KR102519794B1 - Novel compound and organic electroluminescent divice including the same - Google Patents

Abstract

The present application relates to a novel compound and an organic light emitting device including the same. In the novel compound according to an embodiment of the present invention, a linking group is located between the 2-position of fluorene and an arylamine, and the arylamine has two An organic light emitting diode having the above substituents having an aryl group and a phenyl substituent, and including the compound according to the present invention, can implement low voltage, high efficiency, and long lifespan.

Description

Novel compound and organic light emitting device containing 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 including the same.

Materials used as the organic layer in the organic light emitting diode may be classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like according to their functions. In addition, the light emitting material can be classified into high molecular weight and low molecular weight according to molecular weight, and can 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. Materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural colors according to the light emitting color. In addition, in order to increase color purity and increase light emitting 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 a smaller energy band gap and higher luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength range of the dopant, light having a desired wavelength can be obtained according to the type of dopant and host used.

Until now, various compounds have been known as materials used in organic light emitting devices, but in the case of organic light emitting devices using known materials, development of new materials is continuously required due to high driving voltage, low efficiency, and short lifespan. Therefore, efforts have been made to develop an organic light emitting device having low voltage driving, high luminance, and long lifespan using materials having excellent characteristics.

Korean Patent Publication 10-2015-0086721

The present application provides a novel organic compound, a method for preparing the same, and an organic light emitting device including the same.

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

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

[Formula 1]

In Formula 1,

L is a substituted or unsubstituted C _6-30 arylene group or a substituted or unsubstituted C _6-30 heteroaryl group,

Ar _a And Ar _b is each independently a substituted or unsubstituted C _6-30 aryl group or a substituted or unsubstituted C _3-30 heteroaryl group containing nitrogen (provided that it is not substituted with deuterium),

R, R', R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted C _1-30 An alkyl group, a substituted or unsubstituted C _6-30 aryl group or a substituted or unsubstituted C _3-30 heteroaryl group,

R ₃ is hydrogen or a substituted or unsubstituted C _1-30 alkyl group;

l is 0 to 4, m is 0 to 3, n is 0 to 5, p is 1 to 3, q is an integer of 1 to 3, and p+q is an integer of 2 to 4.

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

In the compound according to one embodiment of the present invention, arylamine is bonded to the 2-position of fluorene through a linking group to form a deep HOMO level that is easy for the light emitting auxiliary layer and at the same time maintain a high LUMO that is easy to block electrons. . Accordingly, the compound according to one embodiment of the present invention may be used in an organic light emitting device to realize low voltage and high efficiency of the organic light emitting device.

In addition, the compound according to one embodiment of the present invention has substituents in which arylamines are linked by two or more aryls, so that pi conjugation can increase, and the molecular arrangement is excellent when forming thin films, so that fast hole mobility, roll Off-suppression is possible, so the organic light emitting device can have a long lifespan.

In addition, the compound according to one embodiment of the present invention has a substituent in which arylamine is fixed with phenyl, so that the HOMO level and LUMO level of the compound and high T1 are maintained, so that the exciton confinement effect in the light emitting layer can be maximized, resulting in high efficiency of the organic light emitting device can be achieved.

In addition, since the linking group between fluorene and arylamine and the arylamine have two or more aryl-linked substituents, Tg is improved and recrystallization of the thin film is prevented, thereby improving driving stability of the organic light emitting device.

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

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

However, the present disclosure may be embodied in many different forms and is not limited to the implementations and examples described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

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

Throughout the present specification, when a part "includes" a certain component, it means that it may further include other components without excluding other components unless otherwise stated. As used throughout this specification, the terms "about," "substantially," and the like are used at or approximating that value when manufacturing and material tolerances inherent in the stated meaning are given, and do not convey the understanding of this application. Accurate or absolute figures are used to help prevent exploitation by unscrupulous infringers of the disclosed disclosure. The term "step of (doing)" or "step of" as used throughout the present specification does not mean "step for".

Throughout the present specification, the term "combination thereof" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It means including one or more selected from the group consisting of.

Throughout this specification, reference to "A and/or B" means "A or B, or A and B".

Throughout this specification, the term "aryl" refers to a C _6-30 aromatic hydrocarbon ring group, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, peryle It means containing an aromatic ring such as yl, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzochrysenyl, anthracenyl, stilbenyl, pyrenyl, etc., and "heteroaryl" means at least one As a C _3-30 aromatic ring containing a hetero atom, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, Benzothiophenyl, dibenzothiophenyl, quinolyl group, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, thienyl, 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, thio Ofene ring, oxazole ring, oxadiazole ring, benzooxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzoimidazole ring, pyran ring, dibenzofuran It may mean including a heterocyclic group formed from a ring.

Throughout the present specification, the term "which may be substituted" refers to a halogen, an amino group, a nitrile group, a nitro group, or a C ₁ ~ C ₂₀ alkyl group, a C ₂ ~ C ₂₀ alkenyl group, a C ₁ ~ C ₂₀ alkoxy group, a C ₃ ~ C ₂₀ cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group and C ₃ ~ C ₃₀ It may mean that it may be substituted with one or more groups selected from the group consisting of a heteroaryl group. there is.

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

[Formula 1]

In Formula 1,

L is a substituted or unsubstituted C _6-30 arylene group or a substituted or unsubstituted C _3-30 heteroaryl group,

Ar _a And Ar _b is each independently a substituted or unsubstituted C _6-30 aryl group or a substituted or unsubstituted C _3-30 heteroaryl group containing nitrogen (provided that it is not substituted with deuterium),

R, R', R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted C _1-30 An alkyl group, a substituted or unsubstituted C _6-30 aryl group or a substituted or unsubstituted C _3-30 heteroaryl group,

R ₃ is hydrogen or a substituted or unsubstituted C _1-30 alkyl group;

l is 0 to 4, m is 0 to 3, n is 0 to 5, p is 1 to 3, q is an integer of 1 to 3, and p+q is an integer of 2 to 4.

In the compound of Formula 1 according to an embodiment of the present invention, an arylamine is bonded to position 2 of fluorene through a linking group, and the arylamine has one substituent having two or more aryl groups and one substituent fixed with a phenyl group. have a dog

In the compound according to one embodiment of the present invention, arylamine is bonded to position 2 of fluorene through a linking group to form a deep HOMO level that is easy for the light emitting auxiliary layer and at the same time maintain high LUMO that is easy to block electrons. there is. Accordingly, the compound according to one embodiment of the present invention may be used in an organic light emitting device to realize low voltage and high efficiency of the organic light emitting device.

In addition, the compound according to one embodiment of the present invention has substituents in which arylamines are linked with two or more aryls, so that pi conjugation can increase, and the molecular arrangement is excellent when forming a thin film, resulting in fast hole mobility, roll Off-suppression is possible, so the organic light emitting device can have a long lifespan.

In addition, the compound according to one embodiment of the present invention has a substituent in which arylamine is fixed with phenyl, so that the HOMO level and LUMO level of the compound and high T1 are maintained, so that the exciton confinement effect in the light emitting layer can be maximized, resulting in high efficiency of the organic light emitting device can be achieved.

In addition, since the linking group between fluorene and arylamine and the arylamine have two or more aryl-linked substituents, Tg is improved and recrystallization of the thin film is prevented, thereby improving driving stability of the organic light emitting device.

In one embodiment of the present invention, the Ar _a and Ar _b may be a substituted or unsubstituted C _6-30 aryl group or C _3-30 nitrogen-containing heteroaryl group, but the aryl group and heteroaryl group are not substituted with deuterium. Substitution with deuterium not only complicates the synthesis process, but in this case, it may be difficult to obtain a high-purity compound required for the hole transport layer. This may adversely affect the lifespan of the organic light emitting device.

In one embodiment of the present invention, the nitrogen-containing heteroaryl group is not limited thereto, but may be, for example, pyridine, pyrazine, triazine, or quinoline.

In addition, in one embodiment of the present invention, the compound may be represented by Formula 2 below.

[Formula 2]

In Formula 2, o is an integer of 1 to 4.

In the case of having one or more phenylenes as the linking group (L), it is possible to easily form a deep HOMO level in the light emitting auxiliary layer, and maintain a high LUMO level that is easy to block electrons.

Further, according to one embodiment of the present invention, in Formula 1 or Formula 2, R and R` are each independently a substituted or unsubstituted C _6-30 aryl group or a substituted or unsubstituted C _3-30 It may be a heteroaryl group. In this case, a deeper HOMO can be maintained, and a high Tg can be formed due to excellent molecular arrangement. Accordingly, the efficiency and lifetime of the organic light emitting device may be increased.

In addition, according to one embodiment of the present invention, in Formula 1 or Formula 2, R and R` are each independently hydrogen, substituted or unsubstituted C _1-30 An alkyl group, a substituted or unsubstituted C _6-30 aryl group, or a substituted or unsubstituted C _6-30 heteroaryl group, wherein Ar _a and Ar _b are each independently a substituted or unsubstituted C _6-30 It may be an aryl group of Ar _a And when Ar _b is a substituted or unsubstituted C _6-30 aryl group, a deep HOMO level can be maintained, and thus low voltage and high efficiency effects can be more excellent. More specifically, the Ar _a and Ar _b may be a phenyl group.

According to one embodiment of the present invention, the compound may be represented by Formula 3 below.

[Formula 3]

In Formula 3,

R ₄ and R ₅ are each independently hydrogen, substituted or unsubstituted C _1-24 An alkyl group, a substituted or unsubstituted C _6-24 aryl group or a substituted or unsubstituted C _3-24 heteroaryl group,

o is an integer from 1 to 4;

According to one embodiment of the present invention, the -(Ar _a ) _p -(Ar _b ) _q may be represented by any one of the following formulas [1-1] to [1-6].

In the formulas [1-1] to [1-6],

Ar ₁ to Ar ₄ may each independently be a substituted or unsubstituted C _6-30 aryl group or a substituted or unsubstituted C _3-30 nitrogen-containing heteroaryl group, but is not substituted with deuterium. Further, according to one embodiment of the present invention, Ar ₁ to Ar ₄ in Formulas [1-1] to [1-6] may be a phenyl group.

In addition, according to one embodiment of the present invention, it is possible to achieve a low voltage and high efficiency of an organic light emitting device by maintaining an appropriate balance of the exciton formation region in the light emitting layer by having an appropriately deep HOMO in the hole transport layer with No. 2 of fluorene as a connection position. can

In one embodiment of the present invention, the compound represented by Formula 1 may specifically be the following compound, but may not be limited thereto:

The above compounds of Nos. 1 to 210 have stable Tg, have excellent thermal stability, and are effective in improving lifespan by preventing recrystallization during device operation.

A second aspect of the present application provides an organic light emitting device including the compound represented by Formula 1 above. The organic light emitting device may include one or more organic material layers containing the compound according to the present disclosure 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, when forming the organic material layer, the compound according to the present invention may be used alone or in combination with a known compound.

In one embodiment of the present invention, the organic light emitting device may include an organic material layer containing the compound represented by Formula 1 as a light emitting auxiliary layer, but may not be limited thereto. In addition, as described above, the compound represented by Formula 1 may be a specifically specified compound.

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

For example, the organic light emitting device may be manufactured as shown in FIG. 1 . The organic light emitting element is composed of 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 injection layer 600) from the bottom The injection electrode 2000) may be stacked in order.

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

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

The hole injection layer 200 may be formed by depositing a hole injection layer material on the anode electrode by a method such as a vacuum deposition method, a spin coating method, a cast method, a Langmuir-Blodgett (LB) method, or the like. 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 desired structure and thermal characteristics of the hole injection layer, etc., but generally 50-500 The temperature, the degree of vacuum of 10 ^{- 8} to 10 ^{- 3} torr, the deposition rate of 0.01 to 100 Å/sec, and the layer thickness range of 10 Å to 5 μm can be appropriately selected.

Next, the 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 a vacuum deposition method, a spin coating method, a cast method, or an LB method. In the case of forming the hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but are generally selected within the same range of conditions as those for forming the hole injection layer.

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 one 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 one embodiment of the present invention, an auxiliary light emitting layer may be formed on the hole transport layer 300 . The light emitting auxiliary layer may use the compound according to the present invention, and several types of compounds represented by Formula 1 may be used together. In addition, the light emitting auxiliary layer may be formed by using the compound according to the present invention together with a known compound.

The light emitting layer 400 may be formed by depositing a material for the light emitting layer on the hole transport layer 300 or the light emitting auxiliary layer by a method such as a vacuum deposition method, a spin coating method, a cast method, or an LB method. In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but it is generally preferable to select them within the same range of conditions as those for forming 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, when used with a phosphorescent dopant in the light emitting layer, a hole blocking material (HBL) may be additionally laminated by vacuum deposition or spin coating to prevent diffusion of triplet excitons or holes into the electron transport layer. The hole blocking material that can be used at this time is not particularly limited, but can be selected and used arbitrarily from known ones used as hole blocking materials. For example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, or hole blocking materials described in Japanese Patent Application Laid-Open No. 11-329734 (A1) may be mentioned, and typically Balq (bis(8-hydroxy) oxy-2-methylquinolinato)-aluminum biphenoxide), phenanthrolines-based compounds (eg UDC BCP (vasocuproin)), and the like can be used.

An electron transport layer 500 is formed on the light emitting layer 400 formed as described above. At this time, the electron transport layer can be formed by a method such as a vacuum deposition method, a spin coating method, a cast method, or the like. In addition, although the deposition conditions of the electron transport layer vary depending on the compound used, it is generally preferable to select them within the same range of conditions as those for forming the hole injection layer.

Thereafter, an electron injection layer material may be deposited on the electron transport layer 500 to form an electron injection layer 600. It can be formed by methods such as law.

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

A 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 have a structure of various organic light emitting devices as well as an organic light emitting device having an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode structure. It is also possible to further form a layer or two intermediate layers.

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, 10 to 1,000 nm, and more specifically, 20 to 150 nm.

In the present invention, since the thickness of the organic material layer including the compound represented by Chemical Formula 1 can be controlled in a molecular unit, the surface is uniform and the shape stability is excellent.

All of the contents described in the first aspect of the present disclosure may be applied to the organic light emitting compound according to the present aspect, but may not be limited thereto.

Hereinafter, it will be described in more detail through examples of the present application, and the scope of the present application is not limited by the present examples.

[Example]

intermediate synthesis

For the synthesis of the target compound, the intermediate IM was synthesized by the same reaction as above.

synthesis example 1: intermediate (IM1) synthesis

In a round bottom flask, 8.5 g of (9,9-dimethyl-9H-fluoren-2-yl)boronic acid and 10.0 g of 1-bromo-4-iodobenzene were dissolved in 200 ml of 1,4-dioxan, and 50 ml of K2CO3 (2M) and Pd ( After adding 1.3 g of PPh ₃ ) ₄ , 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, filtered under reduced pressure, and purified by column to obtain 8.27 g of intermediate IM1-1 (yield: 67%).

After dissolving 8.0 g of IM1-1, 2.4 g of aniline, 3.3 g of t-BuONa, 0.85 g of Pd ₂ (dba) ₃ , and 1.0 ml of (t-Bu) ₃ P in 110 ml of toluene in a round bottom flask, 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 6.04 g of IM1 (yield: 73%).

Synthesis Examples 2 to 4: Synthesis of intermediates (IM2 to IM4)

Intermediates IM2 to IM4 were synthesized using the same method as for Intermediate IM1, but using different starting materials as shown in Table 1 below.

synthesis example starting material intermediate 2

9,9-dimethyl-9H-fluoren-2-yl)boronic acid

9,9-dimethyl-9H-fluoren-2-yl)boronic acid

4-bromo-4'-iodo-1,1'-biphenyl

3

9,9-diphenyl-9H-fluoren-2-yl)boronic acid

1-bromo-4-iodobenzene

4

9,9-diphenyl-9H-fluoren-2-yl)boronicacid

4-bromo-4'-iodo-1,1'-biphenyl

compound synthesis

Synthesis of Compound 1

In a round bottom flask, IM1 3.0g, 4-bromo-1,1':4',1''-terphenyl 2.5g, t-BuONa 1.2g, Pd ₂ (dba) ₃ 0.3g, (t-Bu) ₃ P0 After dissolving .3ml in 60ml 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 3.34 g of Compound 1 (70% yield).

Synthesis of compound 2

The same method as in Compound 1 was used, but instead of 4-bromo-1,1':4',1''-terphenyl, 4-bromo-1,1':4',1'':4'',1'' Compound 2 was synthesized using '-quaterphenyl.

Synthesis of compound 3

Compound 3 was synthesized in the same manner as in Compound 1, but using IM2 instead of IM1.

Synthesis of compound 4

Using the same method as in Compound 1, but using IM2 and 4-bromo-1,1':3',1''-terphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl Thus, compound 4 was synthesized.

Synthesis of compound 5

Using the same method as in Compound 1, but using IM2 and 4-bromo-1,1':2',1''-terphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl Thus, compound 5 was synthesized.

Synthesis of compound 6

Compound 6 was synthesized in the same manner as in Compound 1, but using IM3 and 4-bromo-1,1'-biphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl.

Synthesis of compound 7

Compound 7 was synthesized in the same manner as in Compound 1, but using IM3 instead of IM1.

Synthesis of compound 8

Using the same method as in Compound 1, but using IM3 and 4-bromo-1,1':3',1''-terphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl Thus, compound 8 was synthesized.

Synthesis of compound 9

Using the same method as in Compound 1, but using IM3 and 4-bromo-1,1':2',1''-terphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl Thus, compound 9 was synthesized.

Synthesis of compound 10

Using the same method as in Compound 1, but using IM3 and 3-bromo-1,1':4',1''-terphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl Thus, compound 10 was synthesized.

Synthesis of compound 11

Using the same method as in Compound 1, but using IM3 and 3-bromo-1,1':3',1''-terphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl Thus, compound 11 was synthesized.

Synthesis of compound 12

Using the same method as in Compound 1, but using IM3 and 3-bromo-1,1':2',1''-terphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl Thus, compound 12 was synthesized.

Synthesis of compound 13

Using the same method as in Compound 1, but using IM3 and 2-bromo-1,1':4',1''-terphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl Thus, compound 13 was synthesized.

Synthesis of compound 14

Using the same method as in Compound 1, but using IM3 and 2-bromo-1,1':3',1''-terphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl Thus, compound 14 was synthesized.

Synthesis of compound 15

Using the same method as in Compound 1, but using IM3 and 2-bromo-1,1':2',1''-terphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl Thus, compound 15 was synthesized.

Synthesis of compound 16

Compound 16 was synthesized in the same manner as in Compound 1, but using IM4 and 4-bromo-1,1'-biphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl.

Synthesis of compound 17

Compound 17 was synthesized in the same manner as in Compound 1, but using IM4 and 3-bromo-1,1'-biphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl.

Synthesis of compound 18

Compound 18 was synthesized in the same manner as in Compound 1, but using IM4 and 2-bromo-1,1'-biphenyl instead of IM1 and 4-bromo-1,1':4',1''-terphenyl.

Synthesis of compound 19

Using the same method as for compound 1, but replacing IM1 and 4-bromo-1,1':4',1''-terphenyl with IM3 and 4-bromo-5'-phenyl-1,1':3',1' Compound 19 was synthesized using '-terphenyl.

Synthesis of compound 20

The same method as for compound 1 was used, but instead of IM1 and 4-bromo-1,1':4',1''-terphenyl, IM3 and 2-bromo-5'-phenyl-1,1':3',1' Compound 20 was synthesized using '-terphenyl.

The specific chemical formulas of Compounds 1 to 20 synthesized above are shown in [Table 2] below.

compound chemical formula transference number(%) FD-MS One

70 m/z: 589.28 (100.0%), 590.28 (49.1%), 591.28 (11.8%), 592.29 (1.8%) 2

72

m/z: 665.31 (100.0%), 666.31 (56.0%), 667.31 (15.1%), 668.32 (2.7%) 3

75 m/z: 665.31 (100.0%), 666.31 (56.0%), 667.31 (15.1%), 668.32 (2.7%) 4

70 m/z: 665.31 (100.0%), 666.31 (56.0%), 667.31 (15.1%), 668.32 (2.7%) 5

70 m/z: 665.31 (100.0%), 666.31 (56.0%), 667.31 (15.1%), 668.32 (2.7%) 6

75 m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%) 7

70 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 8

68 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 9

72 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 10

65 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 11

60 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 12

62 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 13

70 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 14

65 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 15

65 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 16

72 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 17

60 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 18

69 m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%) 19

65 m/z: 789.34 (100.0%), 790.34 (66.3%), 791.35 (21.7%), 792.35 (4.7%) 20

61 m/z: 789.34 (100.0%), 790.34 (66.3%), 791.35 (21.7%), 792.35 (4.7%)

Organic light emitting device manufacturing

Example One

A glass substrate coated with indium tin oxide (ITO) having a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After cleaning with distilled water, it is ultrasonically cleaned with solvents such as isopropyl alcohol, acetone, and methanol, dried, transferred to a plasma cleaner, and then cleaned by using oxygen plasma for 5 minutes. evaporator) to form a hole injection layer of HI01 of 600 Å and HATCN of 50 Å, a hole transport layer of BPA of 250 Å, and a light emitting auxiliary layer of 100 Å of Compound 1, and then the light emitting layer was doped with 3% of BH01:BD01 to form a 250 Å film. Next, an organic light emitting device was manufactured by forming a 300 Å film of ET01:Liq (1:1) as an electron transport layer, forming a film of 10 Å LiF and 1000 Å of aluminum (Al), and encapsulating the device in a glove box.

Examples 2 to 20

Using the same method as in Example 1, but using Compounds 2 to 20 instead of Compound 1, an organic light emitting device formed into a film was manufactured.

Comparative Examples 1 to 9

Using the same method as in Example 1, but using Ref.1 to Ref.9 of [Table 4] instead of Compound 1, respectively, an organic light emitting device formed into a film was manufactured.

[Performance evaluation of organic light emitting device]

Apply voltage to the 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) By doing so, the performance of the organic light emitting devices of Examples and Comparative Examples was evaluated by measuring current density and luminance with respect to applied voltage under atmospheric pressure conditions, and the results are shown in [Table 5].

Op. V mA/cm2 Cd/A QE (%) CIEx CIEy LT95 Example 1 3.96 10 7.22 6.14 0.140 0.109 115 Example 2 3.95 10 7.25 6.10 0.140 0.110 112 Example 3 3.94 10 7.29 6.19 0.141 0.110 115 Example 4 3.95 10 7.25 6.12 0.140 0.110 110 Example 5 3.94 10 7.27 6.15 0.141 0.110 115 Example 6 3.91 10 7.34 6.23 0.140 0.110 142 Example 7 3.89 10 7.45 6.33 0.140 0.110 156 Example 8 3.90 10 7.53 6.40 0.140 0.111 162 Example 9 3.89 10 7.50 6.42 0.139 0.111 166 Example 10 3.92 10 7.60 6.49 0.141 0.110 162 Example 11 3.93 10 7.62 6.50 0.140 0.110 169 Example 12 3.92 10 7.59 6.50 0.140 0.110 160 Example 13 3.89 10 7.49 6.35 0.140 0.110 165 Example 14 3.90 10 7.52 6.43 0.139 0.111 169 Example 15 3.89 10 7.50 6.40 0.141 0.110 170 Example 16 3.91 10 7.37 6.25 0.140 0.110 147 Example 17 3.93 10 7.40 6.27 0.140 0.110 150 Example 18 3.90 10 7.37 6.23 0.141 0.110 152 Example 19 3.94 10 7.41 6.29 0.140 0.110 165 Example 20 3.95 10 7.43 6.30 0.140 0.109 160 Comparative Example 1 4.40 10 6.45 5.60 0.14 0.111 13 Comparative Example 2 4.20 10 6.77 4.06 0.143 0.113 55 Comparative Example 3 4.22 10 6.90 4.04 0.141 0.113 18 Comparative Example 4 4.10 10 7.10 5.28 0.141 0.112 60 Comparative Example 5 4.13 10 7.00 4.10 0.141 0.111 85 Comparative Example 6 4.18 10 6.95 5.64 0.142 0.112 76 Comparative Example 7 4.05 10 7.05 4.23 0.141 0.113 105 Comparative Example 8 4.11 10 7.06 6.00 0.140 0.115 97 Comparative Example 9 4.30 10 7.00 5.97 0.140 0.112 81

As shown in [Table 5], it can be seen that the embodiments of the present invention are superior in physical properties in all respects, such as lower driving voltage and increased efficiency and lifespan, compared to Comparative Examples 1 to 8.

More specifically, comparing Comparative Examples 1 and 2, which do not have a linking group between fluorene and arylamine, and the embodiment of the present invention, the embodiment of the present invention has a linking group between fluorene and arylamine, so that the light emitting auxiliary layer A deep HOMO level can be easily formed, and a high LUMO with easy electron blocking can be maintained, resulting in low voltage and high efficiency compared to Comparative Examples 1 and 2.

In addition, compared to Comparative Examples 3 and 4, in which both aryl groups of arylamines have phenyl groups or methyl phenyl groups, in the embodiment of the present invention, two or more aryl groups are introduced into one of the two aryl substituents of arylamines, resulting in conjugation of the compound. It can increase, has excellent thin film and molecular arrangement, has faster hole mobility than Comparative Examples 3 and 4, and exhibits long life through roll-off suppression.

In addition, compared with Comparative Example 5 in which one of the two aryl substituents of the arylamine is naphthyl and Comparative Examples 6 and 7 in which both of the two aryl substituents of the arylamine are biphenyl, the embodiment of the present invention The side is fixed with a phenyl group, so the LUMO level, which is easy to block electrons, is maintained, and the exciton confinement effect in the light emitting layer is maximized by forming a high T1, thereby exhibiting high efficiency.

In addition, compared to Comparative Example 8 in which the arylamine has a dibenzofuran group, the embodiment of the present invention does not include a heterocyclic group having heteroatoms such as O and S, which serve as an electron donor, so that a deep HOMO level can be maintained, resulting in low voltage and high efficiency.

In addition, compared to Comparative Example 9 in which fluorene No. 3 is connected, the embodiment of the present invention has an appropriately deep HOMO as a hole transport layer, maintains an appropriate balance of the exciton formation region in the light emitting layer, and achieves low voltage and high efficiency. showed up

The above description of the present application is for illustrative purposes, and those skilled in the art will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting. 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 above, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts thereof 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 (10)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
L is a 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 cycloalkyl group, C ₃ ~ A C _6-30 arylene group unsubstituted or substituted with one or more groups selected from the _group consisting of a C 20 heterocycloalkyl group, a C ₆ ~ C ₃₀ aryl group, and a C ₃ ~ C ₃₀ heteroaryl group; Or 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 cycloalkyl group, C ₃ ~ C _{A 20} -membered heterocycloalkyl group, a C 3-30 heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of a C ₆ ~ C ₃₀ aryl group and a C _{3 ~ C 30 heteroaryl} group,
Ar _a and Ar _b are each independently a halogen, an amino group, a nitrile group, a nitro group, or a C ₁ ~ C ₂₀ alkyl group, a C ₂ ~ C ₂₀ alkenyl group, a C ₁ ~ C ₂₀ alkoxy group, a C ₃ ~ C ₂₀ A cycloalkyl group, a C ₃ ~ C ₂₀ heterocycloalkyl group, a C ₆ ~ C ₃₀ aryl group, and a C ₃ ~ C ₃₀ unsubstituted or substituted with one or more groups selected from the group consisting of a heteroaryl group of C _6-30 an aryl group (provided that it is not substituted with deuterium);
The sum of carbon atoms of L, Ar _a and Ar _b is greater than or equal to C19, or Ar _a contains meta- or ortho-phenylene;
R and R' are each independently a halogen, an amino group, a nitrile group, a nitro group, or a C ₁ ~ C ₂₀ alkyl group, a C ₂ ~ C ₂₀ alkenyl group, a C ₁ ~ C ₂₀ alkoxy group, a C ₃ ~ C ₂₀ C _6-30 aryl unsubstituted or substituted with one or more groups selected from the group consisting _of cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group and C ₃ ~ C 30 heteroaryl group energy; Or 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 cycloalkyl group, C ₃ ~ C _{A 20} -membered heterocycloalkyl group, a C _3-30 heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of a C ₆ ~ C 30 aryl group and a C _{3 ~ C 30 heteroaryl} group,
R ₁ and R ₂ are each independently hydrogen; 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 cycloalkyl group, C ₃ ~ C ₂₀ of C 1-30 unsubstituted or substituted with one or _more groups selected from the group consisting of a heterocycloalkyl group, a C ₆ ~ C ₃₀ aryl group, and a C ₃ ~ C ₃₀ heteroaryl group; an alkyl group; 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 cycloalkyl group, C ₃ ~ C ₂₀ A C _6-30 aryl group unsubstituted or substituted with one _or more groups selected from the group consisting of a heterocycloalkyl group, a C ₆ ~ C 30 aryl group, and a C ₃ ~ C ₃₀ heteroaryl group; 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 cycloalkyl group, C ₃ ~ C ₂₀ A C 3-30 heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of a heterocycloalkyl group, a C ₆ ~ C ₃₀ aryl group, and a C _{3 ~ C 30 heteroaryl} group,
R ₃ is hydrogen; Or 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 cycloalkyl group, C ₃ ~ C _{A 20} -membered heterocycloalkyl group, a C 1-30 alkyl group unsubstituted or substituted _with one or more groups selected from the group consisting of a C ₆ ~ C ₃₀ aryl group and a C ₃ ~ C ₃₀ heteroaryl group,
l is 0 to 4, m is 0 to 3, n is 0 to 5, p is 1 to 3, q is an integer of 1 to 3, and p+q is an integer of 2 to 4. According to claim 1,
The compound is a compound represented by the following [Formula 2]:
[Formula 2]

In Formula 2,
o is an integer from 1 to 4; According to claim 1,
R and R` are each independently a halogen, an amino group, a nitrile group, a nitro group, or a C ₁ ~C ₂₀ alkyl group, a C ₂ ~C ₂₀ alkenyl group, a C ₁ ~C ₂₀ alkoxy group, a C ₃ ~C ₂₀ cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group and C ₃ ~ C ₃₀ heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of C _6-30 of the aryl group; Or 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 cycloalkyl group, C ₃ ~ C _{A 20} -membered heterocycloalkyl group, a C ₆ ~ C ₃₀ aryl group, and a C ₃ ~ C ₃₀ heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of a C _3-30 heteroaryl group compound. According to claim 1,
The compound is a compound represented by the following [Formula 3]:
[Formula 3]

In Formula 3,
R ₄ and R ₅ are each independently hydrogen; 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 cycloalkyl group, C ₃ ~ C ₂₀ of C _1-24 unsubstituted or substituted with one or more groups selected from the group consisting of a heterocycloalkyl group, a C ₆ ~ C ₃₀ aryl group, and a C ₃ ~ C ₃₀ heteroaryl group; an alkyl group; 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 cycloalkyl group, C ₃ ~ C ₂₀ A C _6-24 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a heterocycloalkyl group, a C ₆ ~ C ₃₀ aryl group, and a C ₃ ~ C ₃₀ heteroaryl group; Or 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 cycloalkyl group, C ₃ ~ C _{A 20} -membered heterocycloalkyl group, a C _3-24 heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of a C ₆ ~ C ₃₀ aryl group and a C ₃ ~ C ₃₀ heteroaryl group,
o is an integer from 1 to 4; According to claim 1,
Wherein -(Ar _a ) _p -(Ar _b ) _q is a compound represented by any one of the following formulas [1-1] to [1-6]:

In the formulas [1-1] to [1-6],
Ar ₁ to Ar ₄ are each independently a halogen, an amino group, a nitrile group, a nitro group, or a C ₁ ~ C ₂₀ alkyl group, a C ₂ ~ C ₂₀ alkenyl group, a C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₂₀ A cycloalkyl group, a C ₃ ~ C ₂₀ heterocycloalkyl group, a C ₆ ~ C ₃₀ aryl group, and a C ₃ ~ C ₃₀ unsubstituted or substituted with one or more groups selected from the group consisting of a heteroaryl group of C _6-30 aryl group; Or 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 cycloalkyl group, C ₃ ~ C It is a ₂₀ -membered heterocycloalkyl group, a C 3-30 nitrogen-containing heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of a C ₆ ~ C ₃₀ aryl group and a C _{3 ~ C 30 heteroaryl} group. (but not substituted with deuterium). According to claim 5,
above Ar ₁ to Ar ₄ is a phenyl group. According to claim 1,
The compound 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 7 between the first electrode and the second electrode. According to claim 8,
The organic material layer is an organic light emitting device that is at least one layer of a hole injection layer, a hole transport layer, and a light emitting auxiliary layer. According to claim 8,
The organic material layer is an organic light emitting device that is a light emitting auxiliary layer.

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