KR20200013747A - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

The present invention relates to a novel compound, an organic electric device using the same, and an electronic device thereof. According to the present invention, it is possible to improve the luminous efficiency, color purity, and lifetime of a device, and to lower a driving voltage. Provided is an organic electric device comprising an anode, a cathode, and an organic material layer formed between the anode and the cathode. The organic material layer comprises: a light emitting layer; a light emitting auxiliary layer formed between the anode and the light emitting layer; and a hole transport layer formed between the anode and the light emitting auxiliary layer. The light emitting auxiliary layer includes a compound represented by one among the formula 2, formula 5, and formula 7. The hole transport layer comprises a compound represented by the formula 11.

Description

COMPONENT FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND A 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.

Mr. Eastman Kodak Corporation in the 1980s. W. C. W. Tang et al. Developed a laminated structure element in which various roles were assigned to each material, thereby making organic electroluminescent elements using organic materials practical. They stacked phosphors that could transport electrons and organics that could transport holes, and injected both charges into a layer of phosphor to emit light, so that high brightness of 1000 cd / m2 or more could be obtained at a voltage of 10 V or less. .

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electrical device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions.

The biggest problem for organic electroluminescent devices is lifetime and efficiency. As the display becomes larger, these efficiency and lifetime problems must be solved.

Efficiency, lifespan, and driving voltage are related to each other.As the efficiency increases, the driving voltage decreases relatively, and the crystallization of organic materials due to Joule heating generated during driving decreases as the driving voltage decreases. It shows a tendency to increase the lifetime.

However, simply improving the organic material layer does not maximize the efficiency. This is because a long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value between each organic material layer and intrinsic properties (mobility, interfacial properties, etc.) of the material is achieved.

In addition, in order to solve the light emission problem in the hole transport layer in the recent organic electroluminescent device, a light emitting auxiliary layer must exist between the hole transport layer and the light emitting layer, and different light emission auxiliary according to each light emitting layer (R, G, B) is required. It is time to develop the floor.

In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.

However, in the case of the material used in the hole transport layer, it has a low T1 value because it has to have a low HOMO value, which causes the excitons generated in the light emitting layer to pass to the hole transport layer, resulting in charge unbalance in the light emitting layer. This causes light emission at the hole transport layer interface.

When the light is emitted from the hole transport layer interface, the color purity and efficiency of the organic electric element is lowered and the lifespan is shortened. Therefore, the development of a light emitting auxiliary layer having a high T1 value and a HOMO level between the hole transport layer HOMO energy level and the light emitting layer HOMO energy level is urgently required.

On the other hand, while delaying the diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, stable characteristics, that is, high glass transition even for Joule heating generated when driving the device. There is a need for development of a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has the property of lowering the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great influence on the device life. In addition, the OLED device is mainly formed by a deposition method, which requires development of a material that can withstand a long time during deposition, that is, a material having strong heat resistance.

In other words, in order to fully exhibit the excellent characteristics of the organic electric device, the materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a light emitting auxiliary layer material, etc., are stable and efficient. Supported by the material should be preceded, but development of a stable and efficient organic material layer for an organic electric device has not been made yet. Therefore, the development of new materials is continuously required, and in particular, the development of material combinations of the light emitting auxiliary layer and the hole transport layer is urgently required.

It is an object of the present invention to provide an arylamine-based compound including a carbazole unit capable of improving high luminous efficiency, low driving voltage, high heat resistance, color purity, and lifetime of the device, an organic electric device using the same, and a terminal thereof. .

In addition, the present invention uses an arylamine-based compound containing a carbazole unit as the core of the light emitting auxiliary layer material, but at the same time select the sub-substituent of the core appropriately and excellent device characteristics when combined with such a light emitting auxiliary layer An object of the present invention is to provide an organic electric device capable of improving high luminous efficiency, low driving voltage, high heat resistance, color purity, and lifespan by using a combination of a hole transport layer material capable of exerting a light and an electronic device including the same.

In one aspect, the present invention provides a compound represented by the following formula.

In another aspect, the present invention provides an organic electric device comprising an organic material layer containing a compound represented by the above formula and a compound represented by the following formula.

In another aspect, the present invention provides an electronic device including an organic electric element using the compound represented by the above formula.

By using the compound according to the present invention in an organic electric device, it is possible to greatly improve the high luminous efficiency, low driving voltage, high heat resistance, color purity and lifetime of the device.

1 is an exemplary view of an organic electroluminescent device according to an embodiment of the present invention.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings.

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, if it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

As used herein, the term "halo" or "halogen" includes fluorine, chlorine, bromine, and iodine unless otherwise noted.

As used herein, the term "alkyl" or "alkyl group" has a carbon number of 1 to 60 unless otherwise stated, it is not limited thereto.

As used herein, the terms "alkenyl" or "alkynyl" have a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, and are not limited thereto.

The term "cycloalkyl" as used herein, unless otherwise indicated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.

The term "alkoxy group" used in the present invention has a carbon number of 1 to 60 unless otherwise stated, it is not limited thereto.

As used herein, the terms "aryl group" and "arylene group" each have a carbon number of 6 to 60 unless otherwise stated, it is not limited thereto.

In the present invention, an aryl group or an arylene group means a monocyclic or heterocyclic aromatic, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 3 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. In addition, it includes not only a single ring but also a heterocycle, and adjacent groups may be formed by bonding.

As used herein, the terms "heterocycloalkyl" and "heterocyclic group" include one or more heteroatoms, unless otherwise indicated, have a carbon number from 2 to 60, and include heterocycles as well as monocycles. Adjacent groups may be formed in combination. In addition, "heterocyclic group" may mean an alicyclic and / or aromatic including a heteroatom.

As used herein, the term "heteroatom" refers to N, O, S, P and Si unless otherwise stated.

Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise stated, the term "saturated or unsaturated ring" as used herein means a saturated or unsaturated aliphatic ring or an aromatic ring or heterocyclic ring having 6 to 60 carbon atoms.

Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.

In addition, unless otherwise stated, the term "substituted" in the term "substituted or unsubstituted" is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ coming of the alkyl group, C ₆ ~ C ₂₀ coming aryl Ti, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the An alkynyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₆ to C ₆₀ aryl group, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₈ to C ₂₀ aryl alkenyl group, a silane group, a boron group, Germanium group, and C ₅ ~ C _{20 It} is substituted with one or more substituents selected from the group consisting of a heterocyclic group, it is not limited to these substituents.

1 is an exemplary view of an organic electric device according to an embodiment of the present invention.

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110. It is provided with an organic material layer containing a compound represented by the formula (1) between. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, and the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.

In addition, although not shown, the organic electric device according to the present invention may further include a protective layer formed on one surface of the at least one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer is a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, the electron injection layer 170, the host of the light emitting layer 150 or the material of the dopant or capping layer Can be used as Preferably, the compound of the present invention may be used as the hole transport layer 140 and / or the light emitting auxiliary layer 151.

As described above, in order to solve the light emission problem in the hole transport layer in the organic electroluminescent device, the light emitting auxiliary layer 151 must be present between the hole transport layer 140 and the light emitting layer 150.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD method. For example, the anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on the substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer are formed thereon. After forming the organic material layer including the 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer may be formed by using a variety of polymer materials, but not by a deposition process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be prepared in a number of layers. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double side emission type according to the material used.

In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochrome or white illumination.

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.

Compound according to one aspect of the present invention is represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

n and m are integers of 1 to 4, and when n and m are 2 or more, each of R ₁ and R ₂ is the same as or different from each other, and i) R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; Tritium; C ₆ ~ C ₆₀ aryl group; C ₁ ~ C ₅₀ Alkyl group; C ₂ -C ₄₀ alkenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S and Si; A condensed ring group of an aromatic ring of C ₆ ~ C ₆₀ and an aliphatic ring of C ₄ ~ C ₆₀ ; Amine groups; Nitro group; Nitrile group; Selected from the group consisting of amide groups and silane groups, or ii) when n and / or m are integers of 2 or more, neighboring R ₁ and / or neighboring R ₂ are bonded to each other to form at least one saturated or unsaturated cyclic compound. Form. Here, the "saturated or unsaturated cyclic compound" may be a saturated or unsaturated alicyclic, aromatic or heterocyclic compound, specifically, C ₃ ~ C ₆₀ alicyclic, C ₆ ~ C ₆₀ aromatic ring, C ₂ ~ It may be a heterocyclic ring of C ₆₀ , and more specifically may be a C ₆ ~ C ₂₀ aromatic hydrocarbon. In this case, R ₁ and / or R ₂ which do not form a saturated or unsaturated ring may be defined in the same manner as defined in i).

In addition, in Formula 1, Ar ₁ and Ar ₂ are independently of each other, C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ heterocyclic ring containing at least one heteroatom of O, N, S and Si Or a C ₆ to C ₃₀ aryloxy group, L is a C ₆ to C ₆₀ arylene group, a C ₂ to C ₆₀ heteroarylene group or flu containing at least one heteroatom of O, N, S and Si Orenylene groups.

The aryl group of R ₁ , R ₂ , Ar ₁ and Ar ₂ is a halogen group, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₆ ~ C ₆₀ in the arylamine group, C ₁ ~ C import of ₆₀ alkylthio, C ₆ ~ C ₆₀ arylthio group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl alkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted with a heavy hydrogen aryl, C ₈ ~ C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron ring of the group, Substituted or unsubstituted germanium group, and substituted or unsubstituted C ₂ ~ C ₆₀ It may be substituted with one or more groups selected from the group consisting of; R _1, R _2, Ar ₁ and a group consisting of halogen, CN heterocyclic ring of _{Ar 2, NO 2, C 1} ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkyl amine group, C ₆ ~ C ₆₀ aryl amine group, C ₁ ~ C import of ₆₀ alkylthio, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ of the alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₆₀ aryl group substituted with deuterium, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₂ May be substituted with one or more groups selected from the group consisting of -C ₆₀ heterocyclic groups; Alkyl and alkenyl groups of R ₁ and R ₂ are halogen, C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₁ -C ₂₀ alkoxy groups, C ₆ -C ₆₀ aryl groups, deuterium One selected from the group consisting of a substituted C ₆ -C ₆₀ aryl group, C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₂ -C ₆₀ heterocyclic group, nitrile group and acetylene group May be substituted with more than one group; Amine of R ₁ and R ₂ groups are C ₁ ~ C ₆₀ alkyl group, C ₂ ~ C ₆₀ alkenyl group, C ₆ ~ C ₆₀ of the aryl groups and C ₈ ~ C ₆₀ arylalkenyl with one or more groups selected from the group consisting of May be substituted with a group; The aryloxy group of Ar ₁ and Ar ₂ is hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C for ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, and a C ₂ ~ heteroaryl of C ₆₀ May be substituted with one or more substituents selected from the group consisting of groups; The arylene group and heteroarylene group of L are deuterium, tritium, nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, amino group, C ₂ ~ C ₂₀ heterocyclic group and C It may be substituted with one or more groups selected from the group consisting of ₆ ~ C ₂₀ aryl group, the fluorenylene group of L, deuterium, halogen, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ to C ₂₀ aryl group, C ₇ to C ₂₀ arylalkyl group, C ₈ to C ₂₀ arylalkenyl group, C ₁ to C ₅₀ alkyl group, C ₂ to C ₂₀ heterocyclic group, nitrile group and acetylene group It may be substituted with one or more substituents selected from the group consisting of.

In Formula 1, when adjacent R ₁ and / or adjacent R ₂ combine with each other to form a saturated or unsaturated ring, the cyclic compound is defined in the same manner as the substituent R ₁ or / and R ₂ defined in Formula 1 It may be further substituted with a substituent. In Formula 1, when adjacent R ₁ and / or neighboring R ₂ combine to each other to form an aromatic hydrocarbon ring, Formula 1 may be represented by one of the following formulas.

In Chemical Formulas 2 to 7, R ₁ , R ₂ , L, Ar _1, and Ar ₂ are each defined in the same manner as defined in Chemical Formula 1, and n in Chemical Formulas 2, 4, and 5 is an integer of 1 to 6. Wherein n in Formula 6 and 7 is an integer of 1 to 4, m in Formula 2 and 5 to 7 is an integer of 1 to 6, m in Formula 3 and 4 is an integer of 1 to 4.

Further, in Formula 1, when n = 1 and / or m = 1 and R ₁ and / or R ₂ is a phenyl group, Formula 1 may be represented by one of the following Formulas 8 to 10.

In Formulas 8 to 10, Ar ₁ , Ar ₂ and L are the same as defined in Formula 1.

In Formula 1, Ar ₁ and Ar ₂ may be selected from the following groups.

In addition, in Chemical Formula 1, L may be selected from the following group.

Specifically, the compound represented by Formula 1 may be one of the following compounds.

In another aspect, the present invention provides an organic electric device provided with an organic material layer including a light emitting auxiliary layer formed of the compound represented by Chemical Formula 1 and a hole transport layer formed of the compound represented by the following Chemical Formula 11. In this case, the light emitting auxiliary layer is formed between the anode and the light emitting layer, and the hole transport layer is formed between the light emitting auxiliary layer and the anode. However, the light emitting auxiliary layer and the hole transport layer is preferably formed of different compounds. That is, the same compound of the compounds represented by the formula (1) and formula (11) is excluded when applied to both the light emitting auxiliary layer and the hole transport layer.

[Formula 11]

In Chemical Formula 11,

이다.Ar ₃ is

to be.

Ar ₄ to Ar ₈ are independently of each other, a C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ heterocyclic group or C ₆ ~ C ₃₀ aryl jade containing at least one hetero atom of O, N and S And L is a C ₆ -C ₆₀ arylene group, a C ₂ -C ₆₀ heteroarylene group or a fluorenylene group containing at least one hetero atom of O, N and S.

In addition, in Formula 11, o and p are integers of 1 to 4, when o and p is 2 or more, a plurality of R ₃ , R ₄ Each is the same as or different from each other, iii) R ₃ and R ₄ are, independently from each other, hydrogen; heavy hydrogen; Tritium; C ₆ ~ C ₆₀ aryl group; C ₁ ~ C ₅₀ Alkyl group; C ₂ -C ₄₀ alkenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N and S; A condensed ring group of an aromatic ring of C ₆ ~ C ₆₀ and an aliphatic ring of C ₄ ~ C ₆₀ ; Amine groups; Nitro group; Nitrile group; Selected from the group consisting of an amide group and a silane group, or ii) when o and / or p is an integer of 2 or more, adjacent R ₃ and / or neighboring R ₄ are bonded to each other to form at least one saturated or unsaturated cyclic compound. Form. Here, the "saturated or unsaturated cyclic compound" is the same as described in the formula (1).

The aryl group of R ₃ , R ₄ , Ar ₁ to Ar ₈ is a halogen group, C ₁ ~ C ₆₀ Alkyl group, C ₁ ~ C ₆₀ Alkoxy group, C ₁ ~ C ₆₀ Alkylamine group, C ₆ ~ C ₆₀ in the arylamine group, C ₁ ~ C import of ₆₀ alkylthio, C ₆ ~ C ₆₀ arylthio group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl alkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted with a heavy hydrogen aryl, C ₈ ~ C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron ring of the group, Substituted or unsubstituted germanium group, and substituted or unsubstituted C ₂ ~ C ₆₀ It may be substituted with one or more groups selected from the group consisting of; R _3, R _4, Ar ₁ to Ar ₈ heterocyclic group consisting of halogen, CN a, NO _2, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkyl amine group, C ₆ ~ C ₆₀ aryl amine group, C ₁ ~ C import of ₆₀ alkylthio, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ of the alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₆₀ aryl group substituted with deuterium, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₂ May be substituted with one or more groups selected from the group consisting of -C ₆₀ heterocyclic groups; The alkyl and alkenyl groups of R ₃ and R ₄ are halogen, C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₁ -C ₂₀ alkoxy groups, C ₆ -C ₆₀ aryl groups, deuterium One selected from the group consisting of a substituted C ₆ -C ₆₀ aryl group, C ₈ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₂ -C ₆₀ heterocyclic group, nitrile group and acetylene group May be substituted with more than one group; Of R ₃ and R ₄ amine groups or more selected from the group consisting of a arylalkyl of C ₁ ~ C ₆₀ alkyl group, C ₂ ~ C ₆₀ alkenyl group, C ₆ ~ C ₆₀ aryl group and a C ₈ ~ C ₆₀ of the May be substituted with a group; The aryloxy group of Ar ₁ to Ar ₈ is hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C for ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, and a C ₂ ~ heteroaryl of C ₆₀ May be substituted with one or more substituents selected from the group consisting of groups; The arylene group and heteroarylene group of L are deuterium, tritium, nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, amino group, C ₂ ~ C ₂₀ heterocyclic group and C It may be substituted with one or more groups selected from the group consisting of ₆ ~ C ₂₀ aryl group, the fluorenylene group of L, deuterium, halogen, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ to C ₂₀ aryl group, C ₇ to C ₂₀ arylalkyl group, C ₈ to C ₂₀ arylalkenyl group, C ₁ to C ₅₀ alkyl group, C ₂ to C ₂₀ heterocyclic group, nitrile group and acetylene group It may be substituted with one or more substituents selected from the group consisting of.

이고, 이웃한 R₄끼리 서로 결합하여 C₆인 방향족탄화수소 고리를 형성할 경우 하기 화학식 12 내지 14의 화합물이, 두쌍의 이웃한 R₄끼리 결합하여 각각 C₆인 방향족탄화수소 고리를 형성할 경우 하기 화학식 15의 화합물이 형성될 수 있으며, 이웃한 R₃끼리 및 이웃한 R₄끼리 서로 결합하여 각각 C₆인 방향족탄화수소를 형성할 경우 하기 화학식 16의 화합물이 형성될 수 있을 것이다.Ar ₃ of Formula 11 may be represented by one of the following formula. That is, in Formula 11, Ar ₃ is

When adjacent R ₄ are bonded to each other to form an aromatic hydrocarbon ring which is C _{6. When} the compound of Formula 12 to 14 is bonded to two pairs of adjacent R ₄ to form an aromatic hydrocarbon ring which is each C ₆ . Compounds of Formula 15 may be formed, and when adjacent R ₃ and neighboring R ₄ are bonded to each other to form C ₆ aromatic hydrocarbons, the compound of Formula 16 may be formed.

<Formula 12> <Formula 13> <Formula 14>

<Formula 15> <Formula 16>

Specifically, Formula 11 is P1-1 to P1-176, P2-1 to P2-45, P3-1 to P3-87, P4-1 to P4-81, P5-1 to P5-80, P6-1 to It may be a compound of one of P6-52, P7-1 to P7-64. However, when the compound represented by Formula 1 is used as the light emitting auxiliary layer and the compound represented by Formula 11 is used as the hole transport layer, they are simultaneously P1-1 to P1-176, P2-1 to P2-45, and P3-1 to P3-87. , Except for the same compound among P4-1 to P4-81, P5-1 to P5-80, P6-1 to P6-52, and P7-1 to P7-64. That is, Formulas 1 and 11 are both P1-1 to P1-176, P2-1 to P2-45, P3-1 to P3-87, P4-1 to P4-81, P5-1 to P5-80, and P6. Although it may be represented by one of -1 to P6-52, P7-1 to P7-64, it is preferable that the light emitting auxiliary layer and the hole transport layer are formed of different compounds.

In addition, Formula 11 may be one of the following compounds.

Hereinafter, the synthesis examples of the compounds represented by the formulas (1) and (11) of the present invention and the production examples of the organic electric device will be described in detail by way of examples, but the present invention is not limited to the following examples.

In exemplary embodiments, Chemical Formula 1 may be synthesized by a reaction pathway as in Scheme 1 below.

<Scheme 1>

In Scheme 1, the starting material for synthesizing Sub 1 may be one of the following S1 to S7.

Example 1

Exemplary synthesis methods of the starting materials S1 to S7 are as follows. In the following, n, m is 1, and R1 and R2 are hydrogen, for example. However, even if other substituents defined in Formulas 1 and 11 are combined, an unexpected reaction will not occur.

(One) S1  Synthesis (3,6- diphenyl -9H- carbazole )

<Scheme 2>

Carbazole (16.72 g, 100 mmol), NBS (59.4 g, 210 mmol), BPO (2.42 g, 10 mmol), and 300 mL of methylene chloride were added thereto, followed by stirring at room temperature. After completion of the reaction, the mixture was extracted with methylene chloride, water and NaHCO ₃ aqueous solution, and the obtained organic layer was dried over Na ₂ SO ₄ , concentrated and recrystallized to obtain 23.73 g (73%) of the product. The product obtained (23.73 g, 73.02 mmol), phenylboronic acid (19.6 g, 160.64 mmol), Pd (PPh ₃ ) ₄ (8.44 g, 7.3 mmol), K ₂ CO ₃ (60.55 g, 438.12 mmol), THF (320 mL) and H2O (160 mL) were added and stirred and refluxed at 80 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with methylene chloride and water, and the obtained organic layer was dried over MgSO ₄ , concentrated and recrystallized to obtain 15.9 g (68%) of the product.

(2) S2  Synthesis method (7H- dibenzo [a, g] carbazole )

<Scheme 3>

2-nitro-1,2'-binaphthyl (20.1 g, 67.1 mmol), Triphenylphosphine (44 g, 167.6 mmol) and o-Dichlorobenzene (275 mL) were added and refluxed at 180 ° C. After the reaction was completed, the mixture was cooled to room temperature, and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting organics were purified by silicagel column and recrystallized to give 11.48 g (64%) of the product.

(3) (9H- dibenzo [a, c] carbazole )

<Scheme 4>

11.2 g (62.5%) of the product was obtained by the same experimental method as S2.

(4) S4  Synthesis method (7H- benzo [c] carbazole )

Scheme 5

Intermediate S4 Synthesis of -1 (6,7- dihydro -5H- benzo [c] carbazole )

β-Tetralone (18 g, 123 mmol) and phenyl hydrazine hydrochloride (11 g, 76 mmol) were added to a small amount of acetic acid and refluxed in 150 mL of ethanol under nitrogen atmosphere for 2 hours. After the reaction was completed, the resultant was cooled to room temperature, and the resulting product was filtered and dried to prepare 16.5 g (61%) of Compound S4-1.

Synthesis of S4 (7H- benzo [c] carbazole )

S4-1 compound (16.5 g, 75.34 mmol) and tetrachloro-1,4-benzoquinone (25.93 g, 105.5 mmol) are dissolved in a reaction flask using 300 ml of xylene. The reaction flask was refluxed for 2 hours in a nitrogen atmosphere. After the reaction was completed, the NaOH (10%) aqueous solution and water in the reaction flask was terminated and the organic layer was extracted. The extract was concentrated and recrystallized with ethanol to give compound S4 15.7 g (yield: 96%).

(5) S5  Synthesis method (9H- dibenzo [a, c] carbazole )

<Scheme 6>

10.8 g (60%) of the product was obtained by the same experimental method as S2.

(6) S6  Synthesis method (11H- benzo [a] carbazole )

Scheme 7

11 g (67%) of the product was obtained by the same experimental method as S4.

(7) S7  Synthesis method (5H- benzo [b] carbazole )

Scheme 8

7.6 g (52%) of product was obtained by the same experimental method as S2.

In the case of synthesizing Sub 1 of Scheme 1 using S1 of the starting material, it may be synthesized by the reaction route of Scheme 9 below.

Example 2

Scheme 9

Synthesis examples of the compound belonging to Sub 1 of Scheme 9 are as follows.

(One) Sub  1-1 Synthesis Example

Scheme 10

9 H -carbazole (50.17 g, 300 mmol), a starting material, was dissolved in nitrobenzene in a round bottom flask, followed by L 1-1 (150.8 g, 420.1 mmol) and Na ₂ SO ₄ (42.61 g, 300 mmol), K ₂ CO ₃ (41.41 g, 300 mmol), Cu (5.72 g, 90 mmol) was added and stirred at 200 ° C. After the reaction was completed, nitrobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give 86.04 g (yield: 72%) of the product.

(2) Sub  1-2 Synthesis Example

Scheme 11

9 H -carbazole (45.89 g, 274.4 mmol), L 2-1 (153.33 g, 384.2 mmol), Na ₂ SO ₄ (38.97 g, 274.4 mmol), K ₂ CO ₃ (37.87 g, 274.4 mmol), Cu (5.23 g, 82.3 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 2, to obtain 89.03 g (yield: 74%) of the product.

(3) Sub  1-3 Synthesis Example

Scheme 12

9 H -carbazole (29.01 g, 173.5 mmol), L 3-1 (127.08 g, 242.9 mmol), Na ₂ SO ₄ (24.64 g, 173.5 mmol), K ₂ CO ₃ (23.94 g, 173.5 mmol), Cu (3.31 g, 52 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 2, to obtain 61.48 g (yield: 63%) of the product.

(4) Sub  1-4 Synthesis Example

Scheme 13

9 H -carbazole (23.86 g, 142.7 mmol) in L 4-1 (104.12 g, 199.8 mmol), Na ₂ SO ₄ (20.26 g, 142.7 mmol), K ₂ CO ₃ (19.69 g, 142.7 mmol), Cu (2.72 g, 42.8 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 1, to obtain 47.99 g (yield: 60%) of the product.

(5) Sub 1-5 Synthesis Example

Scheme 14

9 H -carbazole (50.17 g, 300 mmol), L 1-2 (150.8 g, 420.1 mmol), Na ₂ SO ₄ (42.61 g, 300 mmol), K ₂ CO ₃ (41.41 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 1, to obtain 82.45 g (yield: 69%) of the product.

(6) Sub 1-6 Synthesis Example

Scheme 15

9 H -carbazole (50.17 g, 300 mmol), L 1-3 (150.8 g, 420.1 mmol), Na ₂ SO ₄ (42.61 g, 300 mmol), K ₂ CO ₃ (41.41 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 1, to obtain 77.7 g (yield: 65%) of the product.

On the other hand, an example of Sub 1 is as follows, but is not limited to this, Fμ-MS of this μ are shown in Table 1 below.

TABLE 1

Example 3

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 16 below.

Scheme 16

Synthesis examples of the compound belonging to Sub 2 are as follows.

(One) Sub  2-4 Synthesis Example

Scheme 17

After starting bromobenzene (24.18 g, 154.3 mmol) was dissolved in toluene in a round bottom flask, naphthalen-2-amine (44.18 g, 308.6 mmol), Pd ₂ (dba) ₃ (4.24 g, 4.63 mmol), P ( t- Bu) ₃ (6 ml, 9.26 mmol), NaO t -Bu (44.49 g, 462.9 mmol) was added and stirred at 40 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 27.69 g (yield: 82%) of the product.

(2) Sub  2-15 Synthesis Example

Scheme 18

[1,1'-biphenyl] -4-amine (74.71 g, 441.5 mmol), Pd ₂ (dba) ₃ (6.06) to 4-bromo-1,1'-biphenyl (51.46 g, 220.7 mmol) obtained in the above synthesis. g, 6.6 mmol), P ( t -Bu) ₃ (8.7ml, 13.2 mmol), NaO t -Bu (63.63 g, 662.1 mmol), toluene were obtained using the Sub 2-4 synthesis of Example 3 above and product 56.75 g (yield: 80%) was obtained.

(3) Sub  2-20 Synthesis Example

Scheme 19

To 2-bromo-9,9-diphenyl-9 H -fluorene (38.93 g, 98 mmol) obtained in the above synthesis, aniline (18.25 g, 196 mmol), Pd ₂ (dba) ₃ (2.69 g, 2.9 mmol), P ( t -Bu) ₃ (3.9 ml, 5.9 mmol), NaO t -Bu (28.25 g, 294 mmol) and toluene were obtained using the Sub 2-4 synthesis of Example 3, above 28.09 g (yield: 70%) Got.

(4) Sub  2-28 Synthesis Example

Scheme 20

[1,1'-biphenyl] -4-amine (49.86 g, 295 mmol), Pd ₂ (dba) to 2-bromo-9,9-dimethyl-9 H- fluorene (40.24 g, 147 mmol) obtained in the above synthesis. ) ₃ (4.04 g, 4.4 mmol), P ( t -Bu) ₃ (5.8ml, 8.8 mmol), NaO t -Bu (42.38 g, 441 mmol) and toluene were synthesized using the procedure of Sub 2-4 of Example 3. To give 38.26 g (yield: 72%) of product.

(5) Sub  2-37 Synthesis Example

Scheme 21

[1,1'-biphenyl] -4-amine (37.45 g, 221.3 mmol), Pd ₂ (dba) ₃ (3.04 g) to 2-bromodibenzo [ b , d ] thiophene (29.12 g, 110.7 mmol) obtained in the above synthesis. , 3.3 mmol), P ( t -Bu) ₃ (4.3 ml, 6.6 mmol), NaO t -Bu (31.91 g, 332 mmol), toluene using the Sub 2-4 synthesis of Example 3 above, the product 29.95 g (Yield 77%) was obtained.

(6) Sub  2-48 Synthesis Example

Scheme 22

Aniline (17.96 g, 192.9 mmol), Pd ₂ (dba) ₃ (2.65 g, 2.9 mmol) in 3- (4-bromophenyl) -9-phenyl-9 H -carbazole (38.41 g, 96.4 mmol) obtained in the above synthesis. , P ( t -Bu) ₃ (3.7 ml, 5.8 mmol), NaO t -Bu (27.81 g, 289.3 mmol), toluene were obtained using the Sub 2-4 synthesis of Example 3, above, the product was 30.88 g (yield: 78 %) Was obtained.

Meanwhile, examples of Sub 2 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 2 below.

TABLE 2

Example 4

Sub 2 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 1 (1.2 equiv), Pd ₂ (dba) ₃ (0.03 equiv), P ( t -Bu) ₃ (0.08 equiv), NaO t -Bu (3 equiv) was added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain a final product.

(One) P1 -21 Synthesis Example

Scheme 23

Sub 2-15 (6.81 g, 21.2 mmol) obtained in the above synthesis was dissolved in toluene in a round bottom flask, and then Sub 1-1 (10.13 g, 25.4 mmol), Pd ₂ (dba) ₃ (0.58 g, 0.6 mmol) , P ( t -Bu) ₃ (0.8 ml, 1.7 mmol), NaO t -Bu (6.11 g, 63.6 mmol) was added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 11.78 g (yield: 87%) of the product.

(2) P1 -22 Synthesis Example

Scheme 24

To Sub 2-28 (7.17 g, 19.8 mmol) obtained in the above synthesis, Sub 1-1 (9.48 g, 23.8 mmol), Pd ₂ (dba) ₃ (0.54 g, 0.6 mmol), P ( t -Bu) ₃ ( 0.8 ml, 1.6 mmol), NaO t -Bu (5.72 g, 59.5 mmol) and toluene were obtained using the Product P1-21 synthesis method of Example 4 to obtain 11.31 g (yield: 84%) of the product.

(3) P1 -44 Synthesis Example

Scheme 25

To Sub 2-48 (6.49 g, 15.8 mmol) obtained in the above synthesis Sub 1-1 (7.56 g, 19 mmol), Pd ₂ (dba) ₃ (0.43 g, 0.5 mmol), P ( t -Bu) ₃ ( 0.6ml, 1.3 mmol), NaO t -Bu (4.56 g, 47.4 mmol) and toluene were obtained using 9.55 g (yield: 83%) of the product using the Product P1-21 synthesis method of Example 4.

(4) P1 -52 Synthesis Example

Scheme 26

Sub 2-20 (7.34 g, 17.9 mmol) obtained in the above synthesis in Sub 1-2 (10.2 g, 21.5 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.5 mmol), P ( t -Bu) ₃ ( 0.7 ml, 1.4 mmol), NaO t -Bu (5.17 g, 53.8 mmol) and toluene were obtained using the Product P1-21 synthesis method of Example 4, obtaining 11.37 g (yield: 79%) of the product.

(5) P1 -78 Synthesis Example

Scheme 27

Sub 2-15 (5.97 g, 18.6 mmol) obtained in the above synthesis to Sub 1-4 (12.27 g, 22..3 mmol), Pd ₂ (dba) ₃ (0.51 g, 0.6 mmol), P ( t -Bu ) ₃ (0.7 ml, 1.5 mmol), NaO t -Bu (5.36 g, 55.7 mmol) and toluene were obtained using the Product P1-21 synthesis method of Example 4 to obtain 11.75 g (yield: 80%) of the product.

(6) P1 -85 Synthesis Example

Scheme 28

Sub 2-15 (7.36 g, 22.9 mmol) obtained in the above synthesis in Sub 1-5 (12.05 g, 27.5 mmol), Pd ₂ (dba) ₃ (0.63 g, 0.7 mmol), P ( t -Bu) ₃ ( 0.9ml, 1.8 mmol), NaO t -Bu (6.6 g, 68.7 mmol) and toluene were used to obtain the product 11.04 g (yield: 71%) using the Product P1-21 synthesis method of Example 4.

(7) P1 -96 Synthesis Example

Scheme 29

Sub 2-4 (5.3 g, 24.2 mmol) obtained in the above synthesis to Sub 1-7 (16.31 g, 29 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.7 mmol), P ( t -Bu) ₃ ( 0.9 ml, 1.9 mmol), NaO t -Bu (6.97 g, 72.5 mmol) and toluene were obtained using the Product P1-21 synthesis method of Example 4 to obtain 10.84 g (yield: 64%) of the product.

(8) P1 -108 Synthesis Example

Scheme 30

To Sub 2-37 (7.18 g, 20.4 mmol) obtained in the above synthesis, Sub 1-9 (13.74 g, 24.5 mmol), Pd ₂ (dba) ₃ (0.56 g, 0.6 mmol), P ( t -Bu) ₃ ( 0.8 ml, 1.6 mmol), NaO t -Bu (5.89 g, 61.3 mmol) and toluene were obtained using the Product P1-21 synthesis method of Example 4 to obtain 10.02 g (yield: 59%).

On the other hand, FD-MS values of the compounds P1-1 ~ P7-64 of the present invention prepared according to the synthesis examples as described above are shown in Table 3.

TABLE 3

Meanwhile, Chemical Formulas H4-1 to H4-108 according to the present invention may be prepared by reacting Sub 3 and Sub 4 as shown in Scheme 31 below.

Scheme 31

Example 5

Sub  3, synthesis method

Sub 3 of Scheme 31 may be synthesized by the reaction route of Scheme 32 below.

Scheme 32

Intermediate Sub - S8 Example of synthesis

(One) Sub - S8 -One Synthesis Example  ( R ₃ = H, Ar ₆ = Phenyl )

Scheme 33

The starting material 3-bromo-9-phenyl-9 H -carbazole (45.1 g, 140 mmol) was dissolved in DMF in a round bottom flask, followed by Bis (pinacolato) diboron (39.1 g, 154 mmol), PdCl ₂ (dppf) (3.43 g, 4.2 mmol), KOAc (41.3 g, 420 mmol) was added and stirred at 90 ° C. When the reaction was completed, the DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 35.2 g (yield: 68%).

(2) Sub - S8 -2 Synthesis Example  ( R ₃ = H, Ar ₆ = biphenyl )

Scheme 34

9-([1,1'-biphenyl] -4-yl) -3-bromo-9 H -carbazole (55.92 g, 140.4 mmol), Bis (pinacolato) diboron (39.22 g, 154.4 mmol), PdCl ₂ (dppf ) (3.44 g, 4.2 mmol), KOAc (41.34 g, 421.2 mmol) and DMF were obtained using the Sub-S8-1 synthesis method of Example 5, which gave 40 g (yield: 64%) of the product.

Synthesis Example of Sub 3

In the following, the case where R ₃ , Ar ₆ and L are each hydrogen, phenyl / biphenyl, or phenyl / biphenyl group will be described as an example. However, since the following reactions all proceed by Suzuki coupling reaction, other substituents defined in Formula 11 Although combined, the following reaction will not proceed to an unexpected reaction.

(One) Sub  3-1 Synthesis Example  [ R ₃ = H, Ar ₆ = Phenyl , L = biphenyl  ( linear )]

Scheme 35

Sub-S8-1 (29.5 g, 80 mmol) obtained in the continuous synthesis was dissolved in THF in a round bottom flask, and then 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), water were added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 26.56 g (70%) of the product.

(2) Sub  3-2 Synthesis Example  [ R ₃ = H, Ar ₆ = Phenyl , L = phenyl ]

Scheme 36

Sub-S8-1 (29.5 g, 80 mmol) obtained in the above synthesis was subjected to 1-bromo-4-iodobenzene (23.8 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol), THF, water were obtained using the Sub 3-1 synthesis of Example 5 to give 22.9 g (72%) of the product.

(3) Sub  3-3 Synthesis Example  [ R ₃ = H, Ar ₆ = Phenyl , L = biphenyl  ( non - linear )]

Scheme 37

Sub-S8-1 (29.5 g, 80 mmol) obtained in the above synthesis was added to 4'-bromo-3-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), THF, and water were used to obtain the product 24.7 g (65%) using the Sub 3-1 synthesis method of Example 5.

(4) Sub  3-4 Synthesis Example  [ R ₃ = H, Ar ₆ = biphenyl , L = biphenyl  ( linear )]

Scheme 38

Sub-S8-2 (35.63 g, 80 mmol) obtained in the synthesis of 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), THF, and water were obtained using the Sub 3-1 synthesis method of Example 5 to obtain 29.51 g (67%) of the product.

(5) Sub  3-5 Synthesis Example  [ R ₃ = H, Ar ₆ = biphenyl , L = phenyl ]

Scheme 39

Sub-S8-2 (35.63 g, 80 mmol) obtained in the above synthesis was subjected to 1-bromo-4-iodobenzene (23.8 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol), THF, and water were obtained using the Sub 3-1 synthesis method of Example 5 to obtain 25.05 g (66%) of the product.

(6) Sub  3-6 Synthesis Example  [ R ₃ = H, Ar ₆ = biphenyl , L = biphenyl  ( non - linear )]

Scheme 40

Sub-S8-2 (35.63 g, 80 mmol) obtained in the above synthesis was added to 4'-bromo-3-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), THF, and water were obtained using the Sub 3-1 synthesis method of Example 5 to obtain 29.95 g (68%) of the product.

Synthesis Example of Sub 4

Sub 4 can be synthesized by the same method as Sub 2 above.

Example 6

Product ( H4 -1 ~ H4 -108) synthetic

Sub 4 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 3 (1.2 equiv), Pd ₂ (dba) ₃ (0.03 equiv), P ( t -Bu) ₃ (0.08 equiv), NaO t -Bu (3 equiv) was added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain a final product. The FD-MS data of the final compounds H4-1 to H4-108 are shown in Table 4 below.

TABLE 4

Compounds H5-1 to H5-64 according to the present invention are prepared by reacting Sub 5 and Sub 6 as in Scheme 41 below.

Scheme 41

Example 7

Sub  5, synthesis

Sub 3 of Scheme 41 may be synthesized by the reaction route of Scheme 42 below.

Scheme 42

Synthesis Example of Sub 5

(1) Sub 5-1 Synthesis Example

Scheme 43

In the starting material N- phenylnaphthalen-1-amine (65.8 g, 300 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (129.2 g, 360 mmol), Na ₂ SO ₄ (42.6 g, 300 mmol), K ₂ CO ₃ (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 2, to obtain 89.2 g (yield: 66%) of the product.

(2) Sub  5-2 Synthesis Example

Scheme 44

Starting material N -phenylnaphthalen-1-amine (65.8 g, 300 mmol), 2-bromo-7-iodo-9,9-dimethyl-9 H -fluorene (143.7 g, 360 mmol), Na ₂ SO ₄ (42.6 g, 300 mmol), K ₂ CO ₃ (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 2, to obtain 97.1 g (yield: 66%) of the product.

Example 8

Product ( H5 -1 ~ H5 -64) synthetic

Sub 4 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 5 (1.2 equiv), Pd ₂ (dba) ₃ (0.03 equiv), P ( t -Bu) ₃ (0.08 equiv), NaO t -Bu (3 equiv) was added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain a final product. FD-MS data of Product (H5-1 ~ H5-64) is shown in Table 5 below.

TABLE 5

Manufacturing Evaluation of Organic Electrical Device

[ Experimental Example  One: On the hole transport layer  apply]

First, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N ¹ -on the ITO layer (anode) formed on the organic substrate. Phenylbenzene-1,4-diamine (hereinafter abbreviated as 2-TNATA) was vacuum deposited to form a hole injection layer having a thickness of 60 nm. Next, the hole transport layer was formed by vacuum depositing the compound of the present invention (compound corresponding to Chemical Formula 1) to a thickness of 20 nm on the hole injection layer. Then, 90: 1 weight ratio of CBP [4,4'-N, N'-dicarbazole-biphenyl] as a light emitting host and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] as a dopant material on the hole transport layer. A light emitting layer of 30 nm thickness was deposited by doping with. Next, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm to form a hole blocking layer. Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm to form an electron transport layer. Subsequently, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode.

The organic electric device manufactured according to Experimental Example 1 is represented as Examples 1 to 60 in Table 6.

[ Comparative example  One]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, but a hole transport layer was formed using Comparative Compound 1 instead of the compound of the present invention.

<Comparative Compound 1>

N4, N4'-di (naphthalen-1-yl) -N4, N4'-diphenyl- [1,1'-biphenyl] -4,4'-diamine

The electroluminescent (EL) characteristics of the organic light emitting diodes manufactured by Experimental Example 1 and Comparative Example 1 were measured by applying a forward bias DC voltage to PR-650 of photoresearch, as shown in Table 6 below. At this time, the T90 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

TABLE 6

As can be seen in Table 6, the organic electroluminescent device manufactured using the compounds of the present invention compared to Comparative Compound 1 has a relatively low driving voltage and high efficiency and

High lifetime, especially for compounds P1-21, P1-22, P1-23, P3-53, P3-54, P4-52, P4-53, P4-54, P4-74 Could confirm that appeared.

[ Experimental Example  2: On the hole transport layer  apply]

First, a hole injection layer having a thickness of 60 nm is formed by vacuum depositing 2-TNATA on an ITO layer (anode) formed on an organic substrate, and then the compound of the present invention (material corresponding to Formula 11) is deposited on the hole injection layer. Vacuum deposition to a thickness of nm to form a hole transport layer. Next, CBP [4,4'-N, N'-dicarbazole-biphenyl] is used as a light emitting host material, and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] is used as a dopant material in a 90:10 weight ratio. Doped to deposit a 30 nm thick light emitting layer. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer, and then Alq ₃ was formed to a thickness of 40 nm to form an electron transport layer. Subsequently, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode.

The organic electric device manufactured according to Example 2 is represented by Examples 61 to 125 in Table 7.

[ Comparative example  2]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 2, but a hole transport layer was formed using Comparative Compound 1 instead of the compound of the present invention.

As a result of measuring the electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent device manufactured by Experimental Example 2 and Comparative Example 2 as described above in the PR-650 of Photoresearch Co., Ltd. same. At this time, the T90 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

TABLE 7

As a result of using the compounds of Formula 11 as the hole transport layer in Table 7, the H4 compounds showed low driving voltage in terms of driving voltage. In particular, the driving voltage was the lowest measured for the compound H4-45.

Therefore, in order to obtain a much higher result in terms of luminous efficiency and lifetime as well as the driving voltage drop, the following organic electroluminescent device was manufactured by using the compound of H4-45 and the compound of Formula 1 as the hole transport layer and the light emitting auxiliary layer, respectively.

[ Experimental Example  3: On the light emitting auxiliary layer (blue)  apply]

After vacuum depositing 2-TNATA on the ITO layer (anode) formed on the glass substrate to form a hole injection layer having a thickness of 60 nm, Compound 4-45 according to the present invention as a hole transport compound on the hole injection layer was 20 nm thick. Vacuum deposition to form a hole transport layer. Next, the compound of the present invention (material corresponding to Chemical Formula 1) was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emitting auxiliary layer. After forming the light-emitting auxiliary layer, 30 nm by doping 9,10-di (2-naphthalene) anthracene (ADN) as a host material and BD-052X (Idemitus) as a dopant material at a weight ratio of 93: 7 A light emitting layer was deposited to a thickness. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm with a holdoff layer, and Alq ₃ was formed into a thickness of 40 nm with an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting display device.

An organic electric device manufactured according to Experimental Example 3 is represented as Examples 126 to 338 in Table 8 below.

[ Comparative example  3]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 3, except that the Comparative Compound 2 was used to form the emission auxiliary layer instead of the compound of the present invention.

<Comparative Compound 2>

[ Comparative example  4]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 3, except that the Comparative Compound 3 was used to form the emission auxiliary layer instead of the compound of the present invention.

Comparative Compound 3

[ Comparative example  5]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 3, except that the Comparative Compound 4 was used to form the emission auxiliary layer instead of the compound of the present invention.

<Comparative Compound 4>

[ Comparative example  6]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 3, except that the Comparative Compound 5 was used to form the emission auxiliary layer instead of the compound of the present invention.

Comparative Compound 5

[ Comparative example  7]

An organic light emitting diode was manufactured in the same manner as in Experiment 3, but the emission auxiliary layer was not used.

As described above, the result of measuring the electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent device manufactured by Experimental Example 3 and Comparative Examples 3 to 7 with PR-650 of photoresearch company It is shown in Table 8 below. At this time, the T95 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

TABLE 8

As a result of using the compound of Formula 1 as a blue fluorescence emission auxiliary layer material, the following results were shown in [Table 8]. Although having the same carbazole core, the arylamine group (compound according to the present invention) exhibits a charge balance retention and a high T1 value when the arylamine group (compound according to the present invention) comes as a main substituent than the heterocyclic group containing N (Comparative Examples 3 to 7). By lowering the driving voltage and effectively blocking the exciton to stay in the light emitting layer, it can be seen that the efficiency and lifetime are greatly improved as a result.

In other words, when the arylamine group came as the main substituent, the efficiency and lifespan were improved compared to the other substituents. It can be seen that the life span is more than doubled compared to 5.

In addition, the compound P1-21 of the present invention can be seen that the efficiency and life is greatly increased compared to Comparative Example 7 without using the light emitting auxiliary layer, which is a compound of the present invention used as the light emitting auxiliary layer has a high T1 energy level and deep HOMO This is because holes having energy levels are more smoothly transported from the hole transport layer to the light emitting layer, and excitons are confined in the light emitting layer to prevent leakage of light.

As can be seen from the results of Table 8, even in the same carbazole core, band gaps, electrical characteristics, and interface characteristics can be greatly changed depending on which substituents are bonded to each position. In the case of the layer, it is very difficult to infer the characteristics of the compound of the present invention in the light emitting auxiliary layer even if a similar core is used because the interrelationship between the hole transport layer and the light emitting layer (host).

[ Experimental Example  4: On the light emitting auxiliary layer (Red)  apply]

After vacuum depositing 2-TNATA on the ITO layer (anode) formed on the glass substrate to form a hole injection layer having a thickness of 60 nm, Compound H4-45 was vacuum deposited to a thickness of 20 nm as a hole transport compound on the hole injection layer. A hole transport layer was formed. Next, the compound of the present invention (Formula 1) was vacuum deposited to a thickness of 20 nm as a light emitting auxiliary layer material on the hole transport layer to form a light emitting auxiliary layer. After forming the emission auxiliary layer, CBP [4,4'-N, N'-dicarbazole-biphenyl] as a host material on top and (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) as dopant material iridium (III) acetylacetonate] was deposited at a weight ratio of 95: 5 to deposit a light emitting layer having a thickness of 30 nm. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm with a holdoff layer, and Alq ₃ was formed into a thickness of 40 nm with an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting display device.

The organic electric device manufactured according to the present Experimental Example is shown as Example 1 to Example 12 in Table 9.

[ Comparative example  8]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 4, except that the Comparative Compound 2 was used to form the emission auxiliary layer instead of the compound of the present invention.

[ Comparative example  9]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 4, except that the Comparative Compound 3 was used to form the emission auxiliary layer instead of the compound of the present invention.

[ Comparative example  10]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 4, except that the Comparative Compound 4 was used to form the emission auxiliary layer instead of the compound of the present invention.

[ Comparative example  11]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 4, except that the Comparative Compound 5 was used to form the emission auxiliary layer instead of the compound of the present invention.

[ Comparative example  12]

An organic light emitting diode was manufactured in the same manner as in Experiment 4, but the emission auxiliary layer was not used.

As described above, after applying a forward bias DC voltage to the organic EL device manufactured according to Experimental Example 4 and Comparative Examples 8 to 12, the electroluminescence (EL) characteristic of the photoresearch company PR-650 was measured. It is shown in Table 9 below. At this time, the T95 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

TABLE 9

As can be seen from the results of Table 9, the organic light emitting device using the compounds according to the present invention having a carbazole core as a red phosphorescent light emitting auxiliary layer material has a lower driving voltage and higher light emission than Comparative Examples 7 to 11. Efficiency and significant lifespan improvements were shown. In particular, Compound 1-21 of the present invention, which showed superior characteristics as a blue fluorescent auxiliary layer material, showed the best result with low driving voltage, high efficiency, and high lifetime even when used as a red phosphorescent emission layer material.

The present invention has been described above by way of example, and those skilled in the art will appreciate that various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all the technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100: organic electric element 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (9)

An organic electric device comprising an anode, a cathode, and an organic material layer formed between the anode and the cathode.
The organic material layer includes a light emitting layer, a light emitting auxiliary layer formed between the anode and the light emitting layer, and a hole transport layer formed between the anode and the light emitting auxiliary layer,
The light emitting auxiliary layer includes a compound represented by one of the following Chemical Formulas 2, 5, and 7, and the hole transport layer comprises an compound represented by Chemical Formula 11 below:
<Formula 2><Formula5><Formula7>

<Formula 11>

In the above formula,
Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are each independently a C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N and S; And it is selected from the group consisting of C ₆ ~ C ₃₀ aryloxy group,
Ar ₃ is

ego,
Ar ₆ is independently of each other C ₆ ~ C ₆₀ An aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N and S; And it is selected from the group consisting of C ₆ ~ C ₃₀ aryloxy group,
L is independently of each other a C ₆ ~ C ₆₀ arylene group; A C ₂ to C ₆₀ heteroarylene group containing at least one heteroatom of O, N, S and Si; And it is selected from the group consisting of fluorenylene group,
R ₁ to R ₃ are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; C ₁ ~ C ₅₀ Alkyl group; C ₂ -C ₄₀ alkenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N and S; A condensed ring group of an aromatic ring of C ₆ ~ C ₆₀ and an aliphatic ring of C ₄ ~ C ₆₀ ; And selected from the group consisting of a silane group, adjacent R _{1 to} each other, adjacent R ₂ or adjacent R _{3 may} be bonded to each other to form at least one saturated or unsaturated cyclic compound,
In Formulas 2 and 5, n is an integer of 1 to 6, in Formula 7, n is an integer of 1 to 4,
In Formula 2, Formula 5, and Formula 7, m is an integer of 1 to 6,
o is an integer from 1 to 4,
When n, m, o are each an integer of 2 or more, each of a plurality of R _1, each of a plurality of R _{2, and} each of a plurality of R ₃ are the same as or different from each other,
The aryl groups of R ₁ to R ₃ , Ar ₁ , Ar ₂ , Ar ₄ to Ar ₆ are halogen, C ₁ to C ₆₀ alkyl group, C ₁ to C ₆₀ alkoxy group, C ₁ to C ₆₀ alkylthio group, C ₆ ~ arylthio group of C _60, C a ₂ ~ C ₆₀ substituted to the alkenyl group, C ₂ ~ C ₆₀ of the alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, a heavy hydrogen of the C ₆ -C ₆₀ aryl group, C ₈ -C ₆₀ arylalkenyl group, substituted or unsubstituted silane group, substituted or unsubstituted boron group, substituted or unsubstituted germanium group, and substituted or unsubstituted C It may be substituted with one or more groups selected from the group consisting of ₂ ~ C ₆₀ heterocyclic group,
Wherein _{R 1 ~ R 3, Ar 1} , Ar 2, Ar 4 ~ heterocyclic group consisting of halogen, CN in _{Ar 6, NO 2, C 1} ~ C 60 alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C Import of ₆₀ alkylthio, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ of the alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, a substituted C ₆ ~ C with deuterium One or more selected from the group consisting of an aryl group of ₆₀ , a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₂ to C ₆₀ heterocyclic group May be substituted with a group,
The alkyl group and alkenyl group of R ₁ to R ₃ are halogen, C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkoxy group, C ₆ to C ₆₀ aryl group, deuterium C ₆ ~ C ₆₀ aryl group, C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₆₀ heterocyclic group, a nitrile group and an acetylene group selected from May be substituted with one or more groups,
The aryloxy group of Ar ₁ , Ar ₂ , Ar ₄ to Ar ₆ is hydrogen, deuterium, halogen, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, and a C ₂ ~ May be substituted with one or more groups selected from the group consisting of C ₆₀ heteroaryl groups,
The arylene group and heteroarylene group of L is deuterium, nitro group, nitrile group, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₂ ~ C ₂₀ heterocyclic group and C ₆ ~ May be substituted with one or more groups selected from the group consisting of C ₂₀ aryl groups,
The fluorenylene group of L is a deuterium, a halogen group, a C ₂ ~ C ₂₀ alkenyl group, a C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, C ₇ ~ C ₂₀ arylalkyl group, C ₈ Arylalkenyl group of ~ C ₂₀ , C ₁ ~ C ₅₀ Alkyl group, C ₂ ~ C ₂₀ It may be substituted with one or more groups selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group,
In Formula 11, the compound represented by Formula 1 is excluded,
Except for the compound represented by the following formula 3 in Formula 2, Formula 5 and Formula 7,
<Formula 3>

In Formula 3, R ₂ , L, Ar ₁ and Ar ₂ are the same as defined above, m is an integer of 1-4. The method of claim 1,
Ar ₁ and Ar ₂ is an organic electric device, characterized in that selected from the group:

The method of claim 1,
Wherein L is selected from the group:

The method of claim 1,
Compound represented by the formula (2) is an organic electric device, characterized in that one of the following compounds:

. The method of claim 1,
The compound represented by Formula 5 is one of the following compounds:

. The method of claim 1,
Compound represented by Formula 7 is one of the following compounds:

. The method of claim 1,
The compound represented by Formula 11 is one of the following compounds:

. A display device comprising the organic electroluminescent element of claim 1; And
And a controller for driving the display device. The method of claim 8,
The organic electronic device is an electronic device, characterized in that one of an organic electroluminescent device, an organic solar cell, an organic photosensitive member, an organic transistor.

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