KR102392657B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device comprising the same

The present invention relates to a novel 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. 10-2013-073537

The present invention relates to a novel 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,

X is O or S;

Y ₁ , Y ₂ and Y ₃ are each independently CH; or N, provided that at least two of Y ₁ , Y ₂ and Y ₃ are N,

Ar ₁ , Ar ₂ , and Ar ₃ are each independently, substituted or unsubstituted C _6-60 aryl; or C _5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S, provided that at least one of Ar ₁ , Ar ₂ and Ar ₃ is further substituted with deuterium;

R ₁ , R ₂ and R ₃ are each independently hydrogen; or substituted or unsubstituted C _1-60 alkyl;

n is an integer from 0 to 5,

m and o are each independently an integer of 0 to 3.

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 of the present invention as described above.

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 the above-described Chemical Formula 1 may be used as a material for the light emitting layer.

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 shows 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 transport layer 8, and a cathode 4 did it

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

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; a 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 arylphosphine 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, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . 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, 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 number of carbon atoms in the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl 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, 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, thiazolyl group, isoxazolyl group group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, 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 example of the above-described alkyl group. In the present specification, the description of the heterocyclic group described above for heteroaryl among heteroarylamines 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.

Preferably, in Formula 1, when one or more of Ar ₁ , Ar ₂ , or Ar ₃ is further substituted with deuterium, three or more deuterium per ring may be independently substituted.

Preferably, the compound represented by Formula 1 may be any one selected from compounds represented by Formulas 2 to 5:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5,

X, Y ₁ , Y ₂ , Y ₃ , Ar ₁ , Ar ₂ , Ar _{3 ,} R ₁ , R ₂ , R ₃ , n, m and o are as defined above.

Preferably, Ar ₁ , Ar ₂ and Ar ₃ are each independently, phenyl; biphenylyl; terphenylyl; naphthyl; anthracenyl; phenanthrenyl; triphenylenyl; dimethyl fluorenyl; dibenzofuranyl or dibenzothiophenyl.

Preferably, R ₁ , R ₂ and R ₃ may be hydrogen or substituted or unsubstituted C _1-10 alkyl.

Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of:

.

.

In the compound represented by Formula 1 according to the present invention, a monocyclic nitrogen-containing hetero ring which is an electron accepting unit at position 3 of the dibenzofuran or dibenzothiophene structure, and a carbazole group as an electron donor unit at the 2nd position on the opposite side It has a substituted structure. Each position is the most optimized position to act as an electron donor and electron acceptor for dibenzofuran or dibenzothiophene, which is advantageous for both electron transport and hole transport. It has characteristics of voltage and high efficiency. In addition, the structure of Formula 1 includes a structure in which deuterium is substituted, and deuterium has a higher atomic weight than hydrogen, so the material containing it has a smaller vibration mode than a material containing only hydrogen, which is the non-radiative decay time in the excited state In particular, it increases the stability of triplet excitons. Therefore, when the compound represented by Formula 1 is applied as the phosphorescent host material of the light emitting layer in which triplet excitons are mainly involved, device characteristics of a long life can be realized.

The compound represented by Formula 1 may be prepared through the following Reaction Scheme 1, and may be more specific in Preparation Examples to be described later.

[Scheme 1]

In the above formula, variables other than Y ₄ and Y ₅ are as defined above, and Y ₄ and Y ₅ are each independently halogen, preferably bromo or chloro.

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 intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

In addition, the present invention provides an organic light emitting device comprising the compound represented by Formula 1 above. 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 layer of the organic material layer 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 The indicated compounds are included.

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

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously injects and transports electrons includes the compound represented by Formula 1 above. In particular, the compound represented by Formula 1 according to the present invention has excellent thermal stability, a deep HOMO level of 6.0 eV or more, a high triplet energy (ET), and hole stability. In addition, when the compound represented by Formula 1 is used in an organic layer capable of simultaneously performing electron injection and electron transport, an n-type dopant used in the art may be mixed and used.

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.

In addition, 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. In addition, 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 diode 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 shows 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 transport layer 8, and a cathode 4 did it 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 transport layer.

In the organic light emitting device according to the present invention, the organic material layer including the compound represented by Chemical Formula 1 may be a light emitting layer, and preferably, the light emitting layer may further include a compound represented by the following Chemical Formula 6:

[Formula 6]

In Formula 6,

Ar ₄ and Ar ₅ are each independently, substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,

R ₄ and R ₅ are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,

a and b are each independently an integer of 0-7.

Preferably, Ar ₄ and Ar ₅ are each independently phenyl; biphenylyl; terphenylyl; naphthyl; dibenzofuranyl; dibenzothiophenyl; Or it may be dimethyl fluorenyl.

Preferably R ₄ and R ₅ may be hydrogen.

Preferably, the compound represented by Formula 6 may be any one selected from the group consisting of:

.

.

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 diode 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, after forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, 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, spray method, 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 material 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 multi-layered 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 on 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. 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 material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, and conductive polymers of polyaniline and polythiophene series, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. A material capable of transporting holes from the anode or hole injection layer to the light emitting layer as a hole transport material. A material with high hole mobility. 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, and the like, 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 heterocyclic compound containing compound. 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 types. 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, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted 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, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. 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 intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

[ Synthesis example ]

Synthesis example 1: Synthesis of intermediate compound 1-1

Dissolve 2-bromo-7-chlorodibenzo[b,d]furan (20.0g, 71.0mmol) and intermediate a-1 (21.8g, 74.6mmol) in 300ml THF in a 3-neck flask, and potassium carbonate (39.3g, 284.2mmol) is dissolved in 100 ml of H2O. Here, tetrakis(triphenylphosphine)palladium(0) (4.1g, 3.6mmol) was added, and the mixture was stirred for 8 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, and extracted with ethyl acetate. After drying the extract with MgSO4, filtration and concentration, the sample was purified by silica gel column chromatography to obtain 25.2 g of Compound 1-1. (yield 79%, MS[M+H]+= 448)

Synthesis example 2: Synthesis of intermediate compound 1-2

Compound 1-1 (25.0 g, 55.7 mmol), Bis (pinacolato)diboron (17.0 g, 66.8 mmol), Bis(dibenzylideneacetone) palladium(0) (0.6 g, 1.1 mmol), Tricyclohexylphosphine (0.6 g, 2.2 mmol), potassium acetate (10.9 g, 111.4 mmol), and 375 ml of 1,4-dioxane were added thereto, and the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, water was added, and the mixture was extracted with ethyl acetate. After drying the extract with MgSO4, filtration and concentration, the sample was purified by silica gel column chromatography to obtain Compound 1-2. (20.5 g, yield 68%, MS: [M+H] + = 540)

Example 1: Synthesis of compound 1

In a 3-neck flask, dissolve compound 1-2 (20.0 g, 37.0 mmol) and intermediate b-1 (11.4 g, 38.9 mmol) in 300 ml of THF, and dissolve potassium carbonate (20.5 g, 148.0 mmol) in 100 ml of H2O. Here, tetrakis (triphenylphosphine)palladium(0) (2.1g, 1.9mmol) was added, and stirred for 8 hours under reflux condition under argon atmosphere After the reaction was completed, cooled to room temperature, the reaction solution was transferred to a separatory funnel, and extracted with ethyl acetate After the extract was dried over MgSO4, filtered and concentrated, the sample was purified by silica gel column chromatography, and then 7.6 g of compound 1 was obtained through sublimation purification (yield 32%, MS[M+H]+ = 645)

Example 2: Synthesis of compound 2

In Synthesis Example 1, compound 2 was prepared in the same manner as in the preparation of compound 1, except that the intermediate a-1 was changed to the intermediate a-2 and the intermediate b-1 was changed to the intermediate b-2. (MS[M+H] ⁺ = 650)

Example 3: Synthesis of compound 3

In Synthesis Example 1, compound 3 was prepared in the same manner as in the preparation of compound 1, except that the intermediate a-1 was changed to the intermediate a-3 and the intermediate b-1 was changed to the intermediate b-2. (MS[M+H] ⁺ = 740)

Example 4: Synthesis of compound 4

In Synthesis Example 1, compound 4 was prepared by the same preparation method as that of compound 1, except that Intermediate a-1 was changed to Intermediate a-4 and Intermediate b-1 was changed to Intermediate b-3. (MS[M+H] ⁺ = 751)

Example 5: Synthesis of compound 5

In Synthesis Example 1, 2-bromo-7-chlorodibenzo[b,d]furan to 2-bromo-7-chlorodibenzo[b,d]thiophene, intermediate a-1 to intermediate a-5, intermediate b-1 Compound 5 was prepared in the same manner as in the preparation method of Compound 1, except that it was changed to Intermediate b-4 and used. (MS[M+H] ⁺ = 751)

[ Experimental example ]

Experimental example One

A glass substrate coated with ITO (Indium Tin Oxide) to a thickness of 1,400 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, 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, and after drying, it was 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 HT and 5% by weight of PD were thermally vacuum deposited to a thickness of 100 Å, and then only HT material was deposited to a thickness of 1150 Å to form a hole transport layer. The following EB was thermally vacuum-deposited to a thickness of 450 Å as an electron blocking layer thereon. Subsequently, compound 1 and 15 wt% of GD were used as dopants, and vacuum deposition was performed to a thickness of 400 Å. Then, as a hole blocking layer, the following ET-A was vacuum-deposited to a thickness of 50 Å. Then, as the electron transport and injection layer, the following ET-B and Liq were thermally vacuum-deposited at a ratio of 2:1 to a thickness of 250 Å, and then LiF and magnesium were vacuum-deposited to a thickness of 30 Å at a ratio of 1:1. On the electron injection layer, magnesium and silver were deposited in a ratio of 1:4 to a thickness of 160 Å to form a cathode, thereby manufacturing an organic light emitting diode.

By applying a current to the manufactured organic light emitting device, voltage, efficiency, and lifetime (T95) were measured, and the results are shown in Table 1 below. At this time, the voltage and efficiency were measured by applying a current density of 10 mA/cm ² , and T95 is the time until the initial luminance decreases to 95% at the current density of 20 mA/cm ² .

Experimental example 2-10 and comparison Experimental example 1 to 6

Organic light emitting devices of Experimental Examples 2 to 10 and Comparative Experimental Examples 1 to 6 were respectively manufactured using the same method as in Experimental Example 1, except that the host material was changed as shown in Table 1 below. In this case, when a mixture of two types of compounds is used as the host, the weight ratio between the host compounds is indicated in parentheses.

division host
matter @ 10mA/cm ² @ 20mA/cm ² Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Experimental Example 1 compound 1 4.68 47.5 120 Experimental Example 2 compound 2 4.65 47.2 125 Experimental Example 3 compound 3 4.63 47.0 115 Experimental Example 4 compound 4 4.62 48.3 130 Experimental Example 5 compound 5 4.70 49.2 120 Experimental Example 6 PGH:Compound 1 (60:40) 4.45 53.5 175 Experimental Example 7 PGH:Compound 2 (60:40) 4.49 54.1 180 Experimental Example 8 PGH:compound 3 (60:40) 4.43 54.3 180 Experimental Example 9 PGH:Compound 4 (60:40) 4.38 55.5 170 Experimental Example 10 PGH:compound 5 (60:40) 4.47 56.1 175 Comparative Experimental Example 1 GH-A 4.70 47.5 95 Comparative Experimental Example 2 GH-B 6.31 28.1 20 Comparative Experimental Example 3 GH-C 5.38 35.0 90 Comparative Experimental Example 4 GH-D 5.39 41.1 95 Comparative Experimental Example 5 PGH:GH-A (60:40) 4.43 53.2 150 Comparative Experimental Example 6 PGH:GH-C (60:40) 5.27 40.5 110

As shown in Table 1, it can be seen that when the compound of Formula 1 is used as a host of an organic electroluminescent device, it exhibits low voltage, high efficiency, and long lifespan compared to GH-B to GH-D having other connection positions. In particular, it can be confirmed that the lifespan is increased by deuterium substitution when compared with Compound 1 and GH-A. In addition, when used in combination with a compound of Formula 6 such as PGH, the effect becomes more remarkable, and exhibits a superior effect than when a compound of a different structure is mixed with the compound of Formula 6 and used.

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

Claims (12)

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

In Formula 1,
X is O or S;
Y ₁ , Y ₂ and Y ₃ are each independently CH; or N, provided that at least two of Y ₁ , Y ₂ and Y ₃ are N,
Ar ₁ , Ar ₂ , and Ar ₃ are each independently, substituted or unsubstituted C _6-60 aryl; or C _5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S, provided that at least one of Ar ₁ , Ar ₂ and Ar ₃ is further substituted with deuterium;
R ₁ , R ₂ and R ₃ are each independently hydrogen; or substituted or unsubstituted C _1-60 alkyl;
n is an integer from 0 to 5,
m and o are each independently an integer of 0 to 3.

The method of claim 1,
wherein when one or more of Ar ₁ , Ar ₂ and Ar ₃ is further substituted with deuterium, each independently is substituted with at least 3 deuterium per ring.
The method of claim 1,
The compound represented by Formula 1 is any one selected from compounds represented by the following Formulas 2 to 5, a compound:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5,
X, Y ₁ , Y ₂ , Y ₃ , Ar ₁ , Ar ₂ , Ar _{3 ,} R ₁ , R ₂ , R ₃ , n, m and o are as defined in claim 1.
The method of claim 1,
Ar ₁ , Ar ₂ and Ar ₃ are each independently, phenyl; biphenylyl; terphenylyl; naphthyl; anthracenyl; phenanthrenyl; triphenylenyl; dimethyl fluorenyl; dibenzofuranyl; or dibenzothiophenyl.
The method of claim 1,
R ₁ , R ₂ and R ₃ are each independently hydrogen; or substituted or unsubstituted C _1-10 alkyl.
The method of 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 organic material layer includes the compound according to any one of claims 1 to 6 which is an organic light emitting device.
8. The method of claim 7,
The organic material layer including the compound is a light emitting layer, Organic light emitting device.
9. The method of claim 8,
The light emitting layer further comprises a compound represented by the following formula (6), an organic light emitting device:
[Formula 6]

In Formula 6,
Ar ₄ and Ar ₅ are each independently, substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,
R ₄ and R ₅ are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,
a and b are each independently an integer of 0 to 7.
10. The method of claim 9,
Ar ₄ and Ar ₅ are each independently, phenyl; biphenylyl; terphenylyl; naphthyl; dibenzofuranyl; dibenzothiophenyl; or dimethyl fluorenyl, an organic light-emitting device.
10. The method of claim 9,
R ₄ and R ₅ are hydrogen, an organic light emitting device.
10. The method of claim 9,
The compound represented by Formula 6 is any one selected from the group consisting of, an organic light emitting device:

.

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