KR102050572B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound comprising two carbazole groups in a molecule and an organic light emitting device comprising the same.

Description

Novel compound and organic light emitting device comprising the same

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0075026 dated June 14, 2017, and all content disclosed in the literature of that Korean patent application is incorporated as part of this specification.

The present invention relates to a novel compound comprising two carbazole groups in a molecule and an organic light emitting device comprising the same.

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

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

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

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel compound comprising two carbozol groups in a molecule and an organic light emitting device comprising the same.

The present invention provides a compound of formula

[Formula 1]

In Chemical Formula 1,

R is substituted or substituted C _6-60 aryl,

R ₁ and R ₂ are each independently deuterium; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Substituted or unsubstituted C _7-60 arylalkyl; Substituted or unsubstituted C _7-60 alkylaryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,

a1 and a2 are each independently an integer of 0 to 3,

Cy is a polycondensed ring of Formula 2

[Formula 2]

In Formula 2, X ₁ is O, S, or NR ₃ ,

A is a benzene ring of formula 3 fused with two adjacent rings,

B is a ring of Formula 4 to share the A and C ₁ and C ₂ ,

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4, X ₂ is O, S, or NR ₃ , but X ₁ and X ₂ are not NR ₃ simultaneously,

R ₃ is hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Substituted or unsubstituted C _7-60 arylalkyl; Substituted or unsubstituted C _7-60 alkylaryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,

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 selected from the group consisting of O, N, Si and S,

b1 and b2 are the integers of 0-2 each independently.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the compound of Formula 1.

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

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG.
FIG. 2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is.

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a bond connected to another substituent.

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

Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40 ( _C1-40 ). Specifically, it may be a compound having a structure as follows, but is not limited thereto.

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

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

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl And the like, but are not limited thereto.

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

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

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

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

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

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

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

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

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, 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, isoxazolyl group, thiadia Although there are a sleepy group, a phenothiazinyl group, a dibenzofuranyl group, etc., it is not limited to these.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the alkyl group described above. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aforementioned aryl group or cycloalkyl group may be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic group is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding.

On the other hand, the present invention provides a compound of Formula 1:

[Formula 1]

In Chemical Formula 1,

R is substituted or unsubstituted C _6-60 aryl,

R ₁ and R ₂ are each independently deuterium; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Substituted or unsubstituted C _7-60 arylalkyl; Substituted or unsubstituted C _7-60 alkylaryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,

a1 and a2 are each independently an integer of 0 to 3,

Cy is a polycondensed ring of Formula 2

[Formula 2]

In Formula 2, X ₁ is O, S, or NR ₃ ,

A is a benzene ring of formula 3 fused with two adjacent rings,

B is a ring of formula (4) sharing the carbon of A and C _{1 and} the carbon of C ₂ ,

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4, X ₂ is O, S, or NR ₃ , but X ₁ and X ₂ are not NR ₃ simultaneously,

R ₃ is hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Substituted or unsubstituted C _7-60 arylalkyl; Substituted or unsubstituted C _7-60 alkylaryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,

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 selected from the group consisting of O, N, Si and S,

b1 and b2 are the integers of 0-2 each independently.

Specifically, in Formula 1, Cy is a multiple condensed ring in which two 5-membered rings containing O or S, such as furan or thiophene, are alternately condensed with three benzene rings, and according to the condensation position Can be represented as:

[Formula 5]

In Chemical Formula 5,

Cy 'is a benzene ring fused with two adjacent pentagonal rings,

X ₁ and X ₂ are each independently O, S, or NR ₃ , but X ₁ and X ₂ are not NR ₃ at the same time,

R ₃ is hydrogen; Substituted or unsubstituted C _1-20 alkyl; Substituted or unsubstituted C _3-20 cycloalkyl; Substituted or unsubstituted C _2-20 alkenyl; Substituted or unsubstituted C _6-20 aryl; Substituted or unsubstituted C _7-20 arylalkyl; And substituted or unsubstituted C _7-20 alkylaryl.

More specifically, in Chemical Formula 1, Cy may be represented by any one of the following Chemical Formulas 5-1 to 5-6:

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

In Chemical Formulas 5-1 to 5-6,

X ₁ and X ₂ are each independently O, S, or NR ₃ , but X ₁ and X ₂ are not NR ₃ at the same time,

R ₃ is hydrogen; Substituted or unsubstituted C _1-20 alkyl; Substituted or unsubstituted C _3-20 cycloalkyl; Substituted or unsubstituted C _2-20 alkenyl; Substituted or unsubstituted C _6-20 aryl; Substituted or unsubstituted C _7-20 arylalkyl; And it may be selected from the group consisting of substituted or unsubstituted C _7-20 alkylaryl.

More specifically, in Chemical Formula 1, Cy may be represented by any one selected from the group consisting of the following functional groups:

In the above chemical structures,

X ₁ and X ₂ are each independently O, S, or NR ₃ , but X ₁ and X ₂ are not NR ₃ at the same time,

R ₃ is hydrogen; Substituted or unsubstituted C _1-12 alkyl; Substituted or unsubstituted C _3-12 cycloalkyl; Substituted or unsubstituted C _2-12 alkenyl; Substituted or unsubstituted C _6-12 aryl; Substituted or unsubstituted C _7-13 arylalkyl; And it may be selected from the group consisting of substituted or unsubstituted C _7-13 alkylaryl.

More specifically, in the functional groups of Chemical Formulas 5-1 to 5-6,

X ₁ is O or S,

X ₂ is O, S, or NR ₃ ,

R ₃ is hydrogen, C _1-12 alkyl; C _3-12 cycloalkyl; C _6-12 aryl; C _7-13 arylalkyl; And it may be selected from the group consisting of C _7-13 alkylaryl, and more specifically may be hydrogen, methyl or phenyl.

In addition, the functional groups in Chemical Formulas 5 and 5-1 to 5-6 may be substituted with one or two groups by at least one of the functional groups of Ar ₁ and Ar ₂ as in Chemical Formulas 3 and 4.

In this case, Ar ₁ and Ar ₂ is as defined above, more specifically, may be any one selected from the group consisting of the following functional groups:

In addition, in Chemical Formula 1, two carbazole groups may be substituted or unsubstituted, and when substituted, one to three, more specifically, one or two may be substituted by R ₁ and R ₂ , respectively. .

In this case, R ₁ and R ₂ are as defined above, more specifically, each independently, deuterium; halogen; Cyano; Nitro; C _1-20 alkyl; C _6-20 aryl; C _7-20 arylalkyl; Or C _7-20 alkylaryl, and even more specifically R ₁ and R ₂ may each independently be deuterium, halogen, cyano, nitro, methyl, or phenyl.

In addition, in Chemical Formula 1, R may be substituted or unsubstituted C _6-20 aryl, and more specifically, substituted or unsubstituted phenyl.

In addition, when R is substituted, deuterium; halogen; Cyano; Nitro; Amino; C _1-20 alkyl; C _1-20 haloalkyl; C _1-20 alkoxy; C _1-20 haloalkoxy; C _3-20 cycloalkyl; C _2-20 alkenyl; C _6-20 aryl; C _6-20 aryloxy; C _7-20 arylalkyl; C _7-20 alkylaryl; Or one or more C _2-60 heteroaryls including one or more heteroatoms selected from the group consisting of N, O and S, more specifically C _1-12 alkyl; C _3-12 cycloalkyl; C _6-12 aryl; C _7-12 arylalkyl; And it may be substituted with one or more functional groups selected from the group consisting of C _7-12 alkylaryl.

Specifically, R may be selected from the group consisting of the following functional groups.

If the molecular weight is too large, the deposition temperature is increased to reduce the thermal stability, so that R may be phenyl, biphenyl, or naphthalenyl among the functional groups of the above structure in order to secure an appropriate molecular weight.

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

The compound represented by Formula 1 includes two carbazole groups, and the other carbazole is substituted at position 3 of one carbazole group serving as a core and a hetero atom of O, S, or N at position 9 By having a structure in which two condensed ring groups (Cy) in which two five-membered rings are condensed alternately with three benzene rings are substituted, they have an advantageous structure for transporting holes and electrons. Since the carbazole substituted at the 3 position includes an aryl group and the condensed ring group contains a hetero atom of O, S or N, the electron density is increased by the unshared electron pair of these atoms, and thus the hole transporting ability is increased. . Among them, in the case of O, the electronegativity is greater than C, which increases the electron transporting ability, thereby forming a light emitting layer having an appropriate balance between the hole transporting capacity and the electron transporting capacity when applied to the light emitting layer. Therefore, the organic light emitting device using the same may have high efficiency, low driving voltage, high brightness and long life.

On the other hand, the compound of Formula 1 may be prepared by a manufacturing method comprising the step of reacting a dicarbazole compound (II) and a polycondensed ring (Cy) -containing halide (III) as shown in the following reaction scheme, for example. . The manufacturing method may be more specific in the synthesis examples to be described later.

Scheme 1

In Scheme 1, R, R ₁ , R ₂ , a1, a2, and Cy are the same as defined above, and Z is a halogen group such as fluoro, chloro, bromo, or iodo.

Specifically, the reaction of the dicarbazole compound (II) and the halide (III) containing polycondensed ring (Cy) may be carried out in the presence of a platinum-based catalyst compound such as Pd (P-tBu3) 2.

In addition, the reaction is dichloromethane, ethyl acetate, diethyl ether, acetonitrile, isopropyl alcohol, acetone, tetrahydrofuran (THF), N, N- dimethylformamide (DMF), dimethyl sulfoxide (DMSO) Or it may be carried out in one or more organic solvents such as toluene, alkoxide-based reactive agent such as NaOtBu may be further added in the reaction.

Meanwhile, the dicarbazole compound (II) and the polycondensed ring (Cy) -containing halide (III) used as starting materials in the preparation of the compound of Formula 1 may be prepared directly or may be obtained commercially. In the case of direct production, the production method may be more specified in the production examples to be described later.

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

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

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and the like as an organic layer. Further, at least one of an electron blocking layer and a hole blocking layer may be further included between the hole transport layer and the light emitting layer, and between the light emitting layer and the electron transport layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

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

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

In addition, the organic layer may include an electron transport layer, or an electron injection layer, the electron transport layer, or the electron injection layer comprises a compound represented by the formula (1).

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

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

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

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer.

FIG. 2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more layers of the hole injection layer, the hole transport layer, the light emitting layer and the electron transport layer.

In addition, the organic light emitting device according to an embodiment of the present invention, the substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, in the above structure The compound represented by Formula 1 may be included in the emission layer.

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

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. In addition, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer may be formed thereon, and then, a material that may be used as a cathode may be deposited thereon. In addition, when the organic layer further includes an electron blocking layer and a hole blocking layer between the hole transport layer and the light emitting layer, and between the light emitting layer and the electron transport layer, the method may further include forming these layers. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

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

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

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

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

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

The hole injection material is a layer for injecting holes from an electrode, and the hole injection material has a capability of transporting holes, 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 a light emitting layer. The compound which prevents the movement of the excited excitons to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

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

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

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like. The dopant content may be from 1% to 99% relative to the host amount of the light emitting layer.

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

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

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

When the organic light emitting device further comprises at least one of an electron blocking layer and a hole blocking layer between the hole transport layer and the light emitting layer, and between the light emitting layer and the electron transport layer, the electron blocking layer prevents the electrons from reaching the anode. As a layer, it may be formed under the same conditions as the electron injection layer. The electron blocking layer is made of a material having a function of transporting holes and having a small ability to transport electrons, and can improve the probability of recombination of electrons and holes by blocking electrons while transporting holes.

In addition, the hole blocking layer is a layer that can improve the life and efficiency of the device by preventing the injected holes to enter the electron transport layer through the light emitting layer, nitrogen-containing heterocyclic derivatives such as oxadiazole derivatives and triazole derivatives , Phenanthroline derivatives, BCP or aluminum complex, but are not limited thereto. Specifically, the hole blocking layer may include a nitrogen-containing heterocyclic derivative as known in Korean Patent Registration No. 10-1052973 and Korean Patent Registration No. 10-1317495.

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

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

The production 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 only 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)

1-1) Synthesis of Compound 1-1

3-Hydroxydibenzo [b, d] furan (15.0 g, 81.4 mmol) was dissolved in 200 ml of CH ₂ Cl ₂ in a two-necked flask and stirred at 0 ° C. under a nitrogen atmosphere. . In the resulting reaction solution, Br ₂ (5ml, 97.7mmol) was dissolved in 20ml of CH ₂ Cl ₂ and added dropwise over 40 minutes, followed by stirring at room temperature for 12 hours. After the reaction was completed, Na ₂ S ₂ O ₃ aqueous solution was added to the resulting reaction solution, which was transferred to a separating funnel and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and the resulting sample was purified by silica gel column chromatography to give 17.1 g of compound 1-1 solid. (Yield 80%, MS [M + H] ⁺ = 263)

1-2) Synthesis of Compound 1-2

In a three-necked flask, Compound 1-1 (17.0 g, 64.6 mmol) and (4-chloro-2-fluorophenyl) boronic acid (11.8 g, 67.8 mmol) were added. It was dissolved in 650 ml of THF, and K ₂ CO ₃ (35.7 g, 258.5 mmol) was dissolved in 320 ml of H ₂ O and added thereto. Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) was added to the resulting mixed solution, and the mixture was stirred for 8 hours under an argon atmosphere reflux condition. When the reaction was completed, the resulting reaction solution was cooled to room temperature, then transferred to a separating funnel, and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 15.8 g of compound 1-2 solid. (Yield 78%, MS [M + H] ⁺ = 313)

1-3) Synthesis of Compound 1-3

Compound 1-2 (15.0 g, 48.0 mmol), K ₂ CO _{3 in a} two-neck flask (9.9 g, 71.9 mmol) and NMP 200 mL were added, and the mixture was stirred at 150 ° C. for 8 hours in an argon atmosphere. After the reaction was completed, the resulting reaction liquid was cooled to room temperature, transferred to a separating funnel, and 200 mL of H ₂ O was added thereto, followed by extraction with ethyl acetate. The resulting extract was purified by silica gel column chromatography to give 12.5 g of compound 1-3 solid. (Yield 89%, MS [M + H] ⁺ = 293)

1-4) Synthesis of Compound 1-4

3-bromo-9H-carbazole (10.0 g, 40.6 mmol) and 9-phenyl-3- (4,4,5,5-tetramethyl-1, in a three-necked flask 3,2-dioxaborolan-2-yl) -9H-carbazole (9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H -carbazole) (15.8 g, 42.7 mmol) was dissolved in 400 ml of THF, and K ₂ CO ₃ (22.5 g, 162.5 mmol) was added dissolved in 200 ml of H ₂ O. Pd (PPh ₃ ) ₄ (0.5 g, 0.4 mmol) was added to the resulting mixed solution, which was stirred for 8 hours under argon atmosphere reflux conditions. After the reaction was completed, the resulting reaction solution was cooled to room temperature, then transferred to a separating funnel, and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 12.4 g of compound 1-4 solid. (Yield 75%, MS [M + H] ⁺ = 409)

1-5) Synthesis of Compound 1

In a three-necked flask, compound 1-4 (8.0 g, 19.6 mmol) and compound 1-3 (6.3 g, 21.5 mmol) were dissolved in 200 ml of toluene and sodium tert-butoxide (NaOtBu) (2.8 g , 29.4 mmol), and bis (tri-tert-butylphosphine) palladium (0) (Bis (tri-tert-butylphosphine) palladium (0); Pd (P-tBu ₃ ) ₂ ) (0.2 g, 0.4 mmol) After the addition, the mixture was stirred for 6 hours under argon atmosphere reflux conditions. After the reaction was completed, the resulting reaction solution was cooled to room temperature, 200 ml of H ₂ O was added and the mixture was transferred to a separatory funnel to extract. The resulting extract was dried over MgSO ₄ , concentrated, and the resulting sample was purified by silica gel column chromatography, and then 5.9 g of compound 1 was obtained through sublimation tablets. (Yield 45%, MS [M + H] ⁺ = 665)

< Synthesis Example  2> (synthesis of compound 2)

2-1) Synthesis of Compound 2-1

In a three-necked flask, 2-hydroxydibenzo [b, d] furan (15.0 g, 81.4 mmol) was dissolved in 100 ml of acetic acid, and iodine monochloride (idodine monochloride; ICl) (4.48ml, 89.6mmol), a solution of 55ml concentrated hydrochloric acid (conc.HCl) and 35ml acetic acid were added dropwise, followed by stirring at room temperature for 24 hours. When the reaction was completed, 300 ml of H ₂ O was added to the resulting reaction solution, and the resulting precipitate was filtered and washed with H ₂ O. The resulting solid was washed with MeOH to give 18.9 g of compound 2-1 solid. (Yield 75%, MS [M + H] ⁺ = 310)

2-2) Synthesis of Compound 2-2

In a three-necked flask, compound 2-1 (18.0 g, 58.0 mmol) and (4-chloro-2-fluorophenyl) boronic acid (10.6 g, 61.0 mmol) were dissolved in 600 ml of THF, and K ₂ CO ₃ ( 32.1 g, 232.2 mmol) was added dissolved in 300 ml of H ₂ O. Pd (PPh ₃ ) ₄ to the resulting mixed solution. (0.7 g, 0.6 mmol) was added and stirred for 8 h under argon atmosphere reflux conditions. When the reaction was completed, the resulting reaction solution was cooled to room temperature, transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 14.5 g of compound 2-2 solid. (Yield 80%, MS [M + H] ⁺ = 313)

2-3) Synthesis of Compound 2-3

Compound 2-2 (14.0 g, 44.8 mmol), K ₂ CO _{3 in a two} neck flask (9.3g, 67.2mmol) and NMP180mL were added, and it stirred at 150 degreeC for 8 hours in argon atmosphere. After the completion of the reaction, the resulting reaction solution was cooled to room temperature, the resulting sample was transferred to a separating funnel, 200 mL of H ₂ O was added, and extracted with ethyl acetate. The extract was purified by silica gel column chromatography to give 10.6 g of compound 2-3 solid. (Yield 81%, MS [M + H] ⁺ = 293)

2-4) Synthesis of Compound 2-4

3-bromo-9H-carbazole (5.0 g, 20.3 mmol), and 9-([1,1'-biphenyl] -3-yl) -3 in a three-neck flask -(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (9-([1,1'-biphenyl] -3-yl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole) (9.5 g, 21.3 mmol) was dissolved in 200 ml of THF, and K ₂ CO ₃ (11.2 g, 81.3 mmol) was added dissolved in 100 ml of H ₂ O. Pd (PPh ₃ ) ₄ (0.2 g, 0.2 mmol) was added to the resulting mixed solution, which was stirred for 8 hours under argon atmosphere reflux conditions. When the reaction was completed, the resulting reaction solution was cooled to room temperature, then transferred to a separating funnel, and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 7.6 g of compound 2-4 solid. (Yield 77%, MS [M + H] ⁺ = 485)

2-5) Synthesis of Compound 2

In a three-neck flask, compound 2-4 (7.0 g, 14.4 mmol) and compound 2-3 (4.7 g, 15.9 mmol) were dissolved in 140 ml of toluene, NaOtBu (2.1 g, 21.7 mmol) and Pd (P-tBu ₃ ) ₂ ( 0.1 g, 0.3 mmol), and the mixture was stirred for 6 hours under an argon atmosphere reflux condition. When the reaction was completed, the resulting reaction solution was cooled to room temperature, transferred to a separatory funnel, and added with 200 ml of H ₂ O and extracted. The resulting extract was dried over MgSO ₄ , concentrated, and the resulting sample was purified by silica gel column chromatography, and then 5.0 g of Compound 2 was obtained through a sublimation tablet. (Yield 47%, MS [M + H] ⁺ = 665)

< Synthesis Example  3> (synthesis of compound 3)

3-1) Synthesis of Compound 3-1

3-fluorodibenzo [b, d] furan (15.0 g, 80.6 mmol) and THF 400 mL were added to a three neck flask and cooled to -78 ° C. N-BuLi (1.6 M n-hexane solution, 55 mL, 88.6 mmol) was added dropwise thereto, and stirred at -78 ° C for 20 minutes. Boric acid triisopropyl (45.5 g, 241.7 mmol) was added to the resulting mixed solution, followed by stirring at −78 ° C. for 1 hour, followed by further stirring at room temperature for 4 hours. 130 mL of 1N HCl was added to the resulting reaction solution, which was stirred at room temperature for 1 hour, and then concentrated, transferred to a separatory funnel, 200 mL of water was added, and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered, concentrated and recrystallized with toluene-hexane to give 11.1 g of compound 3-1 (yield 60%, MS [M + H] ⁺ = 230). .

3-2) Synthesis of Compound 3-2

In a three-necked flask, compound 3-1 (10.0 g, 43.5 mmol) and 5-chloro-2-iodophenol (11.6 g, 45.7 mmol) were dissolved in 430 ml of THF, and K ₂ CO ₃ (24.0 g, 173.9 mmol) was added dissolved in 220 ml of H ₂ O. Pd (PPh ₃ ) ₄ (0.5 g, 0.4 mmol) was added to the resulting mixed solution, which was stirred for 8 hours under argon atmosphere reflux conditions. When the reaction was completed, the resulting reaction solution was cooled to room temperature, then transferred to a separating funnel, and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 10.5 g of compound 3-2 solid (yield 77%, MS [M + H). ] ⁺ = 313).

3-3) Synthesis of Compound 3-3

Compound 3-2 (10.0 g, 32.0 mmol), K ₂ CO ₃ (6.6 g, 48.0 mmol) and NMP 130 mL were added to a two-necked flask, and the mixture was stirred at 150 ° C. for 8 hours in an argon atmosphere. After the completion of the reaction, the resulting reaction solution was cooled to room temperature, transferred to a separatory funnel, 100 mL of H ₂ O was added, and extracted with ethyl acetate. The resulting extract was purified by silica gel column chromatography to give 6.2 g of compound 3-3 solid (yield 66%, MS [M + H] ⁺ = 293).

3-4) Synthesis of Compound 3-4

3-bromo-9H-carbazole (5.0 g, 20.3 mmol) and 9-([1,1'-biphenyl] -4-yl) -3- (4,4,5,5- in a three-neck flask Tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (9.5 g, 21.3 mmol) was dissolved in 200 ml of THF, and K ₂ CO ₃ (11.2 g, 81.3 mmol) Was dissolved in 100 ml of H ₂ O and added. Pd (PPh ₃ ) ₄ (0.2 g, 0.2 mmol) was added to the resulting mixed solution, and the mixture was stirred for 8 hours under argon atmosphere reflux conditions. When the reaction was completed, the resulting reaction solution was cooled to room temperature, transferred to a separating funnel and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to yield 7.4 g of compound 3-4 solid (yield 74%, MS [M + H). ] ⁺ = 485).

3-5) Synthesis of Compound 3

In a three-necked flask, compound 3-4 (7.0 g, 14.4 mmol), and compound 3-3 (4.7 g, 15.9 mmol) were dissolved in 140 ml of toluene, NaOtBu (2.1 g, 21.7 mmol), Pd (P-tBu ₃ ) ₂ ) (0.1 g, 0.3 mmol) was added, followed by stirring for 6 hours under argon atmosphere reflux conditions. After the reaction was completed, the resultant reaction solution was cooled to room temperature, 200 ml of H ₂ O was added to the separatory funnel and extracted. The resulting extract was dried over MgSO ₄ , concentrated, and the resulting sample was purified by silica gel column chromatography to give 4.7 g of Compound 3 through a sublimation tablet (yield 44%, MS [M + H] ⁺ = 741).

< Synthesis Example  4> (synthesis of compound 4)

3-fluorodibenzo [b, d] furan in <Synthesis Example 3> to 3-fluorodibenzo [b, d] thiophene, and 9-([1,1'-biphenyl] -4- Yl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole 9- (naphthalen-2-yl) -3- (4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole except for use in the same manner as in Synthesis Example 3 Compound 4 was synthesized by the above reaction scheme (yield 10%, MS [M + H] ⁺ = 731).

< Synthesis Example  5> (synthesis of compound 5)

5-1) Synthesis of Compound 5-1

In a three-necked flask, 1,2-difluoro-3,6-diiodobenzene (20.0 g, 54.7 mmol), 2-methoxyphenylboronic acid (19.9 g, 131.2 mmol), 2M Na ₂ CO ₃ aqueous solution ( 110 mL, 218.6 mmol), DME 110 mL, toluene 110 mL, Pd (PPh ₃ ) ₄ (6.3 g, 5.5 mmol) were added thereto, and the mixture was stirred under reflux conditions for 8 hours under argon atmosphere. After the reaction was completed, the resulting reaction solution was cooled to room temperature, then transferred to a separatory funnel, 200 mL of H ₂ O was added and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 11.6 g of compound 5-1 solid (yield 65%, MS [M + H). ] ⁺ = 326).

5-2) Synthesis of Compound 5-2

Compound 5-1 (11.0 g, 33.7 mmol), NBS (6.0, 33.7 mmol), and 340 mL of DMF were added to a two-neck flask, and the mixture was stirred at room temperature for 8 hours under argon atmosphere. After the reaction was completed, the resulting reaction solution was transferred to a separatory funnel, water (300 mL) was added, and the mixture was extracted with ethyl acetate. The sample was purified by silica gel column chromatography to give 11.2 g of compound 5-2 solid. (Yield 82%, MS [M + H] ⁺ = 405)

5-3) Synthesis of Compound 5-3

Into a two-neck flask, compound 5-2 (11.0 g, 27.1 mmol), 1 M BBr ₃ CH ₂ Cl ₂ solution (65 mL, 65.1 mmol), and 163 mL CH ₂ Cl ₂ were added, adjusted to 0 ° C. under argon atmosphere, and stirred for 8 hours. It was. Thereafter, the mixture was further stirred at room temperature for 4 hours and neutralized with saturated aqueous NaHCO ₃ solution. The resulting reaction solution was transferred to a separatory funnel, extracted with CH ₂ Cl ₂ , and the resulting extract was purified by silica gel column chromatography to obtain 8.7 g of compound 5-3 solid. (Yield 85%, MS [M + H] ⁺ = 377)

5-4) Synthesis of Compound 5-4

Compound 5-3 (8.7 g, 23.1 mmol), K ₂ CO ₃ (7.0 g, 50.7 mmol) and NMP 96 mL were added to a two-necked flask, and the mixture was stirred at 150 ° C. for 8 hours in an argon atmosphere. After the reaction was completed, the resulting reaction solution was cooled to room temperature, transferred to a separatory funnel, 100 mL of H ₂ O was added, and extracted with ethyl acetate. The resulting extract was purified by silica gel column chromatography to give 6.9 g of compound 5-4. (Yield 89%, MS [M + H] ⁺ = 337)

5-5) Synthesis of Compound 5

In a three-neck flask, Compound 1-4 (7.0 g, 17.1 mmol) and Compound 5-4 (6.4 g, 18.8 mmol) were dissolved in 170 ml of toluene, NaO (t-bu) (2.5 g, 25.7 mmol), Pd (P- After tBu ₃ ) ₂ (0.2 g, 0.3 mmol) was added, the mixture was stirred for 6 hours under argon atmosphere reflux conditions. After the reaction was completed, the mixture was cooled to room temperature, 200 ml of H ₂ O was added thereto, and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO ₄ , concentrated and the sample was purified by silica gel column chromatography, and then 5.0 g of compound 5 was obtained through sublimation tablets (yield 44%, MS [M + H] ⁺ = 665).

< Synthesis Example  6> (synthesis of compound 6)

The synthesis was carried out except that 1,2-difluoro-3,6-diiodobenzene was changed to 1,4-dibromo-2,5-difluorobenzene in <Synthesis Example 5>. Compound 6 was synthesized through the above scheme in the same manner as in Example 5 (yield 15%, MS [M + H] ⁺ = 665).

< Synthesis Example  7> (synthesis of compound 7)

7-1) Synthesis of Compound 7-1

2-bromo-4-chlorodibenzo [b, d] furan (30.0 g, 106.6 mmol) and 2- (nitrophenyl) boronic acid (19.6 g, 117.2 in a three-neck flask mmol) was dissolved in 450 ml of THF, followed by K ₂ CO ₃ (58.9 g, 426.2 mmol) was added dissolved in 225 ml of H ₂ O. Here Pd (PPh ₃ ) ₄ (4.9 g, 4.3 mmol) was added and stirred for 8 h under argon atmosphere reflux conditions. After the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel and extracted with ethyl acetate. The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography to give 30.4 g of compound 7-1 (yield 88%, MS [M + H] ⁺ = 324).

7-2) Synthesis of Compound 7-2

In a two-neck flask, 300 ml of Compound 7-1 (30.0 g, 92.7 mmol), Triphenylphosphine (PPh ₃ ) (19.2 g, 139.0 mmol) and o-dichlorobenzene (o-DCB) were added. The mixture was stirred for 12 hours under reflux conditions. After the reaction was completed, the reaction mixture was cooled to room temperature, distilled under reduced pressure to remove the solvent, and extracted with water and CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography to give 16.5 g of compound 7-2 (yield 61%, MS [M + H] ⁺ = 292).

7-3) Synthesis of Compound 7-3

Compound 7-2 (15.0 g, 51.4 mmol) and bromobenzene (8.9 g, 56.6 mmol) were dissolved in 510 ml of toluene in a three-necked flask, and sodium tert-butoxide; NaO (t-bu)) (7.4 g, 77.1 mmol), bis (tri-tert-butylphosphine) palladium (O) (Bis (tri-tert-butylphosphine) palladium (0); Pd (P-tBu ₃ ) ₂ ) (0.5 g, 1.0 mmol) was added thereto, followed by stirring for 6 hours under argon atmosphere reflux conditions. After the reaction was completed, the mixture was cooled to room temperature, 200 ml of H ₂ O was added, and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography to give 12.3 g of compound 7-3 (yield 65%, MS [M + H] ⁺ = 368).

7-4) Synthesis of Compound 7

In a three-necked flask, compound 1-4 (10.0 g, 24.5 mmol) and compound 7-3 (9.9 g, 26.9 mmol) were dissolved in 250 ml of toluene and sodium tert-butoxide (NaO (t-bu)) (3.5 g , 36.7 mmol) and bis (tri-tert-butylphosphine) palladium (O) (Pd (P-tBu ₃ ) ₂ ) (0.3 g, 0.5 mmol) were added thereto, followed by stirring for 6 hours under reflux condition of argon atmosphere. . After the reaction was completed, the mixture was cooled to room temperature, 200 ml of H ₂ O was added, and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography, and then 5.6 g of Compound 7 was obtained through a sublimation tablet (yield 31%, MS [M + H] ⁺ =). 740).

[ Device Example ]

< Example  1>

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) having a thickness of 1,400 kPa was put in distilled water in which detergent was dissolved and ultrasonically cleaned. Fischer Co.'s Decon? CON705 was used, and distilled water was filtered using a 0.22 μm sterilizing filter manufactured by Millerpore Co., Ltd. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After the distilled water was washed, ultrasonic washing with a solvent of isopropyl alcohol, acetone and methanol for 10 minutes, dried and then transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

The hole injection layer was formed by thermal vacuum deposition at a thickness of 100 μs at a ratio of 95 wt% of HT-A and 5 wt% of P-DOPANT on the prepared ITO transparent electrode, and formed only HT-A material on the hole injection layer. Deposition to a thickness to form a hole transport layer.

The following HT-B was thermally vacuum deposited to a thickness of 450 증착 on the hole transport layer to form an electron blocking layer.

Subsequently, the light emitting layer was formed by thermal vacuum deposition on the electronic blocking layer to a thickness of 400 kPa in a ratio of 95% by weight of compound 1 as a host material and 5% by weight of GD as a dopant material.

Subsequently, the following ET-A was thermally vacuum deposited to a thickness of 50 kPa on the light emitting layer to form a hole blocking layer.

Subsequently, the following ET-B and Liq were thermally vacuum deposited to a thickness of 250 kPa at a weight ratio of 2: 1 on the hole blocking layer to form an electron transport layer. Deposition was performed to form an electron injection layer.

Magnesium and silver were deposited on the electron injection layer in a thickness ratio of 1: 4 at a thickness of 160 kPa to form a cathode, thereby manufacturing an organic light emitting device.

Example  2 to 7, and Comparative example  1 to 4

Except that the host material was changed as shown in Table 1, the organic light emitting device of Examples 2 to 7, and Comparative Examples 1 to 4 were produced using the same method as in Example 1.

Host substance Example 1 Compound 1 Example 2 Compound 2 Example 3 Compound 3 Example 4 Compound 4 Example 5 Compound 5 Example 6 Compound 6 Example 7 Compound 7 Comparative Example 1 GH-A Comparative Example 2 GH-B Comparative Example 3 GH-C Comparative Example 4 GH-D

The current was applied to the organic light emitting diodes manufactured in Examples 1 to 7, and Comparative Examples 1 to 4 to measure voltage, efficiency, and lifetime (T95), and the results are shown in Table 2 below. At this time, the voltage, efficiency was measured by applying a current density of 10mA / cm ² , T95 means the time until the initial luminance is reduced to 95% at a current density of 20mA / cm ² .

Host
matter @ 10mA / cm ² @ 20mA / cm ² Voltage
(V) efficiency
(cd / A) life span
(T95, hr) Example 1 Compound 1 4.36 58.6 120 Example 2 Compound 2 4.43 54.1 130 Example 3 Compound 3 4.45 51.4 110 Example 4 Compound 4 4.50 53.3 140 Example 5 Compound 5 4.46 55.4 130 Example 6 Compound 6 4.38 52.7 120 Example 7 Compound 7 4.49 56.8 110 Comparative Example 1 GH-A 4.66 42.1 80 Comparative Example 2 GH-B 4.87 38.2 70 Comparative Example 3 GH-C 4.65 43.5 80 Comparative Example 4 GH-D 4.80 47.5 90

The chalcogen atom contained in the compound of Formula 1 has a higher electronegativity than the carbon atom and at the same time has a non-covalent electron pair, which is advantageous for the transport of electrons and holes. As a result, as shown in Table 2, the chalcogen valence It is more suitable as a host of the light emitting layer than GH-A of Comparative Example 1 or GH-C of Comparative Example 3, which is not included. In addition, when there is one oxygen atom as in GH-D of Comparative Example 4 or when there are three oxygen atoms as in GH-B of Comparative Example 2, the characteristics of the device are deteriorated because the charge in the light emitting layer is not balanced. Able to know. Therefore, when the compounds having the structure of Formula 1 are applied to the light emitting layer of the organic light emitting device, a low voltage, high efficiency, and a long lifespan may be realized.

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

Claims (9)

A compound of formula
[Formula 1]

In Chemical Formula 1,
R is substituted or substituted C _6-60 aryl,
R ₁ and R ₂ are each independently deuterium; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Substituted or unsubstituted C _7-60 arylalkyl; Substituted or unsubstituted C _7-60 alkylaryl; Or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,
a1 and a2 are each independently an integer of 0 to 3,
Cy is a polycondensed ring of Formula 2
[Formula 2]

In Formula 2, X ₁ is O or S,
A is a benzene ring of formula 3 fused with two adjacent rings,
B is a ring of Formula 4 to share the A and C ₁ and C ₂ ,
[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4, X ₂ is O or S,
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 selected from the group consisting of O, N, Si and S,
b1 and b2 are the integers of 0-2 each independently.
The method of claim 1,
In Chemical Formula 1, Cy is a functional group represented by Chemical Formula 5 below:
[Formula 5]

In Chemical Formula 5,
Cy 'is a benzene ring fused with two adjacent pentagonal rings,
X ₁ and X ₂ are each independently O or S.
The method of claim 1,
In Chemical Formula 1, Cy is any one of the functional groups represented by Chemical Formulas 5-1 to 5-6:
[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

In Chemical Formulas 5-1 to 5-6,
X ₁ and X ₂ are each independently O or S.
The method of claim 1,
In Formula 1, Cy is any one selected from the group consisting of the following functional groups:

In the above chemical structures,
X ₁ and X ₂ are each independently O or S.
delete The method of claim 1,
R is any one selected from the group consisting of the following functional groups.

The method of claim 1,
Compound which is any one selected from the group consisting of the following compounds.

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.
At least one layer of the organic material layer, the organic light emitting device comprising a compound according to any one of claims 1 to 4, 6 and 7.
The method of claim 8,
The organic material layer containing the compound is a light emitting layer, an organic light emitting device.

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