WO2021029616A1 - Organic light-emitting device - Google Patents

Abstract

The present invention provides an organic light-emitting device having improved driving voltage and/or service life by comprising two types of host compounds in a light-emitting layer.

Description

Organic light emitting element

Cross-reference with related application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0097650 filed on August 9, 2019 and Korean Patent Application No. 10-2020-0097980 filed on August 5, 2020. All contents disclosed in the literature are included as part of this specification.

The present invention relates to an organic light emitting device.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using organic materials. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being 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 made of different materials in order to increase the efficiency and stability of the organic light-emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

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

[Prior technical literature]

[Patent Literature]

(Patent Document 0001) Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting device.

The present invention provides the following organic light emitting device:

anode;

A cathode provided to face the anode; And

Including a light emitting layer provided between the anode and the cathode,

The light-emitting layer includes a first compound represented by Formula 1 and a second compound represented by Formula 2:

[Formula 1]

In Formula 1,

X is O or S,

X ₁ to X ₃ are each independently N or CH, provided that at least one of X ₁ to 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 heteroaryl containing one or more heteroatoms of N, O and S,

R ₁ to R ₃ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms of N, O and S,

a+b is an integer from 0 to 6,

c is an integer from 0 to 8,

[Formula 2]

In Chemical Formula 2,

A is a benzene ring fused with two adjacent pentagonal rings,

Ar ₃ and Ar ₄ are each independently Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms of N, O and S,

R ₄ is hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms of N, O and S,

d is an integer from 0 to 10,

When a, b, c and d are each 2 or more, the substituents in parentheses are the same as or different from each other.

The above-described organic light-emitting device includes two kinds of host compounds in the light-emitting layer, so that efficiency, driving voltage, and/or lifetime characteristics in the organic light-emitting device can be improved.

1 shows an example of an organic light-emitting device comprising 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), an electron blocking layer (7), a light emitting layer (3), a hole blocking layer (8), an electron transport and injection layer. An example of an organic light-emitting device consisting of (8) and a cathode (4) is shown.

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

In this specification,

, or

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

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means a substituted or unsubstituted substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O and S atoms, or linked with two or more substituents among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

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

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

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

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

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, 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 a linear or branched chain, and the number of carbon atoms 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 are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms 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 is preferably 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to 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 phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group 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.

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. However, it is not limited thereto.

In the present specification, the heteroaryl group is a heterocyclic group containing one or more heteroatoms of O, N, Si and S as heterogeneous elements, and the number of carbons is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl groups 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, 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, thiiadia There are a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the above-described description of heteroaryl may be applied. In the present specification, the alkenyl group of 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 above-described heteroaryl 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 aryl group or the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heteroaryl is not a monovalent group, and the description of the above-described heteroaryl may be applied except that the heterocycle is formed by bonding of two substituents.

anode; A cathode provided to face the anode; And an emission layer provided between the anode and the cathode, wherein the emission layer includes a first compound represented by Chemical Formula 1 and a second compound represented by Chemical Formula 2.

The organic light-emitting device according to the present invention may simultaneously include two types of compounds having a specific structure in the light-emitting layer as host materials, thereby improving efficiency, driving voltage, and/or lifetime characteristics in the organic light-emitting device.

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

Anode and cathode

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, etc., 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; There are a multi-layered material such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

Hole injection layer

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

The hole injection layer is a layer positioned 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 for 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 having excellent thin film formation ability is preferable. In particular, it is suitable that the HOMO (highest occupied molecular orbital) 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, perylene Organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

Hole transport layer

The organic light emitting device according to the present invention may include a hole transport layer between the anode and the emission layer. The hole transport layer is a layer that receives holes from an anode or a 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 and having high mobility for holes is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion, but are not limited thereto.

E-low layer

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

Emitting layer

The organic light-emitting device according to the present invention includes an emission layer between an anode and a cathode, and the emission layer includes the first compound and the second compound as a host material. Specifically, the first compound functions as an N-type host material having an electron transport ability superior to that of a hole transporting ability, and the second compound functions as a P-type host material having a hole transport ability greater than an electron transporting ability. It is possible to properly maintain the ratio of the electron to the electron. Accordingly, excitons are evenly emitted from the entire emission layer, so that the luminous efficiency and lifespan characteristics of the organic light-emitting device can be simultaneously improved.

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

(First compound)

The first compound is represented by Chemical Formula 1. Specifically, the first compound is a compound in which a carbazolyl group and an N-containing 6 membered-heterocyclic group are simultaneously substituted on a dibenzofuran/dibenzothiophene core, and these compounds have an intramolecular charge compared to a compound not having all of these substituents. Since inter charge transfer is well performed, the stability of molecules is high, and holes and electrons can be effectively transported. In addition, this effect can be further maximized when the second compound, which will be described later, is used together as a host of the emission layer.

Further, the first compound may contain at least one deuterium.

More specifically, in Formula 1, at least one of Ar ₁ and Ar ₂ is C _6-60 aryl substituted with deuterium; Or C _2-60 heteroaryl containing one or more heteroatoms of N, O and S substituted with deuterium; or

At least one of R ₁ to R ₃ is deuterium; C _6-60 aryl substituted with deuterium; Or C _2-60 heteroaryl including one or more heteroatoms among N, O and S substituted with deuterium, and a+b+c may be 1 or more, or an integer of 1 to 14.

Or C _6-60 aryl in which at least one of Ar ₁ and Ar ₂ is substituted with deuterium; Or C _2-60 heteroaryl including one or more heteroatoms of N, O and S substituted with deuterium, and at least one of R ₁ to R ₃ is deuterium; C _6-60 aryl substituted with deuterium; Or C _2-60 heteroaryl including one or more heteroatoms among N, O and S substituted with deuterium, and a+b+c may be 1 or more.

In this case, the first compound may be represented by the following formula 1':

[Formula 1']

In Formula 1',

One of R ₂₁ to R ₂₄ is

And the rest are each independently referring to the definition of R ₂ , and one of R ₁₁ to R ₁₄ is

And, each of the rest independently refers to the definition of R ₁ , or

R ₂₁ to R ₂₄ each independently refer to the definition of R ₂ , and R ₁₄ is

And one of R ₁₁ to R ₁₃ is

And each of the others independently refers to the definition of R ₁ .

In addition, when the first compound is represented by Formula 1', it may be more advantageous in terms of intramolecular charge transfer and molecular stability than a compound in which a carbazolyl group and an N-containing 6-membered heterocyclic group are substituted at other positions. .

More specifically, the first compound may be represented by any one of the following Formulas 1A' to 1E':

[Formula 1A']

[Formula 1B']

[Chemical Formula 1C']

[Formula 1D']

[Formula 1E']

In Formulas 1A' to 1E',

X, X ₁ to X ₃ , Ar ₁ , Ar ₂ , R ₁ to R ₃ , a+b and c are as defined in Chemical Formula 1.

In this case, in Formulas 1A' to 1D', a and b are each an integer of 0 to 3,

In Formula 1E', a is an integer of 0 to 2, and b is an integer of 0 to 4.

More specifically, the compound represented by Formula 1C' is the following Formula 1A (core 6 position), Formula 1B (core 7 position), and Formula 1C according to the substitution position of the N-containing 6-membered heterocyclic group. (Position 8 of the core), or Formula 1D (position 9 of the core) can be represented:

[Formula 1A]

[Formula 1B]

[Formula 1C]

[Formula 1D]

In Formulas 1A to 1D,

a and b are each an integer of 0 to 3,

Description of the remaining substituents is as defined in Chemical Formula 1.

Preferably, X is O.

Preferably, all of X ₁ to X ₃ are N, or

X ₁ and X ₂ are N, and X ₃ is CH, or

X ₁ and X ₃ are N, X ₂ is CH, or

X ₁ is N, X ₂ and X ₃ are CH, or

X ₂ is N, and X ₁ and X ₃ may be CH.

Preferably, Ar ₁ and Ar ₂ are each independently C _6-20 aryl, or C _2-20 heteroaryl comprising 1 or 2 heteroatoms of N, O and S,

Here, Ar ₁ and Ar ₂ may be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _1-10 alkyl and C _6-20 aryl.

More preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, phenanthryl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, benzoxazolyl, or benzothiazolyl,

Here, Ar ₁ and Ar ₂ may be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _1-10 alkyl and C _6-20 aryl.

For example, Ar ₁ and Ar ₂ may be any one selected from the group consisting of, but is not limited thereto:

Above,

m is an integer from 0 to 7.

In addition, at least one of Ar ₁ and Ar ₂ is

, or

Can be

In addition, Ar ₁ and Ar ₂ may be the same as each other. Or Ar ₁ and Ar ₂ may be different.

Preferably, R ₁ to R ₃ are each independently deuterium; C _6-20 aryl unsubstituted or substituted with deuterium; Or it may be unsubstituted or C _2-20 heteroaryl including one heteroatom of N, O and S substituted with deuterium.

Preferably, R ₁ and R ₂ may each independently be hydrogen, deuterium, phenyl, phenyl substituted with 1 to 5 deuterium, carbazolyl, dibenzofuranyl, or dibenzothiophenyl.

In addition, R ₃ is hydrogen; heavy hydrogen; Phenyl unsubstituted or substituted with deuterium; Carbazolyl unsubstituted or substituted with deuterium; Dibenzofuranyl unsubstituted or substituted with deuterium; Or it may be unsubstituted or dibenzothiophenyl substituted with deuterium.

In addition, the substituent of Formula 1

May be any one of the substituents represented by the following formulas 3a to 3i:

In Formulas 3a to 3i,

p is an integer from 0 to 7,

q is an integer from 0 to 8.

In addition, in Formula 1, a+b, which means the sum of the number of R ₁ and R ₂ , may be 0, 1, 2, 3, 4, 5, or 6, and c means the number of R ₃ It can be 0, 1, 2, 3, 4, 5, 6, 7, or 8.

Preferably, a+b may be 0, 1, 2, or 6, and c may be 0, 1, 2, or 8. In this case, when a+b is 6, R ₁ and R ₂ are both deuterium, and when c is 8, R ₃ may be deuterium.

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

.

On the other hand, the compound represented by Formula 1 may be prepared by a manufacturing method such as the following Scheme 1 as an example. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1]

In Reaction Scheme 3, X _a and X'are each independently halogen, preferably X _a is fluoro, X'is bromo or chloro, and the definitions for other substituents are as described above.

Specifically, the compound represented by Formula 1 may be prepared through steps 1-1 and 1-2.

Step 1-1 is a step of preparing intermediate compound A3 through Suzuki-coupling reaction of starting materials A1 and A2. These Suzuki-coupling reactions are preferably carried out in the presence of a palladium catalyst and a base, respectively, and the reactor for the Suzuki-coupling reaction may be appropriately changed.

In addition, step 1-2 is a step of preparing a compound represented by Formula 1 in which a carbazole group is introduced into the intermediate compound A3 through an amine substitution reaction between the intermediate compound A3 and the compound A4, and such an amine substitution reaction is performed with a palladium catalyst. It is preferred to carry out in the presence of a base. In addition, the reactor for the amine substitution reaction may also be appropriately changed as known in the art.

The method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.

(2nd compound)

The second compound is represented by Chemical Formula 2. Specifically, the second compound is a compound in which Ar ₃ and Ar ₄ substituents are substituted on each of two N atoms of the indolocarbazole core. In particular, since the second compound has an excellent hole property in an indolocarbazole structure, the electron transport property may be controlled by substituting Ar ₃ and Ar ₄ substituents around the indolocarbazole structure. Accordingly, when the second compound is used in the emission layer together with the first compound, the hole and electron transport characteristics can be variously adjusted, which is advantageous in balancing charge in the emission layer.

The second compound may be represented by any one of the following Formulas 2-1 to 2-5, depending on the position at which the benzene ring, which is the A ring, is fused with two adjacent pentagonal rings:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Formulas 2-1 to 2-5,

Each R ₄ is independently deuterium; Substituted or unsubstituted C _6-20 aryl; Or a substituted or unsubstituted C _2-20 heteroaryl containing one or more heteroatoms of N, O and S,

e is an integer from 0 to 4,

f is an integer from 0 to 2,

g is an integer from 0 to 4,

Ar ₃ and Ar ₄ are as defined in Chemical Formula 2.

Preferably, Ar ₃ and Ar ₄ may be hole transporting substituents. Specifically, Ar ₃ and Ar ₄ are each independently C _6-60 aryl; Carbazolyl; Dibenzofuranyl; Or dibenzothiophenyl,

Here, the Ar ₃ and Ar ₄ are unsubstituted or deuterium, C _6-20 aryl, carbazolyl, phenylcarbazolyl, dibenzofuranyl and one or more substituents selected from the group consisting of dibenzothiophenyl Can be substituted.

More preferably, Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, phenanthryl, triphenylenyl, carbazolyl, dibenzofuranyl, or dibenzothio Is phenyl,

Here, Ar ₃ and Ar ₄ may be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, phenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl and dibenzothiophenyl. .

For example, Ar ₃ and Ar ₄ may each independently be any one selected from the group consisting of, but is not limited thereto:

.

Further, preferably, R ₄ is deuterium; C _6-20 aryl unsubstituted or substituted with deuterium; Or it may be unsubstituted or C _2-20 heteroaryl including one heteroatom of N, O and S substituted with deuterium.

Preferably, R ₄ is deuterium; C _6-20 aryl unsubstituted or substituted with deuterium; Carbazolyl unsubstituted or substituted with deuterium; Phenylcarbazolyl unsubstituted or substituted with deuterium; Dibenzofuranyl unsubstituted or substituted with deuterium; Or it may be unsubstituted or dibenzothiophenyl substituted with deuterium.

More preferably, R ₄ is deuterium; Phenyl unsubstituted or substituted with deuterium; Carbazolyl unsubstituted or substituted with deuterium; Phenylcarbazolyl unsubstituted or substituted with deuterium; Dibenzofuranyl unsubstituted or substituted with deuterium; Or it may be unsubstituted or dibenzothiophenyl substituted with deuterium.

For example, R ₄ may be deuterium, or any one selected from the group consisting of, but is not limited thereto:

.

Preferably, d may be 0, 1, 2, or 10. At this time, when d is 10, R ₄ may be deuterium.

Specifically, for example, in Formulas 2-1 to 2-5, e may be 0, 1, or 4, f may be 0, 1, or 2, and g may be 0, 1, or 4. In this case, when e is 4, f is 2, and g is 4, R ₄ may be deuterium.

In addition, since e+f+g is the same as d in Formulas 2-1 to 2-5, e+f+g may be 0, 1, 2, or 10.

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

.

On the other hand, the compound represented by Formula 2 may be prepared by a manufacturing method as shown in Scheme 2 below, for example. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 2]

In Scheme 2, X" is halogen, preferably bromo, or chloro, and the definition of other substituents is as described above.

Specifically, the compound represented by Formula 2 is prepared by combining the starting materials B1 and B2 through an amine substitution reaction. Each of these amine substitution reactions is preferably carried out in the presence of a palladium catalyst and a base. In addition, the reactor 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.

In addition, the first compound and the second compound may be included in a weight ratio of 1:9 to 9:1 in the emission layer. When too little of the first compound is included in the light emitting layer, electron transfer in the light emitting layer is not smooth, so that holes and electrons are not balanced throughout the device, and there may be problems with voltage, efficiency, and lifetime of the fabricated device When the second compound is contained in an excessively small amount compared to the first compound in the emission layer, there may be a problem that the lifespan is reduced. For example, the 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 kinds of host materials. Such dopant substances include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are 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 the light emitting layer in an amount of 1 to 25% by weight based on the total weight of the host material (the sum of the weights of the compound represented by Formula 1 and the compound represented by Formula 2) and the dopant material. have.

Hole bottom

The organic light emitting device according to the present invention may include a hole blocking layer between the light emitting layer and the 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 increasing the probability of hole-electron coupling by controlling electron mobility and preventing excessive movement of holes. It means the layer that plays a role. The hole-blocking layer includes a hole-blocking material, and examples of the hole-blocking material include: a subazine derivative 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 is not limited thereto.

Electron transport layer

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

Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complex; Triazine derivatives and the like, but are not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metal complex compounds , Or a nitrogen-containing 5-membered cyclic derivative, but may be used together, but is not limited thereto.

Electron transport and injection layer

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

The electron transport and injection layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As such an electron injection and 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 mobility for electrons is suitable. Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complex; Triazine derivatives and the like, but are not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and their derivatives, metal complex compounds , Or a nitrogen-containing 5-membered cyclic derivative, but may be used, but is not limited thereto.

The electron transport and injection layer may be formed as separate layers such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the emission layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, benzoimidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metal complex compounds and nitrogen-containing 5-membered ring derivatives, etc. I can.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, 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-naphtholato)gallium, etc. It is not limited thereto.

Organic light emitting element

The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1. 1 shows an example of an organic light-emitting device comprising 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), an electron blocking layer (7), a light emitting layer (3), a hole blocking layer (8), an electron transport and injection layer. An example of an organic light-emitting device consisting of (8) and a cathode (4) 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 configurations. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming each of the above-described 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 of a host and a dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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

Meanwhile, 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.

The fabrication of the organic light emitting device will be described in detail in the following examples. However, the following examples are for illustrating 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, 2-bromo-5-chlorophenol (20 g, 96.4 mmol) and (2,6-difluorophenyl) boronic acid (15.2 g, 96.4 mmol) were added to 400 ml of tetrahydrofuran and stirred and refluxed. . Thereafter, sodium carbonate (30.7 g, 289.2 mmol) was dissolved in 31 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (3.3 g, 2.9 mmol) was added. After reaction for 3 hours, the mixture was allowed to cool to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 464 mL of 20 times chloroform to dissolve it, and after washing 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 white solid compound 1-1-a (16.5g, 71%, MS: [M+H]+ = 241.6).

Step 2) Synthesis of compound 1-1-b

1-1-a (15 g, 62.3 mmol), 0 (15.2 g, 62.3 mmol) and potassium carboenite (25.8 g, 187 mmol) were added, added to 300 ml of dimethylformamide, and stirred and refluxed. After reaction for 3 hours, it was allowed to cool to room temperature, and the resulting solid was filtered. The solid was added to 30 times 413 mL of chloroform to dissolve it, and after washing 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 white solid compound 1-1-b (10.7g, 78%, MS: [M+H]+ = 221.6).

Step 3) Synthesis of compound 1-1-c

In a nitrogen atmosphere, 1-1-b (20 g, 90.6 mmol) and bis (pinacolato) diboron (23 g, 90.6 mmol) were added to 400 ml of Diox, followed by stirring and refluxing. Thereafter, potassium triphosphate (57.7 g, 271.9 mmol) was added and sufficiently stirred, and then palladium dibenzylidene acetone palladium (1.6 g, 2.7 mmol) and tricyclohexylphosphine (1.5 g, 5.4 mmol) were added. After reacting for 2 hours, cooling to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again added to 283 mL of 10 times chloroform to dissolve it, and after washing 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 (22.6g, 80%, MS: [M+H]+ = 313.2).

Step 4) Synthesis of compound 1-1-d

1-c (20 g, 64.1 mmol) and 2-chloro-4- (dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine (22.9 g) in a nitrogen atmosphere , 64.1 mmol) was added to 400 ml of tetrahydrofuran and stirred and refluxed. Thereafter, sodium carbonate (20.4 g, 192.2 mmol) was dissolved in 20 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (2.2 g, 1.9 mmol) was added. After reaction for 3 hours, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 647 mL of 20 times chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 (22.3g, 69%, MS: [M+H]+ = 505.6).

Step 5) Synthesis of compound 1-1

In a nitrogen atmosphere, 1-d (15 g, 29.7 mmol) and 9H-carbazole-1,2,3,4,5,6,7,8-d8 (5.2 g, 29.7 mmol) were added to 300 ml of dimethylformamide. Then, it was stirred and refluxed. After that, potassium carboenite (12.3 g, 89.2 mmol) was added, followed by heating and stirring. After reaction for 3 hours, it was allowed to cool to room temperature, and the resulting solid was filtered. The solid was dissolved in 30 times 591 mL of chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 (11.4g, 58%, MS: [M+H] ⁺ = 663.8).

Synthesis Example 2: Synthesis of Compound 1-2

In Synthesis Example 1, 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine was converted to 9-(4-chloro-6-phenyl- Compound 1-2 (MS: [M+H] by the same method as the preparation method of compound 1-1, except that 1,3,5-triazin-2-yl)-9H-carbazole was used. ⁺ = 662.3)) was prepared.

Synthesis example 3: Synthesis of compound 1-3

In Synthesis Example 1, 2-bromo-5-chlorophenol, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-1-phenyl-1,3,5-triazine and 9H -Carbazole-1,2,3,4,5,6,7,8-d8 respectively 2-bromo-6-chlorophenol, 2-chloro-4-phenyl-6-(phenyl-d5)-1 ,3,5-triazine and 4-phenyl-9H-carbazole, except that the compound was used in the same production method as the production method of 1-1 compound 1-3 (MS[M+H] ⁺ = 646.2) was prepared.

Synthesis Example 4: Synthesis of Compound 1-4

In Synthesis Example 1, (2,6-difluorophenyl) boronic acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-tri Preparation of compound 1-1, except that azine was changed to (2,5-difluorophenyl) boronic acid and 2-chloro-4,6-diphenyl-1,3,5-triazine, respectively. Compound 1-4 (MS[M+H] ⁺ = 573.2) was prepared by the same method as the method.

Synthesis example 5: Synthesis of compound 1-5

In Synthesis Example 1, 2-bromo-5-chlorophenol and (2,6-difluorophenyl) boronic acid were added to 2-bromo-3-chlorophenol and (2,5-difluorophenyl) boron, respectively. Compound 1-5 (MS[M+H] ⁺ = 663.2) was prepared in the same manner as in the preparation method of compound 1-1, except that the acid was used.

Synthesis Example 6: Synthesis of Compound 1-6

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl) boronic acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 respectively 2-bromo-3-chlorophenol, (2,4 -Difluorophenyl)boronic acid, 2-chloro-4,6-diphenyl-1,3,5-triazine and 4-(phenyl-d5)-9H-carbazole, except that the compound was used. Compound 1-6 (MS[M+H] ⁺ = 646.2) was prepared in the same manner as in 1-1.

Synthesis Example 7: Synthesis of Compound 1-7

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl) boronic acid and 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6 -Phenyl-1,3,5-triazine, respectively 2-bromo-3-chlorophenol, (2,4-difluorophenyl) boronic acid and 2-chloro-4- (dibenzo[b,d] Compound 1-7 (MS[M+H) using the same method as the method for preparing compound 1-1, except that furan-4-yl)-6-phenyl-1,3,5-triazine was used. ] ⁺ = 663.2) was prepared.

Synthesis Example 8: Synthesis of Compound 1-8

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl) boronic acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine, respectively 2-bromo-3-chlorophenol, (2,4-difluorophenyl) boronic acid and 2-chloro-4- (dibenzo[b,d] Except for changing to furan-1-yl)-6-phenyl-1,3,5-triazine and used, compound 1-8 (MS[M+H ] ⁺ = 663.2) was prepared.

Synthesis Example 9: Synthesis of Compound 1-9

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl) boronic acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 respectively 2-bromo-3-chloro-6-fluorophenol , (2-fluoro) boronic acid, 2-chloro-4,6-diphenyl-1,3,5-triazine and 4-(phenyl-d5)-9H-carbazole, except that , Compound 1-9 (MS[M+H] ⁺ = 646.2) was prepared in the same manner as in the preparation method of compound 1-1.

Synthesis Example 10: Synthesis of Compound 1-10

In Synthesis Example 1, (2,6-difluorophenyl) boronic acid, 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-tri Azine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 respectively (2,4-difluorophenyl) boronic acid, 2-chloro-4-phenyl-6-( Except for changing to phenyl-d5)-1,3,5-triazine and 3-phenyl-9H-carbazole, the compound 1-10 (MS[ M+H] ⁺ = 646.2) was prepared.

Synthesis example 11: Synthesis of compound 1-11

In Synthesis Example 1, (2,6-difluorophenyl) boronic acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-tri Azine to (2,3-difluorophenyl) boronic acid and 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine, respectively Compound 1-11 (MS[M+H] ⁺ = 648.2) 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 12: Synthesis of Compound 1-12

In Synthesis Example 1, (2,6-difluorophenyl) boronic acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-tri Azine to (2,3-difluorophenyl) boronic acid and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine, respectively Compound 1-12 (MS[M+H] ⁺ = 648.2) 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 13: Synthesis of Compound 1-13

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl) boronic acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine is respectively 2-bromo-3-chlorophenol, (2,3-difluorophenyl) boronic acid and 2-chloro-4- (dibenzo[b,d] Thiophen-4-yl)-6-phenyl-1,3,5-triazine, except that it was used in the same manner as the preparation method of compound 1-1, compound 1-13 (MS[M+ H] ⁺ = 679.2) was prepared.

Synthesis Example 14: Synthesis of Compound 1-14

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl) boronic acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 respectively 2-bromo-3-chlorophenol, (2,3 -Difluorophenyl) boronic acid, 2-chloro-4-phenyl-6- (phenyl-d5) -1,3,5-triazine and 4-phenyl-9H-carbazole except , Compound 1-14 (MS[M+H] ⁺ = 646.2) was prepared in the same manner as in the preparation method of compound 1-1.

Synthesis Example 15: Synthesis of Compound 1-15

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl) boronic acid and 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine is respectively 2-bromo-3-chlorophenol, (2,3-difluorophenyl) boronic acid and 2-chloro-4- (dibenzo[b,d] Furan-1-yl)-6-phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 , Compound 1-15 (MS[M+H] ⁺ = 663.2) was prepared in the same manner as in the preparation method of compound 1-1.

Synthesis Example 16: Synthesis of Compound 2-1

Step 1) Synthesis of compound 2-1-a

In a nitrogen atmosphere, 11,12-dihydroindolo[2,3-a]carbazole (30 g, 117 mmol) and bromobenzene (18.4 g, 117 mmol) were added to 600 ml of toluene, followed by stirring and refluxing. Thereafter, sodium tertiary-butoxide (33.8 g, 351.1 mmol) was added and sufficiently stirred, and then bis (tri tertiary-butylphosphine) palladium (1.8 g, 3.5 mmol) was added. After reacting for 5 hours, after cooling to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again added to 389 mL of 10 times chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 2-1-a (30 g, 77%, MS: [M+H]+ = 333.4).

Step 2) Synthesis of Compound 2-1

2-1-a (30 g, 90.2 mmol) and 4-chloro-1,1':3',1''-terphenyl-2'',3'',4'',5'' in nitrogen atmosphere ,6''-d5 (23.2 g, 90.2 mmol) was added to 600 ml of toluene and stirred and refluxed. Thereafter, sodium tertiary-butoxide (26 g, 270.7 mmol) was added, stirred sufficiently, and then bis (tri tertiary-butylphosphine) palladium (1.4 g, 2.7 mmol) was added. After 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 added to 10 times 511 mL of chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 white solid compound 2-1 (39.3 g, 77%, MS: [M+H]+ = 566.7).

Synthesis example 17: synthesis of compound 2-2

In Synthesis Example 16, 11,12-dihydroindolo[2,3-a]carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2", 3``,4'',5'',6''-d5 respectively 5,7-dihydroindolo[2,3-b]carbazole, 4-chloro-1,1'-biphenyl-2 A method of preparing compound 2-1, except that it was changed to',3',4',5',6'-d5 and 3-chloro-1,1':4',1''-terphenyl Compound 2-2 (MS[M+H] ⁺ = 642.8) was prepared by the same method as described above.

Synthesis Example 18: Synthesis of Compound 2-3

In Synthesis Example 16, 11,12-dihydroindolo[2,3-a]carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2", 3``,4'',5'',6''-d5 respectively 5,8-dihydroindolo[2,3-c]carbazole, 4-chloro-1,1'-biphenyl and 4 -Chloro-1,1':3',1''-Except that it was used after changing to terphenyl, compound 2-3 (MS[M+H] ⁺ = 637.3) was prepared.

Synthesis Example 19: Synthesis of Compound 2-4

In Synthesis Example 16, 11,12-dihydroindolo[2,3-a]carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2", 3``,4'',5'',6''-d5 to 5,8-dihydroindolo[2,3-c]carbazole-1,2,3,4,6,7,9 respectively Compound 2-4 (MS[M+H] ⁺ = 561.2) was prepared in the same manner as in the preparation method of compound 2-1, except that it was changed to 10,11,12-d10 and used.

Synthesis Example 20: Synthesis of Compound 2-5

In Synthesis Example 16, 11,12-dihydroindolo[2,3-a]carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2", 3``,4'',5'',6''-d5 respectively 5,8-dihydroindolo[2,3-c]carbazole, 3-bromodibenzo[b,d]furan and 4 -Chloro-1,1'-biphenyl-2',3',4',5',6'-d5, except that the compound was used in the same manner as the production method of compound 2-1, compound 2 -5 (MS[M+H] ⁺ = 580.2) was prepared.

Synthesis Example 21: Synthesis of Compound 2-6

In Synthesis Example 16, 11,12-dihydroindolo[2,3-a]carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2", 3``,4'',5'',6''-d5 to 5,11-dihydroindolo[3,2-b]carbazole and 3-bromo-1,1'-biphenyl, respectively Compound 2-6 (MS[M+H] ⁺ = 561.2) was prepared in the same manner as in the preparation method of compound 2-1, except that the change was used.

Synthesis Example 22: Synthesis of Compound 2-7

In Synthesis Example 16, 11,12-dihydroindolo[2,3-a]carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2", 3``,4'',5'',6''-d5 to 5,12-dihydroindolo[3,2-a]carbazole and 4-bromo-1,1'-biphenyl, respectively Compound 2-7 (MS[M+H] ⁺ = 561.2) was prepared in the same manner as in the preparation method of compound 2-1, except that the change was used.

Synthesis Example 23: Synthesis of Compound 2-8

In Synthesis Example 16, 11,12-dihydroindolo[2,3-a]carbazole, bromobenzene and 4-chloro-1,1':3',1"-terphenyl-2", Compounds, except that 3``,4'',5'',6''-d5 was changed to 5,7-dihydroindolo[2,3-b]carbazole and bromobenzene, respectively. Compound 2-7 (MS[M+H] ⁺ = 561.2) was prepared in the same manner as in 2-1.

[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 dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HT-A compound and the following PD compound were thermally vacuum-deposited at a thickness of 100 Å at a weight ratio of 95:5 to form a hole injection layer, and then only the following HT-A compound had a thickness of 1150 Å. By evaporation 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 inhibiting layer).

On the electron blocking layer, a light emitting layer was formed by vacuum depositing the compound 1-1 and compound 2-1 prepared previously as a host compound and the following GD compound as a dopant compound to a thickness of 400 Å at a weight ratio of 85:15. At this time, the weight ratio of the compound 1-1 and the compound 2-1 was 1: 1.

On the emission 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 to a thickness of 250 Å at a weight ratio of 2:1, and then LiF and magnesium were vacuum deposited to a thickness of 30 Å at 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 device.

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

Examples 2 to 15

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

At this time, the structure of the compound used in the examples is as follows.

.

Comparative Examples 1 to 7

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

At this time, in Table 1 below, compounds H-2 and C1 are as follows, respectively.

Experimental example

Voltage, efficiency, and lifetime (T95) were measured by applying a current to the organic light-emitting devices manufactured in the above 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 decreases to 95% at a current density of 20 mA/cm ² .

division	Emission layer 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 2-3	3.01	70.0	green	86
Example 3	Compound 1-3, Compound 2-3	3.05	72.1	green	81
Example 4	Compound 1-4, Compound 2-8	3.01	70.0	green	85
Example 5	Compound 1-4, Compound 2-4	3.03	72.3	green	82
Example 5	Compound 1-5, Compound 2-5	3.08	70.7	green	80
Example 6	Compound 1-6, Compound 2-3	3.01	70.2	green	81
Example 7	Compound 1-7, Compound 2-6	3.03	71.2	green	86
Example 8	Compound 1-8, Compound 2-6	3.09	72.5	green	80
Example 9	Compound 1-9, Compound 2-4	3.03	69.5	green	87
Example 10	Compound 1-10, Compound 2-4	3.07	71.3	green	82
Example 11	Compound 1-11, Compound 2-3	3.02	70.1	green	83
Example 12	Compound 1-12, Compound 2-5	3.08	72.2	green	90
Example 13	Compound 1-13, Compound 2-7	3.04	70.3	green	82
Example 14	Compound 1-14, Compound 2-6	3.05	69.0	green	86
Example 15	Compound 1-15, Compound 2-2	3.09	71.0	green	83
Comparative Example 1	Compound 1-2	3.17	65.8	green	71
Comparative Example 2	Compound 1-10	3.22	65.5	green	78
Comparative Example 3	Compound 1-12	3.19	62.0	green	79
Comparative Example 4	Compound C1	3.25	65.5	green	65
Comparative Example 5	Compound C1, Compound H-2	3.12	67.5	green	72
Comparative Example 6	Compound C1, Compound 2-8	3.20	68.2	green	75
Comparative Example 7	Compound 1-10, Compound H-2	3.25	61.8	green	78

As shown in Table 1, the organic light emitting device of the embodiment using both the first compound and the second compound of the present invention as a host, the organic light emitting device of Comparative Examples 1 to 3 using only the first compound and the first compound And compared with the organic light emitting diodes of Comparative Examples 4 and 5 in which neither of the second compounds was used, it can be seen that it exhibits excellent characteristics in terms of efficiency and lifetime.

In addition, the organic light-emitting device of the above embodiment used two kinds of hosts, but the higher efficiency and higher efficiency than the organic light-emitting devices of Comparative Examples 6 and 7 employing a combination of other hosts instead of the combination of the first compound and the second compound It can be seen that it shows an excellent service life.

This is, considering that the luminous efficiency and lifetime characteristics of the organic light-emitting device generally 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 represent.

[Explanation of code]

1: substrate 2: anode

3: light emitting layer 4: cathode

5: hole injection layer 6: hole transport layer

7: electron block 8: hole block

9: electron transport and injection layer

Claims (17)

1. anode;

   A cathode provided to face the anode; And

   Including a light emitting layer provided between the anode and the cathode,

   The emission layer comprises a first compound represented by the following formula 1 and a second compound represented by the following formula 2,

   Organic light emitting element:

   [Formula 1]

   

   In Formula 1,

   X is O or S,

   X ₁ to X ₃ are each independently N or CH, provided that at least one of X ₁ to 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 heteroaryl containing one or more heteroatoms of N, O and S,

   R ₁ to R ₃ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms of N, O and S,

   a+b is an integer from 0 to 6,

   c is an integer from 0 to 8,

   [Formula 2]

   

   In Chemical Formula 2,

   A is a benzene ring fused with two adjacent pentagonal rings,

   Ar ₃ and Ar ₄ are each independently Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms of N, O and S,

   R ₄ is hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms of N, O and S,

   d is an integer from 0 to 10.
2. The method of claim 1,

   C _6-60 aryl in which at least one of Ar ₁ and Ar ₂ is substituted with deuterium; Or C _2-60 heteroaryl containing one or more heteroatoms of N, O and S substituted with deuterium; or

   At least one of R ₁ to R ₃ is deuterium; C _6-60 aryl substituted with deuterium; Or C _2-60 heteroaryl containing at least one heteroatom among N, O and S substituted with deuterium, and a+b+c is 1 or more,

   Organic light emitting device.
3. The method of claim 1,

   The first compound is represented by any one of the following formulas 1A' to 1E',

   Organic light emitting element:

   [Formula 1A']

   

   [Formula 1B']

   

   [Chemical Formula 1C']

   

   [Formula 1D']

   

   [Formula 1E']

   

   In Formulas 1A' to 1E',

   X, X ₁ to X ₃ , Ar ₁ , Ar ₂ , R ₁ to R ₃ , a+b and c are as defined in claim 1.
4. The method of claim 1,

   X is O,

   Organic light emitting device.
5. The method of claim 1,

   X ₁ to X ₃ are all N, or

   X ₁ and X ₂ are N, and X ₃ is CH, or

   X ₁ and X ₃ are N, X ₂ is CH, or

   X ₁ is N, X ₂ and X ₃ are CH, or

   X ₂ is N, and X ₁ and X ₃ are CH,

   Organic light emitting device.
6. The method of claim 1,

   Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, phenanthryl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, benzoxazolyl, or benzothiazolyl,

   Here, Ar ₁ and Ar ₂ are unsubstituted or substituted 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.
7. The method of claim 1,

   Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of,

   Organic light emitting element:

   

   

   Above,

   m is an integer from 0 to 7.
8. The method of claim 1,

   R ₁ and R ₂ are each independently hydrogen, deuterium, phenyl, phenyl substituted with 1 to 5 deuterium, carbazolyl, dibenzofuranyl, or dibenzothiophenyl,

   Organic light emitting device.
9. The method of claim 1,

   R ₃ is hydrogen; heavy hydrogen; Phenyl unsubstituted or substituted with deuterium; Carbazolyl unsubstituted or substituted with deuterium; Dibenzofuranyl unsubstituted or substituted with deuterium; Or dibenzothiophenyl unsubstituted or substituted with deuterium,

   Organic light emitting device.
10. The method of claim 1,

    The substituent

    

    Is any one of the substituents represented by the following formulas 3a to 3i,

    Organic light emitting element:

    

    In Formulas 3a to 3i,

    p is an integer from 0 to 7,

    q is an integer from 0 to 8.
11. The method of claim 1,

    a+b is 0, 1, 2, or 6,

    c is 0, 1, 2, or 8,

    Organic light emitting device.
12. The method of claim 1,

    The first compound is any one selected from the group consisting of the following compounds,

    Organic light emitting element:

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    .
13. The method of claim 1,

    The second compound is represented by any one of the following Formulas 2-1 to 2-5,

    Organic light emitting element:

    [Formula 2-1]

    

    [Formula 2-2]

    

    [Formula 2-3]

    

    [Formula 2-4]

    

    [Formula 2-5]

    

    In Formulas 2-1 to 2-5,

    Each R ₄ is independently deuterium; Substituted or unsubstituted C _6-20 aryl; Or a substituted or unsubstituted C _2-20 heteroaryl containing one or more heteroatoms of N, O and S,

    e is an integer from 0 to 4,

    f is an integer from 0 to 2,

    g is an integer from 0 to 4,

    Ar ₃ and Ar ₄ are as defined in claim 1.
14. The method of claim 1,

    Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, phenanthryl, triphenylenyl, carbazolyl, dibenzofuranyl, or dibenzothiophenyl,

    Here, Ar ₃ and Ar ₄ are unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, phenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl and dibenzothiophenyl,

    Organic light emitting device.
15. The method of claim 1,

    R ₄ is deuterium; Phenyl unsubstituted or substituted with deuterium; Carbazolyl unsubstituted or substituted with deuterium; Phenylcarbazolyl unsubstituted or substituted with deuterium; Dibenzofuranyl unsubstituted or substituted with deuterium; Or dibenzothiophenyl unsubstituted or substituted with deuterium,

    Organic light emitting device.
16. The method of claim 1,

    d is 0, 1, 2, or 10,

    Organic light emitting device.
17. The method of claim 1,

    The second compound is any one selected from the group consisting of the following compounds,

    Organic light emitting element:

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    .

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