KR20180116740A - Novel compound and organic electroluminescent divice including the same - Google Patents

Abstract

The present invention relates to a new compound and an organic light emitting device including the same. The new compound according to an embodiment of the present invention can be applied to an organic light emitting device, thereby ensuring high efficiency, long life, a low driving voltage and driving stability of the organic light emitting device. The compound is represented by chemical formula 1.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, and an organic light emitting device including the same. BACKGROUND OF THE INVENTION [0002]

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

A material used as an organic material layer in an organic light emitting diode can be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending largely on functions. The light emitting material can be classified into a polymer and a low molecular weight according to the molecular weight, and can be classified into a phosphorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from an electron triplet excited state according to an emission mechanism, Materials can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing better natural colors depending on luminescent colors. Further, in order to increase the color purity and to increase the luminous efficiency through energy transfer, a host / dopant system can be used as a luminescent material. The principle is that when a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, the 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 is shifted to the wavelength of the dopant, the light of the desired wavelength can be obtained according to the type of the dopant and the host.

Various compounds have been known as materials for use in such organic light emitting devices. However, 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 lifetime. Accordingly, efforts have been made to develop an organic light emitting device having low voltage driving, high luminance, and long life using a material having excellent characteristics.

Korean Patent Publication No. 10-2015-0086721

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

However, the problems to be solved by the present invention are not limited to the problems described above, and other problems not described can be clearly understood by those skilled in the art from the following description.

A first aspect of the invention provides a compound represented by formula 1:

[Chemical Formula 1]

In Formula 1,

Ar ₁ , Ar ₂ , Ar and Ar 'are each independently a substituted or unsubstituted C _{6 to} C ₃₀ aryl group or a substituted or unsubstituted C _{5 to} C ₃₀ heteroaryl group,

R _1, R _2, R ₃ and R ₄ are each independently hydrogen, deuterium, substituted or unsubstituted C _{1 ~ 30} alkyl group, a substituted or unsubstituted C _{2 ~ 30} alkenyl group, a substituted or unsubstituted C of _{1 to 30} alkoxy group, a substituted or unsubstituted aryl groups, unsubstituted C _{6 ~ 30,} or a substituted heteroaryl or unsubstituted C _{5 ~ 30} group,

L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C _6~30 arylene group, or a substituted or unsubstituted C _5~30 heteroarylene group,

l and m each independently represents an integer of 0 to 3, and n represents an integer of 0 to 4;

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

The compound according to an embodiment of the present invention can form a HOMO level suitable for a hole transport layer because arylamine is linked to diarylfluorene via phenylene and can be used in an organic light emitting device. Low voltage, high efficiency, and long life can be achieved.

In addition, the compounds according to the present invention have a high LUMO level and a high T1, which are easily connected to the meta or ortho positions of phenylene by arylamine and diarylfluorene, It is possible to maximize the efficiency of the organic light emitting device and to realize a long lifetime by effectively holding the excitons in the light emitting layer. In addition, since the diarylfluorene can maintain a high glass transition temperature (Tg), it is possible to prevent recrystallization of the thin film, thereby increasing thermal stability and ensuring drive stability.

In addition, due to the stability of the diarylfluorene linked to the arylamine at the meta or ortho position of the phenylene and the superiority of the molecular thin film arrangement, the hole mobility is increased and the roll-off (roll-off) ) Phenomenon can be suppressed and high efficiency and long life of the organic light emitting element can be achieved.

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

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

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

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term "combination thereof" included in the expression of the machine form means one or more combinations or combinations selected from the group consisting of the constituents described in the expression of the machine form, And the like.

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

Throughout this specification, the term "aryl" refers to a C _6-30 aromatic hydrocarbon ring group, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, Means an aromatic ring such as phenyl, naphthyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, Examples of the C _5-30 aromatic ring containing a hetero element include pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, Benzothiophenyl, dibenzothiophenyl, quinolyl, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, thienyl, and pyridine rings, pyrazine rings, pyrimidine rings , Pyridazine ring, triazine ring, indole ring, quinoline ring , Acridine rings, pyrrolidine rings, dioxane rings, piperidine rings, morpholine rings, piperazine rings, carbazole rings, furan rings, thiophene rings, oxazole rings, oxadiazole rings, May include a heterocyclic group formed from a heterocyclic ring, a thiazole ring, a thiadiazole ring, a thiadiazole ring, a benzothiazole ring, a triazole ring, an imidazole ring, a benzimidazole ring, a pyran ring or a dibenzofuran ring .

"Optionally substituted" term throughout the present specification is a deuterium, a halogen, an amino group, a nitrile group, a nitro group or a C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ of the alkoxy group, Means a group selected from the group consisting of a C ₃ to C ₂₀ cycloalkyl group, a C ₃ to C ₂₀ heterocycloalkyl group, a C ₆ to C ₃₀ aryl group, and a C ₃ to C ₃₀ heteroaryl group can do.

A first aspect of the invention provides a compound represented by formula 1:

[Chemical Formula 1]

In Formula 1,

Ar ₁ , Ar ₂ , Ar and Ar 'are each independently a substituted or unsubstituted C _{6 to} C ₃₀ aryl group or a substituted or unsubstituted C _{5 to} C ₃₀ heteroaryl group,

R _1, R _2, R ₃ and R ₄ are each independently hydrogen, deuterium, substituted or unsubstituted C _{1 ~ 30} alkyl group, a substituted or unsubstituted C _{2 ~ 30} alkenyl group, a substituted or unsubstituted C of _{1 to 20} alkoxy group, a substituted or unsubstituted aryl groups, unsubstituted C _{6 ~ 30,} or a substituted heteroaryl or unsubstituted C _{5 ~ 30} group,

L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C _6~30 arylene group, or a substituted or unsubstituted C _5~30 heteroarylene group,

l and m each independently represents an integer of 0 to 3, and n represents an integer of 0 to 4;

The compounds according to one embodiment of the present invention are arylamines (NAr ₁ Ar ₂ ) linked to diarylfluorene via phenylene.

In addition, the aryl amine and phenylene, phenylene and diaryl fluorene is a direct bond or a linking group can be connected via a (L ₁ or L _2), a diaryl fluorene is phenylene or a linking group to the 2-position (L ₂₎ Lt; / RTI >

The compound according to the present invention can form a HOMO level suitable for a hole transporting layer and can be used in an organic light emitting device, and can achieve low voltage, high efficiency, and long life of the organic light emitting device.

In addition, the compounds according to the present invention have a high LUMO level and a high T1, which are easily connected to the meta or ortho positions of phenylene by arylamine and diarylfluorene, It is possible to maximize the efficiency of the organic light emitting device by effectively blocking the excitons in the light emitting layer. In addition, since the diarylfluorene can maintain a high glass transition temperature (Tg), it is possible to prevent recrystallization of the thin film, thereby increasing thermal stability and ensuring drive stability.

In addition, due to the stability of the diarylfluorene linked to the arylamine at the meta or ortho position of the phenylene and the superiority of the molecular thin film arrangement, the hole mobility is increased and the roll-off (roll-off) ) Phenomenon can be suppressed and high efficiency and long life of the organic light emitting element can be achieved.

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

[Chemical Formula 2] < EMI ID =

In Formula 2 or Formula 3,

_{Ar 1, Ar, Ar ',} R 1, R 2, R 3, R 4, L 1, L 2, l, m and n are defined as in Formula 1,

Ar ₃ And Ar ₄ are each independently a substituted or unsubstituted aryl groups, unsubstituted C _{6 ~ 25,} or a substituted or heterocyclic unsubstituted C _{5 ~ 25} aryl group,

R and R 'are each independently hydrogen, deuterium, a substituted or unsubstituted C _{1 ~ 24} alkyl group, a substituted or unsubstituted C _{2 ~ 24} alkenyl group, a substituted or unsubstituted C _{1 ~ 24} pills of the ring of the alkoxy group, substituted or unsubstituted C _{6 ~ 24} aryl group, or a substituted or unsubstituted ring of the heteroaryl group of C _{5 ~ 24.}

The compound represented by Formula 2 or Formula 3 may form a lower HOMO level suitable for the light-emitting auxiliary layer. In the present invention, the light-emission-assisting layer is a layer formed between the hole transporting layer and the light emitting layer, and may be referred to as a second hole transporting layer or a third hole transporting layer depending on the number of the hole transporting layers.

In one embodiment of the present invention, the compound may be represented by the following formula (3-1). The compound represented by the following formula (3-1) can improve the hole mobility and the stability of the thin film, thereby effectively improving the lifetime.

[Formula 3-1]

In Formula 3-1,

_{Ar 1, R 1, R 2} , R 3, R 4, L 1, L 2, l, m and n are as defined in Formula 1,

Ar ₃ , Ar ₄ , R and R 'have the same definitions as in the above formula (3).

According to an embodiment of the present invention, in Formula 2, Formula 3, or Formula 3-1, R ₃ and R ₄ may be hydrogen. In this case, the bulky characteristics of the molecule can be minimized, the molecular weight can be maintained, the thin film arrangement can be excellent, and the thermal stability can be excellent.

According to an embodiment of the present invention, Ar ₁ , Ar ₃ and Ar ₄ are each independently selected from phenyl, naphthyl, biphenyl, terphenyl, tetra Phenyl, or combinations thereof. In this case, a relatively small molecular weight can be maintained and thermal decomposition of the compound during the deposition process can be prevented.

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

     [Chemical Formula 4]

In Formula 4 or Formula 5,

_{Ar 1, Ar, Ar ',} R 1, R 2, R 3, R 4, L 1, L 2, l, m and n are defined as in Formula 1,

And L ₃ is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted C _{6 ~ 17} heteroaryl group of C _{5 ~ 17,}

R _5, R _6, R _7, and R ₈ are each independently hydrogen, deuterium, substituted or unsubstituted alkenyl group, a substituted or unsubstituted of C _{1 ~ 17} alkyl group, a substituted or unsubstituted C _{2 ~ 17} of the unsubstituted a heteroaryl group of C _{1 ~ 17} alkoxy group, a substituted or unsubstituted C _{6 ~ 17} aryl group, or a substituted or unsubstituted C _{5 ~ 17} of the ring and the ring,

R and R 'are each independently hydrogen, deuterium, a substituted or unsubstituted C _{1 ~ 24} alkyl group, a substituted or unsubstituted C _{2 ~ 24} alkenyl group, a substituted or unsubstituted C _{1 ~ 24} pills of the ring of the alkoxy group, substituted or unsubstituted C _{6 ~ 24} aryl group, or a substituted or unsubstituted ring of the heteroaryl group of C _{5 ~ 24.}

The compound represented by Formula 4 or Formula 5 may form a higher HOMO level suitable for the hole transport layer.

In one embodiment of the present invention, the compound may be represented by the following general formula (5-1). The compound represented by the following formula (5-1) can improve the hole mobility and the stability of the thin film to effectively improve the lifetime.

[Formula 5-1]

In Formula 5-1,

_{Ar 1, Ar, Ar ',} R 1, R 2, R 3, R 4, L 1, L 2, l, m and n are defined as in Formula 1,

L ₃ , R ₅ , R ₆ , R ₇ , R ₈ , R and R 'are as defined in the above formula (5).

According to one embodiment of the present invention, in Formula 4, Formula 5 or Formula 5-1, R ₃ and R ₄ may be hydrogen. In this case, the bulky characteristics of the molecule can be minimized, the molecular weight can be maintained, the thin film arrangement can be excellent, and the thermal stability can be excellent.

According to one embodiment of the invention, formula 4, R ₇ and R ₈ in formula (5) or formula 5-1 may be an alkyl group a substituted or unsubstituted C _{1 ~ 17.} In this case, the HOMO level and the hole mobility can be more suitable for the hole transport layer. Also, although not limited thereto, R ₇ and R ₈ may be a methyl group. In this case, it is possible to have a more suitable HOMO level and have a higher hole mobility.

In one embodiment of the present invention, the compound represented by Formula 1 may be synthesized by the following reaction scheme:

[Reaction Scheme]

In the above reaction formula,

h is a halogen element,

Ar ₁ , Ar ₂ , Ar and Ar 'are each independently a substituted or unsubstituted C _{6 to} C ₃₀ aryl group or a substituted or unsubstituted C _{5 to} C ₃₀ heteroaryl group,

R _1, R _2, R ₃ and R ₄ are each independently hydrogen, deuterium, substituted or unsubstituted C _{1 ~ 30} alkyl group, a substituted or unsubstituted C _{2 ~ 30} alkenyl group, a substituted or unsubstituted C of _{1 to 30} alkoxy group, a substituted or unsubstituted aryl groups, unsubstituted C _{6 ~ 30,} or a substituted heteroaryl or unsubstituted C _{5 ~ 30} group,

L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C _6~30 arylene group, or a substituted or unsubstituted C _5~30 heteroarylene group,

l and m each independently represents an integer of 0 to 3, and n represents an integer of 0 to 4;

In one embodiment of the present invention, the compounds represented by Chemical Formulas 1 to 5 may be any one of compounds 1 to 262 shown below, but not limited thereto:

The second aspect of the present invention provides an organic light emitting device comprising the compound represented by any one of Chemical Formulas 1 to 5. The organic light emitting device may include at least one organic compound layer containing a 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 a hole injection layer, a hole transport layer, and a light emission assisting layer, but may not be limited thereto. The compounds 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, but not limited to, an organic material layer containing a hole transporting material and an organic material layer containing a compound represented by the general formula (1). According to one embodiment of the present invention, as described above, the compound of Chemical Formula 1 may be represented by any one of Chemical Formulas 2 to 5.

The organic light emitting device includes an organic 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 One or more layers may be included.

For example, the organic light emitting device can be fabricated as shown in FIG. The organic light emitting device includes an anode (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, Implantation electrode 2000) may be stacked in this order.

1, the substrate 100 may be a transparent glass substrate or a flexible plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness. have.

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

A hole injecting layer material may be deposited on the anode electrode by a method such as vacuum deposition, spin coating, casting, or Langmuir-Blodgett (LB) method. When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer 200, the structure and thermal properties of the desired hole injection layer, and the like. Generally, Temperature, a degree of vacuum of 10 ^{- 8} to 10 ^{- 3} torr, a deposition rate of 0.01 to 100 Å / sec, and a layer thickness range of 10 Å to 5 탆.

Next, a hole transporting layer material may be deposited on the hole injection layer 200 by a method such as vacuum deposition, spin coating, casting, or LB method to form the hole transporting layer 300. When the hole transporting layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used, but it is generally preferable to select the conditions within the substantially same range as the formation of the hole injection layer.

The hole transport layer 300 may be made of the compound according to the present invention. As described above, the compound according to the present invention may be used alone or a known compound may be used together. In addition, according to 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 only of a known material. In addition, according to an embodiment of the present invention, a light emitting auxiliary layer may be formed on the hole transport layer 300. In the present invention, the light-emission-assisting layer means a layer formed between the hole transporting layer and the light emitting layer, and may be referred to as a second hole transporting layer or a third hole transporting layer depending on the number of the hole transporting layers.

The light emitting layer 400 may be formed by depositing the light emitting layer material 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 casting method, or an LB method. When the light emitting layer is formed by the vacuum vapor deposition method, the deposition conditions vary depending on the compound used, but it is generally preferable to select the conditions within the substantially same range as the formation of the hole injection layer. The light emitting layer material may be a known compound as a host or a dopant.

When the phosphorescent dopant is used together with the phosphorescent dopant, a hole blocking material (HBL) may be further deposited by vacuum evaporation or spin coating to prevent triplet excitons or holes from diffusing into the electron transport layer. The hole blocking material that can be used at this time is not particularly limited, but any known hole blocking material may be used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or a hole blocking material described in Japanese Patent Laid-Open Publication No. 11-329734 (A1) can be exemplified. Typically, Balq (bis Phenanthrolines based compounds such as UDC company BCP (bassocouroin), and the like can be used.

An electron transport layer 500 is formed on the light emitting layer 400 formed as described above. The electron transport layer may be formed by vacuum deposition, spin coating, casting, or the like. The deposition conditions of the electron transporting layer depend on the compound used, but it is generally preferable to select the conditions within the same range as the formation of the hole injection layer.

Then, an electron injection layer material may be deposited on the electron transport layer 500 to form an electron injection layer 600. The electron injection layer may be formed by vacuum deposition, spin coating, casting, And the like.

The hole injecting layer 200, the hole transporting layer 300, the light emitting layer 400 and the electron transporting layer 500 of the organic light emitting diode can be formed using the compound according to the present invention or the following materials. The 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 vacuum evaporation method or a sputtering method. As the cathode, various metals may be used. Specific examples thereof include aluminum, gold, and silver.

The organic light emitting device of the present invention can have an organic light emitting device having various structures as well as an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a cathode structure, Layer or an intermediate layer of two layers may be further formed.

As described above, the thickness of each organic material layer formed according to the present invention can be controlled according to the required degree, specifically 10 to 1,000 nm, and more specifically, 20 to 150 nm.

In addition, since the organic material layer containing the compound represented by the formula (1) can control the thickness of the organic material layer in the molecular unit, the present invention has advantages of uniform surface and excellent shape stability.

The organic light emitting compound according to the present invention may be applied to the first aspect of the present invention, but the present invention is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited by these Examples.

[Example]

Intermediate (IM) synthesis

Intermediate IM was synthesized by the following reaction scheme for synthesis of the target compound.

Production Example 1 : Intermediate (IM1) synthesis

In a round bottom flask, 64.0 g of (9,9-diphenyl-9H-fluoren-2-yl) boronic acid and 50.0 g of 1-bromo-2-iodobenzene were dissolved in 1100 ml of 1,4-dioxane, 270 ml of K2CO3 (2M) PPh ₃ ) ₄ were added, and the mixture was stirred under reflux. After confirming the reaction by TLC, water was added and the reaction was terminated. The organic layer was extracted with MC, filtered under reduced pressure, and recrystallized to obtain 60.2 g (yield: 72%) of intermediate IM1.

IM2 was synthesized by using 9,9-diphenyl-9H-fluoren-2-yl boronic acid and 1-bromo-3-iodobenzene in the same manner as IM1.

Intermediate (OP) synthesis

For the synthesis of the target compound, OP1 was synthesized by the following reaction formula.

The 2-bromo-9,9-dimethyl- 9H-fluorene 15.0g, aniline 5.6g, t-BuONa 7.9g, Pd 2 (dba) 3 2.0g, (t-Bu) 3 P2.5ml round bottom flask Dissolved in 200 ml of toluene, and stirred under reflux. After confirming the reaction by TLC, water was added and the reaction was terminated. The organic layer was extracted with MC, filtered under reduced pressure, and recrystallized to obtain 11.75 g (yield 75%) of OP1.

Using the same method as that of OP1 above, OP2 to OP12 were synthesized by starting materials as shown in Table 1 below.

OP2 formula OP2 starting material OP3 formula OP3 starting material

2-bromo-9,9-dimethyl-9H-fluorene,
[1,1'-biphenyl] -4-amine

2-bromo-9,9-dimethyl-9H-fluorene,
[1,1'-biphenyl] -3-amine OP4 formula OP4 starting material OP5 Chemical formula OP5 starting material

2-bromo-9,9-dimethyl-9H-fluorene,
[1,1'-biphenyl] -2-amine

2-bromo-9,9-dimethyl-9H-fluorene,
9,9-dimethyl-9H-fluorene-2-amine OP6 formula OP6 starting material OP7 Chemical formula OP7 starting material

4-bromo-1,1 ' -biphenyl,
aniline

4-bromo-1,1 ': 4', 1 " -terphenyl,
aniline OP8 formula OP8 starting material OP9 formula OP9 starting material

4-bromo-1,1 ': 3', 1 " -terphenyl,
aniline

4-bromo-1,1 ': 2', 1 " -terphenyl,
aniline OP10 formula OP10 starting material OP11 Chemical formula OP11 starting material

4-bromo-1,1 ' -biphenyl,
[1,1'-biphenyl] -4-amine

4-bromo-1,1 ' -biphenyl,
[1,1'-biphenyl] -3-amine OP12 formula OP12 starting material

4-bromo-1,1 ' -biphenyl,
[1,1'-biphenyl] -2-amine

Compound synthesis

Compound 1  synthesis

3.0 g of IM1, 1.8 g of OP1, 0.9 g of t-BuONa, 0.23 g of Pd ₂ (dba) ₃ and 0.26 ml of (t-Bu) ₃ P were dissolved in 70 ml of toluene and then stirred under reflux. After confirming the reaction by TLC, water was added and the reaction was terminated. The organic layer was extracted with MC, filtered under reduced pressure, and then subjected to column purification and recrystallization to obtain 2.92 g (yield: 68%) of Compound 1. m / z: 677.31 (100.0%), 678.31 (57.1%), 679.31 (15.7%), 680.32 (2.9%

Compound 2  synthesis

Compound 2 was synthesized (yield 72%) in the same manner as compound 1 using OP2 instead of OP1. m / z: 753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35

Compound 3  synthesis

Compound 3 was synthesized (yield 65%) in the same manner as compound 1 using OP3 instead of OP1. m / z: 753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35

Compound 4  synthesis

Compound 4 was synthesized (yield 70%) in the same manner as compound 1 using OP4 instead of OP1. m / z: 753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35

Compound 5  synthesis

Compound 5 was synthesized (yield 69%) in the same manner as compound 1 using OP5 instead of OP1. m / z: 793.37 (100.0%), 794.37 (66.3%), 795.38 (21.8%), 796.38

Compound 6  synthesis

Compound 6 was synthesized (yield 62%) in the same manner as compound 1 using IM2 instead of IM1. m / z: 677.31 (100.0%), 678.31 (57.1%), 679.31 (15.7%), 680.32 (2.9%

Compound 7  synthesis

Compound 7 was synthesized (yield 65%) in the same manner as compound 1 using IM2 and OP2 instead of IM1 and OP1. m / z: 753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35

Compound 8  synthesis

Compound 8 was synthesized (yield 58%) in the same manner as compound 1 using IM2 and OP3 instead of IM1 and OP1. m / z: 753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35

Compound 9  synthesis

Compound 9 was synthesized (yield 60%) in the same manner as compound 1 using IM2 and OP4 instead of IM1 and OP1. m / z: 753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35

Compound 10  synthesis

Compound 10 was synthesized (yield 63%) in the same manner as compound 1 using IM2 and OP5 instead of IM1 and OP1. m / z: 793.37 (100.0%), 794.37 (66.3%), 795.38 (21.8%), 796.38

Compound 11  synthesis

Compound 11 was synthesized (yield: 73%) in the same manner as compound 1 using OP6 instead of OP1. m / z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29

Compound 12  synthesis

Compound 12 was synthesized (yield 70%) in the same manner as compound 1 using OP7 instead of OP1. m / z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32

Compound 13  synthesis

Compound 13 was synthesized (yield 66%) in the same manner as compound 1 using OP8 instead of OP1. m / z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32

Compound 14  synthesis

Compound 14 was synthesized (yield 69%) in the same manner as compound 1 using OP9 instead of OP1. m / z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32

Compound 15  synthesis

Compound 15 was synthesized (yield 75%) in the same manner as compound 1 using OP10 instead of OP1. m / z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32

Compound 16  synthesis

Compound 16 was synthesized (yield 65%) in the same manner as compound 1 using OP11 instead of OP1. m / z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32

Compound 17  synthesis

Compound 17 was synthesized (yield 70%) in the same manner as compound 1 using OP12 instead of OP1. m / z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32

Compound 18  synthesis

Compound 18 was synthesized (yield 67%) in the same manner as compound 1 using IM2 and OP10 instead of IM1 and OP1. m / z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32

Compound 19  synthesis

Compound 19 was synthesized (yield 59%) in the same manner as compound 1 using IM2 and OP11 instead of IM1 and OP1. m / z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32

Compound 20  synthesis

Compound 20 was synthesized (yield 63%) in the same manner as compound 1 using IM2 and OP12 instead of IM1 and OP1. m / z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32

Organic Light Emitting Device Manufacturing

Example 1 (used as a hole transport layer)

A thin glass substrate coated with indium tin oxide (ITO) having a thickness of 1500 Å was washed with distilled water ultrasonic waves. After the distilled water was cleaned, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaner. Then, the substrate was cleaned using oxygen plasma for 5 minutes, and then a thermal vacuum evaporator evaporator to form 250 Å of hole injection layer HI01, 250 Å of HATCN, 250 Å of compound 1 as a hole transport layer, and then doped with 3% of BH01: BDO1 as the light emitting layer to form 250 Å. Next, an ET01: Liq (1: 1) 300 Å film was formed as an electron transport layer, LiF 10 Å and aluminum (Al) 1000 Å were formed, and the device was encapsulated in a glove box to produce an organic light emitting device.

Examples 2 to 10

An organic light emitting device was produced by using the same method as Example 1, except that Compound 2 was used instead of Compound 1.

Comparative Examples 1 to 5

Using the same method as in Example 1, instead of compound 1, an organic light emitting device was produced by using the following Ref.1 to Ref.5.

Example 11: (used as luminescent auxiliary layer)

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

Examples 12 to 20

An organic luminescent device was fabricated by the same method as in Example 11, except that Compound 12 to Compound 20 were used instead of Compound 11.

Comparative Examples 6 to 10

An organic electroluminescent device was fabricated using the same method as in Example 11, except that Compound 11 was used instead of Compound 11, and the following Ref.6 to Ref.10 were used.

[Evaluation of performance of organic light emitting device]

A voltage was applied to the Keithley 2400 source measurement unit to inject electrons and holes and the luminance was measured using a Konica Minolta spectroscope (CS-2000). The performance of the organic luminescent devices of the examples and comparative examples was evaluated by measuring the current density and the luminance with respect to the applied voltage under atmospheric pressure, and the results are shown in [Table 2] and [Table 3], respectively.

Op. V mA / cm2 Cd / A QE (%) CIEx CIEy LT97 Example 1 3.90 10 7.22 6.14 0.140 0.109 145 Example 2 3.89 10 7.25 6.10 0.140 0.110 145 Example 3 3.91 10 7.29 6.19 0.141 0.110 140 Example 4 3.88 10 7.25 6.12 0.140 0.110 150 Example 5 3.85 10 7.27 6.15 0.141 0.110 145 Example 6 3.90 10 7.14 6.23 0.140 0.110 122 Example 7 3.90 10 7.15 6.33 0.140 0.110 126 Example 8 3.90 10 7.13 6.40 0.140 0.111 122 Example 9 3.90 10 7.10 6.42 0.139 0.111 125 Example 10 3.90 10 7.10 6.49 0.141 0.110 122 Comparative Example 1 4.03 10 6.70 5.60 0.14 0.111 98 Comparative Example 2 4.17 10 6.67 4.06 0.143 0.113 43 Comparative Example 3 4.10 10 6.50 4.04 0.141 0.113 80 Comparative Example 4 4.31 10 6.75 5.28 0.141 0.112 90 Comparative Example 5 4.07 10 6.85 4.10 0.141 0.111 100

Op. V mA / cm2 Cd / A QE (%) CIEx CIEy LT97 Example 11 4.00 10 7.62 6.14 0.140 0.109 167 Example 12 4.00 10 7.65 6.10 0.140 0.110 160 Example 13 4.00 10 7.69 6.19 0.141 0.110 165 Example 14 4.00 10 7.65 6.12 0.140 0.110 160 Example 15 4.00 10 7.67 6.15 0.141 0.110 167 Example 16 4.00 10 7.64 6.23 0.140 0.110 162 Example 17 4.00 10 7.45 6.33 0.140 0.110 166 Example 18 4.00 10 7.43 6.40 0.140 0.111 150 Example 19 4.00 10 7.40 6.42 0.139 0.111 145 Example 20 4.00 10 7.40 6.49 0.141 0.110 150 Comparative Example 6 4.08 10 7.00 5.60 0.14 0.111 110 Comparative Example 7 4.20 10 6.82 4.06 0.143 0.113 55 Comparative Example 8 4.16 10 6.95 4.04 0.141 0.113 78 Comparative Example 9 4.40 10 7.06 5.28 0.141 0.112 100 Comparative Example 10 4.11 10 7.00 4.10 0.141 0.111 110

As shown in Table 2, Examples 1 to 10 of the present invention were used as a hole transport layer, and it was confirmed that the efficiency and lifetime were increased as compared with Comparative Examples 1 to 5, and it was confirmed that the properties were excellent in all respects As shown in Table 3, Examples 11 to 20 of the present invention were used as a light-emission-assisting layer (second hole-transporting layer), and it was confirmed that the efficiency and lifetime were increased as compared with Comparative Examples 6 to 10 And it was confirmed that the physical properties were excellent in all respects.

More specifically, in comparison with Comparative Example 1 and Comparative Example 6 in which the arylamine and diphenylfluorene are linked to the para position of phenylene, the embodiments of the present invention are not limited to the case where arylamine and diarylfluorene are substituted with phenylene It is confirmed that the driving voltage of the organic light emitting device is low and the efficiency and lifetime characteristics are improved by maintaining high LUMO and T1 which are connected to meta or ortho and can easily cut off electrons through phi congration suppression there was.

Compared with Comparative Example 2 and Comparative Example 7 in which the arylamine was bonded to dimethylfluorene, the diarylfluorene-containing examples were able to induce the thin film and interfacial alignment of the molecules.

Comparative Example 3 in which arylamine and diphenylfluorene are connected to phenylene meta or ortho but not to position 2 of diphenylfluorene but to phenylene at 3 or 4, 4 and Comparative Examples 8 and 9, the examples show that the second position of the diarylfluorene is connected to phenylene to form a HOMO suitable for the hole transporting layer and the light emitting auxiliary layer, so that the driving voltage is low, Respectively.

Compared with Comparative Example 5 and Comparative Example 10 in which arylamine was coupled with bulky spyrofluorene, it was confirmed that the embodiments had diphenylfluorene that was not spiropluorene, resulting in improved mobility and long life I could.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

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 (15)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
Ar ₁ , Ar ₂ , Ar and Ar 'are each independently a substituted or unsubstituted C _{6 to} C ₃₀ aryl group or a substituted or unsubstituted C _{5 to} C ₃₀ heteroaryl group,
R _1, R _2, R ₃ and R ₄ are each independently hydrogen, deuterium, substituted or unsubstituted C _{1 ~ 30} alkyl group, a substituted or unsubstituted C _{2 ~ 30} alkenyl group, a substituted or unsubstituted C of _{1 to 30} alkoxy group, a substituted or unsubstituted aryl groups, unsubstituted C _{6 ~ 30,} or a substituted heteroaryl or unsubstituted C _{5 ~ 30} group,
L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C _6~30 arylene group, or a substituted or unsubstituted C _5~30 heteroarylene group,
l and m each independently represents an integer of 0 to 3, and n represents an integer of 0 to 4; The method according to claim 1,
Wherein said compound is represented by the following formula (2) or (3):
[Chemical Formula 2] < EMI ID =

In Formula 2 or Formula 3,
_{Ar 1, Ar, Ar ',} R 1, R 2, R 3, R 4, L 1, L 2, l, m and n are defined as in Formula 1,
Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _{6 ~ 25} aryl group, or a substituted heteroaryl or unsubstituted C _{5 ~ 25} group,
R and R 'are each independently hydrogen, deuterium, a substituted or unsubstituted C _{1 ~ 24} alkyl group, a substituted or unsubstituted C _{2 ~ 24} alkenyl group, a substituted or unsubstituted C _{1 ~ 24} pills of the ring of the alkoxy group, substituted or unsubstituted C _{6 ~ 24} aryl group, or a substituted or unsubstituted ring of the heteroaryl group of C _{5 ~ 24.} 3. The method of claim 2,
Wherein said compound is represented by the following Formula 3-1.
[Formula 3-1]

In Formula 3-1,
_{Ar 1, R 1, R 2} , R 3, R 4, L 1, L 2, l, m and n are as defined in Formula 1,
Ar ₃ , Ar ₄ , R and R 'have the same definitions as in the above formula (3). The method according to claim 2 or 3,
Wherein Ar ₁ , Ar ₃ , and Ar ₄ are each independently phenyl, naphthyl, biphenyl, terphenyl, tetraphenyl, or combinations thereof. 3. The method of claim 2,
Wherein said compound is any one of the following compounds:

3. The method of claim 2,
Wherein said compound is any one of the following compounds:

The method according to claim 1,
The compound is represented by the following formula (4) or (5):
[Chemical Formula 4]

In Formula 4 or Formula 5,
_{Ar 1, Ar, Ar ',} R 1, R 2, R 3, R 4, L 1, L 2, l, m and n are defined as in Formula 1,
And L ₃ is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted C _{6 ~ 17} heteroaryl group of C _{5 ~ 17,}
R _5, R _6, R _7, and R ₈ are each independently hydrogen, deuterium, substituted or unsubstituted alkenyl group, a substituted or unsubstituted of C _{1 ~ 17} alkyl group, a substituted or unsubstituted C _{2 ~ 17} of the unsubstituted a heteroaryl group of C _{1 ~ 17} alkoxy group, a substituted or unsubstituted C _{6 ~ 17} aryl group, or a substituted or unsubstituted C _{5 ~ 17} of the ring and the ring,
R and R 'are each independently hydrogen, deuterium, a substituted or unsubstituted C _{1 ~ 24} alkyl group, a substituted or unsubstituted C _{2 ~ 24} alkenyl group, a substituted or unsubstituted C _{1 ~ 24} pills of the ring of the alkoxy group, substituted or unsubstituted C _{6 ~ 24} aryl group, or a substituted or unsubstituted ring of the heteroaryl group of C _{5 ~ 24.} 8. The method of claim 7,
Wherein said compound is represented by the following formula 5-1.
[Formula 5-1]

In Formula 5-1,
_{Ar 1, Ar, Ar ',} R 1, R 2, R 3, R 4, L 1, L 2, l, m and n are defined as in Formula 1,
L ₃ , R ₅ , R ₆ , R ₇ , R ₈ , R and R 'are as defined in the above formula (5). 9. The method according to claim 7 or 8,
Wherein R ₇ and R ₈ are the compound group of the substituted or unsubstituted C ₁ ~ ₁₇ pills. 8. The method of claim 7,
Wherein said compound is any one of the following compounds:

8. The method of claim 7,
Wherein said compound is any one of the following compounds:

An organic light-emitting device comprising an organic compound layer containing a compound according to any one of claims 1 to 11 between a first electrode and a second electrode. 13. The method of claim 12,
Wherein the organic material layer is one or more layers of a hole injecting layer, a hole transporting layer, and a light emitting auxiliary layer. 13. The method of claim 12,
Wherein the organic material layer is a hole transporting layer. 13. The method of claim 12,
Wherein the organic material layer is a light emission-assisting layer.

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