KR102575687B1 - 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, and the novel compound according to one embodiment of the present invention is applied to an organic light emitting device to achieve high efficiency, long lifespan, low driving voltage and driving stability of the organic light emitting device. can be secured

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 organic layers in organic light emitting diodes can be largely classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like according to their functions. And the light emitting materials can be classified into high molecular weight and low molecular weight according to molecular weight, and can be classified into fluorescent materials derived from singlet excited states of electrons and phosphorescent materials derived from triplet excited states of electrons according to light emitting mechanisms, Light emitting materials can 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 a material 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,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group or a substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group;

L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C ₆ ~ C ₁₈ arylene group, or a substituted or unsubstituted C ₃ ~ C ₃₀ heteroarylene group,

R ₁ to R ₇ , R and R' are each independently hydrogen, heavy hydrogen, a substituted or unsubstituted C ₁ ~ C ₃₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₃₀ alkoxy group, a substituted or unsubstituted C ₂ ~ A C ₃₀ alkenyl group, a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, or a substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group, wherein R and R' may be linked to form a ring,

l, m, and n are each independently an integer of 0 to 4, o is an integer of 0 to 2, and p and q are each independently an integer of 0 to 3.

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.

The compound according to one embodiment of the present invention introduces a fluorene linking group between spirobifluorene and arylamine to form a HOMO level that is easy for hole transport, and at the same time, spirobifluorene number 1, 3, or It is easy to block the electrons by maintaining a high LUMO level with No. 4 as the connection position. Accordingly, excitons in the light emitting layer are efficiently formed, so that a low voltage and high efficiency organic light emitting device can be implemented.

In addition, since spirobifluorene is linked to arylamine through a fluorene linking group to increase pi conjugation, it can have fast hole mobility. It is possible to improve thin film arrangement, improve mobility in a thin film, and suppress a roll-off phenomenon, so that a long lifespan device can be implemented.

In addition, since it has high Tg and Td, it has excellent thermal stability and prevents recrystallization of the thin film during driving, thereby securing driving stability of the 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 _5-30 aromatic hydrocarbon ring group, for example, 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 specification, the term "which may be substituted" refers to deuterium, halogen, amino group, nitrile group, nitro group, or C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₂₀ cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group and C ₃ ~ C ₃₀ means that can be substituted with one or more groups selected from the group consisting of a heteroaryl group can do. In addition, the same symbol throughout the present specification may have the same meaning unless otherwise specified.

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

[Formula 1]

In Formula 1,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group or a substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group;

L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C ₆ ~ C ₁₈ arylene group, or a substituted or unsubstituted C ₃ ~ C ₃₀ heteroarylene group,

R ₁ to R ₇ , R and R' are each independently hydrogen, heavy hydrogen, a substituted or unsubstituted C ₁ ~ C ₃₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₃₀ alkoxy group, a substituted or unsubstituted C ₂ ~ A C ₃₀ alkenyl group, a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, or a substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group, wherein R and R' may be linked to form a ring,

l, m, and n are each independently an integer of 0 to 4, o is an integer of 0 to 2, and p and q are each independently an integer of 0 to 3.

The compound of Formula 1 introduces a fluorene linking group between spirobifluorene and arylamine to form a HOMO level that is easy for hole transport, and at the same time connects 1, 3, or 4 of spirobifluorene It is easy to block electrons by maintaining a high LUMO level by positioning it. Accordingly, excitons in the light emitting layer are efficiently formed, so that a low voltage and high efficiency organic light emitting device can be implemented.

In addition, since spirobifluorene is linked to arylamine through a fluorene linking group to increase pi conjugation, it can have fast hole mobility. It is possible to improve thin film arrangement, improve mobility in a thin film, and suppress a roll-off phenomenon, so that a long lifespan device can be implemented.

In addition, since it has high Tg and Td, it has excellent thermal stability and prevents recrystallization of the thin film during driving, thereby securing driving stability of the device.

In one embodiment of the present invention, in Formula 1, Ar ₁ and Ar ₂ are each independently phenyl, biphenyl, terphenyl, naphthyl, fluorene, anthracene, phenanthrene, triphenylene, dibenzofuran, di It may be selected from the group consisting of benzothiophene and combinations thereof. More specifically, in Formula 1, Ar ₁ and Ar ₂ may each independently be selected from the group consisting of phenyl, biphenyl, fluorene, dibenzofuran, dibenzothiophene, and combinations thereof. In this case, the exciton blocking effect can be maximized by having a high T1.

In addition, in one embodiment of the present invention, the compound may be represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

The compound represented by Chemical Formula 2 or Chemical Formula 3 may have a relatively low molecular weight compared to the case of having both the linking groups L ₁ and L ₂ , so that the deposition temperature may be lowered. Accordingly, thermal stability may be obtained during manufacturing of the organic light emitting device.

In one embodiment of the present invention, L ₁ and L ₂ in Chemical Formulas 1 to 3 may each independently represent a direct bond or phenylene.

In one embodiment of the present invention, the compound may be represented by Formula 4 below.

[Formula 4]

In the compound represented by Chemical Formula 4, since fluorene is directly bonded to arylamine and spirobifluorene, high LUMO may be maintained, and thus electron blocking may be more easily performed.

In one embodiment of the present invention, the compound may be represented by any one of Formulas 5 to 7 below.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In the compound represented by Chemical Formula 8, arylamine and spirobifluorene are bonded to positions 2 and 7 of fluorene, which is an intermediate linking group, so that the overall linearity is maintained, resulting in excellent molecular arrangement, thereby exhibiting fast hole mobility ( hole mobility).

In one embodiment of the present invention, in Formulas 2 to 11, Ar ₁ and Ar ₂ are each independently selected from phenyl, biphenyl, terphenyl, naphthyl, fluorene, anthracene, phenanthrene, triphenylene, and dibenzo. It may be selected from the group consisting of furan, dibenzothiophene, and combinations thereof. More specifically, in Formulas 2 to 11, Ar ₁ and Ar ₂ may each independently be selected from the group consisting of phenyl, biphenyl, fluorene, dibenzofuran, dibenzothiophene, and combinations thereof. In this case, the exciton blocking effect can be maximized by having a high T1.

According to one embodiment of the present invention, the compound represented by Chemical Formulas 1 to 8 may be any one of the following compounds, but may not be limited thereto:

In one embodiment of the present invention, the compound represented by Formula 1 is more specifically, compound numbers 1 to 19, 21 to 26, 101 to 104, 130 to 140, 141 to 146, 161 to 166, 191 ~194, 201, 206~208, 231~234, 241, 246~248, 351~369, 371~376, 451~454, 480~491, 519~526, 551~554, 561, 591~594, 601 , 602 to 608, 711 to 729, 731 to 736, 811 to 814, 840 to 851, 869 to 876, 901 to 904, 911, 916 to 918, 941 to 944, 951, may be any one of 956 to 958 . These compounds can reduce excessive conjugation and minimize molecular weight, thereby maintaining appropriate HOMO and at the same time having higher LUMO and T1, and suppressing thermal decomposition of the compound during the deposition process.

According to one embodiment of the present invention, the compound represented by Formula 1 may be synthesized through the following reaction scheme, but may not be limited thereto.

In the above reaction scheme, h is a halogen, and other symbols are the same as in Formula 1 above.

A second aspect of the present application provides an organic light emitting device including a compound represented by any one of Chemical Formulas 1 to 8. 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, the compound of the present invention may be used alone or in combination with known compounds when forming an organic layer.

In one embodiment of the present invention, the organic light emitting device may include an organic material layer containing a hole transport material and an organic material layer containing a compound represented by Formula 1, but may not be limited thereto. According to one embodiment of the present invention, as described above, the compound of Formula 1 may be represented by any one of Formulas 2 to 8.

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 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, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or a hole blocking material described in Japanese Patent 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, 1 to 1,000 nm, and more specifically, 5 to 200 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 as follows.

Preparation Example 1 : Intermediate (IM1) synthesis

In a round bottom flask, 5.12 g of 9,9'-spirobi[fluoren]-3-ylboronic acid and 10.0 g of 2,7-dibromo-9,9-dimethyl-9H-fluorene were dissolved in 220 ml of 1,4-dioxan and K2CO3 (2M ) 45 ml and 1.0 g of Pd(PPh3)4 were added, followed by reflux stirring. 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 11.2 g of intermediate IM1 (yield: 68%).

The following IM2 to IM6 were synthesized using the same method as in IM1, but using different starting materials as shown in Table 1 below.

Starting material for IM2 Starting material for IM3 IM4 starting material , , , 9,9'-spirobi[fluoren]-6-ylboronic acid, 2,7-dibromo-9,9-diphenyl-9H-fluorene 9,9'-spirobi[fluoren]-5-ylboronic acid, 2,7-dibromo-9,9-dimethyl-9H-fluorene 9,9'-spirobi[fluoren]-5-ylboronic acid, 2,7-dibromo-9,9-diphenyl-9H-fluorene Starting material for IM5 Starting material for IM6 , , 9,9'-spirobi[fluoren]-8-ylboronic acid, 2,7-dibromo-9,9-dimethyl-9H-fluorene 9,9'-spirobi[fluoren]-8-ylboronic acid, 2,7-dibromo-9,9-diphenyl-9H-fluorene

compound synthesis

Target compounds 1 to 20 were synthesized using the intermediates IM1 to IM6.

Synthesis of Compound 1

In a round bottom flask, IM1 3.0g, 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine 1.5g, t-BuONa 0.75g, Pd ₂ (dba) ₃ 0.2g, (t-Bu) ₃ P After dissolving 0.2ml in 90ml 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 2.9 g of Compound 1 (72% yield). m/z: 791.36 (100.0%), 792.36 (66.5%), 793.36 (22.0%), 794.37 (4.7%)

Synthesis of compound 2

Use N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine instead of 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (yield 70%) m/z: 867.39 (100.0%), 868.39 (73.0%), 869.39 (26.1%), 870.40 (6.2%), 871.40 (1.1%) )

Synthesis of compound 3

Using 9,9-dimethyl-N-(naphthalen-1-yl)-9H-fluoren-2-amine instead of 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine, in the same manner as in Compound 1 Compound 3 was synthesized. (Yield 63%) m/z: 841.37 (100.0%), 842.37 (70.7%), 843.38 (24.7%), 844.38 (5.7%)

Synthesis of compound 4

Compound 4 was synthesized in the same manner as in Compound 1 using IM2 instead of IM1. (Yield 65%) m/z: 917.40 (100.0%), 918.41 (77.4%), 919.41 (29.5%), 920.41 (7.3%) , 921.42 (1.4%)

Synthesis of compound 5

Compound 5 was synthesized in the same manner as in Compound 1 using IM3 instead of IM1. (Yield 63%) m/z: 791.36 (100.0%), 792.36 (66.5%), 793.36 (22.0%), 794.37 (4.7%)

Synthesis of compound 6

Instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine, IM3 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2 Compound 6 was synthesized in the same manner as in Compound 1 using -amine. (Yield 65%) m/z: 867.39 (100.0%), 868.39 (73.0%), 869.39 (26.1%), 870.40 (6.2%), 871.40 (1.1%)

Synthesis of compound 7

Instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine, IM3 and N-([1,1'-biphenyl]-3-yl)-9,9-dimethyl-9H-fluoren-2 Compound 7 was synthesized in the same manner as in Compound 1 using -amine. (Yield: 58%) 871.40 (1.1%)

Synthesis of compound 8

IM3 and N-([1,1'-biphenyl]-2-yl)-9,9-dimethyl-9H-fluoren-2 instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine Compound 8 was synthesized in the same manner as in Compound 1 using -amine. (Yield 63%) m/z: 867.39 (100.0%), 868.39 (73.0%), 869.39 (26.1%), 870.40 (6.2%), 871.40 (1.1%)

Synthesis of compound 9

Compound 9 was synthesized in the same manner as in Compound 1 using IM5 instead of IM1. (Yield 60%) m/z: 791.36 (100.0%), 792.36 (66.5%), 793.36 (22.0%), 794.37 (4.7%)

Synthesis of compound 10

IM5 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2 instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine Compound 10 was synthesized in the same manner as in Compound 1 using -amine. (Yield 61%) m/z: 867.39 (100.0%), 868.39 (73.0%), 869.39 (26.1%), 870.40 (6.2%), 871.40 (1.1%)

Synthesis of compound 11

Compound 11 was synthesized in the same manner as in Compound 1 using N-phenyl-[1,1'-biphenyl]-4-amine instead of 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine. Yield 65%) m/z: 751.32 (100.0%), 752.33 (63.2%), 753.33 (19.6%), 754.33 (4.0%)

Synthesis of compound 12

Compound 12 was prepared in the same manner as in Compound 1 using 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine and 4-(dibenzo[b,d]furan-4-yl)-N-phenylaniline instead. Synthesized (yield 63%) m/z: 841.33 (100.0%), 842.34 (69.8%), 843.34 (24.2%), 844.34 (5.5%)

Synthesis of compound 13

Compound 13 was synthesized in the same manner as Compound 1 using IM2 and diphenylamine instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine. (Yield 60%) m/z: 799.32 (100.0 %), 800.33 (67.5%), 801.33 (22.4%), 802.33 (4.9%)

Synthesis of compound 14

Compound 14 was prepared in the same manner as in Compound 1 using IM2 and N-phenyl-[1,1'-biphenyl]-4-amine instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine. synthesized. (Yield 65%) m/z: 875.36 (100.0%), 876.36 (74.1%), 877.36 (27.3%), 878.37 (6.5%), 879.37 (1.1%)

Synthesis of compound 15

Compound 15 was prepared in the same manner as in Compound 1 using IM3 and N-phenyl-[1,1'-biphenyl]-4-amine instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine. Synthesized (yield 65%) m/z: 751.32 (100.0%), 752.33 (63.2%), 753.33 (19.6%), 754.33 (4.0%)

Synthesis of compound 16

IM3 and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2- instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine Compound 16 was synthesized in the same manner as in Compound 1 using amine. (Yield 62%) m/z: 827.36 (100.0%), 828.36 (69.7%), 829.36 (24.2%), 830.37 (5.4%)

Synthesis of compound 17

Compound 17 was synthesized in the same manner as in Compound 1, using IM4 and diphenylamine instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine. (Yield 67%) m/z: 799.32 (100.0%), 800.33 (67.5%), 801.33 (22.4%), 802.33 (4.9%)

Synthesis of compound 18

Compound 18 was prepared in the same manner as in Compound 1 using IM4 and N-phenyl-[1,1'-biphenyl]-4-amine instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine. synthesized. (Yield 67%) m/z: 875.36 (100.0%), 876.36 (74.1%), 877.36 (27.3%), 878.37 (6.5%), 879.37 (1.1%)

Synthesis of compound 19

Compound 19 was prepared in the same manner as in Compound 1 using IM5 and di([1,1'-biphenyl]-4-yl)amine instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine. synthesized. (Yield 63%) m/z: 827.36 (100.0%), 828.36 (69.7%), 829.36 (24.2%), 830.37 (5.4%)

Synthesis of compound 20

Compound 20 was synthesized in the same manner as in Compound 1, using IM6 and diphenylamine instead of IM1 and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine. (Yield 58%) m/z: 799.32 (100.0%), 800.33 (67.5%), 801.33 (22.4%), 802.33 (4.9%)

Manufacture of organic light emitting devices

Example 1 (hole transport layer )

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? and a hole transport layer of 250 Å of Compound 1, and then a 250 Å film of 250 Å was formed by doping with 3% of BH01:BD01 as the light emitting layer. 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.

Example 2 to Example 10

In the same manner as in Example 1, a film-formed organic light emitting device was manufactured using Compounds 2 to 10 instead of Compound 1.

comparative example 1-1 to comparative example 1-8

In the same manner as in Example 1, an organic light emitting device formed into a film was manufactured using the following Ref.1 to Ref.8 instead of Compound 1.

Example 11 (light emission auxiliary layer )

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 HI01 600 Å, HATCN 50 Å?, a hole transport layer BPA 250 Å, and a light emitting auxiliary layer of Compound 11 350 Å, and then host PH01:PH02 (5:5) and dopant Ir as the light emitting layer A 350 Å film was formed by doping with 7% of (ppy)3. 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.

Example 12 to Example 20

In the same manner as in Example 11, a film-formed organic light emitting device was manufactured using Compounds 12 to 20 instead of Compound 11.

comparative example 2-1 to comparative example 2-8

In the same manner as in Example 11, an organic light emitting device formed by using Ref.1 to Ref.8 instead of Compound 11 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 2 (Hole transport layer examples) and Table 3 (light emitting auxiliary layer examples) ).

Op. V mA/cm2 Cd/A QE (%) CIEx CIEy LT95 Example 1 3.85 10 7.19 6.12 0.140 0.110 117 Example 2 3.84 10 7.20 6.09 0.140 0.109 120 Example 3 3.85 10 7.21 6.10 0.141 0.109 120 Example 4 3.86 10 7.20 6.10 0.140 0.110 113 Example 5 3.91 10 7.35 6.15 0.141 0.110 128 Example 6 3.90 10 7.32 6.20 0.140 0.110 130 Example 7 3.94 10 7.28 6.19 0.140 0.110 125 Example 8 3.90 10 7.34 6.15 0.140 0.110 132 Example 9 3.91 10 7.24 6.20 0.139 0.110 125 Example 10 3.90 10 7.25 6.20 0.141 0.110 122 Comparative Example 1-1 4.20 10 6.05 4.82 0.142 0.114 15 Comparative Example 1-2 4.23 10 6.27 5.15 0.143 0.112 22 Comparative Example 1-3 4.15 10 6.35 5.20 0.141 0.110 51 Comparative Example 1-4 4.03 10 6.92 5.87 0.140 0.111 95 Comparative Example 1-5 4.30 10 6.70 5.73 0.141 0.111 65 Comparative Example 1-6 4.25 10 6.65 5.50 0.140 0.110 77 Comparative Example 1-7 4.06 10 6.50 5.44 0.141 0.110 85 Comparative Example 1-8 4.11 10 6.80 5.70 0.140 0.111 80

Op. V mA/cm2 Cd/A QE (%) CIEx CIEy LT95 Example 11 4.71 10 57.55 16.52 0.301 0.620 175 Example 12 4.70 105 57.60 16.50 0.300 0.620 170 Example 13 4.73 10 57.80 16.60 0.298 0.619 185 Example 14 4.76 10 57.35 16.53 0.300 0.621 190 Example 15 4.77 10 58.70 16.77 0.300 0.619 182 Example 16 4.81 10 58.51 16.70 0.298 0.619 180 Example 17 4.80 10 59.60 16.78 0.299 0.620 195 Example 18 4.80 10 59.73 16.70 0.300 0.621 200 Example 19 4.81 10 57.00 16.50 0.300 0.621 185 Example 20 4.80 10 57.25 16.50 0.298 0.622 181 Comparative Example 2-1 5.20 10 38.25 12.30 0.301 0.638 22 Comparative Example 2-2 5.15 10 36.90 12.40 0.300 0.635 46 Comparative Example 2-3 5.22 10 40.00 12.61 0.299 0.629 53 Comparative Example 2-4 5.10 10 44.63 12.80 0.300 0.625 72 Comparative Example 2-5 5.13 10 50.10 13.12 0.300 0.626 98 Comparative Example 2-6 5.13 10 49.92 13.00 0.298 0.630 105 Comparative Example 2-7 5.15 10 45.80 12.75 0.298 0.625 68 Comparative Example 2-8 5.10 10 45.00 12.70 0.302 0.627 80

As shown in Tables 2 and 3, in the embodiments of the present invention, compared to Comparative Examples 1 to 8, driving voltage improvement, efficiency, and lifespan can be seen.

More specifically, compared to Comparative Examples 1 to 4 not having a spirobifluorene substituent, the embodiments of the present invention form a HOMO suitable for the hole transport layer through spirobifluorene substitution, and the spirobifluorene located at the terminal Due to this, intermolecular py-overlapping can be induced to improve molecular arrangement and to improve mobility in thin films. In addition, compared to Comparative Examples 5 and 6, which do not have a fluorene linking group, the examples of the present invention have a fluorene linking group, so that pi conjugation can be increased to have fast hole mobility, and spirobifluorene's second Compared to Comparative Examples 7 and 8 in which a linking position is used, the embodiments of the present invention form a high LUMO and T1 by linking 1, 3, or 4 of spirobifluorene as a linking position, so that the exciton confinement effect in the light emitting layer can maximize Accordingly, it was confirmed that the compound according to the present invention can lower the driving voltage of the organic light emitting device and greatly improve the efficiency and lifetime.

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 (11)

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

In Formula 1,
Ar ₁ and Ar ₂ are each independently a C ₆ ~ C ₃₀ aryl group or a C ₃ ~ C ₃₀ heteroaryl group unsubstituted or substituted with a C ₆ ~ C ₃₀ aryl group, or a C ₆ ~ C ₃₀ aryl group Or a C ₃ ~ C ₃₀ heteroaryl group unsubstituted or substituted with a C ₃ ~ C ₃₀ heteroaryl group,
L ₁ and L ₂ are each independently a direct bond;
R ₁ to R ₇ are each independently hydrogen;
R and R' are each independently a C ₁ to C ₃₀ alkyl group or a C ₆ to C ₃₀ aryl group, and R and R' may be linked to form a ring;
l, m, and n are each independently an integer of 0 to 4, o is an integer of 0 to 2, and p and q are each independently an integer of 0 to 3.
delete delete According to claim 1,
The compound is a compound represented by any one of Formulas 5 and 6 below.
[Formula 5]

[Formula 6]

According to claim 1,
The compound is a compound represented by the following formula (8).
[Formula 8]

According to claim 1,
Wherein Ar ₁ and Ar ₂ are each independently selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, fluorene, anthracene, phenanthrene, triphenylene, and combinations thereof. According to claim 1,
Wherein Ar ₁ and Ar ₂ are each independently selected from the group consisting of phenyl, biphenyl, fluorene, and combinations thereof.
delete 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, 4 to 7, and 9 between the first electrode and the second electrode. According to claim 10,
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.

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