KR102057303B1 - 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 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, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.

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

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

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 Formula 1:

[Formula 1]

In Chemical Formula 1,

X ₁ and X ₂ are each independently O or S,

L is a single bond; Substituted or unsubstituted C _6-60 arylene; Or C _1-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si, and S,

n is an integer from 0 to 4,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or C _1-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

R ₁ to R ₅ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or a C _1-60 heterocyclic group containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

a1 is an integer of 0 to 3,

a2 is an integer of 0 to 2,

a3 is an integer of 0-4.

In addition, the present invention is 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 one or more layers of the organic material layers include the compound represented by Chemical Formula 1. .

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

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG.
2 shows an example of an organic light emitting element consisting of 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. It is.

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

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

는 다른 치환기에 연결되는 결합을 의미하고, 단일 결합은 L로 표시되는 부분에 별도의 원자가 존재하지 않은 경우를 의미한다. In this specification,

Means a bond connected to another substituent, and a single bond means a case where no separate atom is present in a portion represented by L.

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

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

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

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

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

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

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

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

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

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

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

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

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

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, 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 (phenanthroline), thiazolyl group, Isooxazolyl group, oxdiazolyl 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, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the above-described alkyl group. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aforementioned aryl group or cycloalkyl group may be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic group is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding.

Meanwhile, in Chemical Formula 1, X ₁ may be O. Thus, X ₁ and X ₂ may be O, or X ₁ may be O and X ₂ may be S.

According to one embodiment, L is a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrenylene, substituted or unsubstituted Anthracenylene, substituted or unsubstituted fluoranthhenylene, substituted or unsubstituted triphenylenylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted fluorenylene Or substituted or unsubstituted spiro-fluorenylene.

For example, L can be a single bond or any one selected from the group consisting of:

Specifically, for example, L may be a single bond or any one selected from the group consisting of:

.

.

According to one embodiment, n may be 0, 1, or 2. For example, n can be 0 or 1. In this case, n represents the number of L, and when n is 2 or more, two or more L may be the same or different from each other. In addition, when n is 0, it means that L is a single bond.

According to one embodiment, Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-20 aryl; Or C _1-20 heteroaryl including 1 to 3 heteroatoms of substituted or unsubstituted O or S.

For example, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted phenyl; Substituted or unsubstituted biphenyl; Substituted or unsubstituted terphenyl; Substituted or unsubstituted naphthyl; Substituted or unsubstituted fluorenyl; Substituted or unsubstituted phenanthrenyl; Substituted or unsubstituted anthracenyl; Substituted or unsubstituted fluoranthenyl; Substituted or unsubstituted triphenylenyl; Substituted or unsubstituted pyrenyl; Substituted or unsubstituted chrysenyl; Substituted or unsubstituted fluorenyl; Substituted or unsubstituted spiro-fluorenyl; Substituted or unsubstituted carbazolyl; Substituted or unsubstituted benzocarbazolyl; Substituted or unsubstituted dibenzofuranyl; Or substituted or unsubstituted dibenzothiophenyl.

Specifically, for example, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of:

In the above,

Y ₁ is O, S, or NZ ₅ ,

Z ₁ to Z ₅ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; C _1-20 alkyl; C _1-20 haloalkyl; C _6-20 aryl; C _1-20 heteroaryl containing one heteroatom of O or S,

c1 is an integer of 0 to 5,

c2 is an integer of 0 to 4,

c3 is an integer of 0 to 7,

c4 is an integer of 0-3.

In the above, Z ₁ to Z ₅ are each independently hydrogen, phenyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl,

c1 to c4 may be each independently 0, 1, or 2.

More specifically, for example, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of:

According to an embodiment, R ₁ to R ₅ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; C _1-20 alkyl; Or C _6-20 aryl.

For example, R ₁ to R ₅ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; methyl; Or phenyl, and a1 to a3 may each independently be 0 or 1.

Specifically, for example, R ₁ to R ₃ may be hydrogen, and R ₄ and R ₅ may be methyl.

In this case, a1 represents the number of R _{1. When} a1 is 2 or more, two or more R ₁ may be the same or different. Description of a2 and a3 may be understood with reference to the description of a1 and the structure of Formula 1.

In addition, c1 represents the number of Z ₁ , and when c1 is 2 or more, two or more Z ₁ may be the same or different from each other. Description of c2 to c4 can be understood with reference to the description of c1 and the structure of the formula.

On the other hand, the compound may be represented by the formula 1A or 1B:

[Formula 1A]

[Formula 1B]

In Chemical Formulas 1A and 1B,

X ₂ is O or S, and descriptions of L, Ar ₁ and Ar ₂ are the same as defined in Formula 1 above.

For example, the compound may be any one selected from the group consisting of the following compounds 1-1 to 1-176:

The compound represented by the formula (1) has a structure in which an arylamine substituent is connected to a specific position of benzofuroxanthene or benzothiophenoxanthene core condensed with benzofuran or benzothiophene and xanthene, and an organic light emitting device using the same It can have high efficiency, low driving voltage, high brightness and long life.

On the other hand, the compound represented by the formula (1A) can be prepared by the production method as shown in Scheme 1, for example, the compound represented by the formula (1B) can be prepared by the production method as shown in Scheme 2 as an example.

 Scheme 1

Scheme 2

In Schemes 1 and 2, the description of X ₂ , L, Ar ₁ and Ar ₂ is the same as defined in Formula 1 above, X means halogen.

The compound represented by Formula 1 may be prepared by appropriately replacing the starting material in accordance with the structure of the compound to be prepared with reference to Schemes 1 and 2.

On the other hand, the present invention provides an organic light emitting device comprising the compound represented by the formula (1). In one embodiment, the present invention is 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 one or more layers of the organic material layers include the compound represented by Chemical Formula 1. .

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer 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 and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

The organic material layer may include a hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting holes, and the hole injection layer, a hole transport layer, or a layer for simultaneously injecting holes and transporting holes may be represented by Chemical Formula 1 above. It may include a compound represented.

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

In addition, the electron transport layer, the electron injection layer, or may include a layer for simultaneously transporting electrons and electron injection, the electron transport layer, the electron injection layer, or a layer for the simultaneous transport and electron injection is represented by the formula (1) It may include a compound.

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

In addition to the organic layer, the organic light emitting diode may include an electron blocking layer (EBL) positioned between the hole transport layer and the light emitting layer and / or a hole blocking layer disposed between the light emitting layer and the electron transport layer. layer: HBL) may be further included. In such a structure, the compound represented by Formula 1 may be included in one or more layers of the electron blocking layer and the hole blocking layer. The electron blocking layer and the hole blocking layer may each be an organic layer adjacent to the emission layer.

In this case, the compound represented by Formula 1 may be included in the hole transport layer or the electron blocking layer.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention further includes a hole injection layer and a hole transport layer between the first electrode and the light emitting layer, an electron transport layer and an electron injection layer between the light emitting layer and the second electrode, in addition to the light emitting layer as an organic layer. It may have a structure to. However, the structure of the organic light emitting device is not limited thereto, and may include fewer or more organic layers.

In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure 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 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 an 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 element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer.

FIG. 2 shows an example of an organic light emitting element consisting of 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 It is. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more layers of the hole injection layer, the hole transport layer, the light emitting layer and the electron transport 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. In addition, 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 physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. In addition, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer may be formed thereon, and then, a material that may be used as a cathode may be deposited thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

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

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

As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SNO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and has a capability of transporting holes to the hole injection material, and has a hole injection effect at the anode, an excellent hole injection effect to the light emitting layer or the light emitting material, and is produced in the light emitting layer The compound which prevents the excitons from moving to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the 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 materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

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

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

The light emitting layer may include a host material and a dopant material as described above. The host material may further include a condensed aromatic ring derivative or a hetero ring-containing compound in addition to the compound represented by Formula 1 above. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

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

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transporting material, a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer is provided. Suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.

The electron injection layer is a layer for injecting electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from the cathode, an excellent electron injection effect to the light emitting layer or the light emitting material, and the hole injection of excitons generated in the light emitting layer The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.

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

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

Production Example  1: Preparation of Compound 1-145

Sodium tert-butoxide (1.97g, 20.47mmol) after completely dissolving Compound A-1 (5.26g, 15.75mmol) and dibiphenyl-4-ylamine (5.56g, 17.32mmol) in 220ml of Xylene in a 500ml round bottom flask under nitrogen atmosphere Was added, Bis (tri- tert- butylphosphine) palladium (0) (0.08g, 0.16mmol) was added thereto, and the mixture was heated and stirred for 2 hours. After the temperature was lowered to room temperature and the base was filtered to remove the base, Xylene was concentrated under reduced pressure, and tetrahydrofuran: hexane = 1:25 was used to prepare Compound 1-145 (7.17 g, yield: 73%).

MS [M + H] ⁺ = 620

Production Example  2: Preparation of Compound 1-43

Compound A-1 (6.28g, 18.80mmol), N- (biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine (7.47g, 20.68mmol) in 500ml round bottom flask under nitrogen atmosphere Was dissolved completely in 180 ml of Xylene, sodium tert-butoxide (2.35g, 24.44mmol) was added, Bis (tri- tert- butylphosphine) palladium (0) (0.10g, 0.19mmol) was added thereto, and the mixture was heated and stirred for 3 hours. . After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and tetrahydrofuran: hexane = 1:30 to prepare the compound 1-43 (10.05 g, yield: 81%).

MS [M + H] ⁺ = 660

Production Example  3: Preparation of Compound 1-81

Compound A-1 (4.38 g, 13.11 mmol), (4- (di ([1,1'-biphenyl] -4-yl) amino) phenyl) boronic acid (6.65g, 15.08 mmol) was completely dissolved in 220 ml of tetrahydrofuran, and 2 M aqueous potassium carbonate solution (110 ml) was added thereto, and tetrakis- (triphenylphosphine) palladium (0.45 g, 0.39 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 160 ml of tetrahydrofuran to prepare compound 1-81 (8.46 g, 93%).

MS [M + H] ⁺ = 696

Production Example  4: Preparation of Compound 1-113

Compound A-1 (5.16 g, 15.45 mmol), (4-([1,1'-biphenyl] -4-yl (9,9-dimethyl-9H-fluoren-2-yl), in a 500 ml round bottom flask in a nitrogen atmosphere ) Amino) phenyl) boronic acid (8.55g, 17.77mmol) is completely dissolved in 240ml of tetrahydrofuran, then 2M potassium carbonate solution (120ml) is added, and tetrakis- (triphenylphosphine) palladium (0.54g, 0.46mmol) ) Was added and the mixture was 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 with 180 ml of tetrahydrofuran to prepare compound 1-113 (9.51 g, 84%).

MS [M + H] ⁺ = 736

Production Example  5: Preparation of Compound 1-161

Compound A-1 (5.38 g, 16.11 mmol), N- (biphenyl-4-yl)-[1,1 ': 4', 1 ''-terphenyl] -4-amine ( After dissolving 7.03g, 17.72mmol) in 240ml of Xylene, add sodium tert-butoxide (2.01g, 20.94mmol), add Bis (tri- tert -butylphosphine) palladium (0) (0.19g, 0.16mmol) The mixture was heated and stirred for 2 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized from 200 ml of tetrahydrofuran to prepare the compound 1-161 (8.39 g, yield: 75%).

MS [M + H] ⁺ = 696

Production Example  6: Preparation of Compound 1-44

Compound D-1 (5.08g, 14.51mmol), N- (biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine (5.76g, 15.97mmol) in 500ml round bottom flask in nitrogen atmosphere Was dissolved completely in 220ml of Xylene, sodium tert-butoxide (1.81g, 18.87mmol) was added, Bis (tri- tert- butylphosphine) palladium (0) (0.17g, 0.15mmol) was added thereto, and the mixture was heated and stirred for 3 hours. . After the temperature was lowered to room temperature and the base was filtered to remove the base, Xylene was concentrated under reduced pressure and recrystallized with 250 ml of ethyl acetate to obtain Compound 1-44 (6.49 g, Yield: 68%).

MS [M + H] ⁺ = 676

Production Example  7: Preparation of Compound 1-114

Compound C-1 (4.77 g, 13.63 mmol), (4-([1,1'-biphenyl] -4-yl (9,9-dimethyl-9H-fluoren-2-yl), in a 500 ml round bottom flask in a nitrogen atmosphere ) Amino) phenyl) boronic acid (7.21g, 14.99mol) is completely dissolved in 280ml of tetrahydrofuran, then 2M potassium carbonate solution (140ml) is added, and tetrakis- (triphenylphosphine) palladium (0.47g, 0.41mmol) ) Was added and the mixture was 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 with 250 ml of tetrahydrofuran to prepare compound 1-114 (9.51 g, 84%).

MS [M + H] ⁺ = 752

Production Example  8: Preparation of Compound 1-169

Compound A-1 (6.13g, 18.35mmol), N- (4- (dibenzo [b, d] furan-4-yl) phenyl)-[1,1'-biphenyl]-in 500ml round bottom flask under nitrogen atmosphere 4-amine (8.30g, 20.19mmol) is completely dissolved in 240ml of Xylene, then sodium tert-butoxide (2.29g, 23.86mmol) is added, Bis (tri- tert -butylphosphine) palladium (0) (0.09g, 0.18mmol) ) Was added and the mixture was heated and stirred for 3 hours. After the temperature was lowered to room temperature and the filter was removed to remove the base, Xylene was concentrated under reduced pressure and recrystallized with 250 ml of ethyl acetate to obtain Compound 1-169 (10.06 g, yield: 77%).

MS [M + H] ⁺ = 710

Example 1-1

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

The hexanitrile hexaazatriphenylene (HAT) of the following formula was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer.

[HAT]

Compound N4, N4, N4 ', N4'-tetra ([1,1'-biphenyl] -4-yl)-[1,1'-biphenyl] -4, which is a material for transporting holes on the hole injection layer, 4'-diamine [HT1] (300 Pa) was vacuum deposited to form a hole transport layer.

[HT1]

Subsequently, the compound 1-145 prepared in Preparation Example 1 was vacuum deposited on the hole transport layer to form a film thickness of 100 kPa to form an electron blocking layer.

Subsequently, the following BH and BD were vacuum-deposited at a weight ratio of 25: 1 on the electron blocking layer with a film thickness of 300 Pa to form a light emitting layer.

[BH] [BD]

 [ET 1]

[LiQ]

The compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum-deposited on the emission layer at a weight ratio of 1: 1 to form an electron transport layer having a thickness of 300 Pa. Lithium fluoride (LiF) and aluminum were deposited to a thickness of 2,000 kPa in order to form an electron injection layer and a cathode on the electron transport layer sequentially.

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

Example 1-2 to Example 1-8

Example 1-2 to 1-8 using the same method as in Example 1-1, except that the electron blocking material was changed to the following Table 1 instead of compound 1-145 when forming the electron blocking layer Each organic light emitting device was produced.

Comparative Example 1-1

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the following EB1 was used instead of the compound 1-1 to form an electron blocking layer.

[EB1]

Experimental Example 1

A current was applied to the organic light emitting diodes manufactured in Examples 1-1 to 1-8 and Comparative Example 1-1 to measure driving voltage, efficiency, and color coordinates, and the results are shown in Table 1 below.

Electron blocking layer
compound Voltage
(V @ 10mA / cm ² ) efficiency
(cd / A @ 10mA / cm ² ) Color coordinates
(x, y) Example 1-1 Compound 1-145 3.71 6.22 (0.142, 0.046) Example 1-2 Compound 1-43 3.75 6.26 (0.141, 0.045) Example 1-3 Compound 1-81 3.84 6.37 (0.141, 0.045) Example 1-4 Compound 1-113 3.76 6.41 (0.142, 0.046) Example 1-5 Compound 1-161 3.78 6.26 (0.141, 0.045) Example 1-6 Compound 1-44 3.77 6.37 (0.141, 0.045) Example 1-7 Compound 1-114 3.79 6.41 (0.142, 0.046) Example 1-8 Compound 1-169 3.77 6.26 (0.141, 0.045) Comparative Example 1-1 EB1 4.16 5.95 (0.141, 0.045)

As shown in Table 1, in the case of the organic light emitting device manufactured by using the compound according to the present invention as an electron blocking layer, compared to the organic light emitting device of Comparative Example 1-1, excellent performance in terms of current efficiency, driving voltage and stability It can be seen that.

Example 2-1

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

Hexanitrile hexaazatriphenylene (HAT) was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer.

Compound 1-145 prepared in Preparation Example 1 was vacuum deposited on the hole injection layer to form a hole transport layer.

Subsequently, EB1 was vacuum deposited on the hole transport layer with a film thickness of 100 μs to form an electron blocking layer.

Subsequently, BH and BD were vacuum-deposited at a weight ratio of 25: 1 on the electron blocking layer to form a light emitting layer with a film thickness of 300 kPa.

Compound ET1 and compound LiQ (Lithium Quinolate) were vacuum-deposited on the emission layer in a weight ratio of 1: 1 to form an electron transport layer having a thickness of 300 GPa. Lithium fluoride (LiF) and aluminum were deposited to a thickness of 2,000 kPa in order to form an electron injection layer and a cathode on the electron transport layer sequentially.

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

Example 2-2 to Example 2-8

The organic materials of Examples 2-2 to 2-8 using the same method as Example 2-1, except that the electron transporting material was changed as shown in Table 1 instead of Compound 1-145 when the hole transport layer was formed. Each light emitting element was produced.

Comparative Example 2-1

An organic light-emitting device was manufactured in the same manner as in Example 2-1, except for using HT1 instead of Compound 1-145 as an electron transport material when forming a hole transport layer.

Experimental Example 2

A current was applied to the organic light emitting diodes manufactured in Examples 2-1 to 2-8 and Comparative Example 2-1 to measure driving voltage, efficiency, and color coordinates, and the results are shown in Table 2.

Hole transport layer
compound Voltage
(V @ 10mA / cm ² ) efficiency
(cd / A @ 10mA / cm ² ) Color coordinates
(x, y) Example 2-1 Compound 1-145 3.81 6.46 (0.141, 0.045) Example 2-2 Compound 1-43 3.82 6.47 (0.141, 0.046) Example 2-3 Compound 1-81 3.92 6.59 (0.141, 0.046) Example 2-4 Compound 1-113 3.81 6.67 (0.141, 0.045) Example 2-5 Compound 1-161 3.85 6.48 (0.142, 0.046) Example 2-6 Compound 1-44 3.84 6.55 (0.141, 0.046) Example 2-7 Compound 1-114 3.83 6.67 (0.141, 0.045) Example 2-8 Compound 1-169 3.82 6.46 (0.141, 0.045) Comparative Example 2-1 HT1 4.16 5.95 (0.141, 0.045)

As shown in Table 2, the organic light emitting device manufactured by using the compound according to the present invention as the hole transport layer has superior performance in terms of current efficiency, driving voltage and stability compared to the organic light emitting device of Comparative Example 2-1. It can be seen that.

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 (16)

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

In Chemical Formula 1,
X ₁ and X ₂ are each independently O or S,
L is a single bond; Substituted or unsubstituted C _6-60 arylene; Or C _1-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si, and S,
n is an integer from 0 to 4,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or C _1-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
R ₁ to R ₃ are hydrogen,
R ₄ and R ₅ are methyl,
a1 is an integer of 0 to 3,
a2 is an integer of 0 to 2,
a3 is an integer of 0-4.
The method of claim 1,
X ₁ is O.
The method of claim 1,
L is a single bond or any one selected from the group consisting of:

The method of claim 3,
L is a single bond or any one selected from the group consisting of:

.
The method of claim 1,
n is 0 or 1;
The method of claim 1,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

In the above,
Y ₁ is O, S, or NZ ₅ ,
Z ₁ to Z ₅ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; C _1-20 alkyl; C _1-20 haloalkyl; C _6-20 aryl; C _1-20 heteroaryl containing one heteroatom of O or S,
c1 is an integer of 0 to 5,
c2 is an integer of 0 to 4,
c3 is an integer of 0 to 7,
c4 is an integer of 0-3.
The method of claim 6,
Z ₁ to Z ₅ are each independently hydrogen, phenyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl,
c1 to c4 are each independently 0, 1, or 2;
The method of claim 7, wherein
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

delete The method of claim 1,
The compound is represented by the formula 1A or 1B, compound:
[Formula 1A]

[Formula 1B]

In Chemical Formulas 1A and 1B,
X ₂ is O or S,
Description of L, Ar ₁ and Ar ₂ is as defined in claim 1.
The method of claim 1,
The compound is any one selected from the group consisting of the following compounds 1-1 to 1-176:

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 is any one of claims 1 to 8, 10 and 11. An organic light emitting device comprising the compound according to one claim.
The method of claim 12,
The organic material layer containing the compound is a hole injection layer; Hole transport layer; Or an organic light emitting device which is a layer for simultaneously injecting holes and transporting holes.
The method of claim 12,
The organic material layer containing the compound is an electron injection layer; Electron transport layer; Or an organic light emitting element, which is a layer for simultaneously performing electron injection and electron transport.
The method of claim 12,
The organic material layer containing the compound is a light emitting layer, an organic light emitting device.
The method of claim 12,
The organic material layer containing the compound is an electron blocking layer, an organic light emitting device.

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