KR20190114635A - Novel compound and organic electroluminescent divice including the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic light emitting device comprising the same, wherein the novel compound according to an embodiment of the present invention is applied to the organic light emitting device to secure high efficiency, long lifespan, low driving voltage, and driving stability of the organic light emitting device. A compound according to an embodiment of the present invention can implement a high efficiency organic light emitting device.

Description

Novel compound and organic light emitting device including the same {NOVEL COMPOUND AND ORGANIC ELECTROLUMINESCENT DIVICE INCLUDING THE SAME}

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

The material used as the organic material layer in the organic light emitting diode may be largely classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function. The light emitting material may be classified into a polymer and a low molecule according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. The luminescent material may be classified into blue, green, and red luminescent materials and yellow and orange luminescent materials required to achieve better natural colors according to the emission color. In addition, in order to increase luminous efficiency through an increase in color purity and energy transfer, a host / dopant system may be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to produce high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant and the host to be used.

To date, various compounds are known as materials used in such organic light emitting devices. However, in the case of organic light emitting devices using materials known to date, development of new materials is continuously required due to high driving voltage, low efficiency, and short lifespan. Therefore, efforts have been made to develop organic light emitting devices having low voltage driving, high brightness and long life using materials having excellent characteristics.

Korea Patent Publication 10-2015-0086721

The present application provides a novel organic compound, and an organic light emitting device comprising the same.

However, the problem to be solved by the present application is not limited to the problem described above, other problems that are not described will be clearly understood by those skilled in the art from the following description.

A first aspect of the present application provides a compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

X is O, S or CRR`,

Y and Z are each independently O or S,

Ar ₁ is a ring forming carbon atoms, a C ₆ ~ C ₁₃ substituted or unsubstituted aryl substituted or unsubstituted C ₆ ~ C ₅₀ containing an aryl group, or a ring forming carbon atoms, a C ₆ ~ C ₁₃ substituted or unsubstituted aryl Substituted or unsubstituted C ₆ ~ C ₅₀ heteroaryl group containing a group,

R, R`, R ₁ to R ₆ are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ -C ₃₀ alkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group , Substituted or unsubstituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ sulfide group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, or substituted or unsubstituted C ₅ to C ₃₀ Is a heteroaryl group, adjacent R and R 'may or may not form a ring with each other,

L ₁ to L ₃ are each independently a direct bond, a substituted or unsubstituted C ₆ to C ₃₀ arylene, or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene,

l and q are each independently 0 or an integer of 1 to 4,

m, n, o and p are each independently 0 or an integer of 1 to 3, and when 1, m, n, o, p or q is 2 or more, R ₁ to R ₆ may be the same or different from each other.

The second aspect of the present application provides an organic light emitting device comprising an organic material layer containing a compound according to the present application between the first electrode and the second electrode.

The compound according to one embodiment of the present invention provides a hole by connecting two linearly linked tricyclic condensed ring groups (dibenzofuran, dibenzothiophene or fluorene and dibenzofuran or dibenzothiophene) to nitrogen of arylamine. It is possible to form a deep HOMO level suitable for the transport layer or the light emitting auxiliary layer and form a high LUMO, thereby realizing an organic light emitting device having high efficiency.

In addition, the compound according to an embodiment of the present invention is a fast hole mobility (Hole Mobility) by introducing two tricyclic condensed ring of linear linkage on one side of the arylamine, and dibenzofuran or dibenzothiophene on the other side ), It is possible to excellent arrangement of molecules in forming a thin film. Accordingly, it is possible to implement a long life organic light emitting device by implementing low voltage and suppressing the rolloff phenomenon.

In addition, the compound according to an embodiment of the present invention maintains high LUMO by introducing dibenzofuran or dibenzothiophene having excellent electron resistance to the other side of the arylamine, and at the same time further improves the durability of the compound when blocking electrons from the light emitting layer. Can improve. Accordingly, high efficiency and long lifespan of the organic light emitting device can be realized.

In addition, the compound according to an embodiment of the present invention can maintain a high T1 by introducing a substituent having a high triplet energy having 6 to 13 carbon atoms to form a ring on one side of the arylamine. Accordingly, an organic light emitting device having high efficiency can be realized by maximizing the exciton confinement effect in the light emitting layer.

In addition, the compound according to an embodiment of the present invention may include a three or more tricyclic condensed ring structure to form a high Tg to prevent thin film recrystallization, thereby ensuring the driving stability of the organic light emitting device have.

1 shows a schematic view of an organic light emitting device according to an embodiment of the present disclosure.

Hereinafter, with reference to the accompanying drawings will be described in detail the embodiments and embodiments of the present application to be easily carried out by those of ordinary skill in the art.

As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise. As used throughout this specification, the terms "about", "substantially" and the like are used at, or in the sense of, numerical values when a manufacturing and material tolerance inherent in the stated meanings is indicated, Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term "step to" or "step of" does not mean "step for."

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B."

Throughout this specification, the term "aryl" refers to an aromatic hydrocarbon ring group of C _5-30 , for example phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perylene It means containing an aromatic ring such as nil, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzocrisenyl, anthracenyl, stilbenyl, pyrenyl, etc., " heteroaryl " As an aromatic ring of C _3-30 containing a hetero element, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindoleyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, Benzothiophenyl, dibenzothiophenyl, quinolyl group, isoquinolyl, quinoxalinyl, carbazolyl, phenantridinyl, acridinyl, phenanthrolinyl, thienyl, and pyridine ring, pyrazine ring, pyrimidine ring , Pyridazine ring, triazine ring, indole ring, quinol Ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadiazole ring, benzo Heterocyclic groups formed from oxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzoimidazole ring, pyran ring, dibenzofuran ring, dibenzothiophene ring It may mean to include.

Throughout this specification, the term "substituted or unsubstituted" is deuterium, halogen, amino group, nitrile group, nitro group or C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₂₀ to a cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group and C ₃ ~ substituted with one or more groups selected from a heteroaryl group the group consisting of C ₃₀ or is replaced in the Can mean. In addition, the same symbol throughout the present specification may have the same meaning unless specifically noted.

Throughout this specification, the term "fluorene" refers to a substituted or unsubstituted C _1-20 alkyl group, a substituted or unsubstituted C _5-30 aryl group, or a substituted or unsubstituted C _3-30 hydrogen bonded to carbon number 9 And substituted with a heteroaryl group.

The first aspect of the present application provides a compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

X is O, S or CRR`,

Y and Z are each independently O or S,

Ar ₁ is a ring forming carbon atoms, a C ₆ ~ C ₁₃ substituted or unsubstituted aryl substituted or unsubstituted C ₆ ~ C ₅₀ containing an aryl group, or a ring forming carbon atoms, a C ₆ ~ C ₁₃ substituted or unsubstituted aryl Substituted or unsubstituted C ₆ ~ C ₅₀ heteroaryl group containing a group,

R, R`, R ₁ to R ₆ are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ -C ₃₀ alkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group , Substituted or unsubstituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ sulfide group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, or substituted or unsubstituted C ₅ to C ₃₀ Is a heteroaryl group, adjacent R and R 'may or may not form a ring with each other,

L ₁ to L ₃ are each independently a direct bond, a substituted or unsubstituted C ₆ to C ₃₀ arylene, or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene,

l and q are each independently 0 or an integer of 1 to 4,

m, n, o and p are each independently 0 or an integer of 1 to 3, and when 1, m, n, o, p or q is 2 or more, R ₁ to R ₆ may be the same or different from each other.

The compound according to one embodiment of the present invention provides a hole by connecting two linearly linked tricyclic condensed ring groups (dibenzofuran, dibenzothiophene or fluorene and dibenzofuran or dibenzothiophene) to nitrogen of arylamine. It is possible to form a deep HOMO level suitable for the transport layer or the light emitting auxiliary layer and form a high LUMO, thereby realizing an organic light emitting device having high efficiency.

Compound according to an embodiment of the present invention can form a deep HOMO level may be more suitable for the light emitting auxiliary layer.

In addition, the compound according to an embodiment of the present invention is a fast hole mobility (Hole Mobility) by introducing two tricyclic condensed ring of linear linkage on one side of the arylamine, and dibenzofuran or dibenzothiophene on the other side ), It is possible to excellent arrangement of molecules in forming a thin film. Accordingly, it is possible to implement a long life organic light emitting device by implementing low voltage and suppressing the rolloff phenomenon.

In addition, the compound according to an embodiment of the present invention maintains high LUMO by introducing dibenzofuran or dibenzothiophene having excellent electron resistance to the other side of the arylamine, and at the same time further improves the durability of the compound when blocking electrons from the light emitting layer. Can improve. Accordingly, high efficiency and long lifespan of the organic light emitting device can be realized.

In addition, the compound according to an embodiment of the present invention can maintain a high T1 by introducing a substituent having a high triplet energy having 6 to 13 carbon atoms to form a ring on one side of the arylamine. Accordingly, an organic light emitting device having high efficiency can be realized by maximizing the exciton confinement effect in the light emitting layer.

In addition, the compound according to an embodiment of the present invention may include a three or more tricyclic condensed ring structure to form a high Tg to prevent thin film recrystallization, thereby ensuring the driving stability of the organic light emitting device have.

According to an embodiment of the present invention, in Formula 1, Ar ₁ is a substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, or a ring containing a substituted or unsubstituted aryl group having ₆ to ₁₃ ring carbon atoms It may be a substituted or unsubstituted C ₆ ~ C ₅₀ heteroaryl group containing a substituted or unsubstituted aryl group having C ₆ ~ C ₁₃ carbon atoms. Ar ₁ may include an aryl group having ₆ to ₁₃ carbon atoms to form a ring, and the aryl group may be substituted or unsubstituted. The total carbon number of Ar ₁ including such an aryl group may be C ₆ ~ C ₅₀ .

In one embodiment of the present invention, the compound may be represented by the following formula (2) or (3).

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

X, Y, Z, Ar ₁ , R, R ′, R ₁ to R ₆ , L ₁ , L ₂ , L ₃ , l, m, n, o, p and q are the same as defined in Formula 1 above.

The compound represented by the formula (2) is a case where L ₁ is a direct bond in the formula (1), two tricyclic condensed ring groups (tricyclic condensed ring including X and tricyclic condensed ring including Y) of one side of the arylamine It is a structure that is directly bonded without a linking group. In this case, it is possible to form a deep HOMO easy to maintain a high T1 and the light emitting auxiliary layer by minimizing the connector, it can be effective in improving the luminous efficiency.

The compound represented by Chemical Formula 3 is a structure in which L ₂ in the above Chemical Formula 1 is a direct bond, and a tricyclic condensed ring including Y is directly bonded to nitrogen.

In this case, by minimizing the linking group, high T1 retention and direct coupling with nitrogen of the arylamine can be advantageous for low voltage driving.

In one embodiment of the present invention, the compound may be represented by the following formula (4) or (5).

[Formula 4]

[Formula 5]

In Chemical Formulas 4 and 5,

X, Y, Z, Ar ₁ , R, R ′, R ₁ to R ₆ , L ₂ , L ₃ , l, m, n, o, p and q are the same as defined in Chemical Formula 1.

The compound represented by the formula (4) or (5) is a structure in which ₂ or 4 of the tricyclic condensed ring containing Y in the formula (1) as a bonding position with L ₂ . In this case, high LUMO can be maintained at the same time as deep HOMO formation, thereby improving luminous efficiency and can be effective in blocking electrons flowing from the light emitting layer into the hole transport layer.

In addition, the linking position number of the tricyclic condensed ring compound may be as follows.

In one embodiment of the present invention, the compound may be represented by the following formula (6) or formula (7).

 [Formula 6]

[Formula 7]

In Chemical Formulas 6 and 7,

X, Y, Z, Ar ₁ , R, R`, R ₁ to R ₆ , L ₃ , 1, m, n, o, p and q are the same as defined in the formula (1).

The compound represented by Formula 6 or Formula 7 is a case where L ₁ and L ₂ in the formula 1 is a direct bond, the tricyclic condensed ring containing Y is directly bonded to nitrogen, tricyclic condensed ring containing Y 2 or 4 of the structure to be the bonding position. In this case, high LUMO can be maintained at the same time as fast hole mobility, and thus it can be effective in blocking low-voltage driving and electrons flowing into the hole transport layer from the light emitting layer.

According to an embodiment of the present invention, in Formula 1 to Formula 7, R ₁ to R ₆ may be each independently hydrogen, deuterium, or a phenyl group. Specifically, all of R ₁ to R ₆ may be hydrogen.

Further, according to one embodiment of the present invention, in Formula 1 to Formula 7, X may be O or S.

In addition, according to an embodiment of the present invention, in Formulas 1 to 7, wherein X, Y and Z may all be O.

In addition, according to an embodiment of the present invention, in Formulas 1 to 7, wherein X and Y may both be S, the tricyclic condensed ring containing Y is 2 or 4 to the bonding position of the arylamine It can be connected to the nitrogen side.

In addition, according to an embodiment of the present invention, in Formula 1 to Formula 7, L ₁ to L ₃ may be each independently selected from the group consisting of a direct bond, phenylene, biphenylene, and combinations thereof.

Further, according to one embodiment of the present invention, at least one of L ₁ to L ₃ in Formula 1 to Formula 7 is substituted or unsubstituted C ₆ ~ C ₃₀ Arylene, or substituted or unsubstituted C ₅ ~ C ₃₀ heteroarylene, and may be specifically selected from the group consisting of phenylene, biphenylene and combinations thereof.

Further, according to one embodiment of the present invention, in Formulas 1 to 7, wherein Ar ₁ is phenyl, biphenyl, terphenyl, fluorene, dialkyl fluorene, dibenzofuran, dibenzothiophene and combinations thereof It may be selected from the group consisting of.

According to an embodiment of the present invention, the compound represented by Formula 1 may be any one of the following compounds, but may not be limited thereto:

The second aspect of the present application provides an organic light emitting device comprising the compound represented by Formula 1. The organic light emitting device may include one or more organic material layers containing a compound according to the present application between the first electrode and the second electrode.

In one embodiment of the present invention, the organic material layer may be a hole injection layer, a hole transport layer and a light emitting auxiliary layer, but may not be limited thereto. In addition, the compounds of the present invention may be used alone or in combination with known compounds when forming the organic layer.

In one embodiment of the present invention, the organic light emitting device may include an organic material layer containing a hole transport material and an organic material layer containing a compound represented by Formula 1, but may not be limited thereto.

The organic light emitting device includes an organic material layer, such as a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), an electron injection layer (EIL), between an anode and a cathode. It may contain one or more layers.

For example, the organic light emitting device may be manufactured as shown in FIG. 1. The organic light emitting device is an anode (hole injection electrode 1000) / hole injection layer 200 / hole transport layer 300 / light emitting layer 400 / electron transport layer 500 / electron injection layer 600 / cathode (electron) from below The injection electrodes 2000 may be stacked in this order.

In FIG. 1, the substrate 100 may be a substrate used in an organic light emitting device, and in particular, may be a transparent glass substrate or a flexible plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance. have.

The hole injection electrode 1000 is used as an anode for hole injection of the organic light emitting device. A material having a low work function may be used to inject holes, and may be formed of a transparent material such as indium tin oxide (ITO), indium zinc oxide (IZO), and graphene.

내지 5 ㎛의 층 두께 범위에서 적절히 선택할 수 있다. The hole injection layer 200 may be formed on the anode by depositing the hole injection layer material by a method such as vacuum deposition, spin coating, casting, or Langmuir-Blodgett (LB). When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer 200, the structure and thermal properties of the desired hole injection layer, and generally, 50-500 deposition. Temperature, vacuum degree of 10 ^-8 to 10 ^-3 torr, deposition rate of 0.01 to 100 kPa / sec, 10 kPa

It can be suitably selected in the layer thickness range of 5 micrometers.

Next, a hole transport layer 300 may be formed by depositing a hole transport layer material on the hole injection layer 200 by a method such as vacuum deposition, spin coating, cast, or LB. In the case of forming the hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, the hole transport layer is preferably selected in the same condition range as the formation of the hole injection layer.

The hole transport layer 300 may use a compound according to the present invention. As described above, the compound according to the present invention may be used alone or a known compound may be used together. In addition, according to an embodiment of the present invention, the hole transport layer 300 may be one or more layers, and may include a hole transport layer formed only of a known material. In addition, according to the exemplary embodiment of the present invention, an auxiliary light emitting layer may be formed on the hole transport layer 300.

The light emitting layer 400 may be formed by depositing a light emitting layer material on the hole transport layer 300 or the light emitting auxiliary layer by a method such as vacuum deposition, spin coating, cast, LB, or the like. In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same condition range as the formation of the hole injection layer. In addition, the light emitting layer material may use a known compound as a host or dopant.

In addition, when used together with a phosphorescent dopant in the light emitting layer, in order to prevent the triplet excitons or holes from diffusing into the electron transport layer, the hole suppressing material (HBL) may be further laminated by vacuum deposition or spin coating. The hole-suppressing material that can be used at this time is not particularly limited, but any one of the well-known ones used as the hole-inhibiting material can be selected and used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (A1) can be cited. Oxy-2-methylquinolinolato) -aluminum biphenoxide), a phenanthrolines-based compound (e.g., BCP (vasocuproin) from UDC) can be used.

The electron transport layer 500 is formed on the light emitting layer 400 formed as described above. The electron transport layer may be formed by a vacuum deposition method, a spin coating method, a casting method, or the like. In addition, although the deposition conditions of the electron transport layer are different depending on the compound used, it is generally preferable to select within the same condition range as the formation of the hole injection layer.

Subsequently, an electron injection layer 600 may be formed by depositing an electron injection layer material on the electron transport layer 500, wherein the electron transport layer may be formed by vacuum deposition, spin coating, or casting a conventional electron injection layer material. It can form by a method, such as a method.

The hole injection layer 200, the hole transport layer 300, the light emitting layer 400, the electron transport layer 500 of the organic light emitting device may use a compound according to the present invention or may use the following materials, or according to the present invention Compounds and known materials can be used together.

The cathode 2000 for electron injection is formed on the electron injection layer 600 by a method such as vacuum deposition or sputtering. Various metals may be used as the cathode. Specific examples include materials such as aluminum, gold, and silver.

The organic light emitting device of the present invention can be not only an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an organic light emitting device having a cathode structure, but also a structure of organic light emitting devices having various structures. It is also possible to form a layer or two intermediate layers.

As described above, the thickness of each organic material layer formed in accordance with the present invention can be adjusted according to the required degree, specifically 1 to 1,000 nm, more specifically may be 5 to 200 nm.

In addition, the present invention has an advantage that the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.

With respect to the organic light emitting compound according to the present aspect may be applied to the contents described with respect to the first aspect of the present application, but may not be limited thereto.

Hereinafter, the embodiments of the present application will be described in more detail, and the scope of the present application is not limited by the present embodiment.

EXAMPLE

Synthesis of Compound Represented by Formula 1

The compound represented by Formula 1 may be synthesized through the following reaction, but is not limited thereto.

Synthesis of Intermediate IM

Intermediate IM may be synthesized through the following reaction for synthesis of the desired compound, but is not limited thereto.

Synthesis of Intermediate IM1

Intermediate IM1 was synthesized in the following manner.

In a round bottom flask, 20.0 g of dibenzo [b, d] furan-4-ylboronic acid and 33.8 g of 2,8-dibromodibenzo [b, d] furan are dissolved in 800 ml of 1,4-dioxan, 140 ml of K2CO3 (2M) and Pd. 3.3 g of (PPh ₃ ) ₄ was added thereto, followed by stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure and recrystallized to obtain 26.1 g of intermediate IM1 (yield 67%).

Synthesis of Intermediates IM2 and IM3

The following IM2 to IM3 was synthesized by different starting materials as shown in Table 1 below.

Starting material of IM2 Starting material of IM3

dibenzo [b, d] furan-4-ylboronic acid, 2,8-dibromodibenzo [b, d] thiophene dibenzo [b, d] furan-4-ylboronic acid, 2,8-dibromodibenzo [b, d] thiophene

Synthesis of Intermediate IM4

Intermediate IM4 was synthesized in the following manner.

In a round bottom flask, 20.0 g of dibenzo [b, d] furan-4-ylboronic acid and 33.8 g of 4,6-dibromodibenzo [b, d] furan are dissolved in 800 ml of 1,4-dioxan, 140 ml of K2CO3 (2M) and Pd. 3.3 g of (PPh ₃ ) ₄ was added thereto, followed by stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure and recrystallized to obtain 25.3 g of intermediate IM4-1 (yield 65%).

In a round bottom flask, 25.0 g of IM4-1 and 20 g of bis (pinacolato) diboron were dissolved in 450 ml of 1,4-dioxan, 17.0 g of KOAc and 0.2 g of Pd (dppf) Cl ₂ were added thereto, followed by stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure and recrystallized to obtain 22.3 g of intermediate IM4-2 (yield 80%).

The round bottom flask IM4-2 22.0 g, 1-bromo- 4-iodobenzene 14.9 g of 1,4-dioxan was dissolved in 550 ml K2CO3 (2M) 70 ml, and Pd (PPh ₃₎ stirring to reflux was placed 1.7 g of ₄ It was. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure and recrystallized to obtain 14.0 g of intermediate IM4 (yield 60%).

Synthesis of Intermediates IM5 and IM13

By varying the starting material as shown in Table 2, the following IM5 to IM13 were synthesized in the same manner as in IM4.

Starting material of IM5 Starting material of IM6 Starting material of IM7

dibenzo [b, d] furan-2-ylboronic acid, 4,6-dibromodibenzo [b, d]
furan dibenzo [b, d] furan-4-ylboronic acid, 2,8-dibromodibenzo [b, d]
furan dibenzo [b, d] furan-2-ylboronic acid, 2,8-dibromodibenzo [b, d]
furan Starting material of IM8 Starting material of IM9 Starting material of IM10

dibenzo [b, d] thiophen-4-ylboronic acid, 4,6-dibromodibenzo [b, d]
furan dibenzo [b, d] thiophen-2-ylboronic acid, 4,6-dibromodibenzo [b, d]
furan dibenzo [b, d] furan-4-ylboronic acid, 4,6-dibromodibenzo [b, d]
thiophene Starting material of IM11 Starting material of IM12 Starting material of IM13

dibenzo [b, d] thiophen-4-ylboronic acid, 4,6-dibromodibenzo [b, d]
thiophene dibenzo [b, d] furan-4-ylboronic acid, 2,8-dibromodibenzo [b, d]
thiophene (9,9-dimethyl-9H-fluoren-2-yl) boronic acid, 4,6-dibromodibenzo [b, d]
furan

Synthesis of Intermediate OP

Intermediate OP1 was synthesized in the following manner.

In a round bottom flask, 30.0 g of 2-bromo-9,9-diphenyl-9H-fluorene, 7.8 g of aniline, 10.9 g of t-BuONa, 2.8 g of Pd ₂ (dba) _{3 and} 3.4 ml of (t-Bu) ₃ P It was dissolved in 570 ml of toluene and stirred under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure and recrystallized to obtain 21 g of OP1 (yield 68%).

Synthesis of Intermediates OP2 to OP5

Different starting materials as shown in Table 3 below, the following OP2 to OP5 were synthesized by the same method as OP1.

Starting material of OP2 Starting material of OP3 Starting material of OP4

2-bromodibenzo [b, d] thiophene, [1,1'-biphenyl] -4-amine 4- (4-bromophenyl) dibenzo [b, d] furan, aniline 4- (4-bromophenyl) dibenzo [b, d] furan, [1,1'-biphenyl] -4-amine Starting material of OP5

2- (4-bromophenyl) dibenzo [b, d] furan, [1,1'-biphenyl] -4-amine

Compound synthesis

The target compounds 1 to 15 were synthesized using the intermediates IM1 to IM13 and OP1 to OP5.

Synthesis of Compound 1

In a round bottom flask, 3.0 g of IM1, 2.7 g of OP1, 1.1 g of t-BuONa, 0.3 g of Pd ₂ (dba) _{3, and} 0.3 ml of (t-Bu) ₃ P were dissolved in 100 ml of toluene, followed by stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure, column purified and recrystallized to obtain compound 1 3.0 g (yield 67%).

m / z: 667.21 (100.0%), 668.22 (52.4%), 669.22 (14.2%), 670.22 (2.6%)

Synthesis of Compound 2

Compound 2 was synthesized in the same manner as Compound 1 using IM2 and OP2 instead of IM1 and OP1 (yield 63%).

m / z: 699.17 (100.0%), 700.17 (53.9%), 701.18 (13.4%), 701.16 (9.0%), 702.17 (4.8%), 702.18 (2.6%), 703.17 (1.3%), 701.17 (1.2% )

Synthesis of Compound 3

Compound 3 was synthesized in the same manner as Compound 1 using IM3 and OP2 instead of IM1 and OP1 (60% yield).

m / z: 715.15 (100.0%), 716.15 (54.7%), 717.15 (14.6%), 717.14 (13.6%), 718.15 (7.5%), 718.16 (2.2%), 719.15 (1.8%)

Synthesis of Compound 4

Compound 4 was synthesized in the same manner as compound 1 using OP3 instead of OP1. (Yield 65%)

m / z: 667.21 (100.0%), 668.22 (52.4%), 669.22 (14.2%), 670.22 (2.6%)

Synthesis of Compound 5

Compound 5 was synthesized in the same manner as Compound 1 using IM4 and OP4 instead of IM1 and OP1. (Yield 71%)

m / z: 819.28 (100.0%), 820.28 (65.4%), 821.28 (21.6%), 822.29 (4.4%)

Synthesis of Compound 6

Compound 6 was synthesized in the same manner as Compound 1 using IM4 and OP5 instead of IM1 and OP1 (yield 67%).

m / z: 819.28 (100.0%), 820.28 (65.4%), 821.28 (21.6%), 822.29 (4.4%)

Synthesis of Compound 7

Compound 7 was synthesized in the same manner as Compound 1 using IM5 and OP4 instead of IM1 and OP1. (Yield 65%)

m / z: 819.28 (100.0%), 820.28 (65.4%), 821.28 (21.6%), 822.29 (4.4%)

Synthesis of Compound 8

Compound 8 was synthesized in the same manner as Compound 1 using IM6 and OP4 instead of IM1 and OP1 (yield 67%).

m / z: 819.28 (100.0%), 820.28 (65.4%), 821.28 (21.6%), 822.29 (4.4%)

Synthesis of Compound 9

Compound 9 was synthesized in the same manner as Compound 1 using IM7 and OP4 instead of IM1 and OP1 (yield 63%).

m / z: 819.28 (100.0%), 820.28 (65.4%), 821.28 (21.6%), 822.29 (4.4%)

Synthesis of Compound 10

Compound 10 was synthesized in the same manner as Compound 1 using IM1 and OP1 instead of IM8 and OP4. (Yield 66%)

m / z: 835.25 (100.0%), 836.26 (65.4%), 837.26 (22.0%), 838.26 (4.9%), 837.25 (4.8%), 838.25 (3.0%), 836.25 (1.2%), 839.26 (1.0% )

Synthesis of Compound 11

Compound 11 was synthesized in the same manner as Compound 1 using IM1 and OP4 instead of IM1 and OP1. (Yield 65%)

m / z: 835.25 (100.0%), 836.26 (65.4%), 837.26 (22.0%), 838.26 (4.9%), 837.25 (4.8%), 838.25 (3.0%), 836.25 (1.2%), 839.26 (1.0% )

Synthesis of Compound 12

Compound 12 was synthesized in the same manner as Compound 1 using IM10 and OP4 instead of IM1 and OP1 (60% yield).

m / z: 835.25 (100.0%), 836.26 (65.4%), 837.26 (22.0%), 838.26 (4.9%), 837.25 (4.8%), 838.25 (3.0%), 836.25 (1.2%), 839.26 (1.0% )

Synthesis of Compound 13

Compound 13 was synthesized in the same manner as Compound 1 using IM11 and OP4 instead of IM1 and OP1 (yield 62%).

m / z: 851.23 (100.0%), 852.24 (65.4%), 853.24 (21.2%), 853.23 (10.3%), 854.23 (6.0%), 854.24 (5.0%), 855.23 (2.0%), 852.23 (2.0% )

Synthesis of Compound 14

Compound 14 was synthesized in the same manner as Compound 1 using IM12 and OP4 instead of IM1 and OP1 (60% yield).

m / z: 835.25 (100.0%), 836.26 (65.4%), 837.26 (22.0%), 838.26 (4.9%), 837.25 (4.8%), 838.25 (3.0%), 836.25 (1.2%), 839.26 (1.0% )

Synthesis of Compound 15

Compound 15 was synthesized in the same manner as Compound 1 using IM13 and OP4 instead of IM1 and OP1. (Yield 65%)

m / z: 845.33 (100.0%), 846.33 (68.6%), 847.34 (23.2%), 848.34 (5.4%)

Organic light emitting device manufacturing

Example 1

An indium tin oxide (ITO) 1500 Å thick thin film coated glass substrate was washed with distilled water ultrasonic waves. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried and transferred to a plasma cleaner, and then the substrate is cleaned for 5 minutes using an oxygen plasma. Using an evaporator, a hole injection layer HI01 600Å, HATCN 50Å, a hole transport layer HT01 250Å and a light emitting auxiliary layer to form a compound 1100Å and then doped with a light emitting layer of BH01: BD01 3% to form a 250Å. Next, ET01: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 막, which were encapsulated in a glove box to produce an organic light emitting device.

Examples 2-15

In the same manner as in Example 1, an organic light-emitting device was manufactured by using Compounds 2 to 15 instead of Compound 1.

Comparative Examples 1 to 7

In the same manner as in Example 1, an organic light-emitting device was manufactured by using Ref. 1 to Ref. 7 instead of compound 1.

Performance evaluation of organic light emitting device

Inject electrons and holes by applying voltage to a Keithley 2400 source measurement unit and measure the luminance when light is emitted using a Konica Minolta spectrophotometer (CS-2000) Thus, the performance of the organic light emitting diodes of Examples and Comparative Examples was evaluated by measuring the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, and the results are shown in Table 4 below.

Op. V mA / cm2 Cd / A QE (%) CIEx CIEy LT95 Example 1 3.7 10 7.6 6.6 0.140 0.109 150 Example 2 3.7 10 7.7 6.6 0.139 0.110 153 Example 3 3.7 10 7.7 6.6 0.140 0.110 150 Example 4 3.7 10 7.7 6.7 0.140 0.110 155 Example 5 3.8 10 8.1 7.2 0.142 0.109 190 Example 6 3.8 10 8.2 7.2 0.140 0.109 185 Example 7 3.8 10 8.0 7.1 0.141 0.109 187 Example 8 3.8 10 8.1 7.0 0.140 0.110 182 Example 9 3.8 10 8.1 7.0 0.141 0.110 180 Example 10 3.8 10 8.0 7.1 0.140 0.109 176 Example 11 3.8 10 8.0 7.0 0.139 0.109 176 Example 12 3.9 10 8.3 7.4 0.140 0.110 172 Example 13 3.9 10 8.4 7.4 0.141 0.110 170 Example 14 3.9 10 8.3 7.3 0.140 0.111 170 Example 15 3.8 10 7.9 7.0 0.140 0.110 165 Comparative Example 1 4.2 10 7.1 6.1 0.140 0.110 105 Comparative Example 2 4.1 10 7.0 6.0 0.141 0.110 113 Comparative Example 3 4.2 10 7.3 6.3 0.140 0.110 125 Comparative Example 4 4.2 10 7.2 6.3 0.142 0.110 120 Comparative Example 5 4.4 10 6.7 5.9 0.140 0.111 110 Comparative Example 6 4.6 10 6.6 5.9 0.141 0.112 100 Comparative Example 7 4.7 10 7.0 6.1 0.140 0.112 92

As shown in Table 4, Examples 1 to 15 using the compound of the present invention as a hole transport layer can be confirmed that the efficiency and life is increased compared to Comparative Examples 1 to 7.

More specifically, compared to Comparative Example 1, Examples 1 to 15 has a substituent having two tricyclic condensed ring connected to one side of the arylamine can have a fast hole mobility (Hole Mobility), more advantageous for low voltage driving Do.

In addition, compared with Comparative Examples 2 and 3, Examples 1 to 15 have a substituent in which two tricyclic condensed rings are connected at one side of the arylamine, and further include a tricyclic condensed ring at the other side to form a molecular array when forming a thin film. Its excellent and improved hole mobility suppresses rolloff and improves lifetime.

In addition, compared with Comparative Examples 4 and 5, Examples 1 to 15, nitrogen of the arylamine is combined with another dibenzofuran or dibenzothiophene in addition to the two tricyclic condensed ring to maintain a deep HOMO and high LUMO It can be formed to implement the characteristics of excellent efficiency and long life.

In addition, compared with Comparative Examples 6 and 7, Examples 1 to 15 has an arylamine having 13 or less carbon atoms having a triple triple energy of Ar ₁ to maintain a high T1 to maximize the exciton confinement effect in the light emitting layer. It is possible to implement an organic light emitting device having a low driving voltage and having greatly improved efficiency and lifespan.

The foregoing description of the application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present application. .

100: substrate
200: hole injection layer
300: hole transport layer
400: light emitting layer
500: electron transport layer
600: electron injection layer
1000: anode
2000: cathode

Claims (14)

A compound represented by Formula 1;
[Formula 1]

In Chemical Formula 1,
X is O, S or CRR`,
Y and Z are each independently O or S,
Ar <sub>1</sub> is a ring forming carbon atoms, a C <sub>6</sub> ~ C <sub>13</sub> substituted or unsubstituted aryl substituted or unsubstituted C <sub>6</sub> ~ C <sub>50</sub> containing an aryl group, or a ring forming carbon atoms, a C <sub>6</sub> ~ C <sub>13</sub> substituted or unsubstituted aryl Substituted or unsubstituted C <sub>6</sub> ~ C <sub>50</sub> heteroaryl group containing a group,
R, R`, R ₁ to R ₆ are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ -C ₃₀ alkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group , Substituted or unsubstituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ sulfide group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, or substituted or unsubstituted C ₅ to C ₃₀ Is a heteroaryl group, adjacent R and R 'may or may not form a ring with each other,
L ₁ to L ₃ are each independently a direct bond, a substituted or unsubstituted C ₆ to C ₃₀ arylene, or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene,
l and q are each independently 0 or an integer of 1 to 4,
m, n, o and p are each independently 0 or an integer of 1 to 3, and when 1, m, n, o, p or q is 2 or more, R ₁ to R ₆ may be the same or different from each other. The method of claim 1,
The compound is a compound represented by the following formula (2) or (3);
[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,
X, Y, Z, Ar ₁ , R, R ′, R ₁ to R ₆ , L ₁ , L ₂ , L ₃ , l, m, n, o, p and q are the same as defined in Formula 1 above. The method of claim 1,
The compound is a compound represented by the following formula (4) or (5);
[Formula 4]

[Formula 5]

In Chemical Formulas 4 and 5,
X, Y, Z, Ar ₁ , R, R ′, R ₁ to R ₆ , L ₂ , L ₃ , l, m, n, o, p and q are the same as defined in Chemical Formula 1. The method of claim 1,
The compound is a compound represented by the following formula (6) or (7);
[Formula 6]

[Formula 7]

In Chemical Formulas 6 and 7,
X, Y, Z, Ar ₁ , R, R`, R ₁ to R ₆ , L ₃ , 1, m, n, o, p and q are the same as defined in the formula (1). The method according to any one of claims 1 to 4,
R ₁ to R ₆ are each independently hydrogen, deuterium, or a phenyl group. The method according to any one of claims 1 to 4,
X is O or S. The method according to any one of claims 1 to 4,
X, Y and Z are all O. The method according to any one of claims 1 to 4,
L ₁ to L ₃ are each independently selected from the group consisting of a direct bond, phenylene, biphenylene and combinations thereof. The method according to any one of claims 1 to 4,
At least one of L ₁ to L ₃ is substituted or unsubstituted C ₆ to C ₃₀ arylene, or substituted or unsubstituted C ₅ to C ₃₀ heteroarylene. The method according to any one of claims 1 to 4,
At least one of L ₁ to L ₃ is selected from the group consisting of phenylene, biphenylene and combinations thereof. The method according to any one of claims 1 to 4,
Ar ₁ is a compound selected from the group consisting of phenyl, biphenyl, terphenyl, fluorene, dialkylfluorene, dibenzofuran, dibenzothiophene, and combinations thereof. The method of claim 1,
The compound is any one of the following compounds.

An organic light emitting device comprising an organic material layer containing a compound according to any one of claims 1 to 12 between the first electrode and the second electrode. The method of claim 13,
The organic material layer is an organic light emitting device of at least one of a hole injection layer, a hole transport layer and a light emitting auxiliary layer.

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