KR20210034445A - Novel compound and organic electroluminescent device 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 ensure high efficiency, long lifespan, low driving voltage, and driving stability of the organic light emitting device. A first aspect of the present invention provides a compound represented by the following chemical formula 1.

Description

A novel compound and an organic light-emitting device comprising the same TECHNICAL FIELD [NOVEL COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE INCLUDING THE SAME}

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

Materials used as an organic material layer in an organic light-emitting device can be 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, depending on their function. And the light-emitting material may be classified into a polymer and a low molecule according to its molecular weight, and according to a light-emitting mechanism, it may be classified into a fluorescent material derived from the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron, The light-emitting material may be classified into blue, green, and red light-emitting materials and yellow and orange light-emitting materials necessary to realize better natural colors according to the light-emitting color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having an energy band gap smaller than that of a host mainly constituting the light emitting layer and having excellent light emission efficiency is mixed in a light emitting layer, excitons generated from the host are transported to the dopant to emit highly efficient light. At this time, since the wavelength of the host moves to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of the dopant used and the host.

Until now, various compounds have been known as materials used in such organic light-emitting devices. However, in the case of organic light-emitting devices using materials known so far, development of new materials is continuously required due to high driving voltage, low efficiency, and short lifespan. Accordingly, efforts have been made to develop organic light emitting devices having low voltage driving, high luminance, and long life using materials having excellent properties.

Korean Patent Application Publication No. 10-2004-0098238

The present invention provides a novel compound and an organic light-emitting device including the same.

However, the problem to be solved by the present invention is not limited to the problem described above, and 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 invention provides a compound represented by the following formula (1):

[Formula 1]

In Formula 1,

X is O, S or CRR',

A is represented by the following formula 1-1,

Ar is a substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₅₀ heteroaryl group,

R, R', R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to 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 Is a _{heteroaryl group of C 5} ~ C ₃₀ , wherein adjacent R and R', a plurality of R ₁ or a plurality of R ₂ may or may not form a ring with each other,

L ₁ to L ₄ are each independently a substituted or unsubstituted C ₆ to C ₃₀ arylene group, or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group,

L ₅ is a direct bond, a substituted or unsubstituted C ₆ ~ C ₃₀ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroarylene group,

l is 0 or an integer of 1 to 4,

m is 0 or an integer of 1 to 3,

[Formula 1-1]

In Formula 1-1,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₅₀ heteroaryl group, wherein adjacent Ar ₁ and Ar ₂ are each ring May or may not form,

R ₃ and R ₄ are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or Unsubstituted C ₁ ~ C ₃₀ alkoxy group, substituted or unsubstituted C ₁ ~ C ₃₀ sulfide group, substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, or substituted or unsubstituted C ₅ ~ C _It is a heteroaryl group of 30, wherein a plurality of adjacent R ₃ or a plurality of R ₄ may or may not form a ring with each other,

n and o are each independently 0 or an integer of 1 to 4.

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

The novel compound according to an embodiment of the present invention assists light emission through a structure including four or more linear linking groups connecting them between a tricyclic compound selected from dibenzofuran, dibenzothiophene or fluorene and an arylamine compound. By having a deep HOMO energy level suitable for the layer, the injection of holes into the light emitting layer is made more smoothly, so that an organic light emitting device having higher efficiency can be implemented.

In addition, the novel compound according to an embodiment of the present invention is formed through a structure including at least four linear linking groups connecting the tricyclic compounds selected from dibenzofuran, dibenzothiophene or fluorene and an arylamine compound. Conjugation is improved, and when a thin film is formed, the molecular arrangement is excellent, so that a fast hole mobility can be obtained, so that a roll-off phenomenon is suppressed, and an organic light emitting device having a low driving voltage and a long life can be implemented.

In addition, the novel compound according to an embodiment of the present invention is a tricyclic compound having excellent electron resistance selected from dibenzofuran, dibenzothiophene or fluorene is introduced to maintain high LUMO, and is easy to block electrons, resulting in high efficiency and long life. It is possible to implement an organic light emitting device having.

In addition, the novel compound according to an embodiment of the present invention is high through a structure comprising four or more linear linking groups connecting them between a tricyclic compound selected from dibenzofuran, dibenzothiophene or fluorene and an arylamine compound. Since it can have a glass transition temperature, recrystallization of a thin film can be prevented, and an organic light emitting device having driving stability can be implemented through this.

1 is a schematic diagram of an organic light-emitting device according to an embodiment of the present invention.

Hereinafter, embodiments and embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily implement the present invention.

However, the present invention may be implemented in various different forms and is not limited to the embodiments and examples described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the present specification, when a member is said to be positioned "on" another member, this includes not only the case where a member is in contact with the other member, but also the case where another member exists between the two members.

Throughout the present specification, when a certain part "includes" a certain constituent element, it means that other constituent elements may be further included instead of excluding other constituent elements unless otherwise stated. The terms "about", "substantially", etc. of the degree used throughout the present specification are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented. For the sake of understanding, accurate or absolute figures are used to prevent unreasonable use of the stated disclosure by unconscionable infringers.

In the entire specification of the present invention, the term "combination of these" included in the expression of the Makushi format refers to one or more mixtures or combinations selected from the group consisting of the constituent elements described in the expression of the Makushi format. It means to include one or more selected from the group consisting of elements.

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

Throughout the present specification, the term "aryl" or "arylene" refers to _{an aromatic hydrocarbon ring group of C 6-50} , for example, phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorenyl, phenanthrenyl , Triphenylenyl, perylenyl, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzocrycenyl, anthracenyl, stilbenyl, pyrenyl, and the like, and "Heteroaryl" or "heteroarylene" is a C _2-50 aromatic ring containing at least one hetero element, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzo Furanyl, isobenzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, quinolyl group, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, thier Neil, and pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, Piperazine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadiazole ring, benzoxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring , It may mean including a heterocyclic group formed from a benzoimidazole ring, a pyran ring, a dibenzofuran ring, and a dibenzothiophene ring.

Throughout the present specification, the term "substituted or unsubstituted" refers to deuterium, halogen, amino group, nitrile group, nitro group or C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkoxy group , C ₃ to C ₂₀ cycloalkyl group, C ₃ to C ₂₀ heterocycloalkyl group, C ₆ to C ₃₀ aryl group and C ₃ to C ₃₀ heteroaryl group substituted or unsubstituted with one or more groups selected from the group consisting of It can mean that.

In addition, throughout the present specification, the same symbols may have the same meaning unless otherwise specified.

Throughout the present 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 hydrogen bonded to the carbon at the 9 position. It may include a case substituted with a cyclic C _{3-30 heteroaryl group.}

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

[Formula 1]

In Formula 1,

X is O, S or CRR',

A is represented by the following formula 1-1,

Ar is a substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₅₀ heteroaryl group,

R, R', R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to 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 Is a _{heteroaryl group of C 5} ~ C ₃₀ , wherein adjacent R and R', a plurality of R ₁ or a plurality of R ₂ may or may not form a ring with each other,

L ₁ to L ₄ are each independently a substituted or unsubstituted C ₆ to C ₃₀ arylene group, or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group,

L ₅ is a direct bond, a substituted or unsubstituted C ₆ ~ C ₃₀ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroarylene group,

l is 0 or an integer of 1 to 4,

m is 0 or an integer of 1 to 3,

[Formula 1-1]

In Formula 1-1,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₅₀ heteroaryl group, wherein adjacent Ar ₁ and Ar ₂ are each ring May or may not form,

R ₃ and R ₄ are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or Unsubstituted C ₁ ~ C ₃₀ alkoxy group, substituted or unsubstituted C ₁ ~ C ₃₀ sulfide group, substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, or substituted or unsubstituted C ₅ ~ C _It is a heteroaryl group of 30, wherein a plurality of adjacent R ₃ or a plurality of R ₄ may or may not form a ring with each other,

n and o are each independently 0 or an integer of 1 to 4.

The novel compound according to an embodiment of the present invention assists light emission through a structure including four or more linear linking groups connecting them between a tricyclic compound selected from dibenzofuran, dibenzothiophene or fluorene and an arylamine compound. As the layer has a deep HOMO energy level suitable for the layer, the injection of holes into the light emitting layer becomes more smooth, and thus an organic light emitting device having higher efficiency can be implemented.

In addition, the novel compound according to an embodiment of the present invention is formed through a structure including at least four linear linking groups connecting the tricyclic compounds selected from dibenzofuran, dibenzothiophene or fluorene and an arylamine compound. Conjugation is improved, and molecular arrangement is excellent when forming a thin film, so that a fast hole mobility can be obtained, so that a roll-off phenomenon is suppressed, and an organic light emitting device having a low driving voltage and a long life can be implemented.

In addition, the novel compound according to an embodiment of the present invention is a tricyclic compound having excellent electron resistance selected from dibenzofuran, dibenzothiophene or fluorene is introduced to maintain high LUMO, and is easy to block electrons, resulting in high efficiency and long life. It is possible to implement an organic light emitting device having.

In addition, the novel compound according to an embodiment of the present invention is high through a structure comprising four or more linear linking groups connecting them between a tricyclic compound selected from dibenzofuran, dibenzothiophene or fluorene and an arylamine compound. Since it can have a glass transition temperature, recrystallization of a thin film can be prevented, and an organic light emitting device having driving stability can be implemented through this.

In one embodiment of the present invention, Formula 1 may be represented by the following Formula 2:

[Formula 2]

In Chemical Formula 2,

X, Ar, R ₁ , R ₂ , l and m are as defined in Formula 1,

A'is represented by the following formula 2-1,

R ₇ is each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted C ₁ ~ C ₃₀ alkoxy group, substituted or unsubstituted C ₁ ~ C ₃₀ sulfide group, substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, or substituted or unsubstituted C ₅ ~ C ₃₀ hetero Is an aryl group,

p is an integer of 4 to 8, and may be specifically 4, and when p is 4, it may have a lower deposition temperature, which may be effective in improving thermal stability,

[Formula 2-1]

In Formula 2-1,

Ar ₁ , Ar ₂ , R ₃ and R ₄ are as defined in Formula 1-1.

In the compound represented by Formula 2, in Formula 1, L ₁ to L ₄ are each independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, or a substituted or In the case of an unsubstituted quarterphenylene group, the total number of linearly linked phenylene groups is 4 to 8. Specifically, when the total number of these linearly connected phenylene groups is less than 4 (when p is less than 4 in Chemical Formula 2), the molecular arrangement becomes poor during the formation of a thin film, and thus fast hole mobility cannot be obtained. When the total number exceeds 8 (when p is greater than 8 in Formula 2), there may be a problem that may cause thermal decomposition of the compound due to a high deposition temperature during the deposition process.

Specifically, the compound represented by Formula 2 is, in Formula 1, i) all of L ₁ to L ₄ are substituted or unsubstituted phenylene groups, or ii) _{3 of L 1} to L ₄ are substituted or unsubstituted phenylene groups And the remaining one is a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, or a substituted or unsubstituted quarterphenylene group, or iii) two of L ₁ to L ₄ are substituted or unsubstituted phenylene groups And the remaining two are two substituted or unsubstituted biphenylene groups, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted biphenylene group, and a substituted or unsubstituted quarterphenyl Ene group, or two substituted or unsubstituted terphenylene groups, or iv) one of L ₁ to L ₄ is a substituted or unsubstituted phenylene group, and the remaining three are 3 substituted or unsubstituted biphenylene groups, substituted Or it may be two unsubstituted biphenylene groups and one substituted or unsubstituted terphenylene group, or two substituted or unsubstituted biphenylene groups and one substituted or unsubstituted quarterphenylene group, but is not limited thereto.

In addition, the compound represented by Formula 2-1 is a case in which both n and o are 1 in Formula 1-1.

In one embodiment of the present invention, Formula 1 may be represented by the following Formula 3:

[Formula 3]

In Chemical Formula 3,

X, Ar, R ₁ , R ₂ , l and m are as defined in Formula 1,

A" is represented by the following formula 3-1,

q is an integer of 3 or 4, and may be specifically 3, and when n is 3, it may have a lower deposition temperature, which may be effective in improving thermal stability,

[Chemical Formula 3-1]

In Formula 3-1,

R ₃ and R ₄ are as defined in Formula 1-1,

R ₅ and R ₆ are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or Unsubstituted C ₁ ~ C ₃₀ alkoxy group, substituted or unsubstituted C ₁ ~ C ₃₀ sulfide group, substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, or substituted or unsubstituted C ₅ ~ C _It is a heteroaryl group of 30.

In the compound represented by Formula 3, in Formula 1, when L ₄ is a 1,4-phenylene group, and L ₁ to L ₃ are each independently a phenylene group or a biphenylene group, the phenyl of L ₁ to L ₃ This is the case when the total number of Rengi is 3 or 4. In this case, since it may have a lower deposition temperature, it may be effective to improve thermal stability.

Specifically, in the compound represented by Formula 3, in Formula 1, L ₄ is a 1,4-phenylene group, i) all of L ₁ to L ₃ are phenylene groups, or ii) two of L ₁ to L ₃ are phenyl It is a ren group, and the other one may be a biphenylene group, but is not limited thereto.

According to an embodiment of the present invention, in Formulas 1 to 3, R, R'and R ₁ to R ₄ may each independently be hydrogen, deuterium, a methyl group, or a phenyl group, and specifically, all of them may be hydrogen. In this case, there is a characteristic that is effective in improving mobility by minimizing the bulky characteristic. In Formula 2, R ₇ may each independently be hydrogen, deuterium, methyl group, or phenyl group, specifically hydrogen, and in Formula 3, R ₅ and R ₆ are each independently hydrogen, deuterium, It may be a methyl group or a phenyl group, and specifically, it may be hydrogen. In this case, there is a characteristic that is effective in improving mobility by minimizing the bulky characteristic.

In addition, according to an embodiment of the present invention, in Chemical Formulas 1 to 3, X may be O or S, and in this case, it has a deep HOMO and can have fast mobility, so that it is effective in improving efficiency and driving. have.

According to an embodiment of the present invention, in Formula 1, _{at least one of L 1} to L ₄ may include a phenylene group of a meta bond, and in Formula 2, at least one of the p phenylene groups is meta A bonded phenylene group may be included, and in Formula 3, at least one of the q phenylene groups may include a meta bonded phenylene group. In the case of including at least one phenylene group of the meta bond as described above, since it has high LUMO and is effective in blocking electrons, there is an advantageous effect in improving efficiency.

According to an embodiment of the present invention, in Formulas 1 to 3, Ar, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted ratio Phenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenylyl number In this case, since it has a high LUMO and can maintain a high T1 at the same time, it is effective in forming excitons, so there is an advantageous effect in improving efficiency.

More specifically, in Formulas 1 to 3, Ar, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted Dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl.

More specifically, in Formulas 1 to 3, Ar may be phenyl, naphthyl, or biphenyl, and Ar ₁ and Ar ₂ may both be phenyl.

More specifically, in Formulas 1 to 3, Ar, Ar ₁ and Ar ₂ may all be phenyl.

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.

A second aspect of the present invention provides an organic light-emitting device including the compound according to the present invention described above. The organic light-emitting device may include at least one organic material layer containing the compound according to the present invention between the first electrode and the second electrode.

In one embodiment of the present invention, the organic material layer may be at least one of a hole injection layer, a hole transport layer, and a light emission auxiliary layer, but may not be limited thereto. In addition, when using the compound of the present invention to form an organic material layer, it may be used alone or in combination with a known compound.

In the present invention, the light emitting auxiliary layer is a layer formed between the hole transport layer and the light emitting layer, and may also be referred to as a second hole transport layer or a third hole transport layer depending on the number of hole transport layers.

In the present invention, the compound according to the present invention contained in the organic material layer may be represented by any one of Chemical Formulas 1 to 3, as described above.

In one embodiment of the present invention, the auxiliary light emitting layer may include the compound according to the present invention.

The organic light emitting device includes a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), and electron injection between a first electrode (anode, anode) and a second electrode (cathode). One or more organic material layers selected from the layers EIL may be included.

For example, the organic light-emitting device may be manufactured as shown in FIG. 1. The organic light emitting device includes a first electrode (hole injection electrode, 1000), a hole injection layer 200, a hole transport layer 300, a light emitting layer 400, an electron transport layer 500, an electron injection layer 600, and a second electrode from below. The electrodes (electron injection electrode, 2000) may be stacked in order.

In FIG. 1, the substrate 100 may be a substrate used in an organic light-emitting device, and in particular, it 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 first electrode 1000 is used as a hole injection electrode for hole injection of an organic light emitting device. A material having a low work function is used to enable hole injection, and may be formed of a transparent material such as indium tin oxide (ITO), indium zinc oxide (IZO), and graphene.

The hole injection layer 200 may be formed by depositing a hole injection layer material on the first electrode 1000 by a method such as a vacuum deposition method, a spin coating method, a cast method, or a Langmuir-Blodgett (LB) method. . When the hole injection layer 200 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 characteristics of the hole injection layer 200, etc. As such, it can be appropriately selected from a deposition temperature of 50-500°C, ^{a vacuum degree of 10 -8} to 10 ^-3 torr, a deposition rate of 0.01 to 100 Å/sec, and a layer thickness of 10 Å to 5 μm.

Next, a hole transport layer material may be deposited on the hole injection layer 200 by a vacuum deposition method, a spin coating method, a cast method, or an LB method to form the hole transport layer 300. When the hole transport layer 300 is formed by the vacuum deposition method, the deposition conditions vary depending on the compound to be used, but in general, it is preferable to select within the same range of conditions as the hole injection layer 200 is formed.

The hole transport layer 300 may use the compound according to the present invention, and 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 have one or more layers, and may include a hole transport layer formed of only known materials. In addition, according to an embodiment of the present invention, an auxiliary light emitting layer may be formed on the hole transport layer 300.

A light emitting layer material is deposited on top of the hole transport layer 300 (if the light emitting auxiliary layer is formed, the top of the light emitting auxiliary layer) by a method such as vacuum deposition, spin coating, cast, LB, etc. to form the light emitting layer 400. Can be formed. In the case where the light emitting layer 400 is formed by the vacuum deposition method, the deposition conditions vary depending on the compound to be used, but in general, it is preferable to select within the same range of conditions as the hole injection layer. In addition, a known compound may be used as a host or dopant for the light emitting layer material.

In addition, in the case of using with a phosphorescent dopant in the light emitting layer 400, a hole inhibiting material (HBL) is additionally used by vacuum deposition or spin coating to prevent diffusion of triplet excitons or holes into the electron transport layer 500. Can be stacked. The hole-suppressing material that can be used at this time is not particularly limited, but an arbitrary one may be selected and used from known ones used as hole-suppressing materials. For example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, or hole-suppressing materials described in Japanese Patent Laid-Open No. Roxy-2-methylquinolinolnato)-aluminum biphenoxide), phenanthrolines-based compounds (eg, UDC's BCP (basocuproin)), and the like can be used.

An electron transport layer 500 is formed on the light emitting layer 400 formed as described above. In this case, the electron transport layer 500 may be formed by a vacuum evaporation method, a spin coating method, or a cast method. In addition, the deposition conditions of the electron transport layer 500 vary depending on the compound to be used, but in general, it is preferable to select the electron transport layer 500 within the same range of conditions as the formation of the hole injection layer 200.

Thereafter, an electron injection layer material may be deposited on the electron transport layer 500 to form the electron injection layer 600, wherein the electron injection layer 600 is a conventional electron injection layer material using a vacuum deposition method, It can be formed by a method such as a spin coating method or a cast method.

The hole injection layer 200, the hole transport layer 300, the emission layer 400, and the electron transport layer 500 of the organic light emitting device may use a compound according to the present invention or a material as shown in Table 1 below, or A compound according to the invention and a known substance can be used together.

HI01 HATCN HT01

BH01 BD01 ET01

Liq

A second electrode 2000, which is an electron injection electrode for electron injection, is formed on the electron injection layer 600 by a method such as a vacuum evaporation method or a sputtering method. Various metals may be used as the second electrode 2000. Specific examples include materials such as aluminum, gold, and silver.

The organic light emitting device of the present invention includes a first electrode 1000, a hole injection layer 200, a hole transport layer 300, a light emission auxiliary layer, a light emission layer 400, an electron transport layer 500, an electron injection layer 600, and a first electrode. In addition to the organic light-emitting device having a two-electrode 2000 structure, a structure of an organic light-emitting device having various structures is possible, and it is also possible to further include one or two intermediate layers as necessary.

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

In addition, according to the present invention, since the organic material layer including the compound represented by Formula 1 can control the thickness of the organic material layer on a molecular basis, the surface thereof is uniform and excellent in shape stability.

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

Hereinafter, in order to help the understanding of the present invention, it will be described in more detail through examples of the present invention, but the following examples are only illustrative of the present invention, and the scope of the present invention is not limited by the following examples.

[Example]

Synthesis of the compound represented by Formula 1

The compound represented by Formula 1 may be synthesized by synthesizing the intermediate IM and then reacting the intermediate IM with an arylamine compound, but is not limited thereto.

Synthesis of intermediate IM 1

5.6 g of (4'-(dibenzo[b,d]furan-4-yl)-[1,1'-biphenyl]-4-yl)boronic acid and 4-bromo-4'-iodo-1 in a round bottom flask , 5.0 g of 1'-biphenyl was dissolved in 200 ml of 1,4-dioxan, 20 ml of _{K 2} CO _{3 (2M) and 7.7 g of Pd(PPh 3} ) ₄ were added and stirred under reflux. The reaction was confirmed through thin layer chromatography (TLC), and water was added to terminate the reaction. The organic layer was extracted with MC (Methylene chloride), filtered under reduced pressure, and recrystallized to obtain 4.0 g of intermediate IM 1 (yield 52%).

Synthesis of intermediates IM 2 to IM 10

Intermediates IM 2 to IM 10 were synthesized by performing the same method as the intermediate IM 1, except that the reaction starting materials were changed as shown in Table 2 below.

Specific chemical structural formulas of the intermediates IM 2 to IM 10 are shown in Table 3 below.

Synthesis of the target compound

The target compound was synthesized as follows using the intermediates IM 1 to IM 10 synthesized above.

Example 1: Synthesis of Compound 1

In a round bottom flask, the intermediates IM 1 3.0g, N,9,9-triphenyl-9H-fluoren-2-amine 2.5g, t-BuONa 0.8g, Pd ₂ (dba) ₃ 0.2g and (t-Bu) ₃ After dissolving 0.3 ml of P in 120 ml of toluene, the mixture was stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after adding water. The organic layer was extracted with MC and filtered under reduced pressure, followed by column purification and recrystallization to obtain 3.0 g (yield 67%) of compound 1.

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Example 2: Synthesis of compound 7

Compound 7 (yield 63%) was obtained in the same manner as in Example 1, except that the intermediate IM 2 was used instead of the intermediate IM 1.

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Example 3: Synthesis of Compound 9

Compound 9 (yield 60%) was obtained in the same manner as in Example 1, except that the intermediate IM 3 was used instead of the intermediate IM 1.

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Example 4: Synthesis of Compound 15

Compound 15 (yield 58%) was obtained in the same manner as in Example 1, except that the intermediate IM 4 was used instead of the intermediate IM 1.

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Example 5: Synthesis of compound 10

Compound 10 (yield 55%) was obtained in the same manner as in Example 1, except that the intermediate IM 5 was used instead of the intermediate IM 1.

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Example 6: Synthesis of Compound 18

Compound 18 (yield 57%) was obtained in the same manner as in Example 1, except that the intermediate IM 6 was used instead of the intermediate IM 1.

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Example 7: Synthesis of Compound 96

Compound 96 (yield 62%) was obtained in the same manner as in Example 1, except that the intermediate IM 7 was used instead of the intermediate IM 1.

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Example 8: Synthesis of Compound 98

Compound 98 (yield 60%) was obtained in the same manner as in Example 1, except that the intermediate IM 8 was used instead of the intermediate IM 1.

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Example 9: Synthesis of Compound 123

Compound 123 (yield 60%) was obtained in the same manner as in Example 1, except that the intermediate IM 9 was used instead of the intermediate IM 1.

m/z: 895.33 (100.0%), 896.33 (73.8%), 897.33 (26.7%), 898.34 (6.2%), 897.32 (4.5%), 898.33 (3.6%), 899.33 (1.2%), 899.34 (1.1%) )

Example 10: Synthesis of Compound 132

Compound 132 (yield 62%) was obtained in the same manner as in Example 1, except that the intermediate IM 10 was used instead of the intermediate IM 1.

m/z: 895.33 (100.0%), 896.33 (73.8%), 897.33 (26.7%), 898.34 (6.2%), 897.32 (4.5%), 898.33 (3.6%), 899.33 (1.2%), 899.34 (1.1%) )

Organic light emitting device manufacturing

Example 11: Fabrication of organic light emitting device

The glass substrate coated with indium tin oxide (ITO) to a thickness of 1,500Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonically clean with a solvent such as isopropyl alcohol, acetone, methanol, etc., dry, transfer to a plasma cleaner, and clean the substrate for 5 minutes using oxygen plasma, and then use a thermal vacuum evaporator on the top of the ITO substrate. evaporator) as a hole injection layer, HI01 600Å and HATCN 50Å, and HT01 250Å as a hole transport layer, and then a compound 100Å prepared in Example 1 as a light emission auxiliary layer was formed. Thereafter, the light emitting layer was doped with 3% BH01:BD01 to form a film of 250 Å. After that, ET01:Liq (1:1) 300 Å was formed as an electron transport layer, and then LiF 10 Å and aluminum (Al) 1,000 Å were formed, and the device was encapsulated in a glove box to form an organic light-emitting device. Was produced.

Examples 12 to 20: Fabrication of an organic light-emitting device

Organic light emitting devices of Examples 12 to 20 were manufactured in the same manner as in Example 11, except that the compound prepared in Examples 2 to 10 was used as a light emitting auxiliary layer in place of the compound prepared in Example 1, respectively. .

Comparative Examples 1 to 5: Fabrication of an organic light-emitting device

Ref. 1 to Ref. The organic light emitting devices of Comparative Examples 1 to 5 were manufactured in the same manner as in Example 11, except that 5 was used.

The materials of HI01, HATCN, HT01, BH01, BD01, ET01 and Liq used in the manufacture of the organic light emitting device are shown in Table 4 below, and the materials of Ref. 1 to Ref. 5 used in Comparative Examples 1 to 5 are shown in Table 4 below. It is shown in Table 5 below.

HI01 HATCN HT01

BH01 BD01 ET01

Liq

Ref.1 Ref.2 Ref.3

Ref.4 Ref.5

Performance evaluation of organic light emitting device

Apply voltage to Keithley 2400 source measurement unit to inject electrons and holes, and measure the luminance when light is emitted using a Konica Minolta spectroradiometer (CS-2000). As a result, the performance of the organic light-emitting devices 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 6 below.

Driving voltage
(Op. V) Current density
(mA/cm ² ) Current efficiency
(Cd/A) QE(%) Color coordinates
(CIEx) Color coordinates
(CIEy) LT95
(@1000nit) Example 11 3.5 10 7.2 6.1 0.140 0.109 160 12 3.5 10 7.6 6.6 0.139 0.110 167 13 3.5 10 7.8 6.7 0.140 0.109 172 14 3.6 10 8.0 6.9 0.140 0.110 175 15 3.6 10 8.2 7.0 0.142 0.110 170 16 3.6 10 8.2 7.1 0.140 0.109 170 17 3.6 10 7.7 6.8 0.141 0.110 166 18 3.5 10 7.8 6.7 0.140 0.109 167 19 3.7 10 8.5 7.4 0.141 0.110 155 20 3.7 10 8.4 7.2 0.140 0.110 154 Comparative example One 4.0 10 6.4 5.3 0.140 0.111 105 2 4.0 10 6.0 5.0 0.141 0.111 85 3 3.9 10 6.5 5.4 0.140 0.110 111 4 3.9 10 6.7 5.6 0.142 0.110 117 5 4.1 10 5.9 4.8 0.140 0.112 80

As shown in Table 6, Examples 11 to 20 using the compound according to the present invention as a light emitting auxiliary layer show a low driving voltage and high efficiency compared to Comparative Examples 1 to 5, and in particular, the lifespan is remarkable. It can be seen that it has increased.

Specifically, the compounds according to the present invention used in Examples 11 to 20 are Ref. 1 and Ref. 2 Compared to (a compound not having a diaryl fluorene group), it is possible to form a deep HOMO through a diaryl fluorene substituent and at the same time have a fast hole mobility, thus realizing a low driving voltage, high efficiency and long life organic light emitting device. have.

In addition, the compounds according to the present invention used in Examples 11 to 20 were used in Comparative Examples 3 and 4 of Ref. 3 and Ref. Compared to 4 (a compound having 3 or less linear linkers), the pi-conjugation increases through the expansion of 4 or more linear linkers, and the molecular arrangement is excellent when forming a thin film, which is effective in improving hole mobility and suppressing the roll-off phenomenon. It is effective in improving the driving and lifespan.

In addition, the compounds according to the present invention used in Examples 11 to 20 were used in Comparative Example 5 Ref. Compared to 5 (a compound having a carbazole group serving as an electron donor), a tricyclic compound having excellent electron resistance selected from dibenzofuran, dibenzothiophene or fluorene was introduced to have deep HOMO and high LUMO at the same time, and excitone The blocking is effective and the charge balance in the emission layer is excellent, so that an organic light emitting device having high efficiency and long life can be implemented.

From the evaluation results as described above, it is determined that the compound according to the present invention is effective in lowering the driving voltage of the organic light-emitting device and improving efficiency and lifespan.

The above description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative and non-limiting in all respects. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims to be described later rather than the detailed description, and it is interpreted that the meaning and scope of the claims, and all changes or modified forms derived from the concept of equivalents thereof are included in the scope of the present invention. It should be.

100: substrate
200: hole injection layer
300: hole transport layer
400: light-emitting layer
500: electron transport layer
600: electron injection layer
1000: first electrode
2000: second electrode

Claims (17)

Compound represented by the following formula (1):
[Formula 1]

In Formula 1,
X is O, S; Or CRR',
A is represented by the following formula 1-1,
Ar is a substituted or unsubstituted C ₆ ~C ₅₀ aryl group; Or a substituted or unsubstituted C ₅ ~C ₅₀ heteroaryl group,
R, R', R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; halogen; Nitro group; Nitrile group; A substituted or unsubstituted C ₁ ~C ₃₀ alkyl group; A substituted or unsubstituted C ₂ ~C ₃₀ alkenyl group; A substituted or unsubstituted C ₁ ~C ₃₀ alkoxy group; A substituted or unsubstituted C ₁ to C ₃₀ sulfide group; A substituted or unsubstituted C ₆ ~C ₃₀ aryl group; Or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroaryl group, wherein adjacent R and R', a plurality of R ₁ or a plurality of R ₂ may or may not form a ring with each other,
L ₁ to L ₄ are each independently a substituted or unsubstituted C ₆ to C ₃₀ arylene group; Or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroarylene group,
L ₅ is a direct bond; A substituted or unsubstituted C ₆ ~ C ₃₀ arylene group; Or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroarylene group,
l is 0 or an integer of 1 to 4,
m is 0 or an integer of 1 to 3,
[Formula 1-1]

In Formula 1-1,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ ~C ₅₀ aryl group; Or a substituted or unsubstituted C ₅ ~C ₅₀ heteroaryl group, wherein adjacent Ar ₁ and Ar ₂ may or may not form a ring with each other,
R ₃ and R ₄ are each independently hydrogen; heavy hydrogen; halogen; Nitro group; Nitrile group; A substituted or unsubstituted C ₁ ~C ₃₀ alkyl group; A substituted or unsubstituted C ₂ ~C ₃₀ alkenyl group; A substituted or unsubstituted C ₁ ~C ₃₀ alkoxy group; A substituted or unsubstituted C ₁ to C ₃₀ sulfide group; A substituted or unsubstituted C ₆ ~C ₃₀ aryl group; Or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroaryl group, wherein a plurality of adjacent R ₃ or a plurality of R ₄ may or may not form a ring with each other,
n and o are each independently 0 or an integer of 1 to 4. The method of claim 1,
Formula 1 is a compound represented by the following Formula 2:
[Formula 2]

In Chemical Formula 2,
X, Ar, R ₁ , R ₂ , l and m are as defined in claim 1,
A'is represented by the following formula 2-1,
Each R ₇ is independently hydrogen; heavy hydrogen; halogen; Nitro group; Nitrile group; A substituted or unsubstituted C ₁ ~C ₃₀ alkyl group; A substituted or unsubstituted C ₂ ~C ₃₀ alkenyl group; A substituted or unsubstituted C ₁ ~C ₃₀ alkoxy group; A substituted or unsubstituted C ₁ to C ₃₀ sulfide group; A substituted or unsubstituted C ₆ ~C ₃₀ aryl group; Or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroaryl group,
p is an integer of 4 to 8,
[Formula 2-1]

In Formula 2-1,
Ar ₁ , Ar ₂ , R ₃ and R ₄ are as defined in claim 1. The method of claim 1,
Formula 1 is a compound represented by the following Formula 3:
[Formula 3]

In Chemical Formula 3,
X, Ar, R ₁ , R ₂ , l and m are as defined in claim 1,
A" is represented by the following formula 3-1,
q is an integer of 3 or 4,
[Chemical Formula 3-1]

In Formula 3-1,
R ₃ and R ₄ are as defined in claim 1,
R ₅ and R ₆ are each independently hydrogen; heavy hydrogen; halogen; Nitro group; Nitrile group; A substituted or unsubstituted C ₁ ~C ₃₀ alkyl group; A substituted or unsubstituted C ₂ ~C ₃₀ alkenyl group; A substituted or unsubstituted C ₁ ~C ₃₀ alkoxy group; A substituted or unsubstituted C ₁ to C ₃₀ sulfide group; A substituted or unsubstituted C ₆ ~C ₃₀ aryl group; Or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroaryl group. The method according to any one of claims 1 to 3,
Wherein R, R'and R ₁ to R ₆ are each independently hydrogen, deuterium, a methyl group or a phenyl group. The method according to any one of claims 1 to 3,
Wherein X is O, the compound. The method according to any one of claims 1 to 3,
Wherein X is S, a compound. The method of claim 1,
At least one of the L ₁ to L ₄ contains a phenylene group of a meta bond, a compound. The method of claim 2,
At least one of the p phenylene groups is a phenylene group of a meta bond, the compound. The method of claim 3,
At least one of q phenylene groups is a phenylene group of a meta bond. The method according to any one of claims 1 to 3,
Ar, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted phenyl; Substituted or unsubstituted naphthyl; Substituted or unsubstituted biphenyl; Substituted or unsubstituted terphenyl; Substituted or unsubstituted phenanthrenyl; Substituted or unsubstituted triphenylenyl; Substituted or unsubstituted dibenzofuranyl; Or a substituted or unsubstituted dibenzothiophenyl, the compound. The method according to any one of claims 1 to 3,
Ar, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted phenyl; Substituted or unsubstituted biphenyl; Substituted or unsubstituted terphenyl; Substituted or unsubstituted dibenzofuranyl; Or a substituted or unsubstituted dibenzothiophenyl, the compound. The method according to any one of claims 1 to 3,
Ar is phenyl; Naphthyl or biphenyl, and Ar ₁ and Ar ₂ are both phenyl. The method according to any one of claims 1 to 3,
Ar, Ar ₁ and Ar ₂ are all phenyl, a compound. The method of claim 1,
The compound represented by Formula 1 is any one of the following compounds:

. An organic light-emitting device comprising an organic material layer containing the compound according to any one of claims 1 to 3, 7 to 9, and 14 between the first electrode and the second electrode. The method of claim 15,
The organic material layer is an organic light-emitting device comprising at least one of a hole injection layer, a hole transport layer, and a light emission auxiliary layer. The method of claim 16,
The organic material layer is an organic light emitting device that is an auxiliary light emitting layer positioned between the hole transport layer and the light emitting layer.

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