KR102280260B1 - Novel hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel heterocyclic compound and organic light emitting device using the same {NOVEL HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

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

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

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

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

Korean Patent Publication No. 10-2000-0051826

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

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

[Formula 1]

In Formula 1,

Q is a substituted or unsubstituted C _10-30 aromatic ring;

Y is O or S;

L is a single bond; Or a substituted or unsubstituted C _6-60 arylene,

each X is independently N or C(R ₄ ) with the proviso that at least one of X is N,

Ar ₁ and Ar ₂ are each independently hydrogen; heavy hydrogen; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,

a to c are each independently an integer of 0 to 3,

R ₁ to R ₄ are each independently hydrogen; heavy hydrogen; halogen; cyano; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 alkoxy; substituted or unsubstituted C _1-60 thioalkyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _6-60 aryl; or tri(C _1-60 alkyl)silyl, or combine with each other to form a substituted or unsubstituted monocyclic or polycyclic ring.

In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1 above. do.

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

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 an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron injection and transport layer 8, and a cathode 4 will show

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

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

,

, 또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

,

, or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an aryl phosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more of the above-exemplified substituents connected . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 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 specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

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

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

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

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

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. 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 preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

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

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, P, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

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

In Formula 1, preferably Q is naphthalene; phenanthrene; or a triphenylene ring.

More preferably, Chemical Formula 1 may be the following Chemical Formulas 1-1 to 1-4.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

Descriptions of Y, a to c, R ₁ to R ₃ , L, X, Ar ₁ and Ar ₂ are as defined above.

Preferably L is a single bond; phenylene; biphenyldiyl; or naphthalenediyl.

Also, preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of the following.

Preferably, a to c may all be 0.

For example, the compound may be selected from the group consisting of:

Meanwhile, the compound represented by Chemical Formula 1 may be prepared by a preparation method as shown in Scheme 1 below.

[Scheme 1]

Reaction Scheme 1 is a Suzuki coupling reaction, and each reaction is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, the present invention provides an organic light emitting device including the compound represented by the formula (1). In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1 above. 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, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In addition, the organic layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 It may include the indicated compound.

In addition, the organic layer may include an emission layer, and the emission layer may include a compound represented by Formula 1 above.

In addition, the organic layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include the compound represented by Formula 1 above.

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously transports and injects electrons may include the compound represented by Formula 1 above.

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

Also, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Also, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, one or more organic 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 .

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 Formula 1 may be included in the light emitting layer.

2 is an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron injection and transport layer 8, and a cathode 4 will show In such a structure, the compound represented by Formula 1 may be included in at least one of the hole injection layer, the hole transport layer, the light emitting layer, and the electron injection and transport layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Formula 1 above. Also, 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, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. and forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Formula 1 may be formed 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 coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode 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.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SNO _{2 :Sb;} conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and 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 the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect with respect to the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. Preferably, 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 material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

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

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, etc., but is not limited thereto.

The emission layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is a substituted or unsubstituted derivative. It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. As an electron transport material, a material that can receive electrons from the cathode and transfer them to the light emitting layer is suitable. Do. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may 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 and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals 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) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

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

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

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

Example 1 (E1)

1) Preparation of E1-P1

The formula 1-(2-bromophenyl)naphthalene compound (20g, 70.6mmol) was added to 200mL of tetrahydrofuran, and n-butyllithium (25.4mL, 63.6mmol) was added dropwise at -78°C, followed by stirring for about 1 hour. do. After adding 2-bromo-9H-xanthene-9-one compound (15.5 g, 56.5 mmol), the mixture was stirred at room temperature for 2 hours. After extraction with ethyl acetate, it was concentrated to prepare a compound represented by the above formula E1-P1 (23.0 g, yield 95%).

MS [M+H]+ = 479

2) Preparation of E1-P2

The formula E1-P1 (23 g, 50.0 mmol) was added to 200 mL of acetic acid, and 1 to 2 drops of sulfuric acid were added at 80°C, followed by reflux for 3 hours. After the reaction was terminated by lowering the temperature to room temperature, the white solid was filtered by filtration. The filtered white solid was washed twice with THF and ethyl acetate, respectively, to prepare a compound represented by Formula E1-P2 (17.7 g, yield 80%).

MS [M+H] ⁺ = 461

3) Preparation of E1-P3

After completely dissolving the compound represented by the formula E1-P2 (17g, 36.8mmol) and the formula E1-P2-A compound (10.3g, 40.5mmol) in Dioxane (170mL), potassium acetate (10.8g, 110.5mmol) was added was added and stirred with heating. After the reaction was terminated by lowering the temperature to room temperature, the potassium carbonate solution was removed and filtered to remove potassium acetate. The filtered solution was solidified with ethanol and filtered. The white solid was washed twice with ethanol, respectively, to prepare a compound (15.3 g, yield 82%) represented by Chemical Formulas E1-P3.

MS [M+H] ⁺ = 509

4) Preparation of E1

After completely dissolving the compound represented by the formula E1-P3 (7 g, 13.8 mmol) and the compound represented by the formula E1-P3-A (3.7 g, 13.8 mmol) in THF (100 mL), potassium carbonate (5.7 g, 41.3 mmol) was dissolved in 40 mL of water and added. After adding tetrakistriphenyl-phosphinopalladium (0.48 g, 0.413 mmol), the mixture was heated and stirred for 8 hours. After the reaction was terminated by lowering the temperature to room temperature, the potassium carbonate solution was removed and the white solid was filtered. The filtered white solid was washed twice with THF and ethyl acetate, respectively, to prepare a compound represented by Formula E1 (5.9 g, yield 70%).

MS [M+H] ⁺ = 614

Example 2 (E2)

A compound represented by Formula E2 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 766

Example 3 (E3)

A compound represented by Chemical Formula E3 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 790

Example 4 (E4)

A compound represented by Formula E4 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 613

Example 5 (E5)

A compound represented by Chemical Formula E5 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 689

Example 6 (E6)

A compound represented by Chemical Formula E6 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 690

Example 7 (E7)

A compound represented by Formula E7 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 740

Example 8 (E8)

A compound represented by Chemical Formula E8 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 642

Example 9 (E9)

A compound represented by Chemical Formula E9 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 706

Example 10 (E10)

A compound represented by Formula E10 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 706

Example 11 (E11)

A compound represented by Chemical Formula E11 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 757

Example 12 (E12)

A compound represented by Formula E12 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 720

Example 13 (E13)

A compound represented by Chemical Formula E13 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 740

Example 14 (E14)

A compound represented by Formula E14 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was prepared as in the above reaction scheme.

MS [M+H] ⁺ = 729

[Experimental Example 1]

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. In this case, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HI-A compound was thermally vacuum deposited to a thickness of 600 Å to form a hole injection layer. A hole transport layer was formed by sequentially vacuum-depositing 50 Å of the following HAT compound and 60 Å of the following HT-A compound on the hole injection layer.

Then, the following BH compound and BD compound were vacuum-deposited in a weight ratio of 25:1 to a thickness of 20 nm on the hole transport layer to form a light emitting layer.

On the light emitting layer, the compound (E1) of Example 1 and the following LiQ compound were vacuum-deposited at a weight ratio of 1:1 to form an electron injection and transport layer to a thickness of 350 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.9 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 1×10 ^{- By maintaining 7} to 5 × 10 ^-5 torr, an organic light emitting device was manufactured.

Experimental Examples 2 to 14

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that compounds (E2 to E14) of Examples 2 to 14 were used instead of Compound (E1) of Example 1.

Comparative Examples 1 to 9

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the following compounds (ET-1-A to ET-1-I) were used instead of the compound (E1) of Example 1.

The driving voltage and luminous efficiency were measured at a current density of ^{10 mA/cm 2} for the organic light-emitting devices prepared in the Experimental Examples and Comparative Examples, and the time at which the luminance becomes 90% compared to the initial luminance at a current density of ^{20 mA/cm 2 (T90)} was measured. The results are shown in Table 1 below.

division compound Voltage
(V@10 mA/cm ² ) efficiency
(cd/A@10 mA/cm ² ) color coordinates
(x, y) Life (h)
T90 at 20 mA/cm ² ) Experimental Example 1 compound E1 4.27 5.15 (0.142, 0.096) 281 Experimental Example 2 compound E2 4.10 5.25 (0.142, 0.096) 222 Experimental Example 3 compound E3 4.22 5.17 (0.142, 0.096) 230 Experimental Example 4 compound E4 4.33 5.27 (0.142, 0.096) 218 Experimental Example 5 compound E5 4.09 5.27 (0.142, 0.096) 212 Experimental Example 6 compound E6 4.29 5.10 (0.142, 0.097) 294 Experimental Example 7 compound E7 4.30 4.98 (0.142, 0.096) 300 Experimental Example 8 compound E8 4.25 5.18 (0.142, 0.099) 269 Experimental Example 9 compound E9 4.17 5.20 (0.142, 0.096) 270 Experimental Example 10 compound E10 4.10 5.23 (0.142, 0.099) 220 Experimental Example 11 compound E11 4.45 4.95 (0.142, 0.096) 297 Experimental Example 12 compound E12 4.44 4.96 (0.142, 0.097) 294 Experimental Example 13 compound E13 4.38 5.00 (0.142, 0.096) 214 Experimental Example 14 compound E14 4.48 5.06 (0.142, 0.096) 200 Comparative Example 1 Compound ET-1-A 6.00 2.11 (0.142, 0.096) 88 Comparative Example 2 Compound ET-1-B 5.89 2.31 (0.142, 0.096) 74 Comparative Example 3 Compound ET-1-C 4.44 4.94 (0.142, 0.096) 100 Comparative Example 4 Compound ET-1-D 4.50 4.83 (0.142, 0.096) 108 Comparative Example 5 Compound ET-1-E 4.41 4.91 (0.142, 0.096) 74 Comparative Example 6 Compound ET-1-F 4.67 4.92 (0.142, 0.096) 66 Comparative Example 7 Compound ET-1-G 4.20 4.99 (0.142, 0.097) 77 Comparative Example 8 Compound ET-1-H 4.20 5.04 (0.142, 0.097) 60 Comparative Example 9 Compound ET-1-I 4.33 4.95 (0.142, 0.097) 81

As shown in Table 1, the compound represented by Formula 1 according to the present invention may be used in an organic material layer capable of simultaneously performing electron injection and electron transport of the organic light emitting device.

Comparing Experimental Examples 1 to 8 and Experimental Example 13 and Experimental Examples 9 to 11 and Experimental Example 14 in Table 1 above, the effects of both cores of xanthene or thioxanthene are all of the organic light emitting diodes without distinction. It was confirmed that it showed remarkably excellent characteristics in terms of driving voltage, efficiency and lifespan.

Comparing the experimental examples in Table 1 and Comparative Examples 1 and 2, the compound in which triazine or pyrimidine is substituted for xanthene or thioxanthene as shown in Formula 1 according to the present invention is triazine or xanthene or thioxanthene It was confirmed that pyrimidine showed significantly superior properties in terms of efficiency and lifespan of the organic light emitting diode compared to the unsubstituted compound.

Comparing the Experimental Example of Table 1 with Comparative Examples 3,4, 7, 8 and 9, the compound in which an aryl ring is formed in the fluorene group of xanthene or thioxanthene as shown in Formula 1 according to the present invention is xanthene or thioxanthene It was confirmed that the organic light emitting diode showed significantly superior characteristics in terms of lifespan compared to the compound in which an aryl ring was not formed in the fluorene group.

Comparing the experimental examples of Table 1 and Comparative Examples 3,4, 7, 8 and 9, as shown in Formula 1 according to the present invention, an aryl ring and a triazine or pyrimidine in the fluorene group of xanthene or thioxanthene are different planes It was confirmed that the compound substituted with xanthene or thioxanthene exhibits significantly superior characteristics in terms of lifespan of the organic light emitting device compared to compounds in which an aryl ring and a triazine or pyrimidine are substituted on the same plane as the fluorene group of xanthene or thioxanthene.

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron injection and transport layer

Claims (8)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
Q is a substituted or unsubstituted C _10-30 aromatic ring;
Y is O or S;
L is a single bond; Or a substituted or unsubstituted C _6-60 arylene,
each X is independently N or C(R ₄ ) with the proviso that at least one of X is N,
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; _{C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted O and S; pyridinyl; or quinolinyl;
a to c are each independently an integer of 0 to 3,
R ₁ to R ₄ are each independently hydrogen; or deuterium.
According to claim 1,
Q is naphthalene; phenanthrene; or a triphenylene ring.
According to claim 1,
Formula 1 is a compound represented by the following Formulas 1-1 to 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
Descriptions of Y, a to c, R ₁ to R ₃ , L, X, Ar ₁ and Ar ₂ are as defined in claim 1.
According to claim 1,
L is a single bond; phenylene; biphenyldiyl; or naphthalenediyl.
According to claim 1,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

According to claim 1,
a to c are all 0;
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 at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to any one of claims 1 to 7 which is an organic light emitting device.

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