KR20220122512A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device. According to the present invention, an organic light emitting device includes: an anode; a cathode provided to face the anode; and a light emitting layer provided between the anode and the cathode. The light emitting layer includes a first compound represented by chemical formula 1 and a second compound represented by chemical formula 2 below. The efficiency, driving voltage, and lifespan characteristics of the organic light emitting device can be improved.

Description

Organic light emitting device

The present invention relates to an organic light emitting device.

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 material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, it may be made of an electron injection layer, etc. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, 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 It lights up when it falls back to the ground state.

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

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting device.

The present invention is

anode;

a negative electrode provided to face the positive electrode; and

a light emitting layer provided between the anode and the cathode;

The light emitting layer comprises a first compound represented by the following formula (1) and a second compound represented by the following formula (2),

Organic light emitting device:

[Formula 1]

In Formula 1,

A is substituted or unsubstituted carbazolyl,

L ₁ is a single bond, or a substituted or unsubstituted C _6-60 arylene,

X ₁ , X ₂ and X ₃ are each independently N, or CH, provided that at least one selected from the group consisting of X ₁ , X ₂ and X ₃ is N,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2-60 including one or more heteroatoms selected from the group consisting of N, O and S heteroaryl;

[Formula 2]

In Formula 2,

B is a benzene ring fused with two adjacent pentacyclic rings,

L' ₁ and L' ₂ are each independently a single bond, or a substituted or unsubstituted C _6-60 arylene;

Ar′ ₁ and Ar′ ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C ₂ containing one or more heteroatoms selected from the group consisting of N, O and S _-60 heteroaryl;

R′ ₁ , R′ ₂ and R′ ₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or one or more heteroatoms selected from the group consisting of N, O and S is a substituted or unsubstituted C _2-60 heteroaryl,

a is an integer from 0 to 4,

b is an integer from 0 to 2,

c is an integer from 0 to 4.

In the above-described organic light emitting device, efficiency, driving voltage, and/or lifespan characteristics may be improved in the organic light emitting device by including two kinds of host compounds in the light emitting layer.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .
2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8 and a cathode 4 An example of an organic light emitting device is shown.

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

, 또는

는 다른 치환기에 연결되는 결합을 의미하고, D는 중수소를 의미하고, Ph는 페닐기를 의미한다. In this specification,

, or

denotes a bond connected to another substituent, D denotes deuterium, and Ph denotes a phenyl group.

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

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably from 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is 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 is 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, adamantyl, 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 heteroaryl group is a heterocyclic group including one or more heteroatoms among O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but is preferably from 2 to 60 carbon atoms. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, the arylamine group, and the arylsilyl group is the same as the examples 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, as for heteroaryl among heteroarylamines, the description regarding heteroaryl described above may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the above-described alkenyl groups. 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 aforementioned heteroaryl 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 heterocycle is not a monovalent group, and the description of the above-described heteroaryl may be applied, except that it is formed by combining two substituents.

As used herein, the term "deuterated or substituted with deuterium" means that at least one available hydrogen in each formula is replaced with deuterium (D). Specifically, substituted with deuterium in the definition of each chemical formula or substituent means that at least one or more of the positions where hydrogen can be bonded in the molecule will be substituted with deuterium, more specifically, at least 10% of the available hydrogen is deuterium means replaced by In one example, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or 100% deuterated in each formula.

On the other hand, an organic light emitting device according to an embodiment includes an anode; a negative electrode provided to face the positive electrode; and a light emitting layer provided between the anode and the cathode, wherein the light emitting layer includes a first compound represented by Formula 1 and a second compound represented by Formula 2, wherein the first compound represented by Formula 1 and The second compound represented by Formula 2 is included as a host material of the emission layer.

The organic light emitting device according to the present invention may include two types of compounds having a specific structure as a host material in the light emitting layer at the same time, thereby improving efficiency, driving voltage, and/or lifespan characteristics in the organic light emitting device.

Hereinafter, the present invention will be described in detail for each configuration.

positive and negative

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; A multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

hole injection layer

The organic light emitting diode according to the present invention may include a hole injection layer between the anode and the hole transport layer to be described later, if necessary.

The hole injection layer is located on the anode and injects holes from the anode, and includes a hole injection material. Such a hole injection material has the ability to transport holes, has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and prevents the movement of excitons generated in the light emitting layer to the electron injection layer or the electron injection material. In addition, a compound excellent in the ability to form a thin film is preferable. In particular, it is suitable 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. organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

hole transport layer

The organic light emitting diode according to the present invention may include a hole transport layer between the anode and the light emitting layer. The hole transport layer receives holes from the anode or the hole injection layer formed on the anode and transports holes to the light emitting layer, and includes a hole transport material. As the hole transport material, a material capable of transporting holes from an anode or a hole injection layer to the light emitting layer is suitable, and a material having high hole mobility 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.

electronic barrier layer

The organic light emitting diode according to the present invention may include an electron blocking layer between the hole transport layer and the light emitting layer, if necessary. The electron blocking layer is formed on the hole transport layer, preferably provided in contact with the light emitting layer, to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling by increasing the efficiency of the organic light emitting device It means a layer that plays a role in improving The electron blocking layer includes an electron blocking material, and an example of such an electron blocking material may be an arylamine-based organic material, but is not limited thereto.

light emitting layer

The organic light emitting device according to the present invention includes a light emitting layer between an anode and a cathode, and the light emitting layer includes the first compound and the second compound as a host compound. Specifically, by using the first compound and the second compound in combination, the ratio of holes to electrons in the light emitting layer may be properly maintained. In particular, when the first compound and the second compound are used simultaneously, holes and electrons are smoothly transferred to the dopant, thereby improving the efficiency and lifespan of the device. When only the compound is used, or compared to a device employing a combination with other compounds, low voltage and long lifespan device characteristics may be exhibited.

Hereinafter, the first compound and the second compound will be sequentially described.

(first compound)

The first compound is represented by the following formula (1). Specifically, the first compound is a compound containing carbazolyl and triazine-based (pyridine, pyrimidine) substituents on triphenylenyl, and the compound has excellent ability to transport electrons to a host material, and a second compound to be described later It is possible to increase the probability of recombination of holes and electrons in the light emitting layer by using in combination with .

[Formula 1]

In Formula 1,

A is substituted or unsubstituted carbazolyl,

L ₁ is a single bond, or a substituted or unsubstituted C _6-60 arylene,

X ₁ , X ₂ and X ₃ are each independently N, or CH, provided that at least one selected from the group consisting of X ₁ , X ₂ and X ₃ is N,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2-60 including one or more heteroatoms selected from the group consisting of N, O and S heteroaryl.

Meanwhile, in Formula 1, the carbon denoted by * means that only hydrogen is substituted, and does not include an additional substituent in the corresponding carbon.

The second compound may be represented by the following Chemical Formula 1-1 or 1-2, depending on the substitution position of A:

[Formula 1-1]

[Formula 1-2]

In Formula 1-1 or Formula 1-2,

L ₁ , X ₁ , X ₂ , X ₃ , Ar ₁ , and Ar ₂ are as defined above,

R ₁ is each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or one or more heteroatoms selected from the group consisting of N, O and S It is a substituted or unsubstituted C _2-60 heteroaryl comprising

R ₂ is substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl;

R ₃ is each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or one or more heteroatoms selected from the group consisting of N, O and S A substituted or unsubstituted C _5-60 heteroaryl comprising

m is an integer from 0 to 8,

n is an integer from 0 to 7.

In this case, m meaning the number of R ₁ is 0, 1, 2, 3, 4, 5, 6, 7, or 8, and n meaning the number of R ₃ is 0, 1, 2, 3, 4, 5, 6, or 7.

Preferably, L ₁ is a single bond, phenylene or biphenylrylene, and the phenylene and biphenylrylene may each independently be substituted or unsubstituted with one or more deuterium.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, dimethylfluorenyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl, benzoxazolyl, benzothiazolyl, 2-phenylbenzooxazolyl or 2-phenylbenzothiazolyl, each independently substituted with one or more deuterium or may be unsubstituted.

Preferably, each R ₁ is independently hydrogen, deuterium, phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl, wherein phenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl are each Independently, it may be unsubstituted or substituted with one or more deuterium.

Preferably, R ₂ may each independently be phenyl unsubstituted or substituted with one or more deuterium.

Preferably, each R ₃ is independently hydrogen, deuterium, phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl, wherein phenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl are one It may be substituted or unsubstituted with more than one deuterium.

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

.

.

Meanwhile, the first compound may be prepared by, for example, a preparation method as shown in Scheme 1 below.

[Scheme 1-A]

[Scheme 1-B]

In Schemes 1-A and 1-B, each X is independently halogen, preferably bromo, or chloro, and definitions of other substituents are as described above.

Specifically, the compound represented by Formula 1 is prepared through a Suzuki coupling reaction and an amine substitution reaction, and these reactions are preferably performed in the presence of a palladium catalyst and a base, respectively. In addition, the reactor for the reaction may be appropriately changed, and the method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.

(second compound)

The second compound is represented by the following formula (2). Specifically, the second compound is an indolocarbazole compound, and the compound has an excellent ability to transport holes as a host compound and a dopant material, and is used in combination with the above-described first compound to form holes and electrons in the light emitting layer. can increase the probability of recombination.

[Formula 2]

In Formula 2,

B is a benzene ring fused with two adjacent pentacyclic rings,

L' ₁ and L' ₂ are each independently a single bond, or a substituted or unsubstituted C _6-60 arylene;

Ar′ ₁ and Ar′ ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C ₂ containing one or more heteroatoms selected from the group consisting of N, O and S _-60 heteroaryl;

R′ ₁ , R′ ₂ and R′ ₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or one or more heteroatoms selected from the group consisting of N, O and S is a substituted or unsubstituted C _2-60 heteroaryl,

a is an integer from 0 to 4,

b is an integer from 0 to 2,

c is an integer from 0 to 4.

The second compound may be represented by any one of the following Chemical Formulas 2-1 to 2-5, depending on the fusion position of B:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Formulas 2-1 to 2-5,

L′ ₁ , L′ ₂ , Ar′ ₁ , Ar′ ₂ , R′ ₁ , R′ ₂ , R′ ₃ , a, b and c are as defined above.

Preferably, L' ₁ and L' ₂ are each independently a single bond, phenylene or biphenylrylene, and the phenylene or biphenylrylene may be each independently substituted or unsubstituted with one or more deuterium. .

Preferably, Ar' ₁ and Ar' ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl , carbazol-9-yl, or 9-phenyl-9H-carbazolyl, wherein Ar' ₁ and Ar' ₂ are each independently selected from the group consisting of deuterium, C _1-10 alkyl and C _6-20 aryl. It may be substituted or unsubstituted with one or more selected substituents.

Preferably, R′ ₁ , R′ ₂ and R′ ₃ are each independently hydrogen, deuterium, phenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-9H- and carbazolyl, and the phenyl, dibenzofuranyl, carbazol-9-yl and 9-phenyl-9H-carbazolyl may each independently be substituted or unsubstituted with one or more deuterium.

In this case, a meaning the number of R' ₁ is 0, 1, 2, 3, or 4, b meaning the number of R' ₂ is 0, 1, or 2, and R' meaning the number of ₃ c is 0, 1, 2, 3, or 4.

Representative examples of the second compound represented by Formula 2 are as follows:

.

.

Meanwhile, the second compound may be prepared by, for example, a preparation method as shown in Scheme 2 below.

[Scheme 2]

In Scheme 2, each X is independently halogen, preferably bromo or chloro, and definitions of other substituents are the same as described above.

Specifically, the compound represented by Formula 2 is prepared by combining starting materials SM'1 and SM'2 through an amine substitution reaction. These amine substitution reactions are preferably performed in the presence of a palladium catalyst and a base, respectively. In addition, the reactive group for the amine substitution reaction may be appropriately changed, and the method for preparing the compound represented by Formula 2 may be more specific in Preparation Examples to be described later.

The first compound and the second compound in the light-emitting layer may be included in a weight ratio of 1:9 to 9:1. When the second compound is included in an excessively small amount compared to the first compound in the light-emitting layer, electron transfer in the light-emitting layer is Because it is not smooth, the balance of holes and electrons is not balanced throughout the device, and there may be problems in voltage, efficiency, and lifespan of the fabricated device. For example, a weight ratio of the first compound and the second compound in the emission layer is 2:8 to 8:2, 3:7 to 7:3, 4:6 to 6:4, or 4:6 to 5:5 can be

Meanwhile, the emission layer may further include a dopant material in addition to the two types of host materials. Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group. 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, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

In this case, the dopant material may be included in an amount of 1 to 25% by weight based on the total weight of the host material and the dopant material in the emission layer.

hole blocking layer

The organic light emitting device according to the present invention may include a hole blocking layer between the light emitting layer and an electron transport layer to be described later, if necessary. The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to improve the efficiency of the organic light emitting device by controlling electron mobility and preventing excessive movement of holes to increase the hole-electron coupling probability. layer that plays a role. The hole-blocking layer includes a hole-blocking material, and examples of the hole-blocking material include: azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; A compound into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but the present invention is not limited thereto.

electron transport layer

The electron transport layer is formed between the light emitting layer and the cathode to receive electrons from the electron injection layer and transport the electrons to the light emitting layer. The electron transport layer includes an electron transport material. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable.

Specific examples of the electron injecting and transporting material include an Al complex of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes; and triazine derivatives, but is not limited thereto. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and derivatives thereof, metal complex compounds , or may be used together with a nitrogen-containing 5-membered ring derivative, and the like, but is not limited thereto.

electron injection layer

The organic light emitting diode according to the present invention may include an electron injection layer between the electron transport layer and the cathode, if necessary.

The electron injection layer is positioned between the electron transport layer and the cathode, and serves to inject electrons from the cathode. The electron injection layer includes an electron injection material, and the electron injection material has the ability to transport electrons, has an excellent electron injection effect with respect to the light emitting layer or the light emitting material, and a material having excellent thin film formation ability is suitable.

Specific examples of the electron injection material include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, Perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like, derivatives thereof, metal complex compounds, nitrogen-containing 5-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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. Accordingly, the present invention is not limited thereto.

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1 . FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 . In such a structure, the first compound and the second compound may be included in the emission layer.

2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8 and a cathode 4 An example of an organic light emitting device is shown. In such a structure, the first compound and the second compound may be included in the emission layer.

The organic light emitting device according to the present invention may be manufactured by sequentially stacking the above-described components. 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 each of the above-mentioned layers 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 light emitting layer may be formed by a solution coating method as well as a vacuum deposition method for the host and dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

In addition to the above 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.

Meanwhile, 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.

Preparation of an organic light emitting device including the compound represented by Formula 1 and the compound represented by Formula 2 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 compound 1-1

Step 1) Synthesis of compound 1-1-a

In a nitrogen atmosphere, 4-bromo-chloro-2-iodoaniline (50 g, 150.4 mmol) and [1,1'-biphenyl]-2-yl boronic acid (29.8 g, 150.4 mmol) were mixed with tetrahydrofuran 1000 ml was added, stirred and refluxed. After that, sodium carbonate (47.8 g, 451.3 mmol) was dissolved in 48 ml of water, and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (5.2 g, 4.5 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put into 20 times 1079 mL of chloroform, dissolved, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and hexane to prepare a brown solid compound 1-1-a (43.2 g, 80%, MS: [M+H] ⁺ = 359.7).

Step 2) Synthesis of compound 1-1-b

Compound 1-1-a (40 g, 111.5 mmol) was added to hydrochloric acid (2 M, 700 mL), stirred at 0° C. for about 15 minutes, and then sodium nitrite (8.5 g, 122.6 mmol) was slowly added. After 1 hour, it was heated at 60° C. for 3 hours, cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put into 800 mL of chloroform 20 times to dissolve, washed twice with an aqueous sodium hydrogen carbonate solution, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and hexane to prepare a dark brown solid compound 1-1-b (27.4 g, 72%, MS: [M+H] ⁺ = 342.0).

Step 3) Synthesis of compound 1-1-c

In a nitrogen atmosphere, 1-1-b (25 g, 73.3 mmol) and bis (pinacolato) diboron (18.6 g, 73.3 mmol) were added to 500 ml of 1,4-dioxane, stirred and refluxed. After that, potassium triphosphate (46.7 g, 219.9 mmol) was added and sufficiently stirred, palladium dibenzylideneacetone palladium (1.3 g, 2.2 mmol) and tricyclohexylphosphine (1.2 g, 4.4 mmol) were added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put into 285 mL of chloroform 10 times to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to prepare a brown solid compound 1-1-c (22.8 g, 80%, MS: [M+H] ⁺ = 389.7).

Step 4) Synthesis of compound 1-1-d

In a nitrogen atmosphere, 1-1-c (20 g, 51.5 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (13.8 g, 51.5 mmol) were added to 400 ml of tetrahydrofuran and stirred. and reflux. Thereafter, sodium carbonate (16.4 g, 154.4 mmol) was dissolved in 16 ml of water, and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (1.8 g, 1.5 mmol) was added. After reaction for 1 hour, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform 20 times 554 mL, dissolved, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a yellow solid compound 1-1-d (19.1 g, 69%, MS: [M+H] ⁺ = 494.8).

Step 5) Synthesis of compound 1-1

In a nitrogen atmosphere, 1-1-d (30 g, 55.7 mmol) and 9H-carbazole- (9.3 g, 55.7 mmol) were added to 600 ml of xylene, stirred and refluxed. Thereafter, sodium tertiary-butoxide (16.1 g, 167.1 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.9 g, 1.7 mmol) was added. After the reaction for 4 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in 351 mL of chloroform 10 times to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 1-1 (19 g, 54%, MS: [M+H] ⁺ = 625.7).

Synthesis Example 2: Synthesis of compound 1-2

In Synthesis Example 1, except that 9H-carbazole was changed to 9H-carbazole-1,3,4,5,6,8-d6 and used, the compound was prepared in the same manner as in the preparation method of Compound 1-1. 1-2 (MS: [M+H] ⁺ = 631.8)) was prepared.

Synthesis Example 3: Synthesis of compound 1-3

In Synthesis Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine and 9H-carbazole were each added to 2-chloro-4,6-bis(phenyl-d5)-1,3, Except for using 5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8, except for using the same preparation method as the preparation method of Compound 1-1 Compound 1 -3 (MS[M+H] ⁺ = 643.8) was prepared.

Synthesis Example 4: Synthesis of compound 1-4

In Synthesis Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine was replaced with 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine Compound 1-4 (MS[M+H] ⁺ = 701.8) was prepared in the same manner as in the preparation method of compound 1-1, except that it was changed to and used.

Synthesis Example 5: Synthesis of compound 1-5

In Synthesis Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine and 9H-carbazole were each treated with 2-chloro-4- (dibenzo [b, d] thiophene-4- yl)-6-phenyl-1,3,5-triazine and 9H-carbazole-1,3,4,5,6,8-d6, except that it was used by changing the method for the preparation of compound 1-1 Compound 1-5 (MS[M+H] ⁺ = 663.2) was prepared by the same preparation method as

Synthesis Example 6: Synthesis of compound 1-6

In Synthesis Example 1, except that 9H-carbazole was changed to 4-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole and used, the same preparation as in the preparation method of compound 1-1 Compound 1-6 (MS[M+H] ⁺ = 807.8) was prepared by the method.

Synthesis Example 7: Synthesis of compound 1-7

In Synthesis Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine was changed to 2-chloro-4,6-diphenylpyrimidine and used, except for using Compound 1-1 Compound 1-7 (MS[M+H] ⁺ = 624.7) was prepared by the same preparation method as the preparation method of

Synthesis Example 8: Synthesis of compound 1-8

1-1-d (30 g, 60.7 mmol) and (9-(phenyl-d5)-9H-carbazol-3-yl-1,2,4,5,6,7,8-d7) in nitrogen atmosphere Boronic acid (18.2 g, 60.7 mmol) was added to 600 ml of 1,4-dioxane, stirred and refluxed. After that, tripotassium phosphate (38.7 g, 182.2 mmol) was dissolved in 39 ml of water and thoroughly stirred, followed by dibenzylideneacetone palladium (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol). was put in. After the reaction for 9 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in 1299 mL of chloroform 30 times, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a yellow solid compound Compound 1-8 (28.1 g, 65%, MS: [M+H] ⁺ = 713.9).

Synthesis Example 9: Synthesis of compounds 1-9

In Synthesis Examples 1 and 8, 2-chloro-4,6-diphenyl-1,3,5-triazine was replaced with 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6- Compound 1-9 (MS[M+H] ⁺ = 804.2) in the same manner as for the preparation of compounds 1-1 and 1-8, except that it was changed to phenyl-1,3,5-triazine and used. was prepared.

Synthesis Example 10: Synthesis of compound 1-10

In Synthesis Example 1, except that 9H-carbazole was changed to 4-(phenyl-d5)-9H-carbazole-1,2,3,5,6,7,8-d7, Compound 1- Compound 1-10 (MS[M+H] ⁺ = 713.9) was prepared by the same preparation method as in Preparation 1.

Synthesis Example 11: Synthesis of compound 2-1

Step 1) Synthesis of compound 2-1-a

600 ml of xylene with 5,8-dihydroindolo[2,3-c]carbazole (30 g, 117 mmol) and 4-bromo-1,1'-biphenyl (27.3 g, 117 mmol) in a nitrogen atmosphere was added, stirred and refluxed. Thereafter, sodium tertiary-butoxide (33.8 g, 351.1 mmol) was added thereto, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (1.8 g, 3.5 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in toluene 10 times 478 mL to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using toluene and ethyl acetate to prepare a white solid compound 2-1-a (31.6 g, 66%, MS: [M+H] ⁺ = 409.5).

Step 2) Synthesis of compound 2-1

In a nitrogen atmosphere, 2-1-a (30 g, 73.4 mmol) and 3-bromo-1,1'-biphenyl (17.1 g, 73.4 mmol) were added to 600 ml of xylene, stirred and refluxed. Thereafter, sodium tert-butoxide (21.2 g, 220.3 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (1.1 g, 2.2 mmol) was added. After the reaction for 4 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in toluene 10 times 412 mL to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using toluene and ethyl acetate to prepare a white solid compound 2-1 (31.3 g, 76%, MS: [M+H] ⁺ = 561.7).

Synthesis Example 12: Synthesis of compound 2-2

In Synthesis Example 11, 5,8-dihydroindolo [2,3-c] carbazole, 4-bromo-1,1'-biphenyl and 3-bromo-1,1'-biphenyl were each 5,8-dihydroindolo[2,3-c]carbazole-1,2,3,4,6,7,9,10,11,12-d10, 4-bromo-1,1'- Method for preparing compound 2-1, except that it was changed to biphenyl-2,3',4'-d3 and 3-bromo-1,1'-biphenyl-2,4',6-d3 Compound 2-2 (MS[M+H] ⁺ = 577.8) was prepared in the same manner as described above.

Synthesis Example 13: Synthesis of compound 2-3

In Synthesis Example 11, 3-bromo-1,1'-biphenyl was replaced with 3-bromo-1,1'-biphenyl-2,2',3',4',5,5',6,6 Compound 2-3 (MS[M+H] ⁺ = 582.8) was prepared in the same manner as in the preparation method of compound 2-1, except that it was changed to '-d8 and used.

Synthesis Example 14: Synthesis of compound 2-4

In Synthesis Example 11, except that 3-bromo-1,1'-biphenyl was changed to 4-bromo-1,1'-biphenyl and used, the same preparation method as the preparation method of Compound 2-1 to prepare compound 2-4 (MS[M+H] ⁺ = 561.7).

Synthesis Example 15: Synthesis of compound 1-15

In Synthesis Example 11, 5,8-dihydroindolo [2,3-c] carbazole, 4-bromo-1,1'-biphenyl and 3-bromo-1,1'-biphenyl were each 5,8-dihydro[2,3-c]carbazole-1,2,4,6,7,9,11,12-d8 and 4-bromo-1,1'-biphenyl-2', Compound 2-5 (MS[M+H] ⁺ = 579.8) was prepared in the same manner as in the preparation method of compound 2-1, except that it was changed to 3,4',5,6'-d5 and used. .

Synthesis Example 16: Synthesis of compound 2-6

In Synthesis Example 11, 5,8-dihydroindolo [2,3-c] carbazole, 4-bromo-1,1'-biphenyl and 3-bromo-1,1'-biphenyl were each 5,8-dihydroindolo[2,3-c]carbazole-1,2,3,4,6,7,9,10,11,12-d10, 3-bromo-1,1'- Compound 2-1, except that it was changed to biphenyl-4',6-d2 and 3-bromo-1,1'-biphenyl-2',4,4',6,6'-d5 Compound 2-6 (MS[M+H] ⁺ = 578.8) was prepared by the same preparation method as the preparation method of

Synthesis Example 17: Synthesis of compound 2-7

In Synthesis Example 11, 5,8-dihydroindolo [2,3-c] carbazole and 3-bromo-1,1'-biphenyl were each 5,8-dihydroindolo [2,3- c] carbazole-1,2,3,4,6,7,9,10,11,12-d10, and changed to 5'-bromo-1,1':3',1''-terphenyl Compound 2-7 (MS[M+H] ⁺ = 647.8) was prepared in the same manner as in the preparation method of compound 2-1 except that it was used.

Synthesis Example 18: Synthesis of compound 2-8

In Synthesis Example 11, 5,8-dihydroindolo [2,3-c] carbazole, 4-bromo-1,1'-biphenyl and 3-bromo-1,1'-biphenyl were each 5,7-dihydro [2,3-b] carbazole, bromobenzene and 4-bromodibenzene [b, d] thiophene, except that it was used in the same manner as in the preparation method of Compound 2-1 Compound 2-8 (MS[M+H] ⁺ = 515.6) was prepared by the preparation method.

Synthesis Example 19: Synthesis of compound 2-9

In Synthesis Example 11, 5,8-dihydroindolo [2,3-c] carbazole, 4-bromo-1,1'-biphenyl and 3-bromo-1,1'-biphenyl were each 5,7-dihydro [2,3-b] carbazole, bromobenzene, and 4-bromodibenzene [b, d] except that the use was changed to furan, the same preparation as in the preparation method of compound 2-1 Compound 2-9 (MS[M+H] ⁺ = 499.6) was prepared by the method.

Synthesis Example 20: Synthesis of compound 2-10

In Synthesis Example 11, 5,8-dihydroindolo [2,3-c] carbazole, 4-bromo-1,1'-biphenyl and 3-bromo-1,1'-biphenyl were each 5,12-dihydro[3,2-a]carbazole and 4-bromo-1,1'-biphenyl, except that the compound was used by the same preparation method as the preparation method of Compound 2-1 2-10 (MS[M+H] ⁺ = 561.7) were prepared.

[Example]

Example 1

A glass substrate coated with a thin film of 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 washing 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-A compound and the following PD compound were thermally vacuum deposited in a weight ratio of 95:5 to a thickness of 100 Å to form a hole injection layer, and then only the following HT-A compound had a thickness of 1150 Å was deposited to form a hole transport layer. On the hole transport layer, the following HT-B compound was thermally vacuum deposited to a thickness of 450 Å to form an electron blocking layer (electron blocking layer).

On the electron blocking layer, compound 1-1 and compound 2-1 prepared previously as a host compound and the following GD compound as a dopant compound were vacuum-deposited in a weight ratio of 85:15 to a thickness of 400 Å to form a light emitting layer. In this case, the weight ratio of the compound 1-1 to the compound 2-1 was 1:1.

On the light emitting layer, the following ET-A compound was vacuum deposited to a thickness of 50 Å to form a hole blocking layer. On the hole blocking layer, the following ET-B compound and the following Liq compound were thermally vacuum deposited in a weight ratio of 2:1 to a thickness of 250 Å, and then LiF and magnesium were vacuum deposited to a thickness of 30 Å in a weight ratio of 1:1. Thus, an electron transport and injection layer was formed. On the electron transport and injection layer, magnesium and silver were deposited to a thickness of 160 Å in a weight ratio of 1:4 to form a cathode, thereby manufacturing an organic light emitting diode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of silver and magnesium was maintained at 2 Å/sec, and the vacuum degree during deposition was 2 ×10 ^-7 to 5×10 ^-6 torr was maintained, an organic light emitting device was manufactured.

Examples 2 to 10

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of Compound 1 in Example 1.

At this time, the structure of Compound 2 used in Examples is summarized as follows.

Comparative Examples 1 to 9

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of Compound 1 in Example 1.

In this case, in Table 1, compounds H-2 and C1 to C3 are as follows, respectively.

Experimental example

Voltage, efficiency, and lifetime (T95) were measured by applying a current to the organic light emitting diodes prepared in Examples and Comparative Examples, and the results are shown in Table 1 below. At this time, voltage and efficiency were measured by applying a current density of 10 mA/cm ² . In addition, T95 in Table 1 below means the time measured until the initial luminance is lowered to 95% at a current density of 20 mA/cm ² .

division light emitting compound Voltage (V)
(@10mA/cm ² ) Efficiency (cd/A)
(@10mA/cm ² ) luminous color T95(hr)
(@20mA/cm ² ) Example 1 compound 1-1, compound 2-1 3.02 69.8 green 80 Example 2 compound 1-2, compound 2-1 3.02 69.8 green 86 Example 3 compound 1-3, compound 2-4 3.01 70.0 green 90 Example 4 compound 1-3, compound 2-5 3.01 70.0 green 101 Example 5 compound 1-3, compound 2-1 3.00 72.1 green 81 Example 6 compound 1-4, compound 2-2 3.01 71.1 green 85 Example 7 compound 1-5, compound 2-6 3.04 72.3 green 89 Example 8 compound 1-6, compound 2-5 3.08 71.5 green 84 Example 9 compound 1-6, compound 2-6 3.09 70.2 green 81 Example 10 compound 1-7, compound 2-7 2.98 70.5 green 82 Example 11 compound 1-8, compound 2-8 3.07 73.5 green 80 Example 12 compound 1-9, compound 2-9 3.02 72.1 green 87 Example 13 compound 1-10, compound 2-10 3.03 71.3 green 86 Comparative Example 1 compound 1-2 3.15 62.1 green 50 Comparative Example 2 compounds 1-8 3.26 59.1 green 40 Comparative Example 3 compounds 1-10 3.12 62.0 green 53 Comparative Example 4 compound C1 3.51 55.1 green 41 Comparative Example 5 compound C2 3.48 53.9 green 29 Comparative Example 6 compound C3 3.26 51.0 green 32 Comparative Example 7 compound C1, compound H-2 3.30 59.5 green 55 Comparative Example 8 compound C1, compound 2-1 3.20 68.2 green 70 Comparative Example 9 compound 1-10, compound H-2 3.25 69.6 green 75

As shown in Table 1, the organic light emitting devices of Examples using both the first compound and the second compound of the present invention as hosts, the organic light emitting devices of Comparative Examples 1 to 3 and the first compound using only the first compound and compared to the organic light emitting devices of Comparative Examples 4 and 7 in which neither the second compound was used, in terms of efficiency and lifespan, excellent characteristics were exhibited.

In addition, the organic light emitting device of the above example uses two types of hosts, but has higher efficiency and higher efficiency than the organic light emitting devices of Comparative Examples 8 and 9 employing a combination of other hosts instead of the combination of the first compound and the second compound. It can be seen that an excellent lifespan is exhibited.

In general, considering that the luminous efficiency and lifespan characteristics of the organic light emitting device have a trade-off relationship with each other, the organic light emitting device employing the compound of the present invention has significantly improved device characteristics compared to the comparative example device. means to indicate

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

Claims (13)

anode;
a negative electrode provided to face the positive electrode; and
a light emitting layer provided between the anode and the cathode;
The light emitting layer comprises a first compound represented by the following formula (1) and a second compound represented by the following formula (2),
Organic light emitting device:
[Formula 1]

In Formula 1,
A is substituted or unsubstituted carbazolyl,
L ₁ is a single bond, or a substituted or unsubstituted C _6-60 arylene,
X ₁ , X ₂ and X ₃ are each independently N, or CH, provided that at least one selected from the group consisting of X ₁ , X ₂ and X ₃ is N,
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2-60 including one or more heteroatoms selected from the group consisting of N, O and S heteroaryl;
[Formula 2]

In Formula 2,
B is a benzene ring fused with two adjacent pentacyclic rings,
L' ₁ and L' ₂ are each independently a single bond, or a substituted or unsubstituted C _6-60 arylene;
Ar′ ₁ and Ar′ ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C ₂ containing one or more heteroatoms selected from the group consisting of N, O and S _-60 heteroaryl;
R′ ₁ , R′ ₂ and R′ ₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or one or more heteroatoms selected from the group consisting of N, O and S is a substituted or unsubstituted C _2-60 heteroaryl,
a is an integer from 0 to 4,
b is an integer from 0 to 2,
c is an integer from 0 to 4.
According to claim 1,
The first compound is represented by Formula 1-1 or Formula 1-2,
Organic light emitting device:
[Formula 1-1]

[Formula 1-2]

In Formula 1-1 or Formula 1-2,
L ₁ , X ₁ , X ₂ , X ₃ , Ar ₁ , and Ar ₂ are as defined in claim 1 ,
R ₁ is each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or one or more heteroatoms selected from the group consisting of N, O and S It is a substituted or unsubstituted C _2-60 heteroaryl comprising
R ₂ is substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl;
R ₃ is each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or one or more heteroatoms selected from the group consisting of N, O and S A substituted or unsubstituted C _5-60 heteroaryl comprising
m is an integer from 0 to 8,
n is an integer from 0 to 7.
According to claim 1,
L ₁ is a single bond, phenylene or biphenylylene,
The phenylene and biphenylrylene are each independently substituted or unsubstituted with one or more deuterium,
organic light emitting device.
According to claim 1,
Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, dimethyl fluorenyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, carbazole-9 -yl, 9-phenyl-9H-carbazolyl, benzoxazolyl, benzothiazolyl, 2-phenylbenzoxazolyl or 2-phenylbenzothiazolyl;
They are each independently substituted or unsubstituted with one or more deuterium,
organic light emitting device.
3. The method of claim 2,
R ₁ is each independently hydrogen, deuterium, phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl;
The phenyl, dibenzofuranyl, dibenzothiophenyl and carbazolyl are each independently unsubstituted or substituted with one or more deuterium,
organic light emitting device.
3. The method of claim 2,
R ₂ are each independently phenyl unsubstituted or substituted with one or more deuterium;
organic light emitting device.
3. The method of claim 2,
R ₃ is each independently hydrogen, deuterium, phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl;
The phenyl, dibenzofuranyl, dibenzothiophenyl and carbazolyl are each independently unsubstituted or substituted with one or more deuterium,
organic light emitting device.
According to claim 1,
The first compound is any one selected from the group consisting of
Organic light emitting device:

.
According to claim 1,
The second compound is represented by any one of the following Chemical Formulas 2-1 to 2-5,
Organic light emitting device:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Formulas 2-1 to 2-5,
L' ₁ , L' ₂ , Ar' ₁ , Ar' ₂ , R' ₁ , R' ₂ , R' ₃ , a, b and c are as defined in claim 1.
According to claim 1,
L' ₁ and L' ₂ are each independently a single bond, phenylene or biphenylylene,
The phenylene or biphenylrylene are each independently substituted or unsubstituted with one or more deuterium,
organic light emitting device.
According to claim 1,
Ar' ₁ and Ar' ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazole- 9-yl, or 9-phenyl-9H-carbazolyl;
Wherein Ar' ₁ and Ar' ₂ are each independently substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, C _1-10 alkyl and C _6-20 aryl,
organic light emitting device.
According to claim 1,
R' ₁ , R' ₂ and R' ₃ are each independently hydrogen, deuterium, phenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl;
The phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl is each independently substituted or unsubstituted with one or more deuterium,
organic light emitting device.
According to claim 1,
The second compound is any one selected from the group consisting of
Organic light emitting device:

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