1-7 Preparation Example 7 4.64 6.59 (0.140, 0.044) 285 Example 1-8 Preparation Example 8 4.46 6.44 (0.141, 0.046) 275 Example 1-9 Preparation Example 9 4.41 6.42 (0.140, 0.045) 280 Example 1-10 Preparation Example 10 4.50 6.53 (0.141, 0.045) 295 Example 1-11 Preparation Example 11 4.53 6.45 (0.140, 0.046) 280 Example 1-12 Preparation Example 12 4.56 6.41 (0.141, 0.045) 270 Example 1-13 Preparation Example 13 4.68 6.36 (0.142, 0.044) 265 Example 1-14 Preparation Example 14 4.63 6.48 (0.143, 0.046) 280 Example 1-15 Preparation 15 4.62 6.33 (0.142, 0.045) 275 Example 1-16 Preparation Example 16 4.61 6.37 (0.141, 0.045) 290 Comparative Example 1-1 EB-1 4.56 5.94 (0.141, 0.044) 235 Comparative Example 1-2 EB-2 4.82 6.26 (0.143, 0.046) 165 Comparative Example 1-3 EB-3 5.02 5.83 (0.143, 0.048) 180 Comparative Example 1-4 EB-4 4.62 5.93 (0.143, 0.048) 220 Comparative Example 1-5 EB-5 5.23 5.64 (0.142, 0.047) 80

As shown in Table 1, the organic light-emitting device using the compound of the present invention as an electron suppressing layer showed a result of improving efficiency by 10% or more and lifetime by 20% or more.

Formula 1 of the present invention has a structure in which the amine substituted with an aryl or heteroaryl group is linked to the phenanthrene core in the 9th direction by a linker, and the aryl or heteroaryl substituent is adjacently connected in the 10th direction.

Comparative Example 1-1 without a substituent at an adjacent position of the phenanthrene core and Comparative Example 1-4 with a substituent not adjacent to each other have similar voltages, but exhibit poor efficiency and lifetime. Although adjacent substituents were connected, Comparative Example 1-2, in which one more amine group was substituted in the other direction of the phenanthrene core, had high efficiency but significantly reduced lifetime. In addition, Comparative Examples 1-3 in which the same two amine groups were connected in adjacent directions also significantly increased in voltage and inferior in efficiency and lifespan characteristics. In addition, the amine group in which the aryl group substituted without the linker (L) is directly connected to the ninth direction of the phenanthrene core, and Comparative Examples 1-5 including an aryl group at an adjacent position show the worst voltage and efficiency characteristics, and particularly have a long service life. The results were significantly reduced.

As shown in Table 1, it was confirmed that the compound according to the present invention has excellent electron blocking ability and is applicable to organic light emitting devices.

1: substrate 2: anode
3: organic layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron suppressing layer 8: emitting layer
9: electron transport layer 10: electron injection layer

Claims (7)

Compound represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
L is substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted C _2-60 heteroarylene containing one or more of N, O and S,
Ar ₁ is any one selected from the group consisting of the following functional groups,

Ar ₂ and Ar ₃ are each independently selected from the group consisting of the following functional groups.

According to claim 1,
L is substituted or unsubstituted C _6-24 arylene,
compound.
According to claim 1,
L is any one selected from the group consisting of the following functional groups:

delete delete According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of:

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer is selected from any one of claims 1 to 3 and 6. Organic light emitting device comprising a compound according to the.

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