KR102224495B1 - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

An object of the present invention is to provide a compound capable of improving a high luminous efficiency, a low driving voltage, and a lifetime of a device, an organic electric device using the same, and an electronic device thereof.

Description

Compound for organic electric device, organic electric device using the same, and electronic device thereof {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT 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 emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic electric device using the organic light emission phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic electronic device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.

Materials used as an organic material layer in an organic electronic device can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions.

It is the lifespan and efficiency that are the most problematic in organic electroluminescent devices, and as displays become large-area, such efficiency and lifespan problems must be solved.

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

However, the efficiency cannot be maximized simply by improving the organic material layer. This is because the long life and high efficiency can be achieved at the same time when the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) are optimally combined.

In addition, in order to solve the problem of light emission in the hole transport layer in recent organic electronic devices, a light emission auxiliary layer (or a second hole transport layer) must exist between the hole transport layer and the light emitting layer, and each light emitting layer (R, G, B) It is the time when it is necessary to develop different light-emitting auxiliary layers according to the following.

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, and excitons are generated by recombination. However, in the case of a material used for the hole transport layer, since it must have a low HOMO value, most have a low T1 value, and this causes excitons generated in the emission layer to pass to the hole transport layer, resulting in charge unbalance in the emission layer. This results in light emission at the hole transport layer interface.

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

On the other hand, at the present time when a large area of organic electroluminescent devices is required, manufacturing a large area display by a solution process is also a reality. Polymer materials have been studied as a material for solution process, but solution process without crosslinking damages the lower film by eroding the lower film due to the solvent used when forming the upper film. This brings about a problem of deterioration in device characteristics and a decrease in process yield.

Crosslinking is applied as an essential element to prevent erosion of the lower layer when forming the upper layer, and the compound having a structure capable of crosslinking must have high solubility in organic solvents before crosslinking and low solubility in organic solvents after crosslinking.

There are largely a crosslinking method through light and a crosslinking method through heat as a method of forming crosslinking. Crosslinking by light has the advantage of enabling rapid crosslinking at low temperatures, but it requires a photoinitiator, which acts as an impurity in the device, leading to a problem of deterioration of properties. On the other hand, crosslinking through heat requires a high temperature for a long time, but is known to improve the characteristics of the device.

The ether connector (Korean Patent Publication 10-2012-0052765) exhibits excellent flexibility and has high solubility, so it is applied as a solution process material. In the case of a compound (Korean Patent Laid-Open Patent 10-2012-0052765) that introduces Ether connectors symmetrically on both sides of a carbazole core in an organic electric device manufactured by the current solution process, it has high solubility, but thin films due to the introduction of excessive Ether connectors. This is not uniformly formed and exhibits a relatively slow hole mobility compared to the electron mobility, and as a result, it is difficult to manufacture an organic electroluminescent device with high efficiency and long life.

As described above, the development of an organic electric device manufactured by a solution process has been progressed, but the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently developed, and accordingly, the development of a new material is urgently required.

The present invention is a structure in which an amine group is bonded to a carbazole and has been proposed to solve the conventional problems as described above, and the present invention has excellent solubility by an organic solvent, so that a solution process is possible when manufacturing an organic electric device. , When forming a thin film, it can be used as a material for a hole injection layer, a hole transport layer, a light emission auxiliary layer (i.e., a second hole transport layer), and a light-emitting layer in an organic electronic device manufactured by a solution process, and in particular, a hole transport layer alone An object of the present invention is to provide a compound that is used in a light-emitting auxiliary layer and a light-emitting layer to increase the efficiency, decrease the driving voltage, increase the lifespan, and increase the stability of the organic electronic device, an organic electronic device using the same, and an electronic device thereof.

In the case of a compound in which an amine group is bonded to a carbazole, the solubility and thin film characteristics change depending on the type and/or number of linking groups, and the hole mobily varies depending on the presence or absence of structural symmetry around the carbazole core. There is a difference. The present invention provides a compound characterized in that it has an asymmetric structure around a carbazole core and is represented by the following formula including a linking group between carbazole and an amine group, and has crosslinking properties.

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 and an electronic device using the compound represented by the above formula.

A more uniform thin film is formed by limiting the type and/or number of the connector, and the hole mobility is relatively fast through the introduction of an asymmetric structure around the carbazole core, thereby realizing a low driving voltage. By introducing a substituent having a crosslinking property to the compound of the present invention in addition to the above characteristics, high luminous efficiency and high heat resistance of the device can be achieved, and the life of the device can be greatly improved.

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

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

In adding reference numerals to elements of each drawing, it should be noted that the same elements are assigned the same numerals as possible, even if they are indicated on different drawings. In addition, in describing the present invention, when it is determined that a detailed description of a related known configuration or function may obscure the subject matter of the present invention, a detailed description thereof will be omitted.

In addition, in describing the constituent elements of the present invention, terms such as first, second, A, B, (a) and (b) may be used. These terms are for distinguishing the constituent element from other constituent elements, and the nature, order, or order of the constituent element is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, the component may be directly connected or connected to that other component, but another component between each component It will be understood that elements may be “connected”, “coupled” or “connected”.

As used in this specification and the appended claims, the meaning of the following terms is as follows, unless stated otherwise.

As used herein, the term "halo" or "halogen" is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise specified.

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms unless otherwise specified, and is a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo It means a radical of saturated aliphatic functional groups including alkyl groups and cycloalkyl-substituted alkyl groups.

As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen unless otherwise specified.

The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

The terms "alkenyl group" or "alkynyl group" used in the present invention each have a double bond or triple bond of 2 to 60 carbon atoms unless otherwise specified, and include a straight or branched chain group, and are limited thereto. It is not.

The term "cycloalkyl" as used herein refers to an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.

The terms "alkoxyl group", "alkoxy group", or "alkyloxy group" as used herein refers to an alkyl group to which an oxygen radical is attached, and has a carbon number of 1 to 60 unless otherwise specified, and is limited thereto. It is not.

The terms "alkenyl group", "alkenoxy group", "alkenyloxy group", or "alkenyloxy group" as used in the present invention mean an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 It has a carbon number of, but is not limited thereto.

The term "aryloxyl group" or "aryloxy group" used in the present invention means an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms, and is not limited thereto.

The terms “aryl group” and “arylene group” used in the present invention each have 6 to 60 carbon atoms, and are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or multiple ring aromatics, and includes an aromatic ring formed by neighboring substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a fluorene group, a spirofluorene group, or a spirobifluorene group.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and a radical substituted with an aryl group has the number of carbon atoms described herein.

In addition, when prefixes are named consecutively, it means that substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxylcarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, it means an alkenyl group substituted with an arylcarbonyl group. And the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term "heteroalkyl" means an alkyl containing one or more heteroatoms unless otherwise specified. The term "heteroaryl group" or "heteroarylene group" as used herein refers to an aryl group or arylene group having 2 to 60 carbon atoms each including one or more heteroatoms, unless otherwise specified, and is limited thereto. No, it includes at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

The term "heterocyclic group" as used in the present invention includes one or more heteroatoms, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, unless otherwise specified, heteroaliphatic ring and hetero It contains an aromatic ring. It may be formed by combining adjacent functional groups.

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

In addition, the "heterocyclic group" may also include a ring including _{SO 2 instead of carbon forming a ring.} For example, "heterocyclic group" includes the following compounds.

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

Unless otherwise specified, the term "ring" used in the present invention refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms, or a combination thereof, It contains saturated or unsaturated rings.

Other hetero compounds or hetero radicals other than the aforementioned hetero compounds include one or more heteroatoms, but are not limited thereto.

Unless otherwise specified, the term "carbonyl" as used herein is represented by -COR', where R'is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Is a cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise stated, the term "ether" used in the present invention is represented by -RO-R', wherein R or R'are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, and 6 to 30 carbon atoms. It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

In addition, unless expressly stated, the term "substituted or unsubstituted" used in the present invention means "substituted" deuterium, halogen, amino group, nitrile group, nitro group, C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkylamine group, C ₁ to C ₂₀ alkylthiophene group, C ₆ to C ₂₀ arylthiophene group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron It means substituted with one or more substituents selected from the group consisting of a group, a germanium group, and a C ₂ ~ C _{20 heterocyclic group, and is not limited to these substituents.}

In addition, unless there is an explicit description, the formula used in the present invention is applied in the same manner as the definition of the substituent 　 in the index definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming a benzene ring, and a is an integer of 2 or 3. Each is bonded as follows, wherein R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the hydrogen bonded to the carbon forming the benzene ring is indicated. Is omitted.

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, and a first electrode 110 and a second electrode 180 formed on a substrate 110. ) Between the organic material layer containing the compound according to the present invention. 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 material layer may sequentially 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 this case, other layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emission auxiliary layer 151, a buffer layer 141, etc. may be further included, and the electron transport layer 160 may serve as a hole blocking layer.

Further, although not shown, the organic electric device according to the present invention may further include a protective layer or a capping layer formed on 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 includes a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, an electron injection layer 170, a light emission auxiliary layer 151, and a host of the emission layer 150. Alternatively, it may be used as a material for a dopant or a light efficiency improvement layer. Preferably, the compound of the present invention may be used as the hole injection layer 130, the hole transport layer 140, the light-emitting auxiliary layer 151, and the light-emitting layer 150.

On the other hand, even with the same core, the band gap, electrical characteristics, and interfacial characteristics may vary depending on which substituent is bonded to any position, so the selection of the core and the combination of sub-substituents bonded thereto are also very It is important, and in particular, long life and high efficiency can be achieved at the same time when an optimum combination of energy level and T1 value between each organic material layer, and intrinsic properties of materials (mobility, interfacial properties, etc.) is achieved.

Therefore, in the present invention, by forming a light emitting layer using the compound represented by Formula 1, the lifespan of the organic electronic device is optimized by optimizing the energy level and T1 value between each organic material layer, and the intrinsic properties of the material (mobility, interface characteristics, etc.). And efficiency can be improved at the same time.

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

In addition, the organic material layer is a solution process or a solvent process other than a vapor deposition method using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, and a doctor blaze. It can be manufactured with fewer layers by a method such as a ding process, a screen printing process, or a thermal transfer method. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the method of forming the organic material layer.

The organic electric device according to the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

WOLED (White Organic Light Emitting Device) is easy to realize high resolution and excellent processability, while there is an advantage that can be manufactured using the existing LCD color filter technology. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Typically, the R(Red), G(Green), B(Blue) light emitting parts are arranged in a side-by-side manner, and the R, G, B light emitting layers are stacked up and down. In addition, there is a color conversion material (CCM) method using electroluminescence by the blue (B) organic light-emitting layer and photo-luminescence of an inorganic phosphor using light therefrom. May be applied to these WOLEDs as well.

In addition, the organic electric 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), and a single color or white lighting device.

Another embodiment of the present invention may include a display device including the organic electric device 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 mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game consoles, various TVs, and various computers.

Hereinafter, a compound according to an aspect of the present invention will be described.

A compound according to an aspect of the present invention is represented by the following formula (1), It has a crosslinking property by including at least one crosslinking forming group represented by at least one of ^{R 1} , R ² , and Ar ¹ to Ar ^3.

<Formula 1>

Here, part A represents the following formula a, part B represents the following formula b, and part Z represents any one of the following formulas z-1 to z-4.

<Formula a> <Formula b>

<Formula z-1> <Formula z-2>

<Formula z-3> <Formula z-4>

In Formula 1,

A is formula a, and B is formula b.

Z is a formula z-1 to a formula z-4.

o is an integer from 0 to 4; p is an integer from 0 to 3.

m and n are integers from 1 to 8.

R ¹ and R ² are each independently deuterium; Tritium; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A C ₁ to C ₅₀ alkyl group; A fused ring group of an aromatic ring of C ₆ to C _{60 and an aliphatic ring of C 3} to C _60; C ₂ ~ C ₂₀ alkenyl group; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; -L ^a -N(R ^a ) (R ^b ); Carbonyl group; -O-Si(R ^c ) ₃ ; R ^c O-Si(R ^c ) ₂ -; C ₇ ~ C ₆₀ arylalkyl group; C ₂ ~ C ₃₀ alkenyloxyl group; Ether group; C ₈ -C ₆₀ alkenyl aryl group; A C ₃ to C ₆₀ cycloalkyl group; Silane group; Siloxane group; C ₇ ~ C ₆₀ aryl alkoxyl group; C ₈ ~ C ₆₀ arylalkenyl group; And C ₂ ~ C ₆₀ alkoxyl carbonyl group; It may be selected from the group consisting of.

Alternatively, R ¹ and R ² may be the same as or different from each other as a plurality of when o and p are 2 or more, and a plurality of R ¹ and R ² may be bonded to each other to form a ring. In this case, R ¹ and R ² that do not form a ring may be defined in the same manner as defined above. In this case, the formed ring is a C ₃ ~ C ₆₀ aliphatic ring or a C ₆ ~ C ₆₀ aromatic ring, a C ₂ ~ C ₆₀ heterocycle, a C ₃ ~ C ₆₀ alicyclic ring, or a fused ring consisting of a combination thereof And the like, and may be a single ring or multiple rings, as well as a saturated or unsaturated ring.

Ar ¹ to Ar ³ are each independently a C ₆ to C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A C ₁ to C ₅₀ alkyl group; A fused ring group of an aromatic ring of C ₆ to C _{60 and an aliphatic ring of C 3} to C _60; C ₂ ~ C ₂₀ alkenyl group; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; -L ^a -N(R ^a ) (R ^b ); Carbonyl group; -O-Si(R ^c ) ₃ ; R ^c O-Si(R ^c ) ₂ -; C ₇ ~ C ₆₀ arylalkyl group; C ₂ ~ C ₃₀ alkenyloxyl group; Ether group; C ₈ -C ₆₀ alkenyl aryl group; A C ₃ to C ₆₀ cycloalkyl group; Silane group; Siloxane group; C ₇ ~ C ₆₀ aryl alkoxyl group; C ₈ ~ C ₆₀ arylalkenyl group; And C ₂ ~ C ₆₀ alkoxyl carbonyl group; It may be selected from the group consisting of.

For example, R ¹ , R ² , Ar ¹ to Ar ³ may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a heterocyclic group, a fluorenyl group, a phenanthryl group, and the like.

L ¹ and L ² are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; It may be selected from the group consisting of a C ₁ -C ₆₀ alkylene group, and a C ₂ to C _{60 alkenylene group.}

L ^a is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ divalent heterocyclic group containing at least one hetero atom of P; A divalent fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; And a divalent aliphatic hydrocarbon group; it may be selected from the group consisting of.

R ^a and R ^b are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of P; And a fused ring group of an aromatic ring of _{C 6} to C _{60 and an aliphatic ring of C 3} to C ₆₀ ; it may be selected from the group consisting of.

R ^c is hydrogen; C ₆ ~ C ₂₀ aryl group; A C ₁ to C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₈ -C ₂₀ arylalkenyl group; C ₇ ~ C ₂₀ aryl alkoxyl group; And C ₂ ~ C ₂₀ alkoxyl carbonyl group; It may be selected from the group consisting of.

At least one of R ¹ , R ² , Ar ¹ to Ar ³ is a vinyl group, acryloyl group, methacyloyl group, cyclic ethers, and siloxane ( siloxanes), styrenes, trifluorovinyl ethers, benzocyclo-butenes, cinnamates, chalcones, and oxetane. Can be.

Here, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, fluorenylene group, carbonyl group, arylalkyl group, alkenyloxyl group, Ether group, alkenylaryl group, cycloalkyl group, silane group, siloxane group, arylalkoxyl group, arylalkenyl group, and alkoxylcarbonyl group, (alkylene alkenylene group) are deuterium, halogen, silane group, siloxane group, boron Group, germanium group, cyano group, nitro group, -L ^b -N(R ^d )(R ^e ) (where L ^b , R ^d and R ^e are the same as those of ^{L a} , R ^a and R ^{b, respectively} ), C ₁ ~ C ₂₀ coming of the alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkenyl in the alkyl group, C ₂ ~ C ₂₀ of the diary, C ₂ ~ C ₂₀ alkynyl, C ₆ ~ of C ₂₀ aryl group, C ₆ to C ₂₀ aryl group substituted with deuterium, fluorenyl group, C ₂ to C ₂₀ heterocyclic group, C ₃ to C ₂₀ cycloalkyl group, C ₇ to C ₂₀ arylalkyl group , C ₈ ~ C ₂₀ arylalkenyl group, carbonyl group, ether group, C ₂ ~ C ₂₀ alkoxyl carbonyl group, C ₆ ~ C ₃₀ aryloxy group, -O-Si(R ^f ) ₃ , and R ^c O -Si(R ^f ) _2- (where R ^f is the ^{same as the definition of R c} ) may be further substituted with one or more substituents selected from the group consisting of.

Specifically, ^{at least one of R 1} , R ² , Ar ¹ to Ar ³ in Formula 1 may include any one of Formulas h-1 to h-12 below.

<Formula h-1> <Formula h-2> <Formula h-3>

<Formula h-4> <Formula h-5> <Formula h-6>

<Formula h-7> <Formula h-8> <Formula h-9>

<Formula h-10> <Formula h-11> <Formula h-12>

In Formula h-7,

q is an integer of 1-6.

When explaining the above formula in more detail,

의 경우, 할로겐으로 치환된 알켄일옥실기, 할로알켄일옥실기, 또는 트리플로오로비닐에테르로 분류될 수 있으며,I) Formula h-2

In the case of, it may be classified as a halogen-substituted alkenyloxyl group, haloalkenyloxyl group, or trifluorovinyl ether,

의 경우, 할로알켄일옥시알킬, 또는 할로겐으로 치환된 에테르기로 분류될 수 있으며,Ii) Formula h-3

In the case of, it may be classified as a haloalkenyloxyalkyl, or an ether group substituted with a halogen,

의 경우, 알켄일아릴기로 분류될 수 있으며,Iii) Formula h-4

In the case of, it may be classified as an alkenylaryl group,

의 경우, 할로알켄일옥실아릴기, 또는 에테르기로 분류될 수 있으며, Iv) Formula h-5

In the case of, it may be classified as a haloalkenyloxyaryl group, or an ether group,

의 경우, 방향족고리와 지방족고리의 융합고리기로 분류될 수 있으며,V) Formula h-6

In the case of, it can be classified as a fused ring group of an aromatic ring and an aliphatic ring,

의 경우, 알켄일아릴알킬옥실기, 또는 알켄일아릴기로 치환된 알콕실기로 분류될 수 있으며,Ⅵ) Formula h-8

In the case of, it may be classified as an alkenylarylalkyloxyl group or an alkoxyl group substituted with an alkenylaryl group,

의 경우, 방향족고리와 지방족고리의 융합고리기로 치환된 알킬옥실기, 또는 에테르기로 명명할 수 있으며,Vii) Formula h-9

In the case of, it may be referred to as an alkyloxyl group or an ether group substituted with a fused ring group of an aromatic ring and an aliphatic ring,

의 경우, 알켄일아릴헤테로알킬기, 또는 에테르기로 분류될 수 있으며,Vii) Formula h-10

In the case of, it may be classified as an alkenylarylheteroalkyl group, or an ether group,

의 경우, 할로알켄일옥실기로 치환된 아릴헤테로알킬기, 또는 할로알켄일옥실기로 치환된 에테르기로 분류될 수 있으며Ix) Formula h-11

In the case of, it may be classified as an arylheteroalkyl group substituted with a haloalkenyloxyl group, or an ether group substituted with a haloalkenyloxyl group, and

의 경우, 알켄일아릴헤테로알킬아릴기, 또는 에테르기로 치환된 아릴기로 분류될 수 있다.Ⅹ) Formula h-12

In the case of, it may be classified as an alkenylarylheteroalkylaryl group or an aryl group substituted with an ether group.

Specifically, the compound represented by Formula 1 may be represented by the following Formulas 2 to 5.

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

In Formulas 2 to 5,

The R ¹ , R ² , Ar ¹ to Ar ³ , L ¹ , L ² , m, n, o and p are R ¹ , R ² , Ar ¹ to Ar ³ , L ¹ , L ^{2 as defined in Formula 1} , m, n, o and p.

Specifically, B in Formula 1 may be represented by one of the following Formulas b-1 to b-18. .

<Formula b-1> <Formula b-2> <Formula b-3>

<Formula b-4> <Formula b-5> <Formula b-6>

<Formula b-7> <Formula b-8> <Formula b-9>

<Formula b-10> <Formula b-11> <Formula b-12>

<Formula b-13> <Formula b-14> <Formula b-15>

<Formula b-16> <Formula b-17> <Formula b-18>

In Formulas b-1 to b-18,

The R ¹ , R ² , Ar ³ , L ¹ , L ² , o and p may be the same as R ¹ , R ² , Ar ³ , L ¹ , L ² , o and p defined in Formula 1 above.

More specifically, the compound represented by Chemical Formulas 1 to 5 may be any one of the following compounds.

As another embodiment, the present invention provides a compound for an organic electric device represented by Formula 1 above.

In another embodiment, the present invention provides an organic electric device containing the compound represented by Formula 1.

In this case, the organic electric device includes a first electrode; A second electrode; And an organic material layer positioned between the first electrode and the second electrode, wherein the organic material layer may include a compound represented by Formula 1, and the compound represented by Formula 1 is a hole injection layer and a hole transport layer of the organic material layer. , A light-emitting auxiliary layer, a light-emitting layer, an electron transport layer, and an electron injection layer may be contained in at least one layer. In particular, the compound represented by Formula 1 may be included in a hole injection layer, a hole transport layer, a light emission auxiliary layer, and a light emission layer.

Specifically, an organic electric device including one of the compounds represented by Chemical Formulas 2 to 5 may be provided in the organic material layer. As an example, an organic electric device including a compound represented by the individual formulas (P-1 to P-66) may be provided in the organic material layer.

In another embodiment, the compound alone is contained in at least one of the hole injection layer, the hole transport layer, the emission auxiliary layer, the emission layer, the electron transport layer, and the electron injection layer of the organic material layer, or the It provides an organic electric device, characterized in that the compound is contained in a combination of two or more different from each other, or the compound is contained in a combination of two or more of the other compounds. In other words, each of the layers may contain a compound corresponding to Formula 1 to Formula 5 alone, and a mixture of two or more compounds of Formula 1 to Formula 5 may be included, and the compounds of claims 1 to 5 and the present Mixtures with compounds that do not correspond to the invention may be included. Herein, a compound that does not correspond to the present invention may be a single compound or may be two or more types of compounds. In this case, when the compound is contained in a combination of two or more of the other compounds, the other compound may be a known compound of each organic material layer or may be a compound to be developed in the future. At this time, the compound contained in the organic material layer may be composed of only the same type of compound, but may be a mixture of two or more different types of compounds represented by the formula (1).

As an example, to provide an organic electric device, characterized in that the molar ratio of a compound containing one crosslinking group among the compounds and another compound containing two or more crosslinking groups is mixed in a range of 99:1 to 1:99 can do.

In another embodiment of the present invention, the present invention provides a light efficiency improvement layer formed on at least one of one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer. It provides an organic electric device further comprising.

Hereinafter, examples for synthesizing the compound represented by Formula 1 according to the present invention and an example for preparing an organic electric device will be described in detail, but the present invention is not limited to the following examples.

Synthesis example

The compound represented by Formula 1 according to the present invention (Final products) is synthesized by reacting Sub 1 and Sub 2 as shown in Scheme 1 below, but is not limited thereto.

<Reaction Scheme 1>

(Z, R ¹ , R ² , Ar ¹ to Ar ³ , L ¹ , L ² , o and p are the same as defined in Formula 1.)

I. Synthesis of Sub 1

Sub 1 of Reaction Scheme 1 may be synthesized by the reaction paths of Scheme 2 and Scheme 3 below, but is not limited thereto.

<Scheme 2> When L ¹ is a single bond

<Reaction Scheme 3> When L ¹ is not a single bond

Synthesis examples of specific compounds belonging to Sub 1 are as follows.

1. Sub 1-9 Synthesis Example

<Reaction Scheme 4>

Starting materials 4,4'-(oxybis(propane-3,1-diyl))bis(bromobenzene) (30.00 g, 72.78 mmol) and N-(4-(((4-vinylbenzyl)oxy)methyl)naphthalen- 1-yl)-9,9'-spirobi[fluoren]-2-amine (43.94 g, 72.78 mmol) was dissolved in toluene (360ml) in a round bottom flask, and then Pd ₂ (dba) ₃ (3.33 g, 3.63 mmol) ), 50% P(t-Bu) ₃ (1.76ml, 7.27 mmol), NaOt-Bu (20.98 g, 218.34 mmol) was added and stirred at 80°C. When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was silicagel column to obtain 47.60 g (yield: 70%) of the product.

2. Sub 1-14 Synthesis Example

<Reaction Scheme 5>

N-(4-(bicyclo[4.2.0]octa-1,3,5-trien-3-yl)phenyl) in the starting material, 1,3-bis(4-bromophenyl)propane (33.04 g, 93.33 mmol) naphthalen-1-amine (30.00 g, 93.33 mmol), Pd ₂ (dba) ₃ (2.56 g, 2.79 mmol), 50% P(t-Bu) ₃ (1.88ml, 4.66 mmol), NaOt-Bu (27.07 g , 279.99 mmol), and toluene (300ml) were obtained using the Sub 1-9 synthesis method to obtain 41.00 g (yield: 75%) of the product.

3. Sub 1-21 Synthesis Example

<Reaction Scheme 6>

N-phenyl-4'-(((4-vinylbenzyl)oxy)methyl)-[1,1'-biphenyl]-4-amine (31.92) in the starting material 4-bromobenzyl 4-bromobenzoate (30.00 g, 81.54 mmol) g, 81.54 mmol), Pd ₂ (dba) ₃ (3.72 g, 4.07 mmol), 50% P(t-Bu) ₃ (1.97ml, 8.15 mmol), NaOt-Bu (9.02 g, 244.62 mmol), toluene ( 410ml) was obtained by using the Sub 1-9 synthesis method to obtain 38.84 g (yield: 70%) of the product.

4. Sub 1-25 Synthesis Example

<Reaction Scheme 7>

The starting material of 4,4 '- (oxybis (methylene) ) bis (bromobenzene) (20.00 g, 56.17 mmol) and ^{N 4, N 4' -diphenyl-} N 4 - (4- (4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-N ⁴ '-(4-vinylphenyl)-[1,1'-biphenyl]-4,4'-diamine (35.98 g, 56.17 mmol) After dissolving toluene (280ml) and water (140ml) in a round bottom flask, K ₂ CO ₃ (23.25 g, 168.51) mmol), Pd(PPh ₃ ) ₄ (3.25 g, 2.80 mmol) was added and stirred at 70°C. When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was silicagel column to obtain 31.50 g (yield: 71%) of the product.

5. Sub 1-52 Synthesis Example

<Reaction Scheme 8>

Starting material 1,3-bis(4-bromophenyl)propan-2-one (30.00 g, 81.50 mmol) N ⁴ -phenyl-N ⁴ '-(9-phenyl-9H-carbazol-3-yl)-N ⁴ -(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-N ⁴ '-(4-vinylphenyl)-[1,1'-biphenyl]- 4,4'-diamine (65.67 g, 81.50 mmol), K ₂ CO ₃ (33.74 g, 244.5 mmol), Pd(PPh ₃ ) ₄ (4.71 g, 4.07 mmol), toluene (400ml), and water (200ml) were used to obtain 63.04 g (yield: 80%) of the product using the Sub 1-25 synthesis method.

Meanwhile, the compound belonging to Sub 1 may be the following compound, but is not limited thereto, and Table 1 shows the FD-MS values of the compound belonging to Sub 1.

[Table 1]

II. Synthesis of Sub 2

Sub 2 of Reaction Scheme 1 may be synthesized by the reaction paths of Scheme 9 and Scheme 10 below, but is not limited thereto.

<Reaction Scheme 9> When L ² is not a single bond

<Formula 10> When L ² is a single bond

Synthesis examples of specific compounds belonging to Sub 2 are as follows.

1. Synthesis Example of Sub 2-13

<Reaction Scheme 11>

(1) Synthesis of Sub 2-I-13

The starting materials naphthalen-1-ylboronic acid (79.53 g, 462.40 mmol) and 4-bromo-2-iodo-1-nitrobenzene (227.44 g, 693.60 mmol) were mixed with THF (1500ml) and water (750ml) in a round bottom flask. After dissolving, K ₂ CO ₃ (191.73 g, 1387.20 mmol), Pd(PPh ₃ ) ₄ (26.72 g, 23.10 mmol) were added and stirred at 70°C. When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 109.26 g (yield: 72%) of the product.

(2) Synthesis of Sub 2-II-13

To Sub 2-I-13 (109.26 g, 332.90 mmol) obtained in the above synthesis, triphenylphosphine (218.32 g, 832.40 mmol) and o- dichlorobenzene (1000ml) were added and stirred at 200°C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 69.02 g (yield: 70%) of the product.

(3) Synthesis of Sub 2-III-13

After dissolving Sub 2-II-13 (69.02 g, 173.20 mmol) obtained in the above synthesis with toluene (600ml) in a round bottom flask, 3-iodobicyclo[4.2.0]octa-1,3,5-triene (59.76 g) , 259.80 mmol), Pd ₂ (dba) ₃ (4.75 g, 5.19 mmol), 50% P( t- Bu) ₃ (3.50ml, 8.66 mmol), NaO t -Bu (72.35 g, 752.70 mmol) were added and It was stirred at 80°C. Upon completion of the reaction, extraction was performed with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 49.66 g (yield: 72%) of the product.

(4) Synthesis of Sub 2-IV-13

After dissolving Sub 2-III-13 (49.66 g, 124.70 mmol) obtained in the above synthesis with DMF (500ml) in a round bottom flask, Bis(pinacolato)diboron (34.83 g, 137.17 mmol), Pd(dppf)Cl ₂ ( 1.01 g, 1.24 mmol), KOAc (36.71 g, 374.1 mmol) was added and stirred at 90°C. Upon completion of the reaction, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 43.36 g (yield: 80%) of the product.

(5) Synthesis of Sub 2-V-13

After dissolving Sub 2-IV-13 (43.36 g, 97.36 mmol) and 1-bromo-4-iodobenzene (41.31 g, 146.04 mmol) obtained in the above synthesis in a round bottom flask with THF (300ml) and water (150ml), K ₂ CO ₃ (40.36 g, 292.08 mmol) and Pd(PPh ₃ ) ₄ (3.37 g, 2.92 mmol) were added and stirred at 80°C. When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 38.28 g (yield: 82%) of the product.

(6) Synthesis of Sub 2-13

After dissolving Sub 2-V-13 (38.28 g, 88.69 mmol) obtained in the above synthesis with DMF (300ml) in a round bottom flask, Bis(pinacolato)diboron (25.35 g, 97.55 mmol), Pd(dppf)Cl ₂ ( 0.72 g, 20.88 mmol), KOAc (26.10 g, 266.04 mmol) was added and stirred at 90°C. Upon completion of the reaction, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 35.05 g (yield: 83%) of the product.

2. Synthesis Example of Sub 2-15

<Reaction Scheme 12>

(1) Synthesis of Sub 2-I-15

Starting material, phenylboronic acid (30 g, 246.04 mmol), 4-bromo-2-iodo-1-nitronaphthalene (92.99 g, 246.04 mmol), Pd(PPh ₃ ) ₄ (14.21 g, 12.30 mmol), K ₂ CO ₃ (101.86 g, 738.12 mmol), THF (1200ml), and water (600ml) were used to obtain 55.71 g (yield: 69%) of the product using the Sub 2-I-13 synthesis method.

(2) Synthesis of Sub 2-II-15

Sub 2-I-15 (55.71 g, 169.76 mmol) obtained in the above synthesis was mixed with triphenylphosphine (111.31 g, 424.40 mmol) and o- dichlorobenzene (850 ml) using the Sub 2-II-13 synthesis method. Yield: 70%).

(3) Synthesis of Sub 2-III-15

1-iodo-4-(((4-vinylbenzyl)oxy)methyl)benzene (41.63 g, 118.88 mmol), Pd ₂ (dba) _{3 in Sub 2-II-15 (35.19 g, 118.88 mmol) obtained in the above synthesis.} (5.44 g, 5.94 mmol), 50% P( t -Bu) ₃ (2.88ml, 11.88 mmol), NaO t -Bu (13.16 g, 356.64 mmol), toluene (600ml) was added to the Sub 2-III-13 synthesis method. Using the product 46.22 g (yield: 75%) was obtained.

(4) Synthesis of Sub 2-15

After dissolving Sub 2-III-15 (46.22 g, 89.15 mmol) obtained in the above synthesis with DMF (500ml) in a round bottom flask, Bis(pinacolato)diboron (24.90 g, 98.06 mmol), Pd(dppf)Cl ₂ ( 3.64 g, 4.45 mmol), KOAc (26.24 g, 374.1 mmol) was added and stirred at 90°C. Upon completion of the reaction, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 32.76 g (yield: 65%) of the product.

3. Synthesis Example of Sub 2-21

<Reaction Scheme 13>

(1) Synthesis of Sub 2-I-21

Starting material, phenylboronic acid (79.53 g, 246.04 mmol), 4-bromo-2-iodo-1-nitrobenzene (80.67 g, 246.04 mmol), Pd(PPh ₃ ) ₄ (14.21 g, 12.30 mmol), K ₂ CO ₃ (101.86 g, 738.12 mmol), THF (1200ml), and water (600ml) were used to obtain 49.26 g (yield: 72%) of the product using the Sub 2-I-13 synthesis method.

(2) Synthesis of Sub 2-II-21

Sub 2-I-21 (49.26 g, 177.13 mmol) obtained in the above synthesis was mixed with triphenylphosphine (116.47 g, 442.82 mmol) and o- dichlorobenzene (885ml) using the Sub 2-II-13 synthesis method. : 70%) was obtained.

(3) Synthesis of Sub 2-III-21

4-iodo-4'-(((4-vinylbenzyl)oxy)methyl)-1,1'-biphenyl (52.84 g, 123.97 mmol) in Sub 2-II-21 (30.51 g, 123.97 mmol) obtained in the above synthesis. , Pd ₂ (dba) ₃ (5.67 g, 6.19 mmol), 50% P( t -Bu) ₃ (3ml, 12.39 mmol), NaO t -Bu (13.72 g, 371.91 mmol), toluene (620ml) in the above Sub Using the 2-III-13 synthesis method, 50.62 g (yield: 75%) of the product was obtained.

(4) Synthesis of Sub 2-21

Bis(pinacolato)diboron (25.96 g, 102.25 mmol), Pd(dppf)Cl ₂ (3.75g, 4.64 mmol), KOAc in Sub 2-III-21 (50.62g, 92.96 mmol) obtained in the above synthesis. (27.36 g, 278.88 mmol) and DMF (500ml) were used to obtain a product 32.99 g (yield: 60%) using the Sub 2-15 synthesis method.

4. Synthesis Example of Sub 2-23

<Reaction Scheme 14>

(1) Synthesis of Sub 2-I-23

Starting material (4'-((9,9-dimethyl-9H-fluoren-2-yl)(4'-vinyl-[1,1'-biphenyl]-4-yl)amino)-[1,1' -biphenyl]-3-yl)boronic acid (50 g, 85.68 mmol) in 4-bromo-2-iodo-1-nitrobenzene (42.14 g, 128.52 mmol), Pd(PPh ₃ ) ₄ (4.94 g, 4.27 mmol) , K ₂ CO ₃ (35.47 g, 257.04 mmol), THF (400ml), and water (200ml) were obtained by using the Sub 2-I-13 synthesis method to obtain a product 27.62g (yield: 43%).

(2) Synthesis of Sub 2-II-23

Sub 2-I-23 (27.62 g, 37.33 mmol) obtained in the above synthesis was mixed with triphenylphosphine (24.47 g, 93.32 mmol) and o -dichlorobenzene (100ml) using the Sub 2-II-13 synthesis method. 62%)

(3) Synthesis of Sub 2-III-23

Sub 2-II-23 (16.38 g, 23.14 mmol) obtained in the above synthesis iodobenzene (4.72 g, 23.14 mmol), Pd ₂ (dba) ₃ (1.05 g, 1.15 mmol), 50% P(t-Bu) ₃ (0.56ml, 2.31 mmol), NaOt-Bu (6.71 g, 69.42 mmol), and toluene (120ml) were used to obtain 16.86 g (yield: 93%) of the product using the Sub 2-III-13 synthesis method.

(4) Synthesis of Sub 2-23

Bis(pinacolato)diboron (6.00 g, 23.66 mmol), Pd(dppf)Cl ₂ (0.87 g, 1.07 mmol), KOAc in Sub 2-III-23 (16.86 g, 21.51 mmol) obtained in the above synthesis (6.33 g, 64.53 mmol) and DMF (120ml) were used to obtain 15.17 g (yield: 90%) of the product using the Sub 2-15 synthesis method.

Meanwhile, the compound belonging to Sub 2 may be the following compound, but is not limited thereto, and Table 2 shows the FD-MS values of the compound belonging to Sub 2.

[Table 2]

III. Product synthesis

After dissolving Sub 1 (1 equivalent) and Sub 2 (1 equivalent) in toluene and water in a round bottom flask, add Pd(PPh ₃ ) ₄ (0.04 equivalent), K ₂ CO ₃ (3 equivalent) and stir at 110℃ I did. When the reaction was completed, CH ₂ Cl ₂ and water were extracted, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was silicagel column to obtain a final product.

1. Synthesis Example of P-9

<Reaction Scheme 15>

After dissolving Sub 1-9 (20 g, 21.39 mmol) and Sub 2-15 (12.09 g, 21.39 mmol) obtained in the above synthesis in a round bottom flask with toluene (110ml) and water (55ml), K ₂ CO ₃ (8.85 g, 64.17 mmol), Pd(PPh ₃ ) ₄ (1.23 g, 1.06 mmol) was added and stirred at ^{110 o C.} When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was silicagel column to obtain 20.75 g (yield: 75%) of the product.

2. Synthesis Example of P-14

<Reaction Scheme 16>

Sub 1-14 (39.96 g, 67.21 mmol) obtained in the above synthesis, Sub 2-13 (35.05 g, 67.21 mmol), Pd(PPh ₃ ) ₄ (3.10 g, 2.68 mmol), K ₂ CO ₃ (27.86 g, 201.63 mmol), toluene (250ml), and water (125ml) were used to obtain 43.90 g (yield: 72%) of the product using the P-9 synthesis method.

3. Synthesis Example of P-21

<Scheme 17>

_{Sub 2-21 (17.37 g, 29.38 mmol), Pd(PPh 3} ) ₄ (1.70 g, 1.47 mmol), K ₂ CO ₃ (5.96 g, in Sub 1-21 (20 g, 29.38 mmol) obtained in the above synthesis) 43.23 mmol), toluene (200ml), and water (100ml) were obtained by using the P-9 synthesis method to obtain 22.53g (yield: 72%) of the product.

4. Synthesis Example of P-25

<Reaction Scheme 18>

_{Sub 2-23 (15.17 g, 18.25 mmol), Pd(PPh 3} ) ₄ (1.06 g, 0.92 mmol), K ₂ CO ₃ (5.96 g, in Sub 1-25 (14.41 g, 18.25 mmol) obtained in the above synthesis) 43.23 mmol), toluene (200ml), and water (100ml) were obtained by using the P-9 synthesis method to give 21.93 g (yield: 85%) of the product.

5. Synthesis Example of P-55

<Reaction Scheme 19>

Sub 1-52 (9.50 g, 12.03 mmol) obtained in the above synthesis Sub 2-23 (10 g, 12.03 mmol), Pd(PPh ₃ ) ₄ (0.70 g, 0.60 mmol), K ₂ CO ₃ (4.98 g, 36.09 mmol), toluene (100ml), and water (50ml) were used to obtain 15.31 g (yield: 80%) of the product using the P-9 synthesis method.

Meanwhile, the FD-MS values of the compounds P-1 to P-66 of the present invention prepared according to the synthesis example as described above are shown in Table 3 below.

[Table 3]

Meanwhile, in the above, exemplary synthesis examples of the present invention represented by Chemical Formula 1 have been described, but these are all Buchwald-Hartwig cross coupling reactions, PPh ₃ -mediated reductive cyclization reactions ( J. Org. Chem . 2005, 70 , 5014.) , Miyaura boration reaction, Suzuki cross-coupling reaction, etc., in addition to the substituents specified in the specific synthesis examples, other substituents defined in Formula 1 (substituents such as R ¹ , R ² , Ar ¹ to Ar ³ , L ¹ , L ² ) It will be readily understood by those skilled in the art that the reaction proceeds even when combined. For example, the starting material -> Sub 1 reaction in Scheme 2 is based on the Buchwald-Hartwig cross coupling reaction, and the Sub 2-I -> Sub 2-II reaction in Scheme 9 is based on the PPh ₃ -mediated reductive cyclization reaction. The reactions from Sub 2-III -> Sub 2-IV and Sub 2-V -> Sub 2 in 9, and Sub 2-III -> Sub 2 in Scheme 10 are all based on the Miyaura boration reaction. Then, starting material in Scheme 3 -> Sub 1 reaction, starting material in Scheme 9 -> Sub 2-I, Sub 2-II -> Sub 2-III, Sub 2-IV -> Sub 2-V reaction, Scheme 15 The reactions in Reaction Scheme 19 are based on the Suzuki cross-coupling reaction, and the above reactions will proceed even if a substituent not specifically specified is bonded thereto.

Manufacturing evaluation of organic electric devices

[Example 1]

After patterning was performed so that the light emitting area of the ITO (Indium Tin Oxide) layer was 3mm X 3mm on the substrate, it was washed. After mounting the substrate on a spin coater, PEDOT:PSS was spin-coated on the ITO layer to a thickness of 50 nm. Then, the solvent was removed by drying on a hot plate at 150° C. for 10 minutes, and then the compound P-1 of the present invention, which is a hole transport material, was dissolved in xylene and spin-coated to a thickness of 30 nm. Then, after drying for 10 minutes on a hot plate at 100°C, it was crosslinked by heating at 200°C for 30 minutes. On the hole transport layer, doped ADN as the host material of the emission layer as the dopant material and DPAVBi as the dopant material in a 96:4 weight ratio, spin-coating the solution dissolved in xylene to a thickness of 30 nm, drying it on a hot plate at 100°C for 10 minutes, and then mounting it in a vacuum chamber. And make the base pressure 1X10 ^-6 torr. Subsequently, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinoleato)aluminum was vacuum-deposited to a thickness of 10 nm as a hole blocking layer, and tris(8-quinolipid) was deposited as an electron transport layer. Nol) aluminum was deposited to a thickness of 40 nm. Thereafter, as the electron injection layer, LiF, which is an alkali metal halide, was deposited to a thickness of 0.5 nm, and then Al was deposited to a thickness of 150 nm to be used as a cathode, thereby manufacturing an organic electroluminescent device.

[Example 2] to [Example 60]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compounds P-2 to P-66 of the present invention described in Table 4 below were used instead of the compound P-1 of the present invention as the hole transport layer material. .

[Comparative Example 1]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 below was used instead of Compound P-1 of the present invention as a material for the hole transport layer.

<Comparative compound 1>

[Comparative Example 2]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 2 below was used instead of Compound P-1 of the present invention as a material for the hole transport layer.

<Comparative compound 2>

Electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent devices manufactured according to Examples 1 to 60 and Comparative Examples 1 and 2 of the present invention with PR-650 of photoresearch Was measured, and as a result of the measurement, the T95 life was measured through a life measurement equipment manufactured by McScience at a reference luminance of 500 cd/m ^{2, and the measurement results are shown in Table 4 below.}

[Table 4]

As can be seen from the results of Table 4, in the case of an organic electric device using the compound of the present invention as a material for a hole transport layer, not only the luminous efficiency was improved compared to the organic electric device using the compound 1 and the comparative compound 2 as a material for the hole transport layer, but also the lifetime. The back has been significantly improved.

In the case of Comparative Compound 2 in which an ether linking group was introduced into the carbazole core, it was confirmed that the luminous efficiency was increased by showing higher solubility due to superior flexibility than Comparative Compound 1. However, since the thin film was not formed uniformly, it was more efficient than the compound of the present invention. It can be seen that this decreases.

In addition, Comparative Compound 1 and Comparative Compound 2, which are symmetrical structures around the carbazole core, have relatively slow hole mobility, whereas the compound of the present invention having an asymmetric structure has a faster hole mobility. It can be seen that the driving voltage is lowered and the thermal damage is reduced, thereby improving the lifespan.

In summary, the characteristics described above (uniform thin film characteristics and fast hole mobility) can be summarized as follows: band gap, electrical characteristics and interface characteristics depending on the type and number of connectors and/or structural symmetry around the carbazole core. This indicates that the compound of the present invention can be changed greatly, which acts as a major factor in improving the performance of the device, and the compound of the present invention, in which a substituent having a crosslinking property is introduced, has a low voltage, high luminous efficiency, and high curability, and at the same time, greatly improves the lifespan. It shows that it is an excellent material as a solution processing material.

In addition, in the evaluation results of the above-described device fabrication, the device characteristics were described in terms of the hole transport layer, but the materials commonly used as the hole transport layer are organic electricity such as the aforementioned electron transport layer, electron injection layer, hole injection layer, light emitting layer and light emitting auxiliary layer. As an organic material layer of the device, it can be used singly or mixed with other materials. Therefore, for the above-described reasons, the compound of the present invention may be used as a single material or a mixture of other materials, such as an electron transport layer, an electron injection layer, a hole injection layer, a light emitting layer and a light emitting auxiliary layer, in addition to the hole transport layer.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification are not intended to limit the present invention, but to explain 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 claims below, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100: organic electric device 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 (11)

Represented by the following formula (1), R ¹ , R ² , Ar ¹ to Ar ³ A compound characterized in that it has cross-linking properties by including at least one cross-linking forming group represented by at least one of.
<Formula 1>

<Formula a><Formulab>

<Formula z-1><Formulaz-2>

<Formula z-3><Formulaz-4>

[In Chemical Formula 1,
A is the formula a, B is the formula b,
Z is a formula z-1 to a formula z-4,
o is an integer from 0 to 4; p is an integer from 0 to 3,
m and n are integers from 1 to 8,
R ¹ and R ² are i) independently of each other deuterium; Tritium; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A C ₁ to C ₅₀ alkyl group; A fused ring group of an aromatic ring of C ₆ to C _{60 and an aliphatic ring of C 3} to C _60; C ₂ ~ C ₂₀ alkenyl group; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; -L ^a -N(R ^a ) (R ^b ); Carbonyl group; -O-Si(R ^c ) ₃ ; R ^c O-Si(R ^c ) ₂ -; C ₇ ~ C ₆₀ arylalkyl group; C ₂ ~ C ₃₀ alkenyloxyl group; Ether group; C ₈ -C ₆₀ alkenyl aryl group; A C ₃ to C ₆₀ cycloalkyl group; Silane group; Siloxane group; C ₇ ~ C ₆₀ aryl alkoxyl group; C ₈ ~ C ₆₀ arylalkenyl group; And C ₂ ~ C ₆₀ alkoxyl carbonyl group; is selected from the group consisting of,
Or ii) when o and p are 2 or more, each of a plurality of the same or different from each other, and a plurality of R ¹ and R ² may be each bonded to form a ring (however, R ¹ and R ^{2 that do not form a ring} Are each the same as defined in i) above),
Ar ¹ to Ar ³ are each independently a C ₆ to C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A C ₁ to C ₅₀ alkyl group; A fused ring group of an aromatic ring of C ₆ to C _{60 and an aliphatic ring of C 3} to C _60; C ₂ ~ C ₂₀ alkenyl group; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; -L ^a -N(R ^a ) (R ^b ); Carbonyl group; -O-Si(R ^c ) ₃ ; R ^c O-Si(R ^c ) ₂ -; C ₇ ~ C ₆₀ arylalkyl group; C ₂ ~ C ₃₀ alkenyloxyl group; Ether group; C ₈ -C ₆₀ alkenyl aryl group; A C ₃ to C ₆₀ cycloalkyl group; Silane group; Siloxane group; C ₇ ~ C ₆₀ aryl alkoxyl group; C ₈ ~ C ₆₀ arylalkenyl group; And C ₂ ~ C ₆₀ alkoxyl carbonyl group; is selected from the group consisting of,
L ¹ and L ² are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₁ -C ₆₀ alkylene group, and C ₂ ~ C ₆₀ alkenylene group; is selected from the group consisting of,
L ^a is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ divalent heterocyclic group containing at least one hetero atom of P; A divalent fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; And a divalent aliphatic hydrocarbon group; is selected from the group consisting of,
R ^a and R ^b are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of P; And a fused ring group of an aromatic ring of _{C 6} to C _{60 and an aliphatic ring of C 3} to C _{60; and}
R ^c is hydrogen; C ₆ ~ C ₂₀ aryl group; A C ₁ to C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₈ -C ₂₀ arylalkenyl group; C ₇ ~ C ₂₀ aryl alkoxyl group; And C ₂ ~ C ₂₀ alkoxyl carbonyl group; is selected from the group consisting of,
Here, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, fluorenylene group, carbonyl group, arylalkyl group, alkenyloxyl group, Ether group, alkenaryl group, cycloalkyl group, silane group, siloxane group, arylalkoxyl group, arylalkenyl group, and alkoxylcarbonyl group, respectively, deuterium, halogen, silane group, siloxane group, boron group, germanium group, cyano group, nitro Group, -L ^b -N(R ^d )(R ^e ) (where L ^b , R ^d and R ^e are the same as the definitions of ^{L a} , R ^a and R ^b _{, respectively), C 1} ~ C ₂₀ alkyl Im coming, substituted alkynyl, aryl, heavy hydrogen of C ₆ ~ C ₂₀ of the C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the C ₆ ~ C ₂₀ aryl group, fluorenyl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ arylalkene Diary, carbonyl group, ether group, C ₂ to C ₂₀ alkoxyl carbonyl group, C ₆ to C ₃₀ aryloxy group, -O-Si(R ^f ) ₃ , and R ^c O-Si(R ^f ) _2- ( Here, R ^f may be further substituted with one or more substituents selected from the group consisting of (the same as the definition of R ^{c ),}
At least one of R ¹ , R ² , Ar ¹ to Ar ³ includes any one of the following formulas.
<Formula h-1><Formulah-2><Formulah-3>

<Formula h-4><Formulah-5><Formulah-6>

<Formula h-7><Formulah-8><Formulah-9>

<Formula h-10><Formulah-11><Formulah-12>

(In Formula h-7, q is an integer of 1 to 6)] delete The method of claim 1,
The compound represented by Formula 1 is a compound characterized in that it is represented by the following formula.
<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

(In Formulas 2 to 5, the R ¹ , R ² , Ar ¹ to Ar ³ , L ¹ , L ² , m, n, o and p are the same as defined in claim 1.) The method of claim 1,
Wherein B is a compound, characterized in that represented by one of the following formula.
<Formula b-1><Formulab-2><Formulab-3>

<Formula b-4><Formulab-5><Formulab-6>

<Formula b-7><Formulab-8><Formulab-9>

<Formula b-10><Formulab-11><Formulab-12>

<Formula b-13><Formulab-14><Formulab-15>

<Formula b-16><Formulab-17><Formulab-18>

(In Formulas b-1 to b-18, R ¹ , R ² , Ar ³ , L ¹ , L ² , o and p are the same as defined in claim 1.) The method of claim 1,
The compound represented by Formula 1 is a compound, characterized in that one of the following compounds.

A first electrode;
A second electrode; And
In the organic electric device comprising; an organic material layer positioned between the first electrode and the second electrode,
An organic electric device, characterized in that the organic material layer contains the compound of any one of claims 1 and 3 to 5. The method of claim 6,
An organic electric device, characterized in that the compound is contained in at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer, and a light emission layer of the organic material layer. The method of claim 6,
An organic electric device, characterized in that the molar ratio of a compound containing one crosslinking group among the compounds and another compound containing at least two crosslinking groups is mixed in a range of 99:1 to 1:99. The method of claim 6,
The organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, or a roll-to-roll process. A display device including the organic electric device of claim 6; And
Electronic device comprising a; a control unit for driving the display device. The method of claim 10,
The organic electroluminescent device is an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and an electronic device, characterized in that one of a single color or white lighting device.

Images