KR20210097497A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention is an organic compound for forming an organic thin film disposed between a first electrode and a second electrode of an organic electric element, wherein a core comprises a compound containing carbazole, and at least two amide functional groups are included at the ends of the core.

Description

A compound for an organic electric device, an organic electric device using the same, and an electronic device thereof

The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic layer is often formed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

A material used as an organic layer in an organic electric device may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.

The term 'organic electronic device' used in the present invention is an organic integrated circuit (OIC), an organic field-effect transistor (OFET), an organic thin film transistor (OTFT), an organic light emitting transistor (OLET), an organic solar cell (OSC), It is defined to include organic photodetectors, organic photoreceptors, organic electro-quenching devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs), and the like.

The present invention is particularly interested in providing novel organic compounds for use in organic electrical devices referred to as OLEDs. The general structure of OLEDs and their functional principles are well known to the person skilled in the art and are described in particular in US 4539507, US 5151629, EP 0676461 and WO 1998/27136.

OLED (organic photoelectric device), which is attracting attention as a next-generation display device, forms an organic light emitting layer between a substrate coated with a transparent anode material such as ITO and a cathode. It is a device using the principle that electrons combine in an organic light emitting layer to emit light. OLEDs are receiving increasing attention for their applications in electronic devices such as flat panel displays, lighting and backlighting. OLED technology is described in Geffroy et al., "Organic Light Emitting Diode (OLED) Technology: Material Device and Display Technology," Polym, Int., 55:572-582 (2006), and in US Pat. Nos. 5,844,363, 6,303,238 and 5,707,745, the various OLED materials and configurations described, all of which are incorporated herein by reference.

An organic electroluminescent device (OLED) has a multilayer structure including a charge blocking layer according to the characteristics of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and a light emitting layer in addition to an organic light emitting layer in order to realize industrially applicable level of performance. is made with

In the prior art, each layer constituting an organic electric device (especially OLED) is generally formed by a vacuum deposition process. Japanese Patent Laid-Open No. 2006-156847 (Patent Document 1) discloses an organic compound and a technique for manufacturing an organic electric device including an organic film having a single layer structure by depositing the same on a substrate by vacuum deposition. The vacuum deposition method is ^{a principle of forming a thin film by applying heat to a sample in a high vacuum atmosphere of 10 -4} Torr or less to sublimate it, and the sublimated sample is grown as a solid on a substrate at a relatively low temperature. However, in the vacuum deposition method, the deposition apparatus is large and not easy to install, the vacuum must be maintained during the process, the process temperature is high, and in particular, because a mask is used for the pattern, the material consumption rate is high, so the productivity is low and the manufacturing cost is high Therefore, it is difficult to manufacture an organic electric device with a large area.

In order to solve this problem, research to form an organic thin film through a low-cost solution process has been continuously conducted. The solution process has the disadvantage that the resolution is not high compared to the vacuum deposition process, but since it can be manufactured at atmospheric pressure and atmospheric temperature, a separate vacuum device is not required. The advantage is that it can be expanded to a large area.

Such solution processes include spin coating, inkjet coating, screen printing, spray coating, roll-to-roll coating, and blade coating. Specific examples of a method for manufacturing a large-area organic thin film based on a solution process and an apparatus thereof are disclosed in Korean Patent Application Laid-Open No. 2016-0069799, Korean Patent Publication No. 10-1618395, Korean Patent Application Laid-Open No. 2017-0066703, It is detailed in Korean Patent Publication No. 10-1618395, Korean Patent Application Laid-Open No. 2016-0141127, and Korean Patent Publication No. 2016-0138845. In addition, thermal printing techniques and devices that can be used are described, for example, in US Patent Application Publications US 2008/0311307 A1, US 2008/0308037 A1, US2006/0115585 A1, US 2010/0188457 A1, US 2011/0008541 A1, US 2010/ 0171780 A1, and those described in US 2010/0201749 A1, which are incorporated herein by reference in their entirety.

However, when coating the multilayer organic film for an organic electric device using a solution process, there is a problem in that the organic thin film of the lower layer is damaged by the organic solvent contained in the organic compound of the upper layer, so it is difficult to form the multilayer thin film. In order to solve this problem, an organic compound having a cross-linking functional group must be used, and the known cross-linking groups are styrene, acrylate, oxetane, and the like. However, since these crosslinking groups require a high crosslinking temperature for the crosslinking reaction, it is difficult to use a plastic substrate. In addition, in the case of UV crosslinking, there is a disadvantage in that a photoinitiator is used or a byproduct is generated, which causes problems in the lifespan and efficiency of the organic electric device.

Therefore, new organic compounds capable of manufacturing an organic electric device having a multi-layer structure without dissolving adjacent layers when a solution process is applied have been developed by the present inventors. First, Korean Patent Application Laid-Open No. 2017-0035228 (Patent Document 2) describes an organic device having solubility in a hydrophilic solvent by binding an alcohol-based functional group to the terminal of a carbazole-based compound and a triphenylamine-based compound having excellent charge transport properties. The compound is provided, and Korean Patent Application Laid-Open No. 2017-0117812 (Patent Document 3) is a novel hole blocking and/or electron transporting small molecule capable of hydrogen bonding and having at least two substituents including a pyrimidine ring. Provides a compound, and Republic of Korea Patent Publication No. 10-1789672 (Patent Document 4) discloses a pyrimidine ring having a property capable of hydrogen bonding at the terminal of a carbazole-based compound comprising carbazole having forward transport properties and phosphorescence properties Providing an organic light emitting compound capable of forming a stable organic thin film by having a functional group containing do.

JP 2006-156847 A US 2017-0035228 A US 2017-0117812 A US 10-1789672 B1

“Organic Light-Emitting Diode (OLED) Technology: Material Devices and Display Technology”, Polym, Int., 55:572-582 (2006)

The technical problem to be achieved by the present invention is to produce a novel compound for an organic electric device that is capable of crosslinking through hydrogen bonding at a low temperature of 120 ° C. or less and has excellent efficiency and lifespan characteristics by not generating byproducts and this compound to provide a way to

In particular, another object of the present invention is to provide an organic thin film for an organic electric device in which hydrogen bonding is generated through heating at a low temperature of about 120° C., which is not soluble in an organic solvent.

In addition, another object of the present invention is to provide an organic electric device including an OLED formed by stacking such an organic thin film in multiple layers, and an electronic device including the organic electric element.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. There will be.

A first aspect of the present invention for achieving the above technical problem is an organic compound for forming an organic thin film disposed between a first electrode and a second electrode of an organic electric device, comprising carbazole in a core It has a compound and is characterized as a material having the following formula including at least two or more amide groups at the ends of the core.

Another second aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, and the core It is characterized in that it is a material having the following formula including at least two or more amide groups at the ends of the.

Another third aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, and the core It is characterized in that it is a material having the following formula including at least two or more amide groups at the ends of the.

Another fourth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, and the core It is characterized in that it is a material having the following formula including at least two or more amide groups at the ends of the.

Another fifth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, and the core It is characterized in that it is a material having the following formula including at least two or more amide groups at the ends of the.

Another sixth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, and the core It is characterized in that it is a material having the following formula including at least two or more amide groups at the ends of the.

Another seventh aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, and the core It is characterized in that it is a material having the following formula including at least two or more amide groups at the ends of the.

Another eighth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, It is characterized in that it is a material having the following formula including at least two or more amide groups at the end of the core.

Another ninth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, It is characterized in that it is a material having the following formula including at least two or more amide groups at the end of the core.

Another tenth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, It is characterized in that it is a material having the following formula including at least two or more amide groups at the end of the core.

Another eleventh aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, It is characterized in that it is a material having the following formula including at least two or more amide groups at the end of the core.

Another twelfth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has a compound containing carbazole in a core, It is characterized in that it is a material having the following formula including at least two or more amide groups at the end of the core.

The organic compound is at least one selected from the group consisting of a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron injection layer material, an electron transport layer material, an electron blocking layer material, and a hole blocking layer material among organic thin film materials for an organic electric device. It is characterized in that it is used for the purpose.

Another thirteenth aspect of the present invention is an ink composition for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, comprising any one of the organic compounds of the first to twelfth aspects. characterized by including.

Another fourteenth aspect of the present invention is an organic electric device in which an organic thin film layer comprising at least a light emitting layer or a plurality of layers is sandwiched between a cathode and an anode, wherein the organic compound for forming the organic thin film layer comprises the first It is characterized in that it is any one of the 1st to 12th aspects.

Hydrogen bonds are formed between amide functional groups at the ends of the organic compounds forming the organic thin film layer.

The organic thin film layer is characterized in that at least one selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer and a hole blocking layer.

The organic electric device according to the fourteenth aspect has a structure in which 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 are stacked in this order. In addition, the organic thin film layer is characterized in that it is prepared by coating the ink composition containing the organic compound by a solution process and drying it to form a film.

Another fifteenth aspect of the present invention is an electronic device including the organic electric device according to the fourteenth aspect.

According to an embodiment of the present invention, by providing an amide group at the end of the compound for an organic electric device, the solubility of a low molecular weight organic compound with low solubility can be improved, and as the solubility is improved, it can be applied to a solution process with high productivity. The first effect that the compound has two or more amide groups, the second effect that a stable organic thin film can be formed by hydrogen bonding between amides, and even if an organic thin film layer having a multilayer structure is formed through a solution process, the adjacent layer is a solution It has a third effect that it is possible to fabricate a device having a stable multi-layer structure without dissolution by

The organic compound according to the present invention may have improved solubility in various solvents by having an amide group capable of hydrogen bonding. In addition, in the prior art, low molecular weight organic compounds are mainly formed through a vapor deposition process due to poor solubility, and the organic compound according to the present invention can provide properties suitable for various solution processes by improving solubility.

In addition, in the prior art, even if an organic thin film is formed through a solution process, there is a problem in that it must be performed under high temperature conditions in order to form a stable organic thin film. However, the organic compound according to the present invention not only has excellent solubility in solvents, but also can form a heat-stable thin film even at a low temperature process due to hydrogen bonding between functional groups provided in the compound. This may enable cost reduction.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments 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 specification, when a part is said to be “connected (connected, contacted, coupled)” with another part, it is not only “directly connected” but also “indirectly connected” with another member interposed therebetween. "Including cases where In addition, when a part "includes" a certain component, this means that other components may be further provided without excluding other components unless otherwise stated.

The terms used herein are used only to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In this specification, terms such as "comprises" or "have" are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

The terminology used in the specification is only used to describe a specific embodiment (aspect, aspect, aspect) (or embodiment), and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as comprises or consists of are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and chemical formulas.

The organic compound according to the present invention comprises a light emitting layer (EML) material, a hole injection layer (HIL) material, a hole transport layer (HTL) material for forming various organic thin films disposed between the first electrode and the second electrode of the organic electric device; It relates to an organic compound that can be used in various ways, such as an electron injection layer (EIL) material, an electron transport layer (ETL) material, an electron blocking layer (EBL) material, and a hole blocking layer (HBL) material.

That is, the organic compound according to the present invention is the light emitting layer (EML), hole injection layer (HIL), hole transport layer (HTL), electron injection layer (EIL), electron transport layer (ETL), electron blocking layer (EBL) and hole blocking layer A compound containing carbazole of the following structural formula is used as a core material to form an organic thin film such as a layer (HBL),

It is characterized in that at least two or more amide groups are formed at the end of the compound containing carbazole.

For this reason, when the organic compound according to the present invention is heated at a temperature of about 120° C., crosslinking occurs due to hydrogen bonding between the at least two or more amide functional groups.

In the case of an organic thin film made of an organic compound in which hydrogen bonds are formed, since it does not dissolve in the organic solvent of the adjacent organic thin film layer, the thin film is not damaged even when multi-layered thin films are stacked through a solution process. is optimized to

In one embodiment of the present invention, a core material for forming an organic thin film for an organic electric device includes a compound containing carbazole, and at least two at the end of the compound containing carbazole Specific examples of the organic compound according to the present invention containing the above amide functional group are as follows.

In another embodiment of the present invention, the organic compound according to the present invention comprising at least two or more amide functional groups at the end of the core material containing carbazole as in the above-mentioned [Formula 1] to [Formula 12] It provides an ink composition comprising.

The ink composition may be a solution or suspension containing a solvent, and the solvent is, for example, anisole, dimethyl anisole, xylene, o-xylene, m-xylene, p-xylene, toluene, mesitylene, methyl. Benzoate, dioxane, tetrahydrofuran, methyl tetrahydrofuran, tetrahydropyran, tetralin, veratrol, chlorobenzene, N-methyl pyrrolidone, N,N-dimethylformamide, dimethylsulfoxide and combinations thereof It may include one selected from the group consisting of.

An organic thin film layer may be formed by coating the ink composition and then forming a film by removing the solvent. The ink composition may further include a pigment or dye. The ink composition may further include a phosphorescent dopant or a fluorescent dopant.

In another embodiment of the present invention, in the organic electric device in which an organic thin film layer comprising at least one layer or a plurality of layers including at least a light emitting layer is stacked between the cathode and the anode in multiple layers, at least one of the organic thin film layers is the [Formula 1] to [Formula 12] provides an organic electric device, characterized in that it contains any one organic compound selected from. In particular, the organic electric device is preferably an organic electroluminescent device (OLED).

The organic thin film layer may be prepared by forming a film by a solution process using the above-described ink composition including the organic compound according to the present invention. This solution process includes any one method selected from the group consisting of spin coating, gravure offset printing, reverse offset printing, screen printing, roll-to-roll printing, slot die coating, dip coating, spray coating, doctor blade coating, and inkjet coating. do.

In the organic thin film layer, the organic compound is a light emitting layer (EML) material, a hole injection layer (HIL) material, a hole transport layer (HTL) material, an electron injection layer (EIL) material, an electron transport layer (ETL) material, an electron blocking layer (EBL) It may include a layer formed by including at least one selected from the group consisting of a material and a hole blocking layer (HBL) material. The light emitting layer (EML) material may be a phosphorescent or fluorescent host and a phosphorescent dopant or a fluorescent dopant material.

In particular, the organic light emitting diode (OLED) may have a structure in which 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 are stacked in this order. The light emitting layer may include a phosphorescent dopant or a fluorescent dopant including red, green, blue, or white, together with the organic compound according to the present invention. For example, the phosphorescent dopant may be an organometallic compound including one or more elements selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb and Tm.

In addition, the hole transport layer, the hole injection layer, the hole blocking layer, the electron injection transport layer, the electron transport layer, the electron injection layer and the electron blocking layer above [Formula 1] to [Formula 12] any one or more organic compounds may include

Hereinafter, an organic electroluminescent device (OLED) as an organic electric device according to the present invention will be described as an example. The organic electroluminescent device of the present invention may have a structure in which an anode (hole injection electrode), a hole injection layer (HIL) and/or a hole transport layer (HTL), a light emitting layer (EML) and a cathode (electron injection electrode) are sequentially stacked. and, preferably, an electron blocking layer (EBL) between the anode and the light emitting layer (EML), and an electron transport layer (ETL), an electron injection layer (EIL) or a hole blocking layer (HBL) between the cathode and the light emitting layer (EML) may further include.

In the method of manufacturing an organic light emitting diode according to the present invention, first, a material for an anode is coated on a substrate surface in a conventional manner to form an anode. In this case, the substrate used is preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and waterproofing properties. In addition, as the material for the anode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), etc. which are transparent and have excellent conductivity may be used.

Next, a hole injection layer (HIL) is formed by spin coating a hole injection layer (HIL) material on the surface of the anode, and a hole transport layer (HTL) material is spin coated on the surface of the hole injection layer (HIL) to form a hole transport layer ( HTL), spin coating an emission layer (EML) material on the surface of the hole transport layer (HTL) to form an emission layer (EML), and spin coating an electron transport layer (ETL) material on the surface of the emission layer (EML) to form an electron transport layer (ETL) is formed.

At this time, optionally, by additionally forming a hole blocking layer (HBL) between the emission layer (EML) and the electron transport layer (ETL) and using a phosphorescent dopant together in the emission layer (EML), triplet excitons or holes are transferred to the electron transport layer ( ETL) can be prevented from spreading. The hole blocking layer (HBL) may be formed by spin coating a hole blocking layer (HBL) material, and in the case of the hole blocking layer (HBL) material, the organic compounds of [Formula 1] to [Formula 12] compounds may be used.

An electron injection layer (EIL) is formed by spin coating an electron injection layer (EIL) material on the surface of the electron transport layer (ETL). Finally, a cathode is formed by vacuum thermal evaporation of a material for a cathode on the surface of the electron injection layer (EIL) in a conventional manner. At this time, as the material for the anode used, lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like can be used. In addition, in the case of a top-emitting organic electroluminescent device, a transparent cathode through which light can pass may be formed using indium tin oxide (ITO) or indium zinc oxide (IZO).

The organic electroluminescent device according to the present invention may be manufactured in the same order as described above, that is, anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode, and vice versa. Electron injection layer / electron transport layer / hole blocking layer / light emitting layer / hole transport layer / hole injection layer / anode may be prepared in the order.

In another embodiment of the present invention, there is provided an electronic device including the organic light emitting device.

Hereinafter, the synthesis method of the [Formula 1] to [Formula 12], which are organic compounds according to the present invention, will be described below through representative examples. However, the method for synthesizing the organic compounds of the present invention is not limited to the methods exemplified below, and the organic compounds of the present invention may be prepared by the methods illustrated below and methods known in the art.

<Synthesis Example 1>

The organic compound of [Formula 1] was synthesized according to the following [Scheme 1].

[Scheme 1]

(1) Preparation of intermediate (a)

In a 250 mL two-neck flask under a nitrogen atmosphere, 3,6-diamine carbazole (5 g, 0.025 mol) and MC (60 mL) were added and stirred. After adjusting the temperature to 0 °C with an ice-bath, heptanoyl chloride (7.7 mL, 0.05 mol) dissolved in MC (10 mL) is slowly added dropwise. Remove the ice-bath, and proceed with the reaction at 80 ℃ for 4 hours. After completion of the reaction, the solid state crude is filtered and washed several times with dichloromethane. Purification by column chromatography (MC:MeOH = 1:20) to obtain an intermediate (a) of the following structural formula.

Intermediate (a)

(2) Preparation of organic compounds

The intermediate (a) (3g, 0.007mol), tris(4-bromophenyl)amine (1.14g, 0.0023mol), potassium phosphate (2.2g, 0.0092mol), CuI in a 250mL one-neck flask under nitrogen atmosphere (0.1g, 0.0002mol), trans-1,2-diaminocyclohexane (0.37mL, 0.0023mol), and 1,4-dioxane (100mL) are added. The reaction is allowed to proceed at 80° C. for 48 hours. After completion of the reaction, quenching was carried out and the organic solvent was removed under reduced pressure. The solid mixture is purified by column chromatography (MC:MeOH = 8:1) to obtain an organic compound of the following [Formula 1] (yield 36%).

[Formula 1]

<Synthesis Example 2>

The organic compound of [Formula 2] was synthesized according to the following [Scheme 2].

[Scheme 2]

(1) Preparation of intermediate (a)

In a 250 mL two-neck flask under a nitrogen atmosphere, 3,6-diamine carbazole (5 g, 0.025 mol) and MC (60 mL) were added and stirred. After adjusting the temperature to 0 °C with an ice-bath, heptanoyl chloride (7.7 mL, 0.05 mol) dissolved in MC (10 mL) is slowly added dropwise. Remove the ice-bath, and proceed with the reaction at 80 ℃ for 4 hours. After completion of the reaction, the solid state crude is filtered and washed several times with dichloromethane. Purification by column chromatography (MC:MeOH = 1:20) to obtain an intermediate (a) of the following structural formula.

Intermediate (a)

(2) Preparation of organic compounds

The intermediate (a) (2.6 g, 0.006 mol), 4,4'-dibromo-1,1'-biphenyl (0.72 g, 0.0023 mol), potassium phosphate (1.86 g, 0.0078) in a 250 mL one-neck flask under nitrogen atmosphere mol), CuI (0.1 g, 0.0002 mol), trans-1,2-diaminocyclohexane (0.37 mL, 0.0023 mol), and 1,4-dioxane (100 mL) are added. The reaction is allowed to proceed at 80° C. for 48 hours. After completion of the reaction, quenching is carried out and the organic solvent is removed under reduced pressure. The solid mixture is purified by column chromatography (MC:MeOH = 8:1) to obtain an organic compound of the following [Formula 2] (yield: 42%).

[Formula 2]

<Synthesis Example 3>

The organic compound of [Formula 3] was synthesized according to the following [Scheme 3].

[Scheme 3]

(1) Preparation of intermediate (a)

In a 250 mL two-neck flask under a nitrogen atmosphere, 3,6-diamine carbazole (5 g, 0.025 mol) and MC (60 mL) were added and stirred. After adjusting the temperature to 0 °C with an ice-bath, heptanoyl chloride (7.7 mL, 0.05 mol) dissolved in MC (10 mL) is slowly added dropwise. Remove the ice-bath, and proceed with the reaction at 80 ℃ for 4 hours. After completion of the reaction, the solid state crude is filtered and washed several times with dichloromethane. Purification by column chromatography (MC:MeOH = 1:20) to obtain an intermediate (a) of the following structural formula.

Intermediate (a)

(2) Preparation of organic compounds

The intermediate (a) (3g, 0.007mol), 1,3,5-tribromobenzene (0.723g, 0.0023mol), potassium phosphate (2.2g, 0.0092mol), CuI (0.1g) in a 250mL one-neck flask under nitrogen atmosphere , 0.0002mol), trans-1,2-diaminocyclohexane (0.37mL, 0.0023mol), and 1,4-dioxane (100mL) are added. The reaction is allowed to proceed at 80° C. for 48 hours. After completion of the reaction, quenching is carried out and the organic solvent is removed under reduced pressure. The solid mixture is purified by column chromatography (MC:MeOH = 8:1) to obtain an organic compound of the following [Formula 3] (yield: 35%).

[Formula 3]

<Synthesis Example 4>

The organic compound of [Formula 4] was synthesized according to the following [Scheme 4].

[Scheme 4]

(1) Preparation of intermediate (a)

In a 250 mL two-neck flask under a nitrogen atmosphere, 3,6-diamine carbazole (5 g, 0.025 mol) and MC (60 mL) were added and stirred. After adjusting the temperature to 0°C with an ice-bath, heptanoyl chloride (7.7 mL, 0.05 mol) dissolved in MC (10 mL) is slowly added dropwise. Remove the ice-bath, and proceed with the reaction at 80 ℃ for 4 hours. After completion of the reaction, the solid state crude is filtered and washed several times with dichloromethane. Purification by column chromatography (MC:MeOH = 1:20) to obtain an intermediate (a) of the following structural formula.

Intermediate (a)

(2) Preparation of organic compounds

Intermediate (a) (2.6g, 0.006mol), 4,4'-dibromo-1,1'-biphenyl (0.72g , 0.0023mol), potassium phosphate (1.86g, 0.0078mol) in a 250mL one-neck flask under nitrogen atmosphere ), CuI (0.1 g, 0.0002 mol), trans-1,2-diaminocyclohexane (0.37 mL, 0.0023 mol), and 1,4-dioxane (100 mL) are added. The reaction is allowed to proceed at 80° C. for 48 hours. After completion of the reaction, quenching was carried out and the organic solvent was removed under reduced pressure. The solid mixture is purified by column chromatography (MC:MeOH = 8:1) to obtain an organic compound of the following [Formula 4] (yield: 42%).

[Formula 4]

<Synthesis Example 5>

The organic compound of [Formula 5] was synthesized according to the following [Scheme 5].

[Scheme 5]

(1) Preparation of intermediate (a)

In a 250 mL two-neck flask under a nitrogen atmosphere, 3,6-diamine carbazole (5 g, 0.025 mol) and MC (60 mL) were added and stirred. After adjusting the temperature to 0°C with an ice-bath, heptanoyl chloride (7.7 mL, 0.05 mol) dissolved in MC (10 mL) is slowly added dropwise. Remove the ice-bath, and proceed with the reaction at 80 ℃ for 4 hours. After completion of the reaction, the solid state crude is filtered and washed several times with dichloromethane. Purification by column chromatography (MC:MeOH = 1:20) to obtain an intermediate (a) of the following structural formula.

Intermediate (a)

(2) Preparation of organic compounds

Intermediate (a) (1.6 g, 0.0039 mol), 2,2',7,7'-Tetrabromo-9,9'-spirobi[9H-fluorene] (0.47 g, 0.00075 mol) in a 250 mL one-neck flask under nitrogen atmosphere ), potassium phosphate (1.4 g, 0.0051 mol), CuI (0.05 g, 0.0001 mol), trans-1,2-diaminocyclohexane (0.12 mL, 0.00075 mol), and 1,4-dioxane (50 mL) are added. The reaction is allowed to proceed at 80° C. for 48 hours. After completion of the reaction, quenching was carried out and the organic solvent was removed under reduced pressure. The solid mixture is purified by column chromatography (MC:MeOH = 8:1) to obtain an organic compound of the following [Formula 5] (yield: 23%).

[Formula 5]

<Synthesis Example 6>

The organic compound of [Formula 6] was synthesized according to the following [Scheme 6].

[Scheme 6]

(1) Preparation of intermediate (a)

In a 250 mL two-neck flask under a nitrogen atmosphere, 3,6-diamine carbazole (5 g, 0.025 mol) and MC (60 mL) were added and stirred. After adjusting the temperature to 0°C with an ice-bath, heptanoyl chloride (7.7 mL, 0.05 mol) dissolved in MC (10 mL) is slowly added dropwise. Remove the ice-bath, and proceed with the reaction at 80 ℃ for 4 hours. After completion of the reaction, the solid state crude is filtered and washed several times with dichloromethane. Purification by column chromatography (MC:MeOH = 1:20) to obtain an intermediate (a) of the following structural formula.

Intermediate (a)

(2) Preparation of organic compounds

Intermediate (a) (2.6 g, 0.006 mol), 2,7-Dibromo-9,9-dimethylfluorene (0.88 g, 0.0025 mol), potassium phosphate (1.86 g, 0.0078 mol) in a 250 mL one-neck flask under nitrogen atmosphere , CuI (0.1 g, 0.0002 mol), trans-1,2-diaminocyclohexane (0.38 mL, 0.0025 mol), and 1,4-dioxane (100 mL) are added. The reaction is allowed to proceed at 80° C. for 48 hours. After completion of the reaction, quenching was carried out and the organic solvent was removed under reduced pressure. The solid mixture is purified by column chromatography (MC:MeOH = 8:1) to obtain an organic compound of the following [Formula 6] (yield: 46%).

[Formula 6]

<Synthesis Example 7>

The organic compound of [Formula 7] was synthesized according to the following [Scheme 7].

[Scheme 7]

(1) Preparation of intermediate (a)

In a 250 mL two-neck flask under a nitrogen atmosphere, 3,6-diamine carbazole (5 g, 0.025 mol) and MC (60 mL) were added and stirred. After adjusting the temperature to 0°C with an ice-bath, heptanoyl chloride (7.7 mL, 0.05 mol) dissolved in MC (10 mL) is slowly added dropwise. Remove the ice-bath, and proceed with the reaction at 80 ℃ for 4 hours. After completion of the reaction, the solid state crude is filtered and washed several times with dichloromethane. Purification by column chromatography (MC:MeOH = 1:20) to obtain an intermediate (a) of the following structural formula.

Intermediate (a)

(2) Preparation of organic compounds

The intermediate (a) (0.86g, 0.002mol), 2-(4-Bromophenyl)-4,6-diphenylpyrimidine (0.77g, 0.002mol), potassium phosphate (0.65g, 0.0026) in a 250mL one-neck flask under nitrogen atmosphere mol), CuI (0.35 g, 6.8E-5 mol), trans-1,2-diaminocyclohexane (0.32 mL, 0.223 mol), and 1,4-dioxane (50 mL) are added. The reaction is allowed to proceed at 80° C. for 48 hours. After completion of the reaction, quenching was carried out and the organic solvent was removed under reduced pressure. The solid mixture is purified by column chromatography (MC:MeOH = 8:1) to obtain an organic compound of the following [Formula 7] (yield: 53%).

[Formula 7]

<Synthesis Example 8>

The organic compound of [Formula 8] was synthesized according to the following [Scheme 8].

[Scheme 8]

(1) Preparation of intermediate (a)

In a 250 mL two-neck flask under a nitrogen atmosphere, 3,6-diamine carbazole (5 g, 0.025 mol) and MC (60 mL) were added and stirred. After adjusting the temperature to 0°C with an ice-bath, heptanoyl chloride (7.7 mL, 0.05 mol) dissolved in MC (10 mL) is slowly added dropwise. Remove the ice-bath, and proceed with the reaction at 80 ℃ for 4 hours. After completion of the reaction, the solid state crude is filtered and washed several times with dichloromethane. Purification by column chromatography (MC:MeOH = 1:20) to obtain an intermediate (a) of the following structural formula.

Intermediate (a)

(2) Preparation of organic compounds

The intermediate (a) (1 g, 0.0024 mol), (3,5-Dibromophenyl) triphenylsilane (0.5 g, 0.001 mol), potassium phosphate (0.75 g, 0.003 mol), CuI (0.05) in a 250 mL one-neck flask under a nitrogen atmosphere g, 0.0001 mol), trans-1,2-diaminocyclohexane (0.18 mL, 0.001 mol), and 1,4-dioxane (50 mL) are added. The reaction is allowed to proceed at 80° C. for 48 hours. After completion of the reaction, quenching was carried out and the organic solvent was removed under reduced pressure. The solid mixture is purified by column chromatography (MC:MeOH = 8:1) to obtain an organic compound of the following [Formula 9] (yield: 36%).

[Formula 8]

<Synthesis Example 9>

The organic compound of [Formula 9] was synthesized according to the following [Scheme 9].

[Scheme 9]

(1) Preparation of intermediate (b)

Under a nitrogen atmosphere, 4-Iodoaniline (5g, 22.8mmol) and MC (50ml) were added to a 250mL two-necked round-bottom flask and stirred. After adjusting the temperature to 0℃ with an ice-bath, butyryl chloride (2.45 mL, 22.8 mmol) dissolved in MC (15 mL) is slowly added dropwise. Remove the ice-bath, and proceed the reaction at 70 ℃ for 8 hours. After completion of the reaction, the resulting powder is filtered and washed several times with MC. After removing the solvent, it is recrystallized from MC-Hexane to obtain an intermediate (b) of the following structural formula (Yield: 4.9 g, 71%).

Intermediate (b)

(2) Preparation of organic compounds

Add dichlorobenzene (50 mL) to a 100 mL two-necked round-bottom flask and add dry nitrogen. The intermediate (b) (4.5 g, 14.8 mmol), 5,11-dihydroindolo [3,2-b] carbazole (1.7 g, 6.7 mmol), Cu powder (1.2 g, 18.4 mmol), potassium carbonate (7.4 g, 53.6mmol) and 18-crown-6 (0.34g, 1.3mmol) were added and stirred under reflux at 180°C for 48 hours. After completion of the reaction, extraction is performed with water and MC. After removing residual moisture with MgSO ₄ , purification is performed by column chromatography using EA: Hex to obtain an organic compound (Yield: 1.8 g, 43%) of the following [Formula 9].

[Formula 9]

<Synthesis Example 10>

The organic compound of [Formula 10] was synthesized according to the following [Scheme 10].

[Scheme 10]

(1) Preparation of intermediate (c)

Add dichlorobenzene (20 mL) to a 100 mL two-neck round-bottom flask, and add dry nitrogen. 1,3,5-tribromobenzene (3g, 9.5mmol), N,N-(9H-carbazole-3,6-diyl)diheptanamide (8.8g, 20.9mmol), Cu powder (1.66g, 26.1mmol), potassium carbonate (10.5g, 76mmol) and 18-crown-6 (0.5g, 1.9mmol) were added and stirred under reflux at 180°C for 48 hours. After completion of the reaction, extraction is performed with water and MC. After removing residual moisture with MgSO ₄ , purification is performed by column chromatography using EA:Hex to obtain an intermediate (c) of the following structural formula (Yield: 4.4 g, 46%).

Intermediate (c)

(2) Preparation of organic compounds

Put magnesium turnings (0.13g, 5.2mmol), ZnCl 2 (0.46g, 3.36mmol) and a small amount of iodine in a 100mL _two- neck round-bottom flask under argon atmosphere and dissolve in THF (10mL). The intermediate (c) (4 g, 4.0 mmol) dissolved in THF (10 mL) in an atmosphere of 0° C. was added thereto, and the mixture was stirred at room temperature for about one day. Benzenesulfonyl chloride (0.35g, 2.0mmol), N,N,N',N'-tetramethylethylenediamine (0.6g, 5.2mmol), CuI (0.64g, 3.36mmol) dissolved in THF (15mL) at 0°C was added, and room temperature agitation in the After completion of the reaction, quenched with NH ₄ Cl aqueous solution and extracted with EA. After removing residual moisture with MgSO ₄ , purification is performed by column chromatography using EA:ether to obtain an organic compound (Yield: 1.59 g, 75%) of the following [Formula 10].

[Formula 10]

<Synthesis Example 11>

The organic compound of [Formula 11] was synthesized according to the following [Scheme 11].

[Scheme 11]

(1) Preparation of organic compounds

3,6-dibromo-9-(4-tert-butylphenyl)-9H-carbazole (2g, 4.4mmol), P(t-Bu) ₃ (0.05g, 0.22mmol) and Pd ₂ ( dba) ₃ (0.12 g, 0.13 mmol) is added, dissolved in toluene (30 mL), and nitrogen is filled. N,N-(4,4-azanediylbis(4,1-phenylene))diheptanamide (4.7g, 11mmol) and NaOtBu (1.27g, 13.2mmol) were added to the reaction mixture and stirred at 100°C for 24 hours. After completion of the reaction, extraction is performed with MC and water. After removing residual moisture with MgSO ₄ , purification is performed by column chromatography using EA: Hex to obtain an organic compound (Yield: 1.85 g, 37%) of the following [Formula 11].

[Formula 11]

<Synthesis Example 12>

The organic compound of [Formula 12] was synthesized according to the following [Scheme 12].

[Scheme 12]

(1) Preparation of organic compounds

9-(4-tert-butylphenyl)-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (2g) in a 100mL two-necked round-bottom flask , 3.6 mmol) and N,N,N -(4,4,4-((-4-bromophenyl)methanetriyl)tris(benzene-4,1-diyl))triheptanamide (6.2g, 7.9mmol), THF (20 mL) and then fill with nitrogen sufficiently. 4M K ₂ CO ₃ aqueous solution (7mL) and ethanol (8mL) are added, and finally Pd(PPh ₃ ) ₄ (0.34g, 0.29mmol) is added to the reaction product, followed by reflux stirring at 80° C. for 13 hours. After completion of the reaction, extraction is performed with MC and water. After removing residual moisture with MgSO ₄ , purification is performed by column chromatography using EA: Hex to obtain an organic compound (Yield: 3.1 g, 51%) of the following [Formula 12].

[Formula 12]

( Experimental example : Solvent resistance test)

The organic compounds synthesized in Synthesis Examples 1 to 12 are dissolved in an organic solvent (chlorobenzene) and spin-coated on a substrate to form a thin film with a thickness of about 40 nm, and then heated in an oven at 120° C. for 30 minutes to bond hydrogen between amides. caused Thereafter, UV/Vis spectrum was measured for the formed thin film before immersion in solvent. Then, the thin film thus formed was immersed in an organic solvent (chlorobenzene) for about 3 minutes, the solvent was removed, and the UV/Vis spectrum was measured after immersion in the solvent.

)을 평가하였다. By comparing the UV/Vis spectrum before the solvent immersion and the UV/Vis spectrum after the solvent immersion, the solvent resistance (

) was evaluated.

solvent resistance Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 menstruum
resistance 100% 100% 100% 100% 100% 100% Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Synthesis Example 11 Synthesis Example 12 menstruum
resistance 92% 98% 93% 100% 100% 100%

Referring to [Table 1], the organic thin films made of the organic compounds of [Formula 1] to [Formula 12] according to the present invention have any meaningful difference between the UV/Vis spectrum before solvent immersion and the UV/Vis spectrum after solvent immersion. There is no difference. That is, it can be confirmed that the organic compounds of the present invention have resistance to solvents. It can be seen that the organic compound of the present invention containing at least two or more amide functional groups at the terminal has resistance to solvents due to hydrogen bonding between the amide functional groups under a specific temperature condition (heating at 120° C. for 30 minutes).

Claims (23)

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device,
The organic compound is an organic compound, characterized in that it has a compound containing carbazole in the core, and is a material having the following chemical formula including at least two or more amide functional groups at the end of the core .

13. The method according to any one of claims 1 to 12,
The organic compound is at least one selected from the group consisting of a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron injection layer material, an electron transport layer material, an electron blocking layer material, and a hole blocking layer material among organic thin film materials for an organic electric device. Organic compounds, characterized in that used for the purpose. An ink composition for forming an organic thin film disposed between a first electrode and a second electrode of an organic electric device, the ink composition comprising:
The ink composition is an ink composition comprising the organic compound of any one of claims 1 to 12. 15. The method of claim 14,
The ink composition is an ink composition, characterized in that the solution or suspension further comprising a solvent. 15. The method of claim 14,
The ink composition is an ink composition, characterized in that it further comprises a pigment or dye. 15. The method of claim 14,
The ink composition further comprises a phosphorescent dopant or a fluorescent dopant. An organic electric device in which an organic thin film layer comprising at least a light emitting layer or a plurality of layers is sandwiched between a cathode and an anode,
An organic electric device comprising an organic compound for forming the organic thin film layer according to any one of claims 1 to 12. 19. The method of claim 18,
An organic electric device, characterized in that hydrogen bonds are formed between amide functional groups at the ends of the organic compound forming the organic thin film layer. 20. The method of claim 19,
The organic thin film layer is an organic electric device, characterized in that at least one selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer and a hole blocking layer. 20. The method of claim 19,
An organic electric device, characterized in that it has a structure in which 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 are stacked in this order. 20. The method of claim 19,
The organic thin film layer is an organic electric device, characterized in that it is manufactured by coating the ink composition containing the organic compound by a solution process and drying it to form a film. An electronic device comprising the organic electric device according to claim 18 .