WO2020106108A1 - Novel compound and organic light emitting device using same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device using same

Cross-citation with relevant application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0146587 on November 23, 2018 and Korean Patent Application No. 10-2019-0150704 on November 21, 2019. All content disclosed in the literature is incorporated as part of this specification.

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

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, for example, 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. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it glows.

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

[Advanced technical literature]

[Patent Document]

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

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

The present invention provides a compound represented by Formula 1:

[Formula 1]

In Chemical Formula 1,

Q is a dibenzofuran, dibenzothiophene, benzofuran, or benzothiophene ring fused with a neighboring pentagonal ring,

R _a and R _b are each hydrogen, or they combine together to form a single bond,

One of HAr ₁ to HAr ₄ is represented by the following Chemical Formula 2, one of the other is represented by the following Chemical Formula 3, and the other is represented by the following Chemical Formula 2 or 3,

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

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

A is a substituted or unsubstituted C _2-60 heteroaryl containing two or more N atoms,

n1 to n4 are each an integer of 0 to 2,

n1 + n2 + n3 + n4 is an integer from 2 to 8,

When n1 to n4 are 2 or more, the structures in parentheses are the same or different, respectively.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. .

The compound represented by Chemical Formula 1 may be used as a material of an organic material layer of an organic light emitting device, and may improve efficiency, low driving voltage, and / or life characteristics in the organic light emitting device.

1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a cathode 6.

Figure 2 is a substrate (1), anode (2), hole injection layer (7), hole transport layer (3), electron suppression layer (8), light emitting layer (4), hole blocking layer (9), electron transport layer (5) , It shows an example of an organic light emitting device consisting of a hole injection layer 10 and the cathode (6).

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

In this specification,

Means a linkage to another substituent.

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above. . For example, "a substituent having two or more substituents" 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 this specification, the number of carbon atoms of the carbonyl group is not particularly limited, but 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 oxygen of the ester group may be substituted 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 this specification, the number of carbon atoms of the imide group is not particularly limited, but 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 is specifically a trimethyl boron group, a triethyl boron group, a t-butyl dimethyl boron group, a triphenyl boron group, a phenyl boron 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 straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are 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 a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. 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, styrenyl group, styrenyl group, and the like, but are not limited thereto.

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

In the present specification, the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be back. However, it is not limited thereto.

In the present specification, heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as heterogeneous elements, and carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil 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, isooxazolyl group, thiadiazolyl Group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above. In the present specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described example of the alkyl group. In the present specification, the heteroarylamine of the heteroaryl may be applied to the description of the heteroaryl described above. In the present specification, the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group. 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 heteroaryl described above 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 cycloalkyl group described above may be applied, except that two substituents are formed by bonding. In the present specification, the heterocycle is not a monovalent group, and the description of the above-described heteroaryl may be applied, except that two substituents are formed by bonding.

Meanwhile, the present invention provides a compound represented by Chemical Formula 1. The compound represented by Chemical Formula 1 includes a substituent represented by Chemical Formula 2 and a substituent represented by Chemical Formula 3 at the same time. In other words, at least one of the substituents HAr ₁ to HAr ₄ in Formula 1 is represented by Formula 2, and at least one is represented by Formula 3. Therefore, the sum of n1, n2, n3, and n4, which means the number of each of the substituents HAr ₁ , HAr ₂ , HAr ₃ and HAr ₄ has a value of 2 or more, where n1 + n2 + n3 + n4 is 2 , One of HAr ₁ to HAr ₄ is a substituent represented by Formula 2, and the other is a substituent represented by Formula 3.

As described above, when the compound represented by Chemical Formula 1 includes two or more N atom-heteroaryl groups represented by Chemical Formula 2 and the cyano group represented by Chemical Formula 3 at the same time, the action of attracting electrons of the cyano group And the transfer of electrons of two or more N atom-containing heteroaryl groups is balanced with each other to control the electron transfer rate, so that the organic light emitting device using the compound does not contain such substituents or contains only one substituent It shows excellent characteristics in terms of driving voltage, efficiency and lifespan compared to the organic light emitting device using.

Specifically, according to the definition of R _a and R _b, the compound represented by Formula 1 is represented by the following Formula 1A when R _a and R _b are each hydrogen, and R _a and R _b are bonded together to form a single bond. When formed, it is represented by Formula 1B:

[Formula 1A]

[Formula 1B]

In Formulas 1A and 1B,

Q is any one selected from the group consisting of:

In the above,

The carbon atoms of two adjacent * are condensed with the carbon atoms of * 1 and * 2 of Formula 1A or 1B, respectively, to form a ring,

Descriptions of HAr ₁ to HAr ₄ and n1 to n4 are as defined in Chemical Formula 1.

In addition, the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-6 when Q is dibenzofuran or dibenzothiophene, depending on the bonding position of Q, and Q is benzofuran or benzo In the case of thiophene, it is represented by any one of the following formulas 1-7 to 1-12:

In Chemical Formulas 1-1 to 1-12,

Y is O or S,

Descriptions of R _a , R _b , HAr ₁ to HAr ₄ and n1 to n4 are as defined in Formula 1.

Preferably, the substituent represented by Formula 2 may be represented by any one of the following Formulas 2-1 to 2-3:

In Chemical Formulas 2-1 to 2-3,

X ₁ to X ₃ are each independently N or CH, but at least two of X ₁ to X ₃ are N,

Ar ₁ to Ar ₄ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

Description of L ₁ is as defined in Formula 1 above.

More preferably, in Formula 2-1, X ₁ to X ₃ are N.

More preferably, in the formulas 2-1 to 2-3, Ar ₁ to Ar ₄ are each independently C _1-10 alkyl, or C _6-20 aryl. Most preferably, in Formulas 2-1 to 2-3, Ar ₁ and Ar ₂ are phenyl, Ar ₃ is ethyl, and Ar ₄ is phenyl.

Preferably, in the above formulas 2 and 3, L ₁ and L ₂ are each independently a single bond, or C _6-20 aryl, more preferably, a single bond, or phenylene, most preferably, single Bond, or 1-4-phenylene.

Preferably, the compound represented by Formula 1 is a compound represented by Formula 1-1 or 1-7.

Specifically, the compound represented by Formula 1 may be represented by any one of the following Formulas 4-1 to 4-4:

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

In Chemical Formulas 4-1 to 4-4,

Y is O or S,

n1 to n4 are each 0 or 1,

n1 + n2 + n3 + n4 is 2,

One of HAr ₁ to HAr ₄ is represented by Chemical Formula 2, and the other one is represented by Chemical Formula 3.

Meanwhile, n1 + n2 + n3 + n4 may be 2 or 3.

Specifically, n1 is 1 and n2, n3 and n4 are 0 or 1, respectively.

More specifically, n1 and n2 are each 1, and n3 and n4 are each 0;

n1 and n3 are each 1, and n2 and n4 are each 0; or

n1 and n4 may be 1, respectively, and n2 and n3 may be 0, respectively.

For example, the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 5-1 or 5-2:

[Formula 5-1]

[Formula 5-2]

In Chemical Formulas 5-1 and 5-2,

R _a and R _b are each hydrogen, or they combine together to form a single bond,

Y is O or S,

HAr ₁ is represented by Chemical Formula 2,

L ₂ is a single bond, or 1,4-phenylene.

Alternatively, the compound represented by Formula 1 may be represented by the following Formula 5-3 or 5-4:

[Formula 5-3]

[Formula 5-4]

In Chemical Formulas 5-3 and 5-4,

R _a and R _b are each hydrogen, or they combine together to form a single bond,

Y is O or S,

L ₂ is a single bond, or 1,4-phenylene,

n3 and n4 are each 0 or 1,

n3 + n4 is 1,

One of HAr ₃ and HAr ₄ is represented by Chemical Formula 2 above.

Alternatively, the compound represented by Formula 1 may be represented by the following Formula 5-5 or 5-6:

[Formula 5-5]

[Formula 5-6]

In the above formula 5-5 and 5-6,

R _a and R _b are each hydrogen, or they combine together to form a single bond,

Y is O or S,

L ₂ is a single bond, or 1,4-phenylene,

n2 to n4 are each 0 or 1,

n2 + n3 + n4 is 1,

One of HAr ₂ to HAr ₄ is represented by Chemical Formula 2 above.

Alternatively, n1, n2 and n3 are each 1 and n4 is 0;

n1, n2 and n4 are each 1, and n3 is 0;

n1, n3 and n4 are each 1, and n2 is 0;

n2, n3 and n4 are each 1, and n1 is 0;

n1 is 2, n2 is 1, and n3 and n4 are each 0;

n1 is 2, n3 is 1, and n2 and n4 are each 0; or

n1 is 2, n4 is 1, and n2 and n3 may each be 0.

For example, the compound may be represented by the following formula 6-1 or 6-2:

[Formula 6-1]

[Formula 6-2]

In Chemical Formulas 6-1 and 6-2,

R _a and R _b are each hydrogen, or they combine together to form a single bond,

Y is O or S,

n1, n2 and n4 are 0, 1, or 2, respectively,

n1 + n2 + n4 is 2,

HAr ₁ , HAr ₂ and One of HAr ₄ is represented by Formula 2, the other is represented by Formula 3, and the other is represented by Formula 2 or 3.

Alternatively, the compound may be represented by the following Chemical Formula 6-3 or 6-4:

[Formula 6-3]

[Formula 6-4]

In Chemical Formulas 6-3 and 6-4,

R _a and R _b are each hydrogen, or they combine together to form a single bond,

Y is O or S,

n1, n3 and n3 are each 0, 1, or 2,

n1 + n3 + n4 is 2,

HAr ₁ , HAr ₃ and One of HAr ₄ is represented by Formula 2, the other is represented by Formula 3, and the other is represented by Formula 2 or 3.

Specifically, for example, the compound may be any one selected from the group consisting of the following compounds:

On the other hand, the compound represented by the formula (1), for example, when HAr ₁ is represented by the formula (1), and HAr ₃ is represented by the formula (3), it can be prepared by the following reaction method 1-1 or 1-2 Can be. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1-1]

[Scheme 1-2]

In Reaction Schemes 1-1 and 1-2, X is halogen, and description of the remaining substituents is as described in Chemical Formula 1. In addition, the reaction is a Suzuki coupling reaction, it is preferable to perform in the presence of a palladium catalyst and a base, the reactor for the Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

On the other hand, the present invention provides an organic light emitting device comprising the compound represented by the formula (1). In one example, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. .

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include fewer organic layers.

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

Also, preferably, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and the electron transport layer includes a compound represented by Chemical Formula 1.

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

Further, the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a cathode 6. In such a structure, the compound represented by Chemical Formula 1 may be included in the electron transport layer 5.

2 is a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron suppressing layer (8), a light emitting layer (4), a hole blocking layer (9), an electron transport layer (5), an example of an organic light emitting device comprising a hole injection layer 10 and a cathode 6 is shown. In such a structure, the compound represented by Chemical Formula 1 may be included in the electron transport layer 5.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer contains the compound represented by Chemical Formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a positive electrode is formed by depositing metal or conductive metal oxides or alloys thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

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

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

The positive electrode material is usually a material having a large work function to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Metal and oxide combinations 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 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 is a multilayer structure material such as LiF / Al or LiO ₂ / Al, but is not limited thereto.

The hole injection layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated in the light emitting layer. A compound that prevents migration of the excitons to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based , Organic anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer. As the hole transport material, the hole is transported from the anode or the hole injection layer to the hole and is transported to the light emitting layer. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

The electron suppressing layer is a layer positioned between the hole transport layer and the light emitting layer, and is mainly provided in contact with the light emitting layer to prevent excessive movement of electrons to increase the probability of hole-electron bonding, thereby improving the efficiency of the organic light emitting device It means layer. The electron suppressing layer includes an electron suppressing material, and an arylamine-based organic material may be used as the electron suppressing material, but is not limited thereto.

The light emitting layer is a layer that transports holes and electrons from the hole transport layer and the electron transport layer, respectively, and the holes and electrons are combined to emit light in the visible light region, and preferably includes a material having good quantum efficiency for fluorescence or phosphorescence. Specifically, the light emitting layer may include a host material and a dopant material.

Examples of the host material include a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material 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, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. Further, examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto.

The hole blocking layer is a layer positioned between the light emitting layer and the electron transport layer, and is mainly provided in contact with the light emitting layer, thereby improving the efficiency of the organic light emitting device by increasing the hole-electron bonding probability that holes move to the electron transport layer It means the layer to do. The hole blocking layer includes a hole blocking material, an example of such a hole blocking material is a triazole derivative; Oxadiazole derivatives; Phenanthroline derivatives may be used, but are not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer, which is a material having high mobility for electrons The compound represented by Chemical Formula 1 may be used. Additionally, an Al complex of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like. In addition, the electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, followed by an aluminum layer or a silver layer in each case.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, LiF, NaF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid , Preoleenylidene methane, anthrone and the like, and derivatives thereof, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

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

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

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

The preparation of the compound represented by Chemical Formula 1 and the organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the invention, and the scope of the invention is not limited by them.

Preparation Example 1 Synthesis of Compound 1

Compound 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorine-9,8'-fluoreno [3,4-b ] Benzofuran] -2-carbonitrile (10.0 g, 17.9 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (5.0 g, 18.8 mmol) in 100 ml of tetrahydrofuran After complete dissolution, potassium carbonate (7.4 g, 53.7 mmol) was dissolved in 43 ml of water and added, and tetrakistriphenyl-phosphine palladium (620 mg, 0.537 mmol) was added, followed by heating and stirring for 7 hours. After lowering the temperature to room temperature and terminating the reaction, the potassium carbonate solution was removed to filter the white solid. The filtered white solid was washed twice with tetrahydrofuran and ethyl acetate, respectively, to thereby prepare Compound 1 (9.5 g, yield 80%).

MS [M + H] ⁺ = 662

Preparation Example 2: Synthesis of Compound 2

Compound 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorine-9,8'-fluoreno [in Preparation Example 1] 3,4-b] benzofuran] -2-carbonitrile instead of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [benzo [b ] Fluoreno [4,3-d] thiophen-8,9'-fluorene] -3'-carbonitrile, except for using the same method as Preparation Example 1, the compound 2 (10.3 g, yield 85%).

MS [M + H] ⁺ = 678

Preparation Example 3: Synthesis of Compound 3

Compound 4- (6-fluoro-8-phenyl-8H-fluoreno [3,4-b] benzofuran-8-yl) benzonitrile (10.0 g, 22.1 mmol) and 2-ethyl-1H-benzo [d ] Imidazole (3.2 g, 22.1 mmol), cesium carbonate (14.4 g, 44.2 mmol) was added and dimethylacetamide (130 ml) was heated and stirred at 120 ° C. or higher for 10 hours. After lowering the temperature to room temperature and terminating the reaction, water was added to obtain a solid after filtration to prepare Compound 3 (10.2 g, yield 80%).

MS [M + H] + = 577

Preparation Example 4 Synthesis of Compound 4

Compound 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorine-9,8'-fluoreno [in Preparation Example 1] 2- (4'-bromospiro [fluorene-9,6'-fluoreno [3,4-b] furan] -2-yl) instead of 3,4-b] benzofuran] -2-carbonitrile) -4-, 6-diphenyl-1,3,5-triazine, (4-cyanophenyl) boronic acid instead of 2-chloro-4,6-diphenyl-1,3,5-triazine The compound 4 (8.6 g, yield 70%) was prepared in the same manner as in Preparation Example 1, except for using.

MS [M + H] + = 688

Preparation Example 5: Synthesis of Compound 5

Compound 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorine-9,8'-fluoreno [in Preparation Example 1] 8'-bromospiro [fluorene-9,6'-fluoreno [3,4-b] furan] -4'-carbonitrile instead of 3,4-b] benzofuran] -2-carbonitrile, 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine The compound 5 (10.7 g, yield 87%) was prepared in the same manner as in Preparation Example 1, except that dioxaboran-2-yl) phenyl) -1,3,5-triazine was used.

MS [M + H] + = 688

Preparation Example 6: Synthesis of Compound 6

Compound 2- (4'-bromospiro [fluorene-9,6'-fluoreno [3,4-b] furan] -2-yl) -4,6-diphenyl-1 in Preparation Example 4 above 2- (4'-bromospiro [fluorene-9,6'-fluoreno [3,4-b] thiophen] -2-yl) -4,6-di instead of, 3,5-triazine Compound 6 (9.7 g, yield 77%) was prepared in the same manner as in Preparation Example 4, except that phenyl-1,3,5-triazine was used.

MS [M + H] + = 704

Preparation Example 7: Synthesis of Compound 7

Compound 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorine-9,8'-fluoreno [in Preparation Example 1] 3,4-b] benzofuran] -2-carbonitrile instead of 6-phenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl ) Phenyl) -6H-fluoreno [3,4-b] The compound 7 (10.1 g, yield 89%) was prepared in the same manner as in Preparation Example 1, except that cyophene-1-carbonitrile was used. Did.

MS [M + H] + = 630

Preparation Example 8: Synthesis of Compound 8

In Preparation Example 4, the compound 2- (4'-bromospiro [fluorene-9,6'-fluoreno [3,4-b] furan] -2-yl) -4,6-diphenyl- 2- (1-Bromo spiro [benzo [b] fluoreno [4,3-d] thiophen-8,9'-fluorene] -2'-yl) instead of 1,3,5-triazine- Compound 8 (10.5 g, yield 82%) was prepared in the same manner as in Preparation Example 4, except that 1-phenyl-1H-benzo [d] imidazole was used.

MS [M + H] + = 715

Preparation Example 9: Synthesis of Compound 9

Compound 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorine-9,8'-fluoreno [in Preparation Example 1] 8-phenyl-8- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) instead of 3,4-b] benzofuran] -2-carbonitrile Compound 9 was prepared in the same manner as in Preparation Example 1, except that phenyl) -8H-fluoreno [3,4-b] benzofuran-2,10-dicarbonitrile was used.

MS [M + H] + = 689

Preparation Example 10 Synthesis of Compound 10

Compound 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorine-9,8'-fluoreno [in Preparation Example 1] 3- (2-ethyl-1H-benzo [imidazol-1-yl) -9 '-(4,4,5,5-tetramethyl-1 instead of 3,4-b] benzofuran] -2-carbonitrile , 3,2-dioxaborolan-2-yl) spiro [fluorene-9,6'-fluoreno [3,4-b] thiophene] -1'-carbonitrile Compound 10 was prepared in the same manner as in Preparation Example 1.

MS [M + H] + = 773

Preparation Example 11: Synthesis of Compound 11

Compound 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorine-9,8'-fluoreno [in Preparation Example 1] 3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorene-] instead of 3,4-b] benzofuran] -2-carbonitrile Compound 11 was prepared by the same method as the preparation example 1 except that 9,8'-fluoreno [3,4-b] benzofuran] -2 ', 10'-dicarbonitrile was used.

MS [M + H] + = 687

Preparation 12: Synthesis of Compound 12

Compound 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorine-9,8'-fluoreno [in Preparation Example 1] 3,4-b] benzofuran] -2-carbonitrile instead of 6-phenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Compound 12 was prepared in the same manner as in Preparation Example 1, except that phenyl) -6H-fluoreno [3,4-b] thiophen-1,8-dicarbonitrile was used.

MS [M + H] + = 655

Example 1-1

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

A compound of the following compound HI1 and the following compound HI2 was thermally vacuum-deposited to a thickness of 100 되도록 to a ratio of 98: 2 (molar ratio) on the prepared ITO transparent electrode, thus forming a hole injection layer. On the hole injection layer, a compound (1150 화합물) represented by the following Chemical Formula HT1 was vacuum-deposited to form a hole transport layer. Subsequently, an EB1 compound was vacuum deposited on the hole transport layer with a thickness of 50 mm 2 to form an electron suppressing layer.

Subsequently, a compound represented by the following Chemical Formula BH and a compound represented by the following Chemical Formula BD with a film thickness of 200 mm 2 were vacuum-deposited on a weight ratio of 50: 1 on the electron suppressing layer to form a light emitting layer.

A hole blocking layer was formed by vacuum-depositing a compound represented by the following Chemical Formula HB1 with a thickness of 50 mm 2 on the light emitting layer. Subsequently, on the hole blocking layer, a compound 1 prepared in Formula 1 and a compound represented by the following Formula LiQ were vacuum-deposited at a weight ratio of 1: 1 to form an electron transport layer with a thickness of 30 MPa. On the electron transport layer, lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 1,000 순차적 were sequentially deposited to form an electron injection layer and a cathode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, During the deposition, a vacuum 2 x 10 ^{- An} organic light emitting device was manufactured by maintaining ⁷ to 5 x 10 ^-6 torr.

The structure of the compound used in the above example is as follows.

Examples 1-2 to 1-9

An organic light-emitting device was manufactured according to the same method as Example 1-1 except for using the compound shown in Table 1 below instead of the compound of Preparation Example 1.

The structures of the compounds used in Examples 1-1 to 1-9 are as follows:

Comparative Examples 1-1 to 1-7

An organic light-emitting device was manufactured according to the same method as Example 1-1 except for using the compound shown in Table 1 below instead of the compound of Preparation Example 1. The structures of the compounds ET1, ET2, ET3, ET4, ET5, ET6 and ET7 used in Table 1 below are as follows.

Experimental Example 1

When current was applied to the organic light emitting devices manufactured in Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-7, voltage, efficiency, color coordinates, and lifetime were measured and the results are shown in Table 1 below. Shown. T95 means the time required for the luminance to decrease from the initial luminance (1600 nit) to 95%.

As shown in Table 1, in the case of an organic light emitting device manufactured using the compound of the present invention as an electron transport layer, it exhibited excellent properties in terms of efficiency, driving voltage, and stability of the organic light emitting device.

In particular, the organic light-emitting device of the embodiment employing the compound represented by Formula 1 may have the same or similar core as well as the organic light-emitting device of Comparative Example 1-3 employing the existing spirodifluorene core compound. Compared to the organic light-emitting devices of Comparative Example 1-1, Comparative Example 1-2 and Comparative Example 1-4 and Comparative Example 1-7 employing a compound having no cyano group, an equivalent level or lower driving voltage, high efficiency and significantly It can be seen that it exhibits improved life characteristics.

[Description of codes]

1: substrate 2: anode

3: hole transport layer 4: light emitting layer

5: electron transport layer 6: cathode

7: hole injection layer 8: electron suppression layer

9: hole blocking layer 10: electron injection layer

Claims (16)

1. Compound represented by the formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   Q is a dibenzofuran, dibenzothiophene, benzofuran, or benzothiophene ring,

   R _a and R _b are each hydrogen, or they combine together to form a single bond,

   One of HAr ₁ to HAr ₄ is represented by the following Chemical Formula 2, the other one is represented by the following Chemical Formula 3, and the other is represented by the following Chemical Formula 2 or 3,

   [Formula 2]

   

   [Formula 3]

   

   In Chemical Formulas 2 and 3,

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

   A is a substituted or unsubstituted C _2-60 heteroaryl containing two or more N atoms,

   n1 to n4 are each an integer of 0 to 2,

   n1 + n2 + n3 + n4 is an integer from 2 to 8.
2. According to claim 1,

   Chemical Formula 2 is represented by any one of the following Chemical Formulas 2-1 to 2-3,

   compound:

   

   In Chemical Formulas 2-1 to 2-3,

   X ₁ to X ₃ are each independently N or CH, but at least two of X ₁ to X ₃ are N,

   Ar ₁ to Ar ₄ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

   The description of L ₁ is as defined in claim 1.
3. According to claim 2,

   X ₁ to X ₃ is N,

   compound.
4. According to claim 2,

   Ar ₁ and Ar ₂ are phenyl,

   Ar ₃ is ethyl,

   Ar ₄ is phenyl,

   compound.
5. According to claim 1,

   L ₁ and L ₂ are each independently a single bond or phenylene,

   compound.
6. According to claim 1,

   The compound is represented by any one of the following formulas 4-1 to 4-4,

   compound:

   [Formula 4-1]

   

   [Formula 4-2]

   

   [Formula 4-3]

   

   [Formula 4-4]

   

   In Chemical Formulas 4-1 to 4-4,

   Y is O or S,

   n1 to n4 are each 0 or 1,

   n1 + n2 + n3 + n4 is 2,

   One of HAr ₁ to HAr ₄ is represented by Chemical Formula 2, and the other one is represented by Chemical Formula 3.
7. According to claim 1,

   n1 + n2 + n3 + n4 is 2 or 3,

   compound.
8. According to claim 1,

   n1 and n2 are each 1, and n3 and n4 are each 0;

   n1 and n3 are each 1, and n2 and n4 are each 0; or

   n1 and n4 are each 1, n2 and n3 are each 0,

   compound.
9. According to claim 1,

   The compound is represented by the following formula 5-1 or 5-2,

   compound:

   [Formula 5-1]

   

   [Formula 5-2]

   

   In Chemical Formulas 5-1 and 5-2,

   R _a and R _b are each hydrogen, or they combine together to form a single bond,

   Y is O or S,

   HAr ₁ is represented by Chemical Formula 2,

   L ₂ is a single bond, or 1,4-phenylene.
10. According to claim 1,

    The compound is represented by the following formula 5-3 or 5-4,

    compound:

    [Formula 5-3]

    

    [Formula 5-4]

    

    In Chemical Formulas 5-3 and 5-4,

    R _a and R _b are each hydrogen, or they combine together to form a single bond,

    Y is O or S,

    L ₂ is a single bond, or 1,4-phenylene,

    n3 and n4 are each 0 or 1,

    n3 + n4 is 1,

    One of HAr ₃ and HAr ₄ is represented by Chemical Formula 2 above.
11. According to claim 1,

    The compound is represented by the following formula 5-5 or 5-6,

    compound:

    [Formula 5-5]

    

    [Formula 5-6]

    

    In the above formula 5-5 and 5-6,

    R _a and R _b are each hydrogen, or they combine together to form a single bond,

    Y is O or S,

    L ₂ is a single bond, or 1,4-phenylene,

    n2 to n4 are each 0 or 1,

    n2 + n3 + n4 is 1,

    One of HAr ₂ to HAr ₄ is represented by Chemical Formula 2 above.
12. According to claim 1,

    n1, n2 and n3 are each 1 and n4 is 0;

    n1, n2 and n4 are each 1, and n3 is 0;

    n1, n3 and n4 are each 1, and n2 is 0;

    n2, n3 and n4 are each 1, and n1 is 0;

    n1 is 2, n2 is 1, and n3 and n4 are each 0;

    n1 is 2, n3 is 1, and n2 and n4 are each 0; or

    n1 is 2, n4 is 1, n2 and n3 are each 0,

    compound.
13. According to claim 1,

    The compound is represented by the following formula 6-1 or 6-2,

    compound:

    [Formula 6-1]

    

    [Formula 6-2]

    

    In Chemical Formulas 6-1 and 6-2,

    R _a and R _b are each hydrogen, or they combine together to form a single bond,

    Y is O or S,

    n1, n2 and n4 are 0, 1, or 2, respectively,

    n1 + n2 + n4 is 2,

    HAr ₁ , HAr ₂ and One of HAr ₄ is represented by Formula 2, the other is represented by Formula 3, and the other is represented by Formula 2 or 3.
14. According to claim 1,

    The compound is represented by the following formula 6-3 or 6-4,

    compound:

    [Formula 6-3]

    

    [Formula 6-4]

    

    In Chemical Formulas 6-3 and 6-4,

    R _a and R _b are each hydrogen, or they combine together to form a single bond,

    Y is O or S,

    n1, n3 and n3 are each 0, 1, or 2,

    n1 + n3 + n4 is 2,

    HAr ₁ , HAr ₃ and One of HAr ₄ is represented by Formula 2, the other is represented by Formula 3, and the other is represented by Formula 2 or 3.
15. According to claim 1,

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

    

    

    

    

    

    

    

    

    

    

    

    

    

    
16. A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 15. That is, an organic light emitting device.

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