KR102583853B1 - 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 containing the same. The novel compound according to an embodiment of the present invention is applied to an organic light-emitting device to improve the organic light-emitting device's high efficiency, long life, low driving voltage, and driving stability. It can be secured.

Description

Novel compounds and organic light-emitting devices containing the same {NOVEL COMPOUND AND ORGANIC ELECTROLUMINESCENT DIVICE INCLUDING THE SAME}

The present application relates to novel compounds and organic light-emitting devices containing the same.

Materials used as organic layers in organic light-emitting diodes can be broadly classified into light-emitting materials, hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function. In addition, the light-emitting materials can be classified into high molecules and low molecules according to their molecular weight, and can be classified into fluorescent materials derived from the singlet excited state of electrons and phosphorescent materials derived from the triplet excited state of electrons depending on the luminescence mechanism, Light-emitting materials can be divided into blue, green, and red light-emitting materials according to their emission color, and yellow and orange light-emitting materials necessary to realize better natural colors. Additionally, in order to increase color purity and increase 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, which has a smaller energy band gap and higher luminous efficiency than the host that mainly constitutes the light-emitting layer, is mixed into the light-emitting layer, excitons generated in the host are transported to the dopant, producing highly efficient light. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of the desired wavelength can be obtained depending on the type of dopant and host used.

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

Korean Patent Publication 10-2015-0086721

The present application provides novel organic compounds and organic light-emitting devices containing the same.

However, the problems to be solved by the present application are not limited to the problems 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 the following formula (1):

[Formula 1]

In Formula 1,

Ar, Ar' and Ar ₁ are each independently a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group, and Ar, and Ar' are connected to form a ring. may or may not form a ring,

R ₁ to R ₄ are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, or a substituted or unsubstituted C ₁ to C ₃₀ alkoxy group. , a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a substituted or unsubstituted C ₅ to C ₃₀ heteroaryl group,

R ₅ and R ₆ are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, or a substituted or unsubstituted C ₁ to C ₃₀ alkoxy It's awesome,

L ₁ to L ₃ are each independently directly bonded, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group, provided that at least one of L ₁ and L ₂ is a substituted or unsubstituted C ₆ to C ₃₀ arylene group or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group,

X is S or O,

l, o, p, and q are each independently an integer from 0 to 4, and m and n are each independently an integer from 0 to 3. However, when L ₃ is phenylene, q is an integer of 1 or more.

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, an arylamine is linked to the 2-position of diarylfluorene, and the aryl on one side of the arylamine has dibenzofuran or dibenzothiophene through an extended meta linking group. It is possible to form a HOMO level that facilitates hole transport and at the same time maintain a high LUMO level that facilitates electron blocking. Accordingly, excitons in the light-emitting layer are efficiently formed, making it possible to implement a low-voltage and high-efficiency organic light-emitting device.

In addition, in the compound according to one embodiment of the present invention, the aryl on the other side of the arylamine is phenyl, or the aryl on the other side of the arylamine has two or more aryls, and one of the aryls is connected to a meta or ortho position. By maintaining a high T1, the exciton confinement effect in the light emitting layer is maximized, making it possible to implement a highly efficient organic light emitting device.

In addition, the compound according to one embodiment of the present invention has an extended meta-linkage group of diarylfluorene, which increases pi-conjugation, has excellent thin film arrangement of molecules, can improve hole mobility, and has excellent roll-off properties. Through suppression, long-life devices can be realized.

In addition, the compound according to one embodiment of the present invention has a high Tg due to diarylfluorene and an extended meta linking group, thereby preventing thin film recrystallization and ensuring device operation stability.

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

Hereinafter, with reference to the attached drawings, implementation examples and embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention.

However, the present application may be implemented in various different forms and is not limited to the implementation examples and examples described herein. In order to clearly explain the present invention in the drawings, parts that are not related to the description are omitted, and similar parts are given similar reference numerals throughout the specification.

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

Throughout the specification of the present application, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary. As used throughout the specification, the terms “about,” “substantially,” and the like are used to mean at or close to a numerical value when manufacturing and material tolerances inherent in the stated meaning are given, and are used to convey the understanding of the present application. Precise or absolute figures are used to assist in preventing unscrupulous infringers from taking unfair advantage of stated disclosures. As used throughout the specification, the terms “step of” or “step of” do not mean “step for.”

Throughout this specification, the term "combination thereof" included in the Markushi format expression means a mixture or combination of one or more components selected from the group consisting of the components described in the Markushi format expression, It means including one or more selected from the group consisting of.

Throughout this specification, description of “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, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perylethyl. It means containing an aromatic ring such as nyl, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzochrysenyl, anthracenyl, stilbenyl, pyrenyl, etc., and “heteroaryl” means at least one ring. 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, t Ophen ring, oxazole ring, oxadiazole ring, benzoxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzoimidazole ring, pyran ring, dibenzofuran , may mean including a heterocyclic group formed from a dibenzothiophene ring.

Throughout the specification herein, “substituted” in the term “substituted or unsubstituted” refers to deuterium, halogen, amino group, nitrile group, nitro group or C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ to be substituted with one or more groups selected from the group consisting of an 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 heteroaryl group. It can mean something that can be done. Additionally, the same symbols throughout the specification may have the same meaning unless otherwise specified.

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

[Formula 1]

In Formula 1,

Ar, Ar' and Ar ₁ are each independently a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group, and Ar, and Ar' are connected to form a ring. may or may not form a ring,

R ₁ to R ₄ are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, or a substituted or unsubstituted C ₁ to C ₃₀ alkoxy group. , a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a substituted or unsubstituted C ₅ to C ₃₀ heteroaryl group,

R ₅ and R ₆ are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, or a substituted or unsubstituted C ₁ to C ₃₀ alkoxy It's awesome,

L ₁ to L ₃ are each independently directly bonded, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group, provided that at least one of L ₁ and L ₂ is a substituted or unsubstituted C ₆ to C ₃₀ arylene group or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group,

X is S or O,

l, o, p, and q are each independently an integer from 0 to 4, and m and n are each independently an integer from 0 to 3. However, when L ₃ is phenylene, q is an integer of 1 or more.

In the compound of Formula 1, an arylamine is connected to the 2-position of diarylfluorene, and the aryl on one side of the arylamine has dibenzofuran or dibenzothiophene through an extended meta linker, making it easy to transport holes. It is possible to form a high HOMO level and at the same time maintain a high LUMO level that facilitates electron blocking. Accordingly, excitons in the light-emitting layer are efficiently formed, making it possible to implement a low-voltage and high-efficiency organic light-emitting device.

In addition, in the above compounds, the aryl on the other side of the arylamine is phenyl, or the aryl on the other side of the arylamine has two or more aryls, and one of the aryls is connected to a meta or ortho position to maintain a high T1 to form a light emitting layer. The exciton confinement effect is maximized, making it possible to implement highly efficient organic light-emitting devices.

In addition, the compound has an extended meta-linkage of diarylfluorene, which increases pi-conjugation, improves hole mobility due to excellent thin film arrangement of molecules, and can implement long-life devices by suppressing roll-off. You can.

In addition, the compound according to one embodiment of the present invention has a high Tg due to diarylfluorene and an extended meta linking group, thereby preventing thin film recrystallization and ensuring device operation stability.

According to one embodiment of the present invention, in Formula 1, Ar ₁ may be selected from the group consisting of phenyl, biphenyl, naphthyl, phenanthrene, triphenylene, dibenzofuran, dibenzothiophene, and combinations thereof. You can. Specifically, Ar ₁ may be selected from the group consisting of phenyl, biphenyl, dibenzofuran, dibenzothiophene, and combinations thereof. In this case, a higher T1 can be maintained, enabling high efficiency and long lifespan of the organic light emitting device.

Additionally, in one embodiment of the present invention, the compound may be represented by the following formula (2).

[Formula 2]

In Formula 2,

R and R' are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₂₄ alkyl group, a substituted or unsubstituted C ₂ to C ₂₄ alkenyl group, a substituted or unsubstituted C ₁ to C ₂₄ alkoxy group, It is a substituted or unsubstituted C ₆ to C ₂₄ aryl group, or a substituted or unsubstituted C ₅ to C ₂₄ heteroaryl group. In Formula 2, the dotted line indicates direct bonding or no bonding.

The compound represented by Chemical Formula 2 facilitates pi-overlapping between molecules due to diphenylfluorene, and has excellent thin film arrangement of molecules, enabling long lifespan of organic light-emitting devices.

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

[Formula 3]

In Formula 3 above,

R and R' are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₂₄ alkyl group, a substituted or unsubstituted C ₂ to C ₂₄ alkenyl group, a substituted or unsubstituted C ₁ to C ₂₄ alkoxy group, A substituted or unsubstituted C ₆ to C ₂₄ aryl group, or a substituted or unsubstituted C ₅ to C ₂₄ heteroaryl group,

r and s are each independently integers from 0 to 3, and the sum of r and s is an integer of 1 or more. In Formula 3, the dotted line indicates direct bonding or no bonding.

The compound represented by Formula 3 has easy pi-overlapping between molecules due to diphenylfluorene, and has excellent thin film arrangement of molecules, enabling long lifespan of organic light-emitting devices. In addition, the aryl on one side of the arylamine connected to the 2-position of the diphenylfluorene contains a phenylene group as an intermediate linker so that it can be linked to dibenzofuran or dibenzothiophene through an extended meta linker, thereby maintaining an appropriate HOMO level. Form and maintain a higher T1.

Additionally, in one embodiment of the present invention, in Formulas 1 to 3, when L ₃ is phenylene, q may be an integer of 1 or more. In this case, the aryl on one side of the arylamine may have three or more aryls, and one or more aryls may be connected to the ortho or meta position to minimize extended conjugation. Accordingly, it is possible to form an appropriate HOMO level, maintain T1, and improve hole mobility.

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

[Formula 4]

In Formula 4 above,

R and R' are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₂₄ alkyl group, a substituted or unsubstituted C ₂ to C ₂₄ alkenyl group, a substituted or unsubstituted C ₁ to C ₂₄ alkoxy group, A substituted or unsubstituted C ₆ to C ₂₄ aryl group, or a substituted or unsubstituted C ₅ to C ₂₄ heteroaryl group,

r and s are each independently integers from 0 to 3, and the sum of r and s is an integer of 1 or more. In Formula 4, the dotted line means direct bond or no bond.

The compound represented by Formula 4 is a case where the aryl on one side of the arylamine is phenyl, and a high T1 can be formed through short conjugation, thereby maximizing the exciton confinement effect.

In one embodiment of the present invention, the compound may be represented by Formula 5 or Formula 6 below.

[Formula 5]

[Formula 6]

In Formula 5 or Formula 6,

R and R' are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₂₄ alkyl group, a substituted or unsubstituted C ₂ to C ₂₄ alkenyl group, a substituted or unsubstituted C ₁ to C ₂₄ alkoxy group, A substituted or unsubstituted C ₆ to C ₂₄ aryl group, or a substituted or unsubstituted C ₅ to C ₂₄ heteroaryl group,

r and s are each independently integers from 0 to 3, and the sum of r and s is an integer of 1 or more. In Formula 5 or Formula 6, the dotted line means direct bond or no bond.

The compound represented by Formula 5 or Formula 6 has two or more aryls on one side of the arylamine, but one aryl is connected to the meta or ortho position to minimize extended conjugation, forming HOMO and maintaining T1 at the same time. Hall mobility can be improved.

According to one embodiment of the present invention, in Formula 2, Formula 3, Formula 5, and Formula 6, Ar ₁ is phenyl, biphenyl, naphthyl, phenanthrene, triphenylene, dibenzofuran, dibenzothi It may be selected from the group consisting of ophene and combinations thereof. Specifically, Ar ₁ may be selected from the group consisting of phenyl, biphenyl, dibenzofuran, dibenzothiophene, and combinations thereof. In this case, a higher T1 can be maintained, enabling high efficiency and long lifespan of the organic light emitting device.

According to one embodiment of the present invention, the compounds represented by Formulas 1 to 6 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, numbers 1, 2, 29, 30, 53, 54, 77 to 84, 85, 86, 113, 114, 137 among the specific compounds. , 138, 161~168, 169, 170, 197, 198, 221, 222, 245~252, 253, 254, 281, 282, 305, 306, 329, 336, 449, 450, 478, 501, 502, 5 25 ~532, 533, 534, 561, 562, 585, 586, 609~616, 617, 618, 645, 646, 669, 670, 693~700, 701, 702, 729, 730, 753, 754, and 777~ It may be any one of the compounds of 784. In these compounds, the aryl on one side of the arylamine is phenyl, forming a high T1 through short conjugation, thereby maximizing the exciton confinement effect.

In addition, in one embodiment of the present invention, the compound represented by Formula 1 is more specifically, numbers 3, 4, 16 to 28, 31, 32, 40 to 52, 55, 56, 64 to 76 among the specific compounds. , 87, 88, 100~112, 115, 116, 124~136, 139, 140, 148~160, 171, 172, 184~196, 199, 200, 208~220, 223, 224, 232~244, 255 , 256, 268~280, 283, 284, 292~304, 307, 308, 316~328, 447, 451, 452, 464~476, 479, 480, 488~500, 503, 504, 512~524, 535 , 536, 548~560, 563, 564, 572~584, 587, 588, 596~608, 619, 620, 632~644, 647, 648, 656~668, 671, 672, 680~692, 703, 704 , 716-728, 731, 732, 740-752, 755, 756, and 764-776. In these compounds, the aryl on one side of the arylamine has two or more aryl groups, but one aryl group is connected to the meta or ortho position to minimize extended conjugation, forming HOMO and maintaining T1, while improving hole mobility.

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.

[Reaction formula]

In the above reaction formula, h is 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 comprising a compound represented by any one of Formulas 1 to 6 above. The organic light emitting device may include one or more organic 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. Additionally, the compounds of the present invention can be used alone or together with known compounds when forming an organic layer.

In one embodiment of the present invention, the organic light-emitting device may include, but may not be limited to, an organic material layer containing a hole transport material and an organic material layer containing the compound represented by Chemical Formula 1. 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 6.

The organic light-emitting device has an organic material layer such as a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL) between an anode and a cathode. It may include more than one floor.

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

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

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

The hole injection layer 200 may be formed by depositing a hole injection layer material on the anode electrode using a method such as vacuum deposition, spin coating, casting, or Langmuir-Blodgett (LB) method. When forming a hole injection layer by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material for the hole injection layer 200, the structure and thermal characteristics of the desired hole injection layer, but generally 50-500 deposition. Temperature, vacuum degree of 10 ^-8 to 10 ^-3 torr, deposition rate of 0.01 to 100 Å/sec, and layer thickness of 10 Å to 5 ㎛ can be appropriately selected.

Next, the hole transport layer 300 can be formed by depositing a hole transport layer material on top of the hole injection layer 200 by a method such as vacuum deposition, spin coating, casting, or LB method. When forming a hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but it is generally better to select conditions within the same range as those for forming the hole injection layer.

The hole transport layer 300 may be formed using a compound according to the present invention. As described above, the compound according to the present invention may be used alone or a known compound may be used together. Additionally, according to one embodiment of the present invention, the hole transport layer 300 may have one or more layers and may also include a hole transport layer formed only of known materials. Additionally, according to one embodiment of the present invention, a light emitting auxiliary layer can be formed on the hole transport layer 300.

The light emitting layer 400 can be formed by depositing a light emitting layer material on the hole transport layer 300 or the light emitting auxiliary layer by a method such as vacuum deposition, spin coating, casting, or LB method. When forming a light-emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but it is generally better to select conditions within the same range as those for forming the hole injection layer. Additionally, the light emitting layer material may use a known compound as a host or dopant.

In addition, when used with a phosphorescent dopant in the light emitting layer, a hole blocking material (HBL) can 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 any material can be selected from known hole blocking materials and used. For example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, or hole blocking materials described in Japanese Patent Application Laid-Open No. 11-329734 (A1), etc., representative examples include Balq (bis (8-hyde) Roxy-2-methylquinolinolnato)-aluminum biphenoxide), phenanthrolines-based compounds (e.g., UDC's BCP (bassocuproin)), etc. can be used.

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

Thereafter, the electron injection layer material can be deposited on top of the electron transport layer 500 to form the electron injection layer 600. At this time, the electron transport layer is formed by using a typical electron injection layer material using vacuum deposition, spin coating, or cast. It can be formed through methods such as laws.

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 be formed using a compound according to the present invention, or the following materials may be used, or a material according to the present invention may be used. Compounds and known substances 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 can be used as the cathode. Specific examples include materials such as aluminum, gold, and silver.

The organic light emitting device of the present invention is capable of having various structures as well as an organic light emitting device having an anode, hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer, and cathode structure. Depending on the need, 1 It is also possible to further form a layer or an intermediate layer of two layers.

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

In addition, the present invention has the advantage that the organic material layer containing the compound represented by Formula 1 has a uniform surface and excellent morphological stability because the thickness of the organic material layer can be adjusted on a molecular basis.

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

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

[ Example ]

Intermediate synthesis

To synthesize the target compound, the intermediate IM was synthesized as follows.

Manufacturing example 1 : Intermediate (IM1) synthesis

In a round bottom flask, dissolve 30.0 g of dibenzo[b,d]furan-4-ylboronic acid and 55.8 g of 4'-bromo-3-iodo-1,1'-biphenyl in 1000 ml of 1,4-dioxan and dissolve with K ₂ CO ₃ ( 210ml of 2M) and 4.9g of Pd(PPh ₃ ) ₄ were added, followed by refluxing and 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 recrystallized to obtain 40.7 g of intermediate IM1 (yield 72%).

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

Starting material of IM2 Starting material of IM3 Starting material of IM4 , , , dibenzo[b,d]furan-4-ylboronic acid, 3-bromo-4'-iodo-1,1'-biphenyl dibenzo[b,d]furan-4-ylboronic acid, 3,3'-dibromo-1,1'-biphenyl dibenzo[b,d]furan-2-ylboronic acid, 4'-bromo-3-iodo-1,1'-biphenyl Starting material of IM5 Starting material of IM6 , , dibenzo[b,d]thiophen-4-ylboronic acid, 4'-bromo-3-iodo-1,1'-biphenyl dibenzo[b,d]thiophen-2-ylboronic acid, 4'-bromo-3-iodo-1,1'-biphenyl

Manufacturing example 2 : Intermediate (OP) synthesis

OP1 was synthesized as follows.

In a round bottom flask, 20.0g of bromobenzene, 46.7g of 9,9-diphenyl-9H-fluoren-2-amine, 18.7g of t-BuONa, 4.7g of Pd2(dba)3, and 5.7ml of (t-Bu)3P were mixed with 700ml of toluene. It was dissolved in and 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 recrystallized to obtain 35.5 g of OP1 (yield 68%).

The following OP2 to OP5 were synthesized using the same method as OP1, but using different starting materials as shown in Table 2 below.

Starting material of OP2 Starting material of OP3 Starting material of OP4 , , , 9,9-diphenyl-9H-fluoren-2-amine, 3-bromo-1,1'-biphenyl 9,9-diphenyl-9H-fluoren-2-amine, 2-bromo-1,1'-biphenyl 9,9-diphenyl-9H-fluoren-2-amine, 4-bromo-1,1':3',1''-terphenyl Starting material of OP5 , 9,9-diphenyl-9H-fluoren-2-amine, 4-(2-bromophenyl)dibenzo[b,d]furan

compound synthesis

Target compounds 1 to 10 were synthesized using the intermediates IM1 to IM6 and OP1 to OP5.

Synthesis of Compound 1

In a round bottom flask, 3.0 g of IM1, 3.4 g of OP1, 1.1 g of t-BuONa, 0.3 g of Pd ₂ (dba) ₃ , and 0.3 ml of (t-Bu) ₃ P were dissolved in 90 ml of toluene and 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, then column purified and recrystallized to obtain 3.88 g of Compound 1 (yield 71%).

m/z: 727.29 (100.0%), 728.29 (60.0%), 729.29 (17.8%), 730.30 (3.5%)

Synthesis of Compound 2

Compound 2 was synthesized in the same manner as Compound 1 using OP2 instead of OP1 (yield 65%).

m/z: 803.32 (100.0%), 804.32 (66.4%), 805.33 (21.7%), 806.33 (4.8%)

Synthesis of Compound 3

Compound 3 was synthesized in the same manner as Compound 1 using O3 instead of OP1 (yield 70%).

m/z: 803.32 (100.0%), 804.32 (66.4%), 805.33 (21.7%), 806.33 (4.8%)

Synthesis of Compound 4

Compound 4 was synthesized in the same manner as Compound 1 using OP4 instead of OP1 (yield 70%).

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

Synthesis of compound 5

Compound 5 was synthesized in the same manner as Compound 1 using OP5 instead of OP1 (yield 67%).

m/z: 893.33 (100.0%), 894.33 (72.9%), 895.34 (26.3%), 896.34 (6.5%), 897.34 (1.2%)

Synthesis of compound 6

Compound 6 was synthesized in the same manner as Compound 1 using IM2 instead of IM1 (yield 65%).

m/z: 727.29 (100.0%), 728.29 (60.0%), 729.29 (17.8%), 730.30 (3.5%)

Synthesis of compound 7

Compound 7 was synthesized in the same manner as Compound 1 using IM3 instead of IM1 (yield 65%).

m/z: 727.29 (100.0%), 728.29 (60.0%), 729.29 (17.8%), 730.30 (3.5%)

Synthesis of compound 8

Compound 8 was synthesized in the same manner as Compound 1 using IM4 instead of IM1 (yield 75%).

m/z: 727.29 (100.0%), 728.29 (60.0%), 729.29 (17.8%), 730.30 (3.5%)

Synthesis of compound 9

Compound 9 was synthesized in the same manner as Compound 1 using IM5 instead of IM1 (yield 75%).

m/z: 743.26 (100.0%), 744.27 (59.9%), 745.27 (18.3%), 745.26 (4.5%), 746.27 (3.5%), 746.26 (2.7%), 744.26 (1.2%)

Synthesis of compound 10

Compound 10 was synthesized in the same manner as Compound 1 using IM6 instead of IM1 (yield 70%).

m/z: 743.26 (100.0%), 744.27 (59.9%), 745.27 (18.3%), 745.26 (4.5%), 746.27 (3.5%), 746.26 (2.7%), 744.26 (1.2%)

Organic light emitting device manufacturing

Example 1

A glass substrate coated with a 1500 Å thin film of indium tin oxide (ITO) was washed with distilled water ultrasonic waves. After cleaning with distilled water, ultrasonic cleaning with solvents such as isopropyl alcohol, acetone, and methanol, drying, and transferring to a plasma cleaner, the substrate is cleaned for 5 minutes using oxygen plasma, and then a thermal vacuum evaporator (thermal vacuum evaporator) is placed on the top of the ITO substrate. Using an evaporator, HI01 600 Å, HATCN 50 Å?, HT01 250 Å as a hole transport layer, and Compound 1 100 Å as a light-emitting auxiliary layer were deposited, and then the light-emitting layer was doped with 3% BH01:BD01 to form a 250 Å film. Next, 300Å of ET01:Liq (1:1) was deposited as an electron transport layer, followed by 10Å of LiF and 1000Å of aluminum (Al), and the organic light-emitting device was manufactured by encapsulating the device in a glove box.

Examples 2 to 10

An organic light-emitting device was manufactured using compounds 2 to 10 instead of compound 1 in the same manner as in Example 1.

Comparative Examples 1 to 7

An organic light-emitting device was manufactured in the same manner as in Example 1 using Ref.1 to Ref.7 below instead of Compound 1.

[Performance evaluation of organic light emitting devices]

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 the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, and the results are shown in Table 3 below.

Op. V mA/cm2 Cd/A QE(%) CIEx CIey LT97 Example 1 3.91 10 7.41 6.34 0.140 0.109 135 Example 2 3.95 10 7.48 6.30 0.140 0.110 123 Example 3 3.92 10 7.43 6.39 0.140 0.109 131 Example 4 3.91 10 7.45 6.30 0.140 0.110 128 Example 5 3.94 10 7.40 6.35 0.141 0.110 125 Example 6 3.96 10 7.50 6.40 0.140 0.110 120 Example 7 3.95 10 7.51 6.41 0.140 0.110 120 Example 8 3.95 10 7.43 6.40 0.140 0.109 130 Example 9 3.93 10 7.40 6.36 0.139 0.110 125 Example 10 3.93 10 7.43 6.36 0.141 0.110 125 Comparative Example 1 4.10 10 6.70 5.68 0.142 0.112 58 Comparative example 2 4.21 10 6.73 5.76 0.143 0.112 65 Comparative Example 3 4.31 10 6.78 5.44 0.141 0.113 72 Comparative Example 4 3.97 10 7.01 5.50 0.141 0.111 100 Comparative Example 5 4.00 10 6.90 5.35 0.141 0.110 85 Comparative Example 6 4.12 10 6.85 5.50 0.143 0.111 80 Comparative example 7 3.98 10 7.15 5.71 0.141 0.110 105

As shown in Table 3, the embodiments of the present invention were confirmed to have improved driving voltage and increased efficiency and lifespan compared to Comparative Examples 1 to 7.

More specifically, comparing Comparative Examples and Examples, compared to Comparative Example 1, the compounds of Examples had an extended meta-connector, and hole mobility was improved by increasing pi-conjugation, realizing long lifespan, and Comparative Examples 2 and 3 In comparison, the driving voltage of the compounds in the examples was improved by linking an arylamine to the 2-position of diarylfluorene to form a HOMO suitable for hole transport. In addition, compared to Comparative Example 4, the compounds of the Examples have high LUMO and T1 due to the extended meta linkage, and the compounds of the Examples facilitate intermolecular pi-overlapping due to diarylfluorene substitution compared to Comparative Examples 5 and 6. As a result, the molecular arrangement of the thin film was improved and the hole mobility was increased. Compared to Comparative Example 7, the compounds of the Examples had the aryl on one side of the arylamine directly bonded to the 2-position of diarylfluorene being phenylene, or It contains phenylene with an aryl group at the ortho or meta position and maintains HOMO and LUMO, which are very suitable for a light-emitting auxiliary layer, and high T1, enabling low driving voltage, and greatly improved efficiency and lifespan.

The description of the present application described above is for illustrative purposes, and those skilled in the art will understand that the present application can be easily modified into other specific forms without changing its technical idea or essential features. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as unitary may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.

The scope of the present application is indicated by the claims described below rather than the detailed description above, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts 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 the following formula (1);
[Formula 1]

In Formula 1,
Ar, Ar' and Ar ₁ are each independently a substituted or unsubstituted aryl group of C ₆ to C ₃₀ , and Ar and Ar' may be connected to form a ring or may not form a ring,
R ₁ to R ₄ are each independently hydrogen, deuterium, or a substituted or unsubstituted C ₆ to C ₃₀ aryl group,
R ₅ and R ₆ are each independently hydrogen and deuterium,
L ₁ to L ₃ are each independently a direct bond, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, provided that at least one of L ₁ and L ₂ is a substituted or unsubstituted C ₆ to C ₃₀ arylene group,
X is S or O,
l, o, p, and q are each independently an integer from 0 to 4, and m and n are each independently an integer from 0 to 3. However, when L ₃ is phenylene, q is an integer of 1 or more. According to paragraph 1,
The compound is represented by the following formula.
[Formula 2]

In Formula 2,
R and R' are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₂₄ alkyl group, a substituted or unsubstituted C ₂ to C ₂₄ alkenyl group, a substituted or unsubstituted C ₁ to C ₂₄ alkoxy group, It is a substituted or unsubstituted aryl group of C ₆ to C ₂₄ ,
The dotted line indicates direct binding or no binding. According to paragraph 1,
The compound is represented by the following formula (3).
[Formula 3]

In Formula 3 above,
R and R' are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₂₄ alkyl group, a substituted or unsubstituted C ₂ to C ₂₄ alkenyl group, a substituted or unsubstituted C ₁ to C ₂₄ alkoxy group, It is a substituted or unsubstituted aryl group of C ₆ to C ₂₄ ,
r and s are each independently integers from 0 to 3, and the sum of r and s is an integer of 1 or more,
The dotted line indicates direct binding or no binding. According to paragraph 1,
The compound is represented by the following formula (4).
[Formula 4]

In Formula 4 above,
R and R' are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₂₄ alkyl group, a substituted or unsubstituted C ₂ to C ₂₄ alkenyl group, a substituted or unsubstituted C ₁ to C ₂₄ alkoxy group, It is a substituted or unsubstituted aryl group of C ₆ to C ₂₄ ,
r and s are each independently integers from 0 to 3, and the sum of r and s is an integer of 1 or more,
The dotted line indicates direct binding or no binding. According to paragraph 1,
The compound is represented by the following Chemical Formula 5 or Chemical Formula 6.
[Formula 5]

[Formula 6]

In Formula 5 or Formula 6,
R and R' are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₂₄ alkyl group, a substituted or unsubstituted C ₂ to C ₂₄ alkenyl group, a substituted or unsubstituted C ₁ to C ₂₄ alkoxy group, It is a substituted or unsubstituted aryl group of C ₆ to C ₂₄ ,
r and s are each independently integers from 0 to 3, and the sum of r and s is an integer of 1 or more,
The dotted line indicates direct binding or no binding. According to paragraph 1,
Wherein Ar ₁ is a compound selected from the group consisting of phenyl, biphenyl, and combinations thereof. According to paragraph 1,
The compound is any one of the following compounds.





According to paragraph 1,
The compound is any one of the following compounds:





An organic light-emitting device comprising an organic layer containing the compound according to any one of claims 1 to 8 between the first electrode and the second electrode. According to clause 9,
An organic light emitting device wherein the organic material layer is at least one of a hole injection layer, a hole transport layer, and a light emitting auxiliary layer.