KR102478798B1 - Compound for organic electric element, organic electric element comprising the same and electronic device thereof - Google Patents

Abstract

The present invention provides a compound capable of improving high luminous efficiency, low driving voltage and lifetime of a device, an organic electric device using the same, and an electronic device thereof.

Description

Compound for organic electric element, organic electric element using the same, and electronic device thereof

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material.

An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, 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 may 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.

Currently, the size of the portable display market tends to increase with large-area displays, and as a result, power consumption greater than that required for existing portable displays is required. Therefore, power consumption has become a very important factor for portable displays that have a limited power supply source such as a battery, and efficiency and lifespan problems must also be solved.

Efficiency, lifespan, driving voltage, etc. are related to each other. As the efficiency increases, the driving voltage relatively decreases. indicates a tendency to increase life expectancy.

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

That is, in order to fully exhibit the excellent characteristics of organic electric devices, materials constituting the organic material layer in 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, etc. are stable and efficient. Although supporting by materials should precede, the development of stable and efficient organic material layer materials for organic electric devices has not yet been sufficiently accomplished. Therefore, development of new materials is continuously required, and in particular, development of a material for a light emitting layer, particularly a host material of the light emitting layer, is urgently required.

An object of the present invention is to provide a compound capable of improving luminous efficiency, stability and lifespan of a device, an organic electric device using the same, and an electronic device thereof.

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

In addition, the present invention provides an organic electric device using a compound having the above chemical formula and a terminal including the organic electric device.

The compound of the present invention can play various roles in organic electric devices and terminals, and when applied to organic electric devices and terminals, can lower the driving voltage of the devices, improve light efficiency, lifespan, and stability of the devices.

1 is a cross-sectional view of an organic light emitting device according to an embodiment of 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 components of each drawing, it should be noted that the same components have the same numerals as much as possible even if they are displayed on different drawings. In addition, 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.

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

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

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

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

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

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

As used herein, the term "alkenyl group" or "alkynyl group" has a double bond or triple bond of 2 to 60 carbon atoms, respectively, and includes straight or branched chain groups, unless otherwise specified, and is limited thereto. It is not.

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

As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" refers to an alkyl group to which an oxygen radical is attached, and has 1 to 60 carbon atoms, unless otherwise specified, and is limited thereto. It is not.

As used herein, 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, 2 to 60 It has a carbon number of, but is not limited thereto.

As used herein, the term "aryloxyl group" or "aryloxy group" 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 herein have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, an aryl group or an arylene group refers to a single-ring or multi-ring aromatic ring, and includes an aromatic ring formed by bonding or reacting with adjacent substituents. For example, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, anthracenyl group, a fluorene group, a spirofluorene group, or a 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 carbon atoms described herein.

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

The term "heteroalkyl" as used herein, unless otherwise specified, means an alkyl containing one or more heteroatoms. As used herein, the term "heteroaryl group" or "heteroarylene group" refers to an aryl group or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom, unless otherwise specified, and is limited thereto It does not, and includes at least one of a single ring and a multi-ring, and may be formed by combining adjacent functional groups.

As used herein, the term "heterocyclic group" includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes a heteroaliphatic ring and a heterocyclic group, unless otherwise specified. Contains an aromatic ring. It may also 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 containing SO ₂ instead of carbon forming the ring. For example, "heterocyclic group" includes the following compounds.

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

Unless otherwise specified, the term "ring" used herein refers to a fused ring composed of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, Contains saturated or unsaturated rings.

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

Unless otherwise specified, the term "carbonyl" as used herein is represented by -COR', where R' is hydrogen, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, or a carbon atom of 3 to 30 carbon atoms. 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 specified, the term "ether" as used herein is represented by -R-O-R', wherein R or R' are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, or a carbon atom of 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 explicitly stated otherwise, “substituted” in the term “substituted or unsubstituted” as used herein means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ 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, deuterium-substituted C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and C ₂ ~ C ₂₀ means substituted with one or more substituents selected from the group consisting of heterocyclic groups, but is not limited to these substituents.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention applies the same as the substituent definition by the exponent definition of the following formula.

Here, when a is an integer of 0, substituent R ¹ does not exist, and when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbon atoms forming the benzene ring, and when a is an integer of 2 or 3 Each is combined 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 indicating the hydrogen bonded to the carbon forming the benzene ring. is omitted.

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

Referring to FIG. 1, an organic electric element 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. ) is provided with an organic material layer containing the compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), and the second electrode 180 may be a cathode (negative electrode), 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 . At this time, other layers except for the light emitting layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and an electron transport layer 160 may serve as a hole blocking layer.

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

The compound according to the present invention applied to the organic 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. material can be used. Preferably, the compound of the present invention may be used as the light emitting layer 150 .

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

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 the intrinsic properties (mobility, interface properties, etc.) of the material are optimized to optimize the lifetime of the organic electric device. and efficiency can be improved at the same time.

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

In addition, the organic material layer is formed by a solution process or a solvent process other than a 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 blading process. It can be manufactured with a smaller number of layers by a method such as a printing process, a screen printing process, or a thermal transfer method. Since the organic layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the forming method.

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

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent processability, and can be manufactured using the color filter technology of the existing LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting units are arranged in parallel on a mutually flat surface, and a stacking method in which R, G, and B light emitting layers are stacked up and down There is, and there is a color conversion material (CCM) method using electroluminescence by a blue (B) organic light emitting layer and photo-luminescence of an inorganic phosphor using light from the electroluminescent layer. may also be applied to these WOLEDs.

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

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

Hereinafter, a compound according to an aspect of the present invention will be described. A compound according to one aspect of the present invention is represented by Formula 1 below.

1) X is one of NR ¹ , S, O, CR'R”,

2) n and m are 0 or 1, n + m is 1 or more,

3) A and B are each independently one of a single bond, NR ¹ , S, O, CR ^a R ^b ,

4) Z ¹ to Z ¹² are independently of each other CR ² , N and at least one is N,

5) R ¹ and R ² are independently of each other hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of,

(Where L' is a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ fused ring group of an aromatic ring; and C ₂ ~C It is selected from the group consisting of ₆₀ -membered heterocyclic group; wherein R _a and R _b are each independently C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ A fused ring group of an aromatic ring; and a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; selected from the group consisting of), or adjacent R ¹ , Adjacent R ² may bond to each other to form a ring,

When at least two of Z ¹ to Z ¹² are CR ² , each CR ² is independent of each other, so each CR ² may be the same or different.

6) R' and R” are each independently hydrogen, a C ₁ ~ C ₅₀ alkyl group; C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, and P; is selected from the group consisting of, and may be bonded to each other to form a spyro compound;

6) R ^a and R ^b are each independently hydrogen or a C ₁ to C ₅₀ alkyl group; C ₆ ~ C ₆₀ aryl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, and P; selected from the group consisting of, and may be bonded to each other to form a spy compound.

R ¹ , R ² , R _a , R _b , R', R”, R ^a , R ^b are an aryl group, a fluorenyl group, a heterocyclic group, a fused ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group , In the case of an arylene group or a fluorenylene group, each of which is 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; 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 alkynyl group; C ₆ -C ₂₀ aryl group; A deuterium-substituted C ₆ -C ₂₀ aryl group; 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 C ₈ -C ₂₀ may be further substituted with one or more substituents selected from the group consisting of arylalkenyl groups, and when each of these substituents are adjacent, they may be bonded to each other to form a ring.

Here, the aryl group may have 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and in the case of the heterocyclic group, carbon atoms 2 to 60, preferably 2 carbon atoms ~ 30, more preferably, it may be a heterocyclic ring having 2 to 20 carbon atoms, and in the case of the alkyl group, the number of carbon atoms is 1 to 50, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 20 carbon atoms 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 each 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 rene group or a phenanthrylene group.

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

Formula 1 may be represented by one of Formulas 2 to 3 below.

The Z ¹ to Z ¹² , X, A, and B are the same as Z ¹ to Z ¹² , X, A, and B defined in Formula (1).

Formula 1 may be represented by one of Formulas 4 to 11 below.

The Z ¹ to Z ¹² , X, A, and B are the same as Z ¹ to Z ¹² , X, A, and B defined in Formula (1).

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

At this time, the organic electric element 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 Chemical Formula 1, wherein the compound represented by Chemical 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 light emitting auxiliary layer.

That is, the compound represented by Formula 1 may be used as a material for a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer, or an electron injection layer. In particular, the compound represented by Formula 1 may be used as a material for the light emitting layer. Specifically, an organic electric device including one of the compounds represented by Formula 1 is provided in the organic layer, and more specifically, the An organic electric device including compounds represented by the individual chemical formulas (1-1 to 8-24) in the organic material layer is provided.

In another embodiment, in at least one layer of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer of the organic material layer, the compound is contained alone, or the 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 may include a mixture of two or more types of compounds represented by Formula 1, and the compounds of claims 1 to 4 and compounds not applicable to the present invention. Mixtures with may be included. Here, the 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 above compounds are contained in a combination of two or more kinds of other compounds, the other compounds may be known compounds of each organic material layer or may be compounds to be developed in the future. In this case, the compound contained in the organic material 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 Formula 1.

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

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

[ synthesis example ]

The final product represented by Chemical Formula (1) according to the present invention is prepared by the method of Sub 1 (1) to (4) as shown in Scheme 1 below.

<Scheme 1>

Sub A Synthesis Example

Sub A of Scheme 1 may be synthesized by the reaction pathways of Schemes 2 to 5 below, but is not limited thereto.

One) Sub Synthesis of A(1)

<Scheme 2>

Synthesis of Sub A(1)-3

Sub A(1)-1, Sub A(1)-2 K ₂ CO ₃ , Pd(PPh ₃ ) ₄ were dissolved in anhydrous THF and a small amount of water, and then refluxed at 80 °C for 12 hours. When the reaction was completed, the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After drying the organic layer with MgSO ₄ and concentrating, the resulting organic material was separated using a silica gel column to obtain the desired Sub A(1)-3.

Synthesis of Sub A(1)-4

Obtained Sub A(1)-3 and triphenylphosphine were dissolved in o -dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using vacuum distillation, and the concentrated product was recrystallized using a silica gel column to obtain desired Sub A(1)-4.

Synthesis of Sub A(1)

After dissolving Sub A(1)-4 in toluene, add Sub A(1)-5, add Pd ₂ (dba) ₃ , P(t-Bu) ₃ , NaO t -Bu, and toluene, respectively, and then add 100 Stir and reflux for 24 hours at ° C. After the reaction was completed, the organic layer was extracted with ether and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain Sub A (1).

2) Synthesis of Sub A (2)

<Scheme 3>

Sub A(2)-1, Sub A(2)-2, and NH ₃ were reacted at room temperature for 10 minutes. After the reaction was completed, the organic layer was dried with MgSO ₄ and concentrated, and the resulting organic material was separated using a silica gel column to obtain the desired Sub A (2).

3) Synthesis of Sub A (3)

<Scheme 4>

Cs ₂ CO ₃ , Pd(OAc) ₂ , and PPh ₃ were added to Sub A(3)-1 and Sub A(3)-2, dissolved in DMF, and reacted at 140 °C for 15 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, the organic layer was dried and concentrated, and the resulting organic material was separated using a silica gel column to obtain the desired Sub A (3).

4) Synthesis of Sub A (4)

<Scheme 5>

Synthesis of Sub A(4)-2

ET ₃ N, Pd(OAc) ₂ , and PPH ₃ were added to Sub A(4)-1, dissolved in DMF and a small amount of water, and reacted at 130 °C for 22 hours. After the reaction was completed, the reactant was cooled to room temperature, the organic layer was dried and concentrated, and the resulting organic material was separated using a silica gel column to obtain the desired Sub A (4)-2.

Synthesis of Sub A(4)-3

Sub A(4)-2 was dissolved in diethylether and AlCl ₃ was added slowly. After stirring for 15 minutes, it was cooled to 0° C. and lithium aluminum hydride (LAH) was added slowly. After that, the mixture was stirred under reflux for 1 hour, and when the reaction was completed, it was slowly cooled to room temperature, and EA was slowly added thereto until bubbles did not occur. Then, HCL was added, followed by distillation and extraction with ethyl acetate. After drying and concentrating the organic layer with MgSO ₄ , the resulting organic material was separated using a silica gel column to obtain the desired Sub A(4)-3.

Synthesis of Sub A(4)-4

After dissolving Sub A(4)-3 in DMSO, sodium tert-butoxide was added at room temperature and stirred at 70°C for 15 minutes. When the reaction was completed, it was cooled at room temperature, distilled water was added, and the mixture was stirred for 20 minutes. At this time, a solid was produced, which was filtered, and the obtained solid was recrystallized from methanol and acetone to obtain Sub A (4).

[Example of final product 1, 2 synthesis: route (1)]

Products 1 and 2 of Reaction Scheme 1 may be synthesized by the reaction pathway of Reaction Scheme 6 below, but are not limited thereto.

<Scheme 6>

Synthesis of Sub 2-1

Sub A(1)-1 (46.6g, 0.11 mol), Sub 1-1 (21.7g, 0.13 mol), K ₂ CO ₃ (46.03 g, 0.33 mol), Pd(PPh ₃ ) ₄ (5.13 g, 4 mol%) was dissolved in anhydrous THF and a small amount of water, and then refluxed at 80 °C for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. The organic layer was dried over MgSO ₄ , concentrated, and the organic material produced was separated using a silica gel column to form the desired Sub 2-1 ( 41.0 g, 80%) was obtained.

Synthesis of Sub 3-1

The obtained Sub 2-1 (41.0 g, 0.09 mol) and triphenylphosphine (0.3 mol) were dissolved in o -dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using vacuum distillation, and the concentrated product was recrystallized using a silica gel column to obtain the desired Sub 3-1 (29.8 g, 78%).

Synthesis of 5-17

After dissolving Sub 3-1 (10.4g, 24mmol) in toluene, Sub 5-1 (3.8g, 20mmol) was added and Pd ₂ (dba) ₃ (0.5g, 0.6mmol), P(t-Bu) ₃ (0.2g, 2mmol), NaO t -Bu (5.8g, 60mmol), and toluene (300 mL) were added, respectively, and stirred and refluxed at 100℃ for 24 hours. After the reaction was completed, extraction was performed with ether and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 10.0 g of the final compound (yield: 82%).

Synthesis of Sub 2-2

Sub A(2)-1 (34.6g, 0.11 mol) and Sub 1-1 (21.7g, 0.13 mol) were synthesized using the same synthesis method as Sub 2-1 to obtain desired Sub 2-2 (32.1g, 82%). got

Synthesis of Sub 3-2

The desired Sub 3-2 (223.6 g, 81%) was obtained by using the same synthesis method as the above Sub 3-1 Sub 3-1 for the obtained Sub 2-2 (32.1 g, 0.09 mol).

Synthesis of 2-18

After dissolving Sub 3-2 (7.8g, 24mmol) in toluene, Sub 5-1 (4.7g, 20mmol) was added and the final compound was 9.0g (yield: 79%) using the same synthesis method as in 5-17. got

[Example of final product 3, 4 synthesis: route (2)]

Product 3.4 of Reaction Scheme 1 may be synthesized by the reaction pathway of Reaction Scheme 7 below, but is not limited thereto.

<Scheme 7>

Sub 6-1 synthesis method

Sub A(3)-1 (32.7 g, 0.11 mol) and Sub 5-1 (22.0 g, 0.13 mol) were synthesized using the same synthesis method as Sub 2-1 to obtain desired Sub 6-1 (29.3 g, 78%). got

Sub 7-1 synthesis method

Sub 6-1 (30.7g, 0.09mol) was dissolved in acetic acid and hydrogen peroxide was dissolved in acetic acid dropwise and stirred at room temperature for 6 hours. When the reaction was completed, acetic acid was removed using a pressure reducing device and separated using column chromatography to obtain the desired Sub 7-1 (26.1 g, 81%).

3-19 synthesis method

The obtained Sub 7-1 (25.7g, 0.7mol) was added to an excess of trifluoromethanesulfonic acid and stirred at room temperature for 24 hours, followed by water and pyridine (8:1) (pyridine (8:1)). Add slowly and reflux for 30 minutes. Lower the temperature, extract with CH ₂ Cl ₂ and wash with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was separated using column chromatography to obtain 17.3 g of the desired 3-19. (Yield: 74%)

Synthesis example of 8-20

Sub 6-2 synthesis method

Sub A (4)-1 (35.7 g, 0.11 mol) and Sub 5-2 (21.8 g, 0.13 mol) were synthesized using the same synthesis method as Sub 2-1 to obtain desired Sub 6-2 (30.7 g, 76%). got

Sub 7-2 synthesis method

Sub 6-2 (33.1 g, 0.09 mol) was synthesized using the same method as that of Sub 7-1 to obtain the desired Sub 7-2 (26.9 g, 78%).

8-20 synthesis method

18.0 g of the desired Sub 7-2 (27.6 g, 0.7 mol) was obtained by using the same synthesis method as in the above 3-19. (Yield: 71%)

[Example of final product 5, 6 synthesis: route (3)]

Products 5 and 6 of Reaction Scheme 1 can be synthesized by the reaction pathway of Reaction Scheme 8 below, but are not limited thereto.

<Scheme 8>

Sub 9-1 synthesis method

Sub A(1)-2 (58.1 g, 0.11 mol) and Sub 8-1 (17.9 g, 0.13 mol) were synthesized using the same synthesis method as Sub 2-1 above to obtain the desired Sub 9-1 (38.7 g, 65%). got

1-15 synthesis method

Sub 9-1 (5.4g, 10mmol) obtained in the above synthesis was put together with Pd(OAc) ₂ (0.2g, 1mmol) and 3-nitropyridine (0.1g, 1mmol) in a round bottom flask, and C ₆ F ₆ (15ml) , after dissolving with DMI (10ml), tert -butyl peroxybenzoate (3.92g, 21 mmol) was added and stirred at 90°C. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 2.4 g of the product (yield: 45%).

Synthesis example of 6-13

Sub 9-2 synthesis method

Sub A(2)-2 (37.5 g, 0.11 mol) and Sub 8-2 (17.9 g, 0.13 mol) were synthesized using the same synthesis method as Sub 2-1 to obtain desired Sub 9-2 (24.5 g, 68%). got

6-13 synthesis method

Sub 9-2 (3.3 g, 10 mmol) obtained in the above synthesis was obtained by using the same synthesis method as in 6-13 to obtain 1.6 g (yield: 48%) of the desired product.

[Example of final product 7, 8 synthesis: route (4)]

Products 7 and 8 of Reaction Scheme 1 can be synthesized by the reaction pathway of Reaction Scheme 8 below, but are not limited thereto.

<Scheme 8>

Synthesis example of 7-21

Sub 10-1 synthesis method

Sub A(3)-1 (32.7 g, 0.11 mol) and Sub 10-1 (23.4 g, 0.13 mol) were synthesized using the same synthesis method as Sub 2-1 to obtain the desired Sub 11-1 (27.6 g, 71%). got

7-21 synthesis method

After dissolving Sub 11-1 (21.6g, 61mmol) obtained in the above synthesis in THF (305ml) in a round bottom flask, methylmagnesium bromide 1.0M in THF (243.2ml, 243.21mmol) was slowly added dropwise, followed by stirring at room temperature. . Upon completion of the reaction, the mixture was extracted with diethyl ether and water, and the organic layer was dried over MgSO ₄ and concentrated to obtain an intermediate product. This intermediate product was dissolved in acetic acid solution (250ml) and refluxed after adding HCl (5ml). When the reaction was completed, water was added, and the solid produced after stirring was filtered under reduced pressure and washed with water and methanol to obtain 14.9 g of the product as a white powder (yield: 73% over two steps).

Synthesis example of 4-23

Sub 11-2 synthesis method

Sub A(4)-2 (35.6 g, 0.11 mol) and Sub 10-2 (23.5 g, 0.13 mol) were synthesized using the same synthesis method as Sub 2-1 to obtain the desired Sub 11-2 (31.7 g, 76%). got

4-23 synthesis method

Sub 11-2 (23.1 g, 61 mmol) obtained in the above synthesis was obtained by using the same synthesis method as 7-21 to obtain 21.9 g of the desired 4-23 (yield: 74% over two steps).

Manufacturing evaluation of organic electric devices

[ Example One] Red Fabrication and testing of organic light emitting devices

First, as a hole injection layer on the ITO layer (anode) formed on the glass substrate, N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl )-N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a thickness of 60 nm. Subsequently, 4,4-bis[ N- (1-naphthyl) -N -phenylamino]biphenyl (hereinafter abbreviated as -NPB) as a hole transport compound was vacuum deposited on the film to a thickness of 60 nm to form a hole transport layer. was formed. The compound P1-12 represented by Formula (1) was used as a host on the upper hole transport layer, and (piq) ₂ Ir(acac) [bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] was used as a dopant at 95: A light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by doping with 5 weight. As a hole-blocking layer, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm, and an electron transport layer was formed. A film of tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed to a thickness of 40 nm. Thereafter, 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, thereby manufacturing an organic light emitting device.

[ Example 2] to [ Example 32] Red Fabrication and testing of organic light emitting devices

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compound of the present invention shown in Table 2 was used instead of the compound P 1-12 according to Example 1 of the present invention as the green host material of the light emitting layer. .

A forward bias DC voltage was applied to the organic light emitting devices of Examples and Comparative Examples prepared as described above to measure electroluminescence (EL) characteristics with PR-650 of Photoresearch, and as a result of the measurement, pulse at 2500 cd/m2 standard luminance T95 life was measured through life measurement equipment manufactured by Science. Table 2 below shows the results of device fabrication and evaluation.

[ comparative example 1] to [ comparative example 5]

An organic light emitting diode was manufactured in the same manner as in Example 1, except for using Comparative Compounds A to E as host materials.

As can be seen from the results of Table 2, the organic light emitting device using the organic light emitting device material of the present invention as a phosphorescent host can significantly improve light emitting efficiency, lifespan, and driving voltage.

In other words, Comparative Compounds B to E, which have a 6-ring heterocyclic core as compared to Comparative Compound A, which is CBP, which is generally used as a host material, showed improved device results, and the same 6-cyclic heterocyclic core as Comparative Compounds B to E The compound according to the above-described example in which N is substituted showed the best device result with the lowest driving voltage and maximized efficiency and lifetime.

As one or more N is substituted in the 6-ring heterocyclic core, the LUMO energy value is relatively low, and electrons can be easily received by the electron transport layer, thereby improving the charge balance in the light emitting layer, resulting in low driving voltage and high efficiency and lifetime. It is believed to have caused the result. Therefore, this suggests that when one or more N is substituted in the 6-ring heterocyclic core, chemical and physical properties may be significantly different from those of a compound in which N is not substituted.

In addition, in the evaluation results of the above-described device fabrication, the device characteristics in which the compound of the present invention was applied to the light emitting layer as a host material were described, but the compound of the present invention was used as a hole injection layer, a hole transport layer and a light emitting auxiliary layer, an electron transport layer, an electron injection layer, etc. All other layers may be applied and used.

The above description is merely illustrative 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. Therefore, the embodiments disclosed in this specification are intended to explain, not limit, the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed according to the claims, and all techniques within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (10)

A compound represented by the following formula (1).

1) X is one of NR ¹ , S, O, CR'R”,
2) n and m are 0 or 1, n + m is 1,
3) A and B are each independently one of a single bond, NR ¹ , S, O, CR ^a R ^b ,
4) Z ¹ to Z ¹² are independently of each other CR ² , N and at least one is N,
5) R ¹ is hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of, R ² is hydrogen;
(Where L' is a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ fused ring group of an aromatic ring; and C ₂ ~C It is selected from the group consisting of ₆₀ -membered heterocyclic group; wherein R _a and R _b are each independently C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ A fused ring group of an aromatic ring; and a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; selected from the group consisting of), or adjacent R ¹ , Adjacent R ² may bond to each other to form a ring,
6) R' and R” are each independently hydrogen, a C ₁ ~ C ₅₀ alkyl group; C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, and P; is selected from the group consisting of, and may be bonded to each other to form a spy compound;
6) R ^a and R ^b are each independently hydrogen or a C ₁ to C ₅₀ alkyl group; C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si, and P; is selected from the group consisting of, and may be bonded to each other to form a spy compound;
Wherein R ¹ , R ² , R _a , R _b , R', R”, R ^a , R ^b are an aryl group, a fluorenyl group, a heterocyclic group, a fused ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group , In the case of an arylene group or a fluorenylene group, each of which is 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; 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 alkynyl group; C ₆ -C ₂₀ aryl group; A deuterium-substituted C ₆ -C ₂₀ aryl group; 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 C ₈ -C ₂₀ It may be further substituted with one or more substituents selected from the group consisting of an arylalkenyl group, and when each of these substituents are adjacent, they may be bonded to each other to form a ring. According to claim 1,
A compound characterized in that the compound represented by the above formula (1) is represented by the following formulas (2) and (3).

The Z ¹ to Z ¹² , X, A, and B are the same as Z ¹ to Z ¹² , X, A, and B defined in Formula (1). According to claim 1,
A compound characterized in that the compound represented by the above formula (1) is represented by the following formulas (4) to (11).

The Z ¹ to Z ¹² , A, and B are the same as Z ¹ to Z ¹² , A, and B defined in Formula (1). According to claim 1,
A compound represented by the above formula (1) as shown below.

a first electrode;
a second electrode; and
An organic electric device comprising: an organic material layer positioned 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 claim 5,
The compound is contained in at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, and the light emitting layer of the organic material layer, and the compound includes one single compound or two or more compounds as components of a mixture. An organic electric device. According to claim 5,
The organic electric device, characterized in that the compound is used as a phosphorescent host material of the light emitting layer of the organic material layer. According to claim 5,
The organic layer is an organic electric device 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 comprising the organic electric element of claim 5; and
An electronic device including a controller for driving the display device. According to claim 9,
The electronic device according to claim 1 , wherein the organic electric element is one of an organic light emitting element, an organic solar cell, an organic photoreceptor, an organic transistor, and an element for monochromatic or white light.

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