KR102620119B1 - Compound for organic electric element, organic electric element comprising the same and electronic device thereof - Google Patents

Abstract

The present invention provides a compound that can improve the high luminous efficiency, low driving voltage, and lifespan of the device, an organic electric device using the same, and an electronic device thereof.

Description

Compounds for organic electric devices, organic electric devices using the same, and their electronic devices {COMPOUND FOR ORGANIC ELECTRIC ELEMENT, ORGANIC ELECTRIC ELEMENT COMPRISING THE SAME AND ELECTRONIC DEVICE THEREOF}

These embodiments relate to compounds for organic electric devices, organic electric devices using the same, and electronic devices thereof.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic electric devices that utilize the organic light emission phenomenon usually have a structure including an anode, a cathode, and an organic material layer between them. Here, the organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic electric device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as organic layers in organic electric devices 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, depending on their function.

Currently, the portable display market is increasing in size toward large-area displays, which requires greater power consumption than that required by existing portable displays. Therefore, power consumption has become an important factor for portable displays that have a limited power source such as batteries, and issues of efficiency and lifespan are also important factors that must be resolved.

Efficiency, lifespan, and driving voltage are related to each other. As efficiency increases, the driving voltage relatively decreases. As the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, resulting in less crystallization of organic substances. It indicates a tendency for lifespan to increase. However, efficiency cannot be maximized simply by improving the organic layer. This is because when the energy level between each organic layer, the triplet excitation energy value (hereinafter referred to as T1), and the intrinsic properties of the material (mobility, interface properties, etc.) are optimally combined, long lifespan and high efficiency can be achieved simultaneously. Because you can.

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

Generally, in organic electroluminescent devices, 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 of electrons and holes.

However, the material used in the hole transport layer must have a low HOMO value, so most have a low T1 value. This causes excitons generated in the light-emitting layer to pass to the hole transport layer, resulting in a charge unbalance in the light-emitting layer. This causes light to be emitted within the hole transport layer or at the interface of the hole transport layer, resulting in decreased color purity, reduced efficiency, and low lifespan.

Additionally, when a material with high hole mobility is used to create a low driving voltage, efficiency tends to decrease. This is because hole mobility is faster than electron mobility in a typical organic electroluminescent device, resulting in charge unbalance within the light emitting layer, resulting in reduced efficiency and low lifespan.

Therefore, the light emitting auxiliary layer has hole mobility (within the blue device driving voltage range of a full device) and a high T1 (electron block) value to have an appropriate driving voltage to solve the problems of the hole transport layer. , it must be a material with a wide bandgap. However, this cannot be achieved simply by the structural characteristics of the core of the light-emitting auxiliary layer material, but is possible when the characteristics of the core and sub-substituents of the material are combined. Therefore, in order to improve the efficiency and lifespan of organic electric devices, there is an urgent need for the development of light-emitting auxiliary layer materials with high T1 values and wide band gaps.

In other words, in order to fully demonstrate the excellent characteristics of organic electric devices, the materials that make up the organic layer within the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, electron injection materials, and light-emitting auxiliary layer materials, must be stable and efficient. Support by materials must be a priority, but the development of stable and efficient organic material layer materials for organic electric devices has not yet been sufficiently developed. Therefore, the development of new materials continues to be required, and in particular, the development of materials for the light-emitting auxiliary layer and hole transport layer is urgently needed.

The purpose of the present invention is to provide a compound that can improve the luminous efficiency and lifespan of the device while lowering the driving voltage of the device by utilizing the characteristics of polycyclic ring compounds, an organic electric device using the same, and an electronic device thereof.

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

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

By using the compound of the present invention, not only can the driving voltage of the device be lowered, but also the luminous efficiency and lifespan of the device can be greatly improved.

1 is a cross-sectional view of an organic light-emitting device according to an embodiment of the present invention.
Figure 2 is a diagram showing the difference in structure and electron cloud between the compound of the present invention and a comparative compound.

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

When adding reference numerals to components in each drawing, it should be noted that identical components are given the same reference numerals as much as possible even if they are shown in different drawings. Additionally, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

Additionally, when describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, sequence, or order of the component is not limited by the term. When a component is described as being “connected,” “coupled,” or “connected” to another component, that component may be directly connected or connected to that other component, but there is another component between each component. It will be understood that elements may be “connected,” “combined,” or “connected.”

As used in this specification and the appended claims, unless otherwise noted, the following terms have the following meanings.

As used herein, the term “halo” or “halogen” refers to fluorine (F), bromine (Br), chlorine (Cl), or iodine (I), unless otherwise specified.

As used in the present invention, the term "alkyl" or "alkyl group", unless otherwise specified, has a single bond of 1 to 60 carbon atoms, and includes straight chain alkyl group, branched chain alkyl group, cycloalkyl (cycloaliphatic) group, and alkyl-substituted cyclo. It refers to radicals of saturated aliphatic functional groups, including alkyl groups and cycloalkyl-substituted alkyl groups.

As used in the present invention, the term “haloalkyl group” or “halogenalkyl group” means an alkyl group substituted with halogen, unless otherwise specified.

The term “heteroalkyl group” used in the present invention means that one or more of the carbon atoms constituting the alkyl group are replaced with a heteroatom.

As used in the present invention, the term "alkenyl group" or "alkynyl group", unless otherwise specified, has a double or triple bond of 2 to 60 carbon atoms each, and includes straight or branched chain groups, and is limited thereto. That is not the case.

The term “cycloalkyl” used in the present invention refers to alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.

As used in the present invention, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" refers to an alkyl group to which an oxygen radical is attached, and has a carbon number of 1 to 60, and is limited thereto, unless otherwise specified. That is not the case.

As used in the present invention, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" refers to an alkenyl group to which an oxygen radical is attached, and, unless otherwise specified, refers to an alkenyl group having an oxygen radical attached thereto. It has a carbon number of, and is not limited to this.

The term “aryloxyl group” or “aryloxy group” used in the present invention refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

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

The prefix “aryl” or “ar” refers to 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 carbon number described in this specification.

Additionally, when prefixes are named consecutively, it means that the substituents are listed in the order they are listed first. For example, an arylalkoxy group refers to an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group refers to a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group refers to an alkenyl group substituted with an arylcarbonyl group. And here, the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term “heteroalkyl” means alkyl containing one or more heteroatoms, unless otherwise specified. As used in the present invention, the term “heteroaryl group” or “heteroarylene group” refers to an aryl group or arylene group having 2 to 60 carbon atoms each containing one or more heteroatoms, unless otherwise specified. 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" used in the present invention, unless otherwise specified, contains one or more heteroatoms, has a carbon number of 2 to 60, includes at least one of a single ring and a multiple ring, and includes a heteroaliphatic ring and a heterocyclic group. Contains an aromatic ring. It may also be formed by combining neighboring functional groups.

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

Additionally, the “heterocyclic group” may also include a ring containing SO2 instead of ring-forming carbon. For example, “heterocyclic group” includes the following compounds:

Unless otherwise specified, the term "aliphatic" used in the present invention refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the term "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 an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocycle having 2 to 60 carbon atoms, or a fused ring consisting of a combination thereof, Contains saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the above-described heterocompounds include one or more heteroatoms, but are not limited thereto.

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

Unless otherwise specified, the term "ether" used in the present invention is represented by -R-O-R', where R or R' are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 30 carbon atoms. It is an aryl group, a cycloalkyl group with 3 to 30 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an alkynyl group with 2 to 20 carbon atoms, or a combination thereof.

Also, unless explicitly stated otherwise, in the term “substituted or unsubstituted” used in the present invention, “substituted” refers to deuterium, halogen, amino group, nitrile group, nitro group, C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₈ ~ C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and C ₂ to C ₂₀ heterocyclic group, but is not limited to these substituents.

Additionally, unless explicitly stated otherwise, the chemical formula used in the present invention is applied identically to the substituent definition according to the exponent definition in the following chemical 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 the carbons forming the benzene ring, and when a is an integer of 2 or 3, Each is bonded as follows, where 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 indicating the hydrogen bonded to the carbon forming the benzene ring is omitted.

1 is an exemplary diagram 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. ) and an organic material layer containing the compound according to the present invention is provided between them. At this time, the first electrode 120 may be an anode and the second electrode 180 may be a cathode. In the case of the inverted type, the first electrode may be the cathode and the second electrode may be the 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. At this time, the remaining layers except for the light emitting layer 150 may not be formed. It may further include a hole blocking layer, an electron blocking layer, a light emission auxiliary layer 151, a buffer layer 141, etc., and an electron transport layer 160, etc. may serve as a hole blocking layer.

In addition, although not shown, the organic electric device according to the present invention may further include a protective layer or a light efficiency improvement layer (capping layer) formed on at least one side 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 host or dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, and the light emitting layer 150, or the light efficiency improvement layer. It could be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150.

Meanwhile, even if it is the same core, the band gap, electrical properties, and interface properties may vary depending on which substituent is attached to which position, so the selection of the core and the combination of sub-substituents attached to it are very important. It is important, and in particular, long life and high efficiency can be achieved at the same time when the energy level and T1 value between each organic layer and the intrinsic properties of the material (mobility, interface properties, etc.) are optimally combined.

Therefore, in the present invention, by forming a light-emitting layer using the compound represented by Formula 1, the energy level and T1 value between each organic material layer, and intrinsic properties of the material (mobility, interface properties, etc.) are optimized to improve the lifespan of the organic electric device. and efficiency can be improved simultaneously.

An organic electric 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, and an electron transport layer ( It can be manufactured by forming an organic material layer including 160) and an electron injection layer 170, and then depositing a material that can be used as a cathode 180 thereon.

In addition, the organic material layer uses a variety of polymer materials, such as a solution process or solvent process rather than a deposition method, such as spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, and doctor bleed process. It can be manufactured with fewer layers by methods such as a printing process, screen printing process, or 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 formation method.

The organic electric device according to the present invention may be a front-emitting type, a rear-emitting type, or a double-sided emitting type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to achieve high resolution and having excellent fairness, while being manufactured using the color filter technology of existing LCDs. Various structures for white organic electric devices, mainly used as backlight devices, are being proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are arranged in parallel with each other in a plane, and a stacking method in which R, G, and B light emitting layers are stacked top and bottom. There is a color conversion material (CCM) method that uses electroluminescence by a blue (B) organic light-emitting layer and photo-luminescence of an inorganic phosphor using light therefrom, and the present invention. can be applied to these WOLEDs as well.

Additionally, the organic electric device according to the present invention may be one of an organic electric device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), and a device for monochromatic or white lighting.

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 that controls the display device. At this time, 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 one aspect of the present invention will be described. The compound according to one aspect of the present invention is represented by the following formula (1).

In Formula 1,

(1) Ar ¹ and Ar ² are each independently the same or different,

C ₆ -C ₆₀ aryl group; fluorenyl group; C ₂ -C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P; C ₁ -C ₆₀ alkyl group; Fused ring group of C ₆ -C ₆₀ aromatic ring and C ₃ -C ₆₀ aliphatic ring; C ₂ -C ₆₀ alkenyl group; C ₁ -C ₆₀ alkoxyl group; and C ₆ -C ₆₀ aryloxy group; and -L'-N(Ra)(Rb); or Ar ¹ and Ar ² may be combined with each other to form a ring, and the ring formed may be monocyclic or polycyclic.

(2) Each of the A and B rings may be a C ₆ to C ₁₈ aryl group,

(3) L is a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; A C ₂ to C ₆₀ divalent heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; A divalent fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; and a divalent aliphatic hydrocarbon group,

(4) R ₁ to R ₁₀ are each independently the same or different,

hydrogen; heavy hydrogen; halogen; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(Ra)(Rb); is selected from the group consisting of,

L' is a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; And C ₂ ~ C ₆₀ heterocyclic group; Ra and Rb are each independently selected from the group consisting of C ₆ ~ C ₆₀ aryl group; fluorenyl group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; and a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P;

(5) m and n are each integers from 0 to 8.

The aryl group, fluorenyl group, heterocyclic group, alkyl group, fused ring group, alkenyl group, alkynyl group, alkoxy group, and aryloxy group each contain deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; siloxane group; boron group; Germanium group; Cyano group; nitro group; -L'-N(Ra)(Rb) (where L', Ra, Rb are the same as the definitions of L', Ra, Rb); C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxyl group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne group; C ₆ -C ₂₀ aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; and may be further substituted with one or more substituents selected from the group consisting of C ₈ -C ₂₀ arylalkenyl groups.

Here, in the case of the aryl group, the aryl group may have 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, and more preferably 6 to 30 carbon atoms. In the case of the heterocyclic group, the aryl group may have 2 to 60 carbon atoms, preferably 2 carbon atoms. It may be a heterocycle having ~30 carbon atoms, more preferably 2-20 carbon atoms, and in the case of the alkyl group, the carbon number is 1-50, preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, especially preferably. It may be an alkyl group of 1 to 10.

In the case of the above-mentioned aryl group or arylene group, specifically, the aryl group or arylene group is independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group or a phenylene group, a biphenylene group, a terphenylene group, or a naphthyl group. It may be a ren group or a phenanthrylene group.

More specifically, the compound represented by Formula 1 may be any one of the following compounds, and is not limited to the following compounds.

Specifically, in Formula 1, Ar ¹ and Ar ² are each independently selected from a phenyl group unsubstituted or substituted with deuterium or phenyl, a biphenylyl group, a naphthyl group, a fluorenyl group unsubstituted or substituted with methyl or phenyl, or a spirobi group. Fluorenyl group, pyrimidinyl group substituted or unsubstituted by phenyl, phenyl, naphthyl, biphenyl, terphenyl, phenanthrenyl, triphenyl, fluorenyl, carbazole, dibenzothienyl or dibenzofuryl. It may be a substituted or unsubstituted quinazolinyl group or dibenzothienyl group.

Ring A and Ring B of Formula 1 may independently have one of the following formulas.

In the A ring and the B ring, * represents the bonding portion that combines with Formula 1 to form a fused ring.

Specifically, the structure in which the A ring and the B ring are bonded to Formula 1 may be represented by one of the following Formulas A-1 to Formula A-22, but Formula 1 is not limited thereto.

More specifically, the compound represented by Formula 1 may be any one of the following compounds (P-1) to (P-71), but Formula 1 is not limited thereto.

As another example, the present invention provides a compound for organic electric devices represented by Formula 1 above.

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

At this time, the organic electric device includes a first electrode; second electrode; And an organic material layer located between the first electrode and the second electrode; 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. , it may be contained in at least one layer of a light-emitting auxiliary layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In particular, the compound represented by Formula 1 may be included in the hole transport layer or the auxiliary light emitting layer.

That is, the compound represented by Formula 1 can be used as a material for a hole injection layer, a hole transport layer, an auxiliary light emitting layer, a light emitting layer, an electron transport layer, or an electron injection layer. In particular, the compound represented by Formula 1 can be used as a material for the light-emitting layer. Specifically, providing an organic electric device containing one of the compounds represented by Formula 1 in the organic material layer, and more specifically, one of the compounds represented by the individual formulas (P-1 to P-71) in the organic material layer. It provides an organic electric device containing a.

In another embodiment, the compound is contained alone in at least one layer of the hole injection layer, the hole transport layer, the auxiliary light emitting layer, the light emitting layer, the electron transport layer, and the electron injection layer of the organic material layer, or It provides an organic electric device characterized in that the compound is contained in a combination of two or more different types, or the compound is contained in a combination of two or more types with other compounds. In other words, each layer may contain a compound corresponding to Formula 1 alone or a mixture of two or more compounds of Formula 1, the compounds of claims 1 to 3, and compounds that do not correspond to the present invention. A mixture of and may be included. Here, the compound that does not fall under the present invention may be a single compound, or may be two or more types of compounds. At this time, when the compound is contained in a combination of two or more types of other compounds, the other compounds may be already known compounds of each organic layer, or may be compounds to be developed in the future. At this time, the compound contained in the organic layer may be composed of only the same type of compound, but may also be a mixture of two or more different types of compounds represented by Chemical Formula 1.

In another embodiment of the present invention, it further includes 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. Provides an organic electric device that

Hereinafter, the synthesis example of the compound represented by Formula 1 and the manufacturing example of the organic electric device according to the present invention will be described in detail through examples, but the present invention is not limited to the following examples.

Synthesis example

The final products according to the present invention are synthesized by reacting Sub 1 and Sub 2 as shown in Scheme 1 below, but are not limited thereto.

I. Synthesis of Sub 1

Sub 1 of Scheme 1 may be synthesized through the reaction route of Scheme 2 below, but is not limited thereto.

(X1=Cl, Br, I; X2=Br, I; a = 0, 1; b = 1, 2)

(1) Sub 1-I-1 synthesis

After dissolving 2'-bromo-4-chlorobiphenyl (15.0g, 56.1mmol) and 4H-cyclopenta[def]phenanthren-4-one (11.45g, 56.1mmol) in THF (600ml), the temperature of the reactants was -78℃. Then, n-BuLi (2.5M in hexane) (23.6ml, 58.9mmol) was slowly added dropwise, and the reaction was stirred at room temperature for 4 hours. When the reaction was completed, the reactant was quenched in H ₂ O, water was removed, the organic layer was dried with MgSO ₄ and concentrated, and the resulting organic material was recrystallized using a silicagel column to obtain 18.7 g of product. (yield: 85%)

(2) Sub 1-II-1 synthesis

Add HCl and Acetic acid (50ml) to Sub 1-I-1 (10.0g, 25.5mmol) and stir at 80°C for 1 hour. When the reaction was completed, the organic solvent was concentrated, and the resulting organic matter was recrystallized using a silicagel column to obtain 8.8 g of product. (yield: 92%)

(1) Sub 1-I- 2Synthesis

Add phenylboronic acid 13.45g, 110.29mmol) to a round bottom flask, 1-bromo-3-chloro-2-iodobenzene (35g, 110.29mmol), Pd(PPh ₃ ) ₄ (1.27g, 1.10mmol), NaOH (4.41 g, 110.29mmol), THF (485mL), and water (243mL) are added. Afterwards, it is heated and refluxed at 80°C. When the reaction is complete, it is diluted with distilled water at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 18.59 g of product. (yield: 63%)

(2) Sub 1-II-2 synthesis

Sub 1-I-2 (18.59g, 69.48mmol), 4H-cyclopenta[def]phenanthren-4-one (14.19g, 69.48mmol), THF (660ml), n-BuLi (2.5M in hexane) obtained from the above synthesis ) (29.18ml, 72.96mmol) was obtained using the Sub 1-I-1 synthesis method above to obtain 22.66g of product. (yield: 83%)

(3) Sub 1-4 synthesis

Sub 1-II-2 (22.66g, 57.68mmol), HCl, and Acetic acid (127ml) obtained in the above synthesis were used to obtain 18.81g of product using the Sub 1-II-1 synthesis method. (yield: 87%)

(One) Sub 1-I-3 synthesis

(2-bromophenyl)boronic acid (29.93g, 200.83mmol), 1-chloro-4-iodonaphthalene (43g, 149.04mmol), Pd(PPh ₃ ) ₄ (1.72g, 1.49mmol), NaOH (5.96mmol) in a round bottom flask. g, 149.04mmol), THF (656mL), and water (328mL) were used to obtain 36.45g of the product using the Sub 1-I-2 synthesis method. (yield: 77%)

(2) Sub 1-II-3 synthesis

Sub 1-I-3 (25g, 78.71mmol), 4H-cyclopenta[def]phenanthren-4-one (16.08g, 78.71mmol), THF (748ml), n-BuLi (2.5M in hexane) obtained from the above synthesis. (33.06ml, 82.65mmol) was used to obtain 27.89g of product using the Sub 1-I-1 synthesis method. (yield: 80%)

(3) Sub 1-7 synthesis

Sub 1-II-8 (20.92g, 47.23mmol), HCl, and Acetic acid (104ml) obtained in the above synthesis were used to obtain 17.06g of product using the Sub 1-II-1 synthesis method. (yield: 85%)

(1) Sub 1-I-4 synthesis

2-Bromo-7-naphthaleneboronic acid (20.0g, 79.7mmol), 1-chloro-4-iodobenzene (22.8g, 95.7mmol), Pd(PPh ₃ ) ₄ (2.76g, 2.4mmol), NaOH (9.57g, 239.1 mmol), THF (880 mL), and water (440 mL) were used to obtain 18.7 g of product using the Sub 1-I-2 synthesis method. (yield: 74%)

(2) Sub 1-II-4 synthesis

Sub 1-I-4 (18.0g, 56.7mmol), 4H-cyclopenta[def]phenanthren-4-one (11.57g, 56.7mmol), THF (570ml), n-BuLi (2.5M in hexane) obtained from the above synthesis ) (23.8ml, 59.5mmol) was used to obtain 19.6g of product using the Sub 1-I-1 synthesis method. (Yield: 78%)

(3) Sub 1-6 synthesis

Sub 1-II-4 (15.0g, 33.9mmol), HCl, and Acetic acid (75ml) obtained in the above synthesis were used to obtain 12.27g of the product using the Sub 1-II-1 synthesis method. (yield: 88%)

(1) Sub 1-I-5 synthesis

Add 2-Naphthylboronic acid (15.60g, 90.69mmol) to a round bottom flask, 2-bromo-4-chloro-1-iodobenzene (28.78g, 90.69mmol), and Pd(PPh ₃ ) ₄ (1.05g, 0.91mmol). , add NaOH (3.63g, 90.69mmol), THF (399mL), and water (200mL). Afterwards, it is heated and refluxed at 80°C. When the reaction is complete, it is diluted with distilled water at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 21.03 g of product. (yield: 73%)

(2) Sub 1-II-5 synthesis

Sub 1-I-5 (14.0g, 44.1mmol), 4H-cyclopenta[def]phenanthren-4-one (9.0g, 44.1mmol), THF (441ml), n-BuLi (2.5M in hexane) obtained from the above synthesis ) (18.5ml, 46.3mmol) was used to obtain 15.8g of product using the Sub 1-I-1 synthesis method. (yield: 81%)

(3) Sub 1-III-5 synthesis

Sub 1-II-5 (21g, 47.41mmol), HCl, and Acetic acid (44ml) obtained in the above synthesis were used to obtain 17.33g of product using the Sub 1-II-1 synthesis method. (Yield: 86%)

(4) Sub 1-11 synthesis

To Sub 1-III-1 (17.33g, 40.78mmol) obtained in the above synthesis, (4-chlorophenyl)boronic acid (6.38g, 40.78mmol), Pd(PPh ₃ ) ₄ (1.41g, 1.22mmol), NaOH (4.89 g, 122.35mmol), THF (179mL), and water (89mL) were used to obtain 14.10g of the product using the Sub 1-I-2 synthesis method. (yield: 69%)

Sub 1-II-1 (10.0g, 26.68mmol), (4'-chloro-[1,1'-biphenyl]-3-yl)boronic acid (6.20g, 26.68mmol), Pd(PPh) obtained from the above synthesis ₃ ) 9g of product was obtained using ₄ (0.46g, 0.4mmol), NaOH (1.6g, 40.01mmol), THF (117mL), and water (59mL) using the Sub 1-I-2 synthesis method. (yield: 64%)

Sub 1-II-1 (9g, 24.01mmol), (7-chloro-9,9-dimethyl-9H-fluoren-2-yl)boronic acid (6.54g, 24.01mmol), Pd(PPh ₃ ) obtained from the above synthesis ) ₄ (0.42g, 0.36mmol), NaOH (1.44g, 36.01mmol), THF (106mL), and water (53mL) were used to obtain 9.8g of product using the Sub 1-I-2 synthesis method. (Yield: 72%)

(One) Sub One- IV -1 synthesis

After dissolving Sub 1-II-1 (15g, 40.01mmol) obtained in the above synthesis with DMF (252ml) in a round bottom flask, Bis(pinacolato)diboron (11.18g, 44.02mmol), Pd(dppf)Cl ₂ (0.88g, 1.20mmol), KOAc (11.78g, 120.04mmol) was added and stirred at 90°C. When the reaction was completed, DMF was removed through distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 16.24 g of product. (yield: 87%)

(2) Sub 1-19

Sub 1-IV-1 (10g, 31.77mmol), 1,3,5-tribromobenzene (14.82g, 31.77mmol), Pd(PPh ₃ ) ₄ (0.37g, 0.32mmol), NaOH (1.27g) obtained from the above synthesis. , 31.77 mmol), THF (139 mL), and water (70 mL) to obtain 12.04 g of product using the Sub 1-I-2 synthesis method. (Yield: 66%)

(1) Sub 1-I-6 synthesis

In a round bottom flask, 2-Naphthylboronic acid (20.59g, 119.74mmol), 1-bromo-4-chloro-2-iodobenzene (38g, 119.74mmol), Pd(PPh ₃ ) ₄ (1.38g, 1.2mmol), NaOH ( 4.79g, 119.74mmol), THF (527mL), and water (263mL) were used to obtain 27.38g of product using the Sub 1-I-2 synthesis method. (Yield: 72%)

(2) Sub 1-II-6 synthesis

Sub 1-I-6 (27.38g, 86.21mmol), 4H-cyclopenta[def]phenanthren-4-one (17.61g, 86.21mmol), THF (819ml), n-BuLi (2.5M in hexane) obtained from the above synthesis ) (36.21ml, 90.52mmol) was used to obtain 29.02g of product using the Sub 1-I-1 synthesis method. (Yield: 76%)

(3) Sub 1-24 synthesis

Sub 1-II-6 (20.92g, 47.23mmol), HCl, and Acetic acid (104ml) obtained in the above synthesis were used to obtain 18.06g of product using the Sub 1-II-1 synthesis method. (Yield: 90%)

(One) Sub 1-I-7 synthesis

In a round bottom flask, 1-Naphthylboronic acid (20.59g, 119.74mmol), 1-bromo-4-chloro-2-iodobenzene (38g, 119.74mmol), Pd(PPh ₃ ) ₄ (1.38g, 1.20mmol), NaOH ( 4.79g, 119.74mmol), THF (527ml), and water (263mL) were used to obtain 25.86g of product using the Sub 1-I-2 synthesis method. (yield: 68%)

(2) Sub 1-II-7 synthesis

Sub 1-I-7 (20.0g, 63.0mmol), 4H-cyclopenta[def]phenanthren-4-one (12.86g, 63.0mmol), THF (600ml), n-BuLi (2.5M in hexane) obtained from the above synthesis ) (26.5ml, 66.1mmol) was used to obtain 20.92g of product using the Sub 1-I-1 synthesis method. (yield: 75%)

(3) Sub 1-25 synthesis

Sub 1-II-7 (20.92g, 47.23mmol), HCl, and Acetic acid (104ml) obtained in the above synthesis were used to obtain 17.66g of product using the Sub 1-II-1 synthesis method. (yield: 88%)

(One) Sub 1-I-9 synthesis

In a round bottom flask, (3-bromonaphthalen-2-yl)boronic acid (16.52g, 65.86mmol), 1-chloro-3-iodonaphthalene (19.00g, 65.86mmol), Pd(PPh ₃ ) ₄ (1.14g, 0.99mmol) ), NaOH (3.95g, 98.98mmol), THF (289mL), and water (145mL) were used to obtain 17.7g of product using the Sub 1-I-2 synthesis method. (yield: 73%)

(2) Sub One- II -9 synthesis

Sub 1-I-9 (17.6g, 47.87mmol), 4H-cyclopenta[def]phenanthren-4-one (9.78g, 47.87mmol), THF (455ml), n-BuLi (2.5M in hexane) obtained from the above synthesis ) (20.1ml, 50.26mmol) was used to obtain 18.41g of product using the Sub1-I-1 synthesis method. (Yield: 78%)

(3) Sub 1-26 synthesis

Sub 1-II-9 (18.4g, 37.3mmol), HCl, and Acetic acid (82ml) obtained in the above synthesis were used to obtain 14.5g of product using the Sub 1-II-1 synthesis method. (yield: 82%)

(One) Sub One- II -8 synthesis

Sub 1-I-8 (20.0g, 74.75mmol), 4H-cyclopenta[def]phenanthren-4-one (15.27g, 74.75mmol), THF (748ml), n-BuLi (2.5M in hexane) obtained from the above synthesis ) (31.4ml 78.49mmol) was used to obtain 23.49g of product using the Sub 1-I-1 synthesis method. (yield: 80%)

(2) Sub 1-III-8 synthesis

Sub 1-II-8 (12.3g, 31.31mmol), HCl, and Acetic acid (69ml) obtained in the above synthesis were used to obtain 9.98g of product using the Sub 1-II-1 synthesis method. (yield: 85%)

(3) Sub 1-30 synthesis

Sub 1-III-8 (11g, 29.34mmol), (7-chloronaphthalen-2-yl)boronic acid (6.06g, 29.34mmol), Pd(PPh ₃ ) ₄ (0.51g, 0.44mmol) obtained in the above synthesis, NaOH (1.76g, 44.02mmol), THF (129mL), and water (65mL) were used to obtain 11.17g of product using the Sub 1-I-2 synthesis method. (Yield: 76%)

(One) Sub 1-I-11 synthesis

(2-bromophenyl)boronic acid (20.88g, 103.98mmol), 1-chloro-3-iodonaphthalene (30g, 103.98mmol), Pd(PPh ₃ ) ₄ (1.80g, 1.56mmol), NaOH (6.24mmol) in a round bottom flask. g, 155.97mmol), THF (458mL), and water (229mL) were used to obtain 23.5g of the product using the Sub 1-I-2 synthesis method. (yield: 71%)

(2) Sub One- II -11 synthesis

Sub 1-I-11 (23.4g, 73.7mmol), 4H-cyclopenta[def]phenanthren-4-one (15.05g, 73.7mmol), THF (700ml), n-BuLi (2.5M in hexane) obtained from the above synthesis ) (30.9ml 77.4mmol) was used to obtain 26.1g of product using the Sub1-I-1 synthesis method. (yield: 80%)

(3) Sub One- III -11 synthesis

Sub 1-II-11 (26g, 58.7mmol), HCl, and Acetic acid (129ml) obtained in the above synthesis were used to obtain 21.2g of the product using the Sub 1-II-1 synthesis method. (yield: 85%)

(4) Sub 1-34 synthesis

Sub 1-III-11 (21.2g, 49.89mmol), (3-chlorophenyl)boronic acid (7.78g, 49.89mmol), Pd(PPh ₃ ) ₄ (0.86g, 0.75mmol), NaOH (2.99mmol) obtained from the above synthesis. g, 74.84mmol), THF (220mL), and water (110mL) to obtain 19g of product using the Sub 1-I-2 synthesis method. (Yield: 76%)

(One) Sub 1-I-12 synthesis

In a round bottom flask, (10-bromophenanthren-9-yl)boronic acid (26.08g, 86.65mmol), 1-chloro-3-iodonaphthalene (25g, 86.65mmol), Pd(PPh ₃ ) ₄ (1g, 0.87mmol), 22.4g of product was obtained using NaOH (3.47g, 86.65mmol), THF (381mL), and water (191mL) using the Sub 1-I-2 synthesis method. (yield: 62%)

(2) Sub One- II -12 synthesis

Sub 1-I-12 (22.4g, 53.62mmol), 4H-cyclopenta[def]phenanthren-4-one (10.95g, 53.62mmol), THF (509ml), n-BuLi (2.5M in hexane) obtained from the above synthesis ) (22.52ml, 56.30mmol) was used to obtain 21.55g of the product using the Sub1-I-1 synthesis method. (yield: 74%)

(3) Sub 1-35 synthesis

Sub 1-II-12 (21.55g, 39.7mmol), HCl, and Acetic acid (87ml) obtained in the above synthesis were used to obtain 16.67g of product using the Sub 1-II-1 synthesis method. (yield: 80%)

(One) Sub 1-I-13 synthesis

(2-bromonaphthalen-1-yl)boronic acid (22.61g, 90.12mmol), 1-chloro-4-iodonaphthalene (26g, 90.12mmol), Pd(PPh ₃ ) ₄ (1.04g, 0.90mmol) in a round bottom flask. , NaOH (3.60g, 90.12mmol), THF (397mL), and water (198mL) were used to obtain 22.2g of product using the Sub 1-I-2 synthesis method. (yield: 67%)

(2) Sub One- II -13 synthesis

Sub 1-I-13 (22.2g, 60.38mmol), 4H-cyclopenta[def]phenanthren-4-one (12.33g, 60.38mmol), THF (574ml), n-BuLi (2.5M in hexane) obtained from the above synthesis ) (25.36ml, 63.40mmol) was obtained using the Sub1-I-1 synthesis method above to obtain 25.30g of product. (yield: 85%)

(3) Sub 1-36 synthesis

Sub 1-II-13 (25.3g, 51.32mmol), HCl, and Acetic acid (113ml) obtained in the above synthesis were used to obtain 20.23g of the product using the Sub 1-II-1 synthesis method. (yield: 83%)

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

compound FD-MS compound FD-MS Sub 1-1 m/z=374.09(C ₂₇ H ₁₅ Cl=374.87) Sub 1-4 m/z=374.09(C ₂₇ H ₁₅ Cl=374.87) Sub 1-6 m/z=424.10(C ₃₁ H ₁₇ Cl=424.93) Sub 1-7 m/z=424.10(C ₃₁ H ₁₇ Cl=424.93) Sub 1-11 m/z=500.13(C ₃₇ H ₂₁ Cl=501.03) Sub 1-13 m/z=527.06(C ₃₉ H ₂₃ Cl=527.06) Sub 1-16 m/z=566.18(C ₄₂ H ₂₇ Cl=567.13) Sub 1-19 m/z=571.98(C ₃₃ H ₁₈ Br ₂ =574.32) Sub 1-24 m/z=424.10(C ₃₁ H ₁₇ Cl=424.93) Sub 1-25 m/z=424.10(C ₃₁ H ₁₇ Cl=424.93) Sub 1-26 m/z=472.12(C ₃₅ H ₁₉ Cl=474.99) Sub 1-30 m/z=500.13(C ₃₇ H ₂₁ Cl=501.03) Sub 1-34 m/z=500.13(C ₃₇ H ₂₁ Cl=501.03) Sub 1-35 m/z=524.13(C ₃₉ H ₂₁ Cl=525.05) Sub 1-36 m/z=474.12(C ₃₅ H ₁₉ Cl=474.99)

II . Sub Composition of 2

Sub 2 can be synthesized through the reaction route of Scheme 3 below, but is not limited thereto.

In a round bottom flask, [1,1'-biphenyl]-4-amine (10.78g, 63.69mmol), bromobenzene (10g, 63.69mmol), Pd ₂ (dba) ₃ (1.75g, 1.91mmol), P(t- bu) ₃ (1.03g, 5.1mmol), NaO t -Bu (18.36g, 191.07mmol), and toluene (669mL) were added and the reaction was performed at 80°C. When the reaction was completed, extraction was performed with ether and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting organic material was recrystallized using a silicagel column to obtain 11.72 g of product. (yield: 75%)

The starting material, 9,9-dimethyl-9H-fluoren-2-amine (8.91g, 38.22mmol), 3-bromo-1,1'-biphenyl (8g, 38.22mmol), Pd ₂ (dba) ₃ (1.05g) , 1.15mmol), P(t-bu) ₃ (0.62g, 3.06mmol), NaO t -Bu (11.02g, 114.67mmol), and toluene (401mL) were used to produce 10.92g of the product using the Sub 2-3 synthesis method. got it (Yield: 79%)

The starting material, 9,9-dimethyl-9H-fluoren-2-amine (8.19g, 39.14mmol), 3-bromodibenzo[b,d]thiophene (10.3g, 39.14mmol), Pd ₂ (dba) ₃ (1.08g) , 1.17mmol), P(t-bu) ₃ (0.63g, 3.13mmol), NaO t -Bu (11.28g, 117.42mmol), and toluene (411mL) were used to produce 12.87g of the product using the Sub 2-1 synthesis method. got it (yield: 84%)

Starting material aniline (4.81g, 51.61mmol), 2-Bromo-9,9'-spirobifluorene (20.4g, 51.61mmol), Pd ₂ (dba) ₃ (1.42g, 1.55mmol), P(t-bu) ₃ (0.84g, 4.13mmol), NaO t -Bu (14.88g, 154.82mmol), and toluene (542mL) were used to obtain 15.35g of product using the sub 2-3 synthesis method. (yield: 73%)

Starting material aniline (6.30g, 37.24mmol), 2-bromo-9-phenyl-9H-carbazole (12g, 37.24mmol), Pd ₂ (dba) ₃ (1.02g, 1.12mmol), P(t-bu) ₃ (0.6g, 2.98mmol), NaO t -Bu (10.74g, 111.73mmol), and toluene (391mL) were used to obtain 11.77g of product using the sub 2-3 synthesis method. (yield: 77%)

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

III. Product synthesis

After dissolving Sub 1 (1 equivalent) in toluene in a round bottom flask, Sub 2 (1 equivalent), Pd ₂ (dba) ₃ (0.03 equivalent), P(t-bu) ₃ (0.08 equivalent), NaO t -Bu (3 equivalents) was added and stirred at 80°C. When the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized on a silicagel column to obtain the final product.

After dissolving Sub 1-2 (6g, 16.01mmol) obtained in the above synthesis with Toluene (168mL) in a round bottom flask, Sub 2-2 (3.51g, 16.01mmol), Pd ₂ (dba) ₃ (0.44g, 0.48 mmol), P(t-bu) ₃ (0.26g, 1.28mmol), NaO t -Bu (4.61g, 48.02mmol) were added and stirred at 80°C. When the reaction was completed, extraction was performed with ether and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 7.32 g of product (yield: 82%).

Sub 1-2 (4g, 10.67mmol), Toluene (112mL), Sub 2-20 (4.9g, 10.67mmol), Pd ₂ (dba) ₃ (0.29g, 0.32mmol), P(t-bu) ₃ ( 0.17g, 0.85mmol) and NaO t -Bu (3.08g, 32.01mmol) were used to obtain 6.30g of product (yield: 74%) using the P-1 synthesis method.

Sub 1-5 (4.5g, 10.59mmol), Toluene (111mL), Sub 2-36 (4.25g, 10.59mmol), Pd ₂ (dba) ₃ (0.29g, 0.32mmol), P(t-bu) ₃ (0.17g, 0.85mmol) and NaO t -Bu (3.05g, 31.77mmol) were used to obtain 6.61g of product (yield: 79%) using the P-1 synthesis method.

Sub 1-8 (5.5g, 12.2mmol), Toluene (128mL), Sub 2-16 (4.09g, 12.2mmol), Pd ₂ (dba) ₃ (0.34g, 0.37mmol), P(t-bu) ₃ (0.2g, 0.98mmol) and NaO t -Bu (3.52g, 36.59mmol) were used to obtain 6.59g of product (yield: 72%) using the P-1 synthesis method.

Sub 1-9 (4.5g, 9.98mmol), Toluene (105mL), Sub 2-31 (3.85g, 9.98mmol), Pd ₂ (dba) ₃ (0.27g, 0.30mmol), P(t-bu) ₃ (0.16g, 0.8mmol) and NaO t -Bu (2.88g, 29.94mmol) were used to obtain 6.47g of product (yield: 81%) using the P-1 synthesis method.

Sub 1-12 (5.5g, 10.44mmol), Toluene (110mL), Sub 2-3 (2.56g, 10.44mmol), Pd ₂ (dba) ₃ (0.29g, 0.31mmol), P(t-bu) ₃ (0.17g, 0.83mmol) and NaO t -Bu (3.01g, 31.31mmol) were used to obtain 6.60g of product (yield: 86%) using the P-1 synthesis method.

Sub 1-15 (6g, 11.38mmol), Toluene (120mL), Sub 2-14 (3.25g, 11.38mmol), Pd ₂ (dba) ₃ (0.31g, 0.34mmol), P(t-bu) ₃ ( 0.18g, 0.91mmol) and NaO t -Bu (3.28g, 34.15mmol) were used to obtain 6.27g of product (yield: 71%) using the P-1 synthesis method.

Sub 1-16 (6g, 10.58mmol), Toluene (111mL), Sub 2-4 (3.4g, 10.58mmol), Pd ₂ (dba) ₃ (0.29g, 0.32mmol), P(t-bu) ₃ ( 0.17g, 0.85mmol) and NaO t -Bu (3.05g, 31.74mmol) were used to obtain 6.67g of product (yield: 74%) using the P-1 synthesis method.

Sub 1-18 (5g, 9.24mmol), Toluene (97mL), Sub 2-21 (4.77g, 9.24mmol), Pd ₂ (dba) ₃ (0.25g, 0.28mmol), P(t-bu) ₃ ( 0.15g, 0.74mmol) and NaO t -Bu (2.66g, 27.72mmol) were used to obtain 6.51g of product (yield: 69%) using the P-1 synthesis method.

Sub 1-19 (4.5g, 7.84mmol), Toluene (82mL), Sub 2-34 (4.32g, 15.67mmol), Pd ₂ (dba) ₃ (0.43g, 0.47mmol), P(t-bu) ₃ (0.25g, 1.25mmol) and NaO t -Bu (4.52g, 47.01mmol) were used to obtain 6.57g of product (yield: 87%) using the P-1 synthesis method.

Sub 1-26 (5g, 10.53mmol), Toluene (111mL), Sub 2-19 (8.24g, 21.05mmol), Pd ₂ (dba) ₃ (0.58g, 0.63mmol), P(t-bu) ₃ ( 0.34g, 1.68mmol) and NaO t -Bu (6.07g, 63.16mmol) were used to obtain 6.73g of product (yield: 77%) using the P-1 synthesis method.

Sub 1-31 (5g, 9.98mmol), Toluene (105mL), Sub 2-45 (9.19g, 19.96mmol), Pd ₂ (dba) ₃ (0.55g, 0.6mmol), P(t-bu) ₃ ( 0.32g, 1.60mmol) and NaO t -Bu (5.75g, 59.88mmol) were used to obtain 6.47g of product (yield: 70%) using the P-1 synthesis method.

Sub 1-4 (5g, 13.34mmol), Toluene (140mL), Sub 2-3 (6.54g, 26.68mmol), Pd ₂ (dba) ₃ (0.73g, 0.8mmol), P(t-bu) ₃ ( 0.43g, 2.13mmol) and NaO t -Bu (7.69g, 80.03mmol) were used to obtain 6.93g of product (yield: 89%) using the P-1 synthesis method.

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

compound FD-MS compound FD-MS P-1 m/z=557.21(C ₄₃ H ₂₇ N=557.70) P-2 m/z=659.26(C ₅₁ H ₃₃ N=659.83) P-5 m/z=699.29(C ₅₄ H ₃₇ N=699.90) P-6 m/z=797.31(C ₆₂ H ₃₉ N=797.31) P-7 m/z=745.28(C ₅₈ H ₃₅ N=745.93) P-9 m/z=673.82(C ₅₁ H ₃₁ NO=673.82) P-10 m/z=663.20(C ₄₉ H ₂₉ NS=663.84) P-12 m/z=748.29(C ₅₇ H ₃₆ N ₂ =748.93) P-13 m/z=798.30(C ₆₁ H ₃₈ N ₂ =798.99) P-14 m/z=828.26(C ₆₁ H ₃₆ N ₂ S=823.03) P-19 m/z=789.25(C ₅₉ H ₃₅ NS=790.00) P-21 m/z=735.29(C ₅₇ H ₃₇ N=735.93) P-22 m/z=749.31(C ₅₈ H ₃₉ N=749.96) P-23 m/z=689.22(C ₅₁ H ₃₁ NS=689.88) P-25 m/z=659.26(C ₅₁ H ₃₃ N=659.83) P-26 m/z=799.29(C ₆₁ H ₃₇ NO=799.97) P-27 m/z=709.28(C ₅₅ H ₃₅ N=709.89) P-28 m/z=699.29(C ₅₄ H ₃₇ N=699.90) P-29 m/z=735.29(C ₅₇ H ₃₇ N=735.93) P-30 m/z=785.31(C ₆₁ H ₃₉ N=785.99) P-31 m/z=749.27(C ₅₇ H ₃₅ NO=749.91) P-32 m/z=775.32(C ₆₀ H ₄₁ N=776.00) P-33 m/z=851.36(C ₆₆ H ₄₅ N=852.09) P-34 m/z=815.26(C ₆₁ H ₃₇ NS=816.03) P-35 m/z=1019.32(C ₇₆ H ₄₅ NOS=1020.26) P-36 m/z=902.37(C ₆₉ H ₄₆ N ₂ =903.14) P-38 m/z=962.28(C ₆₉ H ₄₂ N ₂ S ₂ =963.23) P-44 m/z=633.25(C ₄₉ H ₃₁ N=633.79) P-45 m/z=821.31(C ₆₄ H ₃₉ N=822.02) P-46 m/z=861.34(C ₆₇ H ₄₃ N=862.09) P-47 m/z=713.27(C ₅₄ H ₃₅ NO=713.88) P-48 m/z=647.22(C ₄₉ H ₂₉ NO=647.78) P-49 m/z=613.19(C ₄₅ H ₂₇ NS=613.78) P-50 m/z=703.20(C ₅₁ H ₂₉ NOS=703.86) P-51 m/z=748.29(C ₅₇ H ₃₆ N- ₂ =748.93) P-52 m/z=683.26(C ₅₃ H ₃₃ N=683.85) P-53 m/z=739.23(C ₅₅ H ₃₃ NS=739.94) P-55 m/z=829.28(C ₆₂ H ₃₉ NS=830.06) P-56 m/z=659.26(C ₅₁ H ₃₃ N=659.83) P-58 m/z=789.25(C ₅₉ H ₃₅ NS=790.00) P-59 m/z=735.29(C ₅₇ H ₃₇ N=735.93) P-60 m/z=735.29(C ₅₇ H ₃₇ N=735.93) P-61 m/z=902.37(C ₆₉ H ₄₆ N ₂ =903.14) P-63 m/z=924.35(C ₇₁ H ₄₄ N ₂ =925.15) P-64 m/z=633.25(C ₄₉ H ₃₁ N=633.79) P-65 m/z=613.19(C ₄₅ H ₂₇ NS=613.78) P-66 m/z=583.23(C ₄₅ H ₂₉ N=583.73) P-67 m/z=748.29(C ₅₇ H ₃₆ N ₂ =748.93)

Manufacturing evaluation of organic electric devices

[ Example One] Green organic electric device ( hole transport layer )

An organic electric device was manufactured according to a conventional method using the compound of the present invention as a hole transport layer material. First, a 2-TNATA film was vacuum deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer with a thickness of 60 nm, and then compound P-1 of the present invention was deposited on the hole injection layer to a thickness of 60 nm. A hole transport layer was formed by vacuum deposition. 4,4'-N,N'-dicarbazole-biphenyl (hereinafter abbreviated as “CBP”) was used as a host on the top of the hole transport layer, and Ir(ppy) ₃ was doped at a weight ratio of 90:10 as a dopant material. The light emitting layer was deposited to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm as a hole blocking layer, and Alq ₃ was deposited to a thickness of 40 nm as an electron transport layer. Afterwards, LiF, 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 and used as a cathode to manufacture an organic electric device.

[ Example 2] to [ Example 30] Green organic electric devices

An organic electric device was manufactured in the same manner as Example 1, except that the compound of the present invention shown in Table 4 below was used as the hole transport layer material instead of Compound P-1 according to Example 1 of the present invention.

[ Comparative example 1] to [ Comparative example 3]

An organic electric device was manufactured in the same manner as in Example 1, except that one of Comparative Compounds 1 to 3 shown in Table 4 below was used as the hole transport layer material instead of Compound P-1 according to Example 1 of the present invention. Manufactured.

Electroluminescence (EL) characteristics were obtained using PR-650 from Photoresearch by applying a forward bias direct current voltage to the organic electric devices manufactured in Examples 1 to 30 and Comparative Examples 1 to 3 of the present invention. As a result of the measurement, the T95 lifespan was measured using a lifespan measuring device manufactured by McScience at a standard luminance of 5000 cd/m ² , and the measurement results are shown in Table 4 below.

As can be seen from the results in Table 4, the organic electric device using the compound of the present invention as a material for the hole transport layer has a lower driving voltage and relatively higher efficiency than the organic electric device using Comparative Examples 1 to 3 as the material for the hole transport layer. And it was confirmed that it shows long lifespan.

In other words, Comparative Example 2, in which Comparative Compound 2, in which phenanthrene is condensed with fluorene and an amine group is bonded to the phenanthrene group, was used as the hole transport layer rather than Comparative Example 1, which used NPB as the hole transport layer, had higher driving voltage, efficiency, and It showed better device results in terms of lifespan, and Comparative Example 3, which used Comparative Compound 3, in which triphenylene was condensed with fluorene and an amine group bonded to the fluorene group, showed relatively higher efficiency than Comparative Example 2. However, the lifespan was significantly lower than that of organic electric devices using the compound of the present invention as a hole transport layer material.

Meanwhile, with reference to Figure 2, when compared with Comparative Compounds 2 and 3, which are core similar to the compound of the present invention, Comparative Compound 2, unlike the compound of the present invention, binds to phenanthrene rather than fluorene at the binding site of the amine group. As a result, it shows low efficiency and lifespan.

In the case of the compound of the present invention, LUMO is formed in phenanthrene, and in the case of comparative compound 2, it can be seen that a LUMO electron cloud is formed in the phenanthrene portion. In this case, the amine group bonded to phenanthrene controls the LUMO energy level. It is judged that

Therefore, Comparative Compound 2 has a similar HOMO level to the compound of the present invention, but due to the low LUMO energy level, excess polarons generated in the light-emitting layer are transferred and emit light at the hole transport layer interface, which may result in decreased color purity, reduced efficiency, and low lifespan. .

In the case of comparative compound 3, the benzene ring was fused to have triphenylene, so the efficiency was relatively high, but the lifespan was significantly lower than that of the compound according to the present invention. This is due to the influence of triphenylene, which has a wide bandgap. As the difference in HOMO energy level with the hole injection layer (HIL) increases, holes accumulate at the interface of the hole injection layer, causing interfacial degradation and resulting in low temperature. It is believed to represent a longevity phenomenon.

In other words, the compounds of the present invention have a moderately high LUMO level that can block electrons and a deep HOMO level that can efficiently transport holes. In other words, it shows that the band gap, electrical properties, and interface properties can be greatly changed depending on the bonding position of the amine group and the condensation position and number of benzene rings that are additionally condensed to spirofluorene, which helps improve device performance. It can be confirmed that it acts as a major factor.

[ Example 31] Blue organic electric device ( Luminous auxiliary layer )

An organic electric device was manufactured according to a conventional method using the compound of the present invention as a light-emitting auxiliary layer material. First, 2-TNATA was vacuum deposited to a thickness of 60 nm on the ITO layer (anode) formed on the glass substrate to form a hole injection layer, and then NPB was vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. did. Subsequently, compound P-2 of the present invention was vacuum deposited to a thickness of 20 nm on the hole transport layer to form a light-emitting auxiliary layer, and then 9,10-Di(2-naphthyl)anthracene (hereinafter) was added on the light-emitting auxiliary layer. Abbreviated as “ADN”) was used as a host material and BD-052X (manufactured by Idemitsu Kosan) was used as a dopant material, doped at a weight ratio of 93:7, and vacuum deposited to a thickness of 30 nm to form a light emitting layer. Next, BAlq was vacuum deposited to a thickness of 10 nm on the emission layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Afterwards, LiF, a halogenated alkali metal, 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, thereby manufacturing an organic electric device.

[ Example 32] to [ Example 58] Blue organic electric device ( Luminous auxiliary layer )

An organic electric device was manufactured in the same manner as in Example 31, except that the compound of the present invention shown in Table 5 below was used as the light emitting auxiliary layer material instead of the compound P-2 of the present invention.

[ Comparative example 4]

An organic electric device was manufactured in the same manner as Example 31, except that the light-emitting auxiliary layer material was not used.

[ Comparative Example 5 ]

An organic electric device was manufactured in the same manner as in Example 31, except that Comparative Compound 2 to Comparative Compound was used instead of Compound P-2 of the present invention as the light emitting auxiliary layer material.

Forward bias direct current voltage was applied to the organic electric devices manufactured in Examples 31 to 58 and Comparative Example 4 of the present invention, and the electroluminescence (EL) characteristics were measured using PR-650 from Photoresearch. Measurement results: The T95 lifespan was measured using a lifespan measuring device manufactured by McScience at a standard luminance of 500 cd/m ² , and the measurement results are shown in Table 5 below.

As can be seen from the results in Table 5, it was confirmed that luminous efficiency and lifespan can be improved when the material for organic electric devices of the present invention is used as a light-emitting auxiliary layer.

In other words, it can be confirmed that the efficiency and lifespan are increased when the light-emitting auxiliary layer is used compared to when the light-emitting auxiliary layer is not used, and when the compound of the present invention is used as the light-emitting auxiliary layer rather than Comparative Compound 2, the driving voltage It was confirmed that the slightly increased, showing higher efficiency and higher lifespan.

As can be seen in Table 4, the reason for the increase in efficiency and lifespan when using the present invention compound as a light-emitting auxiliary layer is believed to be that it has a moderately high T1 energy level and a deep HOMO level that can efficiently transport holes. .

In addition, it has an appropriate T1 level with the host, which prevents excess electrons from passing to the hole transport layer, thereby reducing color purity and thermal damage caused by light emission from the hole transport layer, which is believed to increase lifespan.

In addition, the evaluation results of the above-described device fabrication described the device characteristics in which the compound of the present invention was applied to the light emitting layer as a host material and the hole transport layer as the hole transport material, but the compound of the present invention was used in the hole injection layer, the light emitting auxiliary layer, the electron transport layer, It can be used by applying it to all other layers, such as the electron injection layer and the light emitting auxiliary layer.

The above description is merely an illustrative description of the present invention, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in this specification are for illustrative purposes rather than limiting 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 in accordance with the claims, and all technologies within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.

Claims (11)

A compound represented by the following formula (1).

In Formula 1,
(1) Ar ¹ and Ar ² are each independently the same or different,
C ₆ -C ₃₀ aryl group; fluorenyl group; C ₂ -C ₃₀ heterocyclic group containing at least one hetero atom among O, N and S; C ₁ -C ₁₀ alkyl group; Fused ring group of C ₆ -C ₃₀ aromatic ring and C ₃ -C ₃₀ aliphatic ring; C ₂ -C ₁₀ alkenyl group; and -L'-N(Ra)(Rb); or Ar ¹ and Ar ² may be combined with each other to form a ring, and the ring formed may be monocyclic or polycyclic.
(2) Each of the A and B rings may be a C ₆ to C ₁₈ aryl group,
(3) L is a single bond; C ₆ ~ C ₃₀ arylene group; fluorenylene group; A C ₂ to C ₃₀ divalent heterocyclic group containing at least one hetero atom selected from O, N, and S; Can be selected from the group consisting of,
(4) R ₁ to R ₁₀ are each independently the same or different,
hydrogen; Deuterium; C ₆ ~ C ₃₀ aryl group; fluorenyl group; C ₂ ~ C ₃₀ heterocyclic group containing at least one hetero atom among O, N and S; A fused ring group of an aliphatic ring from C ₃ to C ₃₀ and an aromatic ring from C ₆ to C ₃₀ ; C ₁ ~ C ₁₀ alkyl group; C ₂ ~ C ₁₀ alkenyl group; C ₂ ~ C ₁₀ alkyne group; C ₁ ~ C ₁₀ alkoxyl group; and -L'-N(Ra)(Rb); is selected from the group consisting of,
L' is a single bond; C ₆ ~ C ₃₀ arylene group; fluorenylene group; A fused ring group of an aliphatic ring from C ₃ to C ₃₀ and an aromatic ring from C ₆ to C ₃₀ ; And C ₂ ~ C ₃₀ heterocyclic group; Ra and Rb are each independently selected from the group consisting of C ₆ ~ C ₃₀ aryl group; fluorenyl group; A fused ring group of an aliphatic ring from C ₃ to C ₃₀ and an aromatic ring from C ₆ to C ₃₀ ; and a C ₂ to C ₃₀ heterocyclic group containing at least one hetero atom selected from O, N, and S;
(5) m and n are each integers from 3 to 8.
The aryl group, arylene group, fluorenyl group, heterocyclic group, alkyl group, fused ring group, alkenyl group, alkynyl group, alkoxy group, and aryloxy group each contain deuterium; halogen; Silane group substituted or unsubstituted with a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₂₀ aryl group; siloxane group; Cyano group; nitro group; -L'-N(Ra)(Rb) (where L', Ra, Rb are the same as the definitions of L', Ra, Rb); C ₁ -C ₁₀ alkylthio group; C ₁ -C ₁₀ alkoxyl group; C ₁ -C ₁₀ alkyl group; C ₂ -C ₁₀ alkenyl group; C ₂ -C ₁₀ alkyne group; C ₆ -C ₂₀ aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; and may be further substituted with one or more substituents selected from the group consisting of C ₈ -C ₂₀ arylalkenyl groups.
According to clause 1,
A compound in which the A ring and the B ring of Formula 1 are independently one of the following formulas.

In the A ring and B ring, * represents the bonding portion that combines with Formula 1 to form a fused ring.
According to clause 1,
A compound characterized in that the structure in which the A ring and the B ring are bonded to Formula 1 is represented by one of the following Formulas A-1 to Formula A-22.

According to clause 1,
Formula 1 is one of the following compounds.

first electrode;
second electrode; and
An organic electric device comprising an organic material layer located between the first electrode and the second electrode, wherein the organic material layer contains the compound of any one of claims 1 to 4.
According to clause 5,
The compound is contained in at least one layer of the hole injection layer, hole transport layer, auxiliary light emitting layer, and light emitting layer of the organic material layer, and the compound is characterized in that it contains one type of single compound or two or more types of compounds as a component of a mixture. Organic electric device.
According to clause 5,
An organic electric device characterized in that the compound is used as a hole transport layer or a light-emitting auxiliary layer.
According to clause 5,
An organic electric device further comprising a light efficiency improvement layer formed on at least one side of the first electrode and the second electrode opposite to the organic material layer.
According to clause 5,
The organic material layer is an organic electric device characterized in that it is formed by a spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, or roll-to-roll process.
A display device including the organic electric element of claim 5; and
An electronic device including a control unit that drives the display device.
According to clause 10,
An electronic device, wherein the organic electric device is one of an organic light-emitting device, an organic solar cell, an organic photoreceptor, an organic transistor, and a monochromatic or white lighting device.

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