WO2015072730A1 - Compound for organic electronic device, organic electronic device using same, and electronic device using same - Google Patents

Abstract

Disclosed is a compound represented by chemical formula (1). In addition, disclosed is an organic electronic device comprising a first electrode, a second electrode and an organic layer provided between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by chemical formula (1). As the organic layer comprises the compound represented by chemical formula (1), the light-emitting efficiency, stability, life, etc. of the organic electronic device can be enhanced.

Description

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

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

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

The material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.

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

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

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

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

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

However, in the case of the material used in the hole transport layer, since it has to have a low HOMO value, most have a low T1 value, which causes the exciton generated in the light emitting layer to be transferred to the hole transport layer, and as a result, in the hole transport layer or at the hole transport layer interface. The light emission results in a decrease in color purity, efficiency and lifespan of the organic electric element.

In addition, the driving voltage can be reduced by using a material having a high hole mobility, but the hole mobility is faster than the electron mobility, resulting in charge unbalance in the light emitting layer. The color purity and efficiency of the electric device is lowered and the lifespan is shortened.

Therefore, there is an urgent need to develop a light emitting auxiliary layer having a high T1 value and having a HOMO level between the hole transport layer HOMO energy level and the light emitting layer HOMO energy level.

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

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

The present invention uses a non-linear linking group (a structure broken upon bonding with an amine group) to a carbazole core, which is widely used as an OLED hole transport material, and also a bulky substituent on the nitrogen (N) of the carbazole. The compound having high T1 value, wide band gap and excellent charge balance, which can improve the device's high luminous efficiency, low driving voltage, high heat resistance, color purity and lifetime, An object of the present invention is to provide an organic electric element and its electronic device using the same.

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

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

By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and life of the device can be greatly improved.

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

[Description of the code]

100: organic electric element 110: substrate

120: first electrode 130: hole injection layer

140: hole transport layer 141: buffer layer

150: light emitting layer 151: light emitting auxiliary layer

160: electron transport layer 170: electron injection layer

180: second electrode

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

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

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

As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows.

The term "halo" or "halogen" as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.

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

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

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

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

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

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

As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.

As used herein, the term "aryloxyl group" or "aryloxy group" means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but is not limited thereto.

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.

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

Also, when prefixes are named consecutively, it means that the substituents are listed in the order described 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.

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.

The term "heteroatom" as used herein refers to N, O, S, P or Si unless otherwise stated.

"Heterocyclic groups" may also include rings comprising SO ₂ in place of the carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.

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

Unless otherwise stated, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof. Saturated or unsaturated rings.

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

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" refers to deuterium, halogen, amino groups, nitrile groups, nitro groups, C ₁ -C ₂₀ alkyl groups, 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, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron Substituted by at least one substituent selected from the group consisting of a group, a germanium group, and a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P It is not limited to these substituents.

In addition, unless otherwise stated, the formula used in the present invention is applied in the same manner as the substituent definition by the index definition of the following formula.

Herein, when a is an integer of 0, the substituent R ¹ is absent, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Are each bonded as follows, where R ¹ may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of 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, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110. ) Is provided with an organic material layer containing a compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

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

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

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

Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of cores and the combination of sub-substituents bound thereto are also very significant. Importantly, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

As described above, in order to solve the light emission problem in the hole transport layer in the organic electroluminescent device, it is preferable to form a light emitting auxiliary layer between the hole transport layer and the light emitting layer, and according to each of the light emitting layers R, G, and B, It is time to develop different light emitting auxiliary layers. Meanwhile, in the case of the light emitting auxiliary layer, it is difficult to infer the characteristics of the organic material layer used even if a similar core is used, since the correlation between the hole transport layer and the light emitting layer (host) must be understood.

Therefore, in the present invention, by forming a light emitting layer or an auxiliary light emitting layer using a compound represented by the formula (1) by optimizing the energy level (level) and T1 value between each organic material layer, the intrinsic properties (mobility, interface characteristics, etc.) of the organic material The life and efficiency of the electric device can be improved at the same time.

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

In addition, the organic material layer is a solution or solvent process (e.g., spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blading) using various polymer materials. It can be produced in fewer layers by methods such as ding process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention may 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-sided emission type depending on the material used.

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

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

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

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

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

<Formula 1>

In Formula 1, Ar ¹ and Ar ² are each independently a C ₆ -C ₆₀ aryl group; Or a fluorenyl group; specifically, phenyl, biphenyl, naphthyl, fluorene, and the like.

In Formula 1, L is

It is selected from the group consisting of. At this time, the part marked * is connected to the nitrogen (N) of the formula (1).

In Formula 1, X is O or S, m and p are each independently an integer of 0 to 3, n and o are each independently an integer of 0 to 4.

In Formula 1, R ¹ to R ⁴ are i) independently of each other deuterium; halogen; C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; C ₆ -C ₃₀ aryloxy group; And -L'-N (R ') (R "); or ii) neighboring groups may be bonded to each other to form at least one ring. Forming means that neighboring R ¹ , neighboring R ² , neighboring R ³ , or neighboring R ⁴ combine with each other to form a ring when m, n, o, and p are each an integer of 2 or more. , Wherein the ring is C ₃ -C ₆₀ aliphatic ring, C ₆ -C ₆₀ aromatic ring, O, N, S, Si and P containing at least one hetero atom selected from the group consisting of C ₂ -C ₆₀ Refers to a fused ring consisting of a heterocycle or a combination thereof, and includes saturated or unsaturated rings.

L 'is a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; And C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P,

R ′ and R ″ are each independently C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₃ -C ₆₀ aliphatic ring and C ₆ -C ₆₀ aromatic ring group; and O, N, It is selected from the group consisting of; C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of S, Si and P.

Here, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, fluorenylene group, each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R ') (R "); Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Of C ₆ -C ₂₀ Aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; And an arylalkenyl group of C ₈ -C _20. It may be further substituted with one or more substituents selected from the group consisting of.

Specifically, the compound represented by Chemical Formula 1 may be represented by the following Chemical Formulas 2 to 8.

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

<Formula 7>

<Formula 8>

In Formulas 2 to 8, Ar ¹ , Ar ² , X, R ¹ to R ⁴ , m, n, o and p are the same as defined in Formula 1.

More specifically, the compound represented by Formula 1 to Formula 8 may be any one of the following compounds.

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

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

In this case, the organic electric element includes a first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Chemical Formula 1, and Chemical Formula 1 may include a hole injection layer, a hole transport layer, and an emission auxiliary layer of the organic material layer. Or it may be contained in at least one layer of the light emitting layer. That is, the compound represented by Formula 1 may be used as a material of a hole injection layer, a hole transport layer, a light emitting auxiliary layer or a light emitting layer. Specifically, to provide an organic electroluminescent device comprising one of the compounds represented by Formula 2 to Formula 8 in the organic material layer, more specifically, the present invention provides an organic electroluminescent device comprising a compound represented by the individual formula in the organic material layer To provide.

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

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

Synthesis Example

Compound (Final Product) according to the present invention is prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1, but is not limited thereto.

<Scheme 1>

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

I. Synthesis of Sub 1

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

<Scheme 2>

Sub 1-1 (1 equiv), Sub 1-2 (1 equiv), Pd ₂ (dba) ₃ (0.05 equiv), PPh ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5mL / sub1-1 1mmol) was added and the reaction proceeded at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain Sub 1.

(1) Sub 1 (1) Synthesis

3-bromo-9H-carbazole (4.9g, 20mmol), 4-iododibenzo [b, d] thiophene (6.2g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ ( 0.5 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, followed by reaction at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 6.7 g (yield: 78%) of the product.

(2) Sub 1 (3) synthesis

3-bromo-9H-carbazole (4.9g, 20mmol), 2-iododibenzo [b, d] thiophene (6.2g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ ( 0.5 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, followed by reaction at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 6.5g (yield: 76%) of the product.

(3) Sub 1 (6) synthesis

3-bromo-9H-carbazole (4.9g, 20mmol), 3-iododibenzo [b, d] furan (5.9g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ ( 0.5 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, followed by reaction at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 6.2g (yield: 75%) of the product.

(4) Sub 1 (8) Synthesis

3-bromo-9H-carbazole (4.9g, 20mmol), 1-iododibenzo [b, d] furan (5.9g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ ( 0.5 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, followed by reaction at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 6.1g (yield: 74%) of the product.

Meanwhile, examples of Sub 1 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 1 below.

TABLE 1

II. Synthesis of Sub 2

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 3, but is not limited thereto.

<Scheme 3>

1.Synthesis of Sub 2-3

Sub 2-1 (1 equiv), Sub 2-2 (1 equiv), Pd ₂ (dba) ₃ (0.05 equiv), PPh ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5mL / sub2-1 1mmol) was added and the reaction proceeded at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain Sub 2-3.

(1) Sub 2-3-1 synthesis

1-bromo-2-iodobenzene (5.7g, 20mmol), diphenylamine (3.4g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol) and toluene (210mL) were added and the reaction was proceeded at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 4.9 g (yield: 76%) of the product.

(2) Sub 2-3-2 synthesis

1-bromo-3-iodobenzene (5.7g, 20mmol), N-phenyl- [1,1'-biphenyl] -4-amine (4.9g, 20mmol), Pd ₂ (dba) ₃ (0.9g) , 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), toluene (210mL) was added and the reaction proceeded at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 6.2g (yield: 78%) of the product.

(3) Sub 2-3-3 synthesis

2-bromo-2'-iodo-1,1'-biphenyl (7.2g, 20mmol), N-phenyl- [1,1 ': 3', 1 ''-terphenyl] -3-amine in a round bottom flask ( 6.4g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), toluene (210mL) and then at 100 ℃ Proceed. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain the product 7.7g (yield: 74%).

(4) Sub 2-3-4 synthesis

4-bromo-2'-iodo-1,1'-biphenyl (7.2g, 20mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (5.7g, 20mmol) in a round bottom flask, Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), toluene (210mL) was added to the reaction at 100 ℃. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain the product 8.1g (yield: 78%).

(5) Sub 2-3-5 synthesis

4-bromo-3'-iodo-1,1'-biphenyl (7.2g, 20mmol), N-([1,1'-biphenyl] -4-yl) naphthalen-1-amine (5.9g) in a round bottom flask , 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), toluene (210mL) and then proceed the reaction at 100 ℃ Let's do it. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to give the product 7.8g (yield: 74%).

(6) Sub 2-3-6 synthesis

4'-bromo-2-iodo-1,1'-biphenyl (7.2g, 20mmol), N-([1,1'-biphenyl] -4-yl) naphthalen-2-amine (5.9g) , 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), toluene (210mL) and then proceed the reaction at 100 ℃ Let's do it. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain a product 7.6g (yield: 72%).

(7) Sub 2-3-7 synthesis

4'-bromo-3-iodo-1,1'-biphenyl (7.2g, 20mmol), di ([1,1'-biphenyl] -4-yl) amine (6.4g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), toluene (210mL) was added to the reaction at 100 ℃. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain a product 8.6g (yield: 78%).

2. Synthesis of Sub 2

Sub 2-3 (1 equiv) was dissolved in anhydrous Ether, the temperature of the reactant was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.1 equiv) was slowly added dropwise, and the reaction was stirred for 30 minutes. I was. Then the temperature of the reaction was lowered to -78 ℃ and Triisopropylborate (1.5 equiv) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After the reaction was completed, the mixture was extracted with ethyl acetate and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain Sub 2.

(1) Sub 2 (1) Synthesis

Dissolve 2-bromo-N, N-diphenylaniline (6.5g, 20mmol) in anhydrous Ether, lower the temperature of the reaction to -78 ℃, slowly add dropwise n-BuLi (2.5M in hexane) (1.4g, 22mmol) After that, the reaction was stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ℃ and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with ethyl acetate and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallization to obtain 3.2g (Yield: 56%) of Sub2 (1).

(2) Sub 2 (6) synthesis

Dissolve N- (3-bromophenyl) -N-phenyl- [1,1'-biphenyl] -4-amine (8.0 g, 20 mmol) in anhydrous Ether, lower the temperature of the reaction to -78 ° C, and n-BuLi ( 2.5 M in hexane) (1.4 g, 22 mmol) was slowly added dropwise and the reaction stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ℃ and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with ethyl acetate and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallization to obtain 4.2 g (Yield: 58%) of Sub2 (6).

(3) Sub 2 (11) synthesis

N- (2'-bromo- [1,1'-biphenyl] -2-yl) -N-phenyl- [1,1 ': 3', 1 ''-terphenyl] -3-amine (11.1 g, 20 mmol ) Was dissolved in anhydrous Ether, and the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.4 g, 22 mmol) was slowly added dropwise, and the reaction was stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ℃ and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After the reaction was completed, the mixture was extracted with ethyl acetate and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silicagel column and recrystallization to obtain 5.4 g (Yield: 52%) of Sub2 (11).

(4) Sub 2 (18) synthesis

N- (4'-bromo- [1,1'-biphenyl] -2-yl) -9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (10.3 g, 20 mmol) was dissolved in anhydrous Ether. The temperature of the reaction was lowered to −78 ° C., n-BuLi (2.5 M in hexane) (1.4 g, 22 mmol) was slowly added dropwise, and the reaction was stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ℃ and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with ethyl acetate and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallization to obtain 5.4g (Yield: 56%) of Sub2 (18).

(5) Sub 2 (23) Synthesis

N-([1,1'-biphenyl] -4-yl) -N- (4'-bromo- [1,1'-biphenyl] -3-yl) naphthalen-1-amine (10.5 g, 20 mmol) After dissolving in anhydrous Ether, the temperature of the reaction was lowered to -78 ℃, n-BuLi (2.5M in hexane) (1.4g, 22mmol) was slowly added dropwise, and the reaction was stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ℃ and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After the reaction was completed, the mixture was extracted with ethyl acetate and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallization, to obtain 5.1 g (yield: 52%) of Sub2 (23).

(6) Sub 2 (28) Synthesis

N-([1,1'-biphenyl] -4-yl) -N- (4'-bromo- [1,1'-biphenyl] -2-yl) naphthalen-2-amine (10.5 g, 20 mmol) After dissolving in anhydrous Ether, the temperature of the reaction was lowered to -78 ℃, n-BuLi (2.5M in hexane) (1.4g, 22mmol) was slowly added dropwise, and the reaction was stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ℃ and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with ethyl acetate and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallization to obtain 5.4g (Yield: 55%) of Sub2 (28).

(7) Sub 2 (32) Synthesis

N, N-di ([1,1'-biphenyl] -4-yl) -4'-bromo- [1,1'-biphenyl] -3-amine (11.1 g, 20 mmol) is dissolved in anhydrous Ether, and the reactant The temperature of was lowered to -78 ℃, n-BuLi (2.5M in hexane) (1.4g, 22mmol) was slowly added dropwise, the reaction was stirred for 30 minutes. Then the temperature of the reaction was lowered to -78 ℃ and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the mixture was extracted with ethyl acetate and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallization to give 6.2 g (yield: 60%) of Sub2 (32).

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

TABLE 2

III. Synthesis of Final Product

In a round bottom flask, Sub 1 (1 equiv), Sub 2 (1 equiv), Pd (PPh ₃ ) ₄ (0.03 equiv), NaOH (3 equiv), THF (3 mL / 1 mmol), and water (1.5 mL / 1 mmol) Put it in. Thereafter, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to obtain a final product.

1.1-1 Synthesis

3-bromo-9- (dibenzo [b, d] thiophen-4-yl) -9H-carbazole (8.6g, 20mmol), (2- (diphenylamino) phenyl) boronic acid (5.8g, 20mmol) in a round bottom flask Add Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (2.4 g, 60 mmol), THF (60 mL) and water (30 mL). Thereafter, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 7.6g (yield: 64%).

2. 2-6 Synthesis

3-bromo-9- (dibenzo [b, d] furan-4-yl) -9H-carbazole (8.2g, 20mmol), (3- (naphthalen-1-yl (phenyl) amino) phenyl) in a round bottom flask Add boronic acid (6.8 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (2.4 g, 60 mmol), THF (60 mL), and water (30 mL). Thereafter, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 7.6g (yield: 61%).

3. 3-11 Synthesis

3-bromo-9- (dibenzo [b, d] thiophen-3-yl) -9H-carbazole (8.6g, 20mmol), (2 '-([1,1': 2 ', 1') in a round bottom flask '-terphenyl] -2-yl (phenyl) amino)-[1,1'-biphenyl] -2-yl) boronic acid (10.3 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), Add NaOH (2.4 g, 60 mmol), THF (60 mL) and water (30 mL). Thereafter, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 9.5g (yield: 58%).

4. 4-16 Synthesis

3-bromo-9- (dibenzo [b, d] thiophen-2-yl) -9H-carbazole (8.6g, 20mmol), (3 '-([1,1': 4 ', 1') in a round bottom flask '-terphenyl] -3-yl (phenyl) amino)-[1,1'-biphenyl] -2-yl) boronic acid (10.3 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), Add NaOH (2.4 g, 60 mmol), THF (60 mL) and water (30 mL). Thereafter, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 9.4g (yield: 57%).

5. 5-17 Synthesis

3-bromo-9- (dibenzo [b, d] thiophen-1-yl) -9H-carbazole (8.6g, 20mmol), (4 '-([1,1': 2 ', 1') in a round bottom flask '-terphenyl] -4-yl (phenyl) amino)-[1,1'-biphenyl] -2-yl) boronic acid (10.3 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), Add NaOH (2.4 g, 60 mmol), THF (60 mL) and water (30 mL). Thereafter, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 9.5g (yield: 58%).

6. 6-22 Synthesis

3-bromo-9- (dibenzo [b, d] thiophen-4-yl) -9H-carbazole (8.6g, 20mmol), (2 '-((9,9-dimethyl-9H-fluoren-) in a round bottom flask 2-yl) (phenyl) amino)-[1,1'-biphenyl] -4-yl) boronic acid (9.6g, 20mmol), Pd (PPh ₃ ) ₄ (0.7g, 0.6mmol), NaOH (2.4g , 60 mmol), THF (60 mL), water (30 mL). Thereafter, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product 8.6g (yield: 55%).

7. 7-27 Synthesis

3-bromo-9- (dibenzo [b, d] furan-3-yl) -9H-carbazole (8.6g, 20mmol), (3 '-([1,1'-biphenyl] -4- yl (naphthalen-1-yl) amino)-[1,1'-biphenyl] -4-yl) boronic acid (9.8g, 20mmol), Pd (PPh ₃ ) ₄ (0.7g, 0.6mmol), NaOH (2.4 g, 60 mmol), THF (60 mL), water (30 mL). Thereafter, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 9.2 g (yield: 59%) of the product.

On the other hand, FD-MS values of the compounds 1-1 to 7-40 of the present invention prepared according to the synthesis examples as described above are shown in Table 3.

TABLE 3

Manufacturing Evaluation of Organic Electrical Device

Example 1 Green Organic Electroluminescent Device (Hole Transport Layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a hole transport layer material. First, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N ¹ on the ITO layer (anode) formed on the organic substrate. -phenylbenzene-1,4-diamine (hereinafter abbreviated as "2-TNATA") was vacuum deposited to a thickness of 60 nm to form a hole injection layer, and then the compound 1-33 of the present invention on the hole injection layer 60 nm thick Vacuum deposition to form a hole transport layer. Subsequently, 4,4'-N, N'-dicarbazole-biphenyl (hereinafter abbreviated as "CBP") is used as a host on the hole transport layer, and tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) ₃ "). And a dopant in a weight ratio of 90:10 to form a light emitting layer by vacuum deposition at a thickness of 30 nm. Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolinoleito) aluminum (hereinafter abbreviated as "BAlq") was vacuum-deposited on the light emitting layer to a thickness of 10 nm. A hole blocking layer was formed, and tris (8-quinolinol) aluminum (hereinafter abbreviated as "Alq ₃ ") was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Example 2] to [Example 55] green organic electroluminescent device (hole transport layer)

Compound 1-33 to 1-40, 2-33 to 2-40, 3-33 to 3-40, 4-33 to 4 of the present invention shown in Table 4, instead of the compound 1-33 of the present invention as a hole transport layer material An organic electroluminescent device was manufactured in the same manner as in Example 1, except that -39, 5-33 to 5-40, 6-33 to 6-40, and 7-33 to 7-40 were used.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound A was used instead of Compound 1-33 of the present invention as a hole transport layer material.

Comparative Compound A

Comparative Example 2

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound B was used instead of Compound 1-33 of the present invention as a hole transport layer material.

Comparative Compound B

Comparative Example 3

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound C was used instead of Compound 1-33 of the present invention as a hole transport layer material.

Comparative Compound C

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 1 to 55 and Comparative Examples 1 to 3 of the present invention The T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at a luminance of 5000 cd / m 2, and the measurement results are shown in Table 4 below.

TABLE 4

As can be seen from the results of Table 4, the organic electroluminescent device using the compound of the present invention as the material of the hole transport layer has improved luminous efficiency compared to the organic electroluminescent device using the comparative compound A to Comparative Compound C as the material of the hole transport layer. And the service life is significantly improved. That is, the compound of the present invention is superior to the compound A of the present invention in which the amine group is a non-linear type compared to the comparative compound A, which is NPB, and the linear compound in which the amine group is connected to the para-position, and the compound C in the linear form. Indicated.

Conjugation lengths are shorter when the amine groups are connected in a non-linear type than in the linear type, resulting in a wider band gap, deep HOMO energy levels, and high T1. It will have a value. Therefore, due to the deep HOMO energy level, holes are smoothly transported to the light emitting layer, and the ability to block electrons with a high T1 value is enhanced, so that excitons are more easily generated in the light emitting layer, thereby improving efficiency and lifespan.

Example 56 Red Organic Electroluminescent Device (Emitting Auxiliary Layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, a hole injection layer is formed by vacuum depositing 2-TNATA with a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate, and then 4,4-bis [N- (1-naphthyl) on the hole injection layer. ) -N-phenylamino] biphenyl (abbreviated as "NPD") was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, Compound 1-1 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. Thereafter, CBP is used as a host and bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate (hereinafter abbreviated as "(piq) ₂ Ir (acac)") is used as a dopant on a light emitting auxiliary layer at a 95: 5 weight ratio. Doped to vacuum deposition to a thickness of 30nm to form a light emitting layer. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer, and Alq ₃ was vacuum-deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Example 57] to [Example 125] red organic electroluminescent device (light emitting auxiliary layer)

Instead of compound 1-1 of the present invention as a light emitting auxiliary layer material, compounds 1-2 to 1-10, 2-1 to 2-10, 3-1 to 3-10, and 4-1 to 1-1 of the present invention shown in Table 5 below. An organic light emitting diode was manufactured according to the same method as Example 56 except for using 4-10, 5-1 to 5-10, 6-1 to 6-10, and 7-1 to 7-10.

[Comparative Example 4]

An organic electroluminescent device was manufactured in the same manner as in Example 56, except that the light emitting auxiliary layer was not formed.

[Comparative Example 5]

An organic electroluminescent device was manufactured in the same manner as in Example 56, except that Comparative Compound A was used instead of Compound 1-1 of the present invention as a light emitting auxiliary layer material.

Comparative Example 6

An organic electroluminescent device was manufactured in the same manner as in Example 56, except that Comparative Compound B was used instead of Compound 1-1 of the present invention as a light emitting auxiliary layer material.

Comparative Example 7

An organic electroluminescent device was manufactured in the same manner as in Example 56, except that Comparative Compound C was used instead of Compound 1-1 of the present invention.

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples 56 to 125 and Comparative Examples 4 to 7 of the present invention The T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at a luminance of 2500 cd / m 2, and the measurement results are shown in Table 5 below.

TABLE 5

Example 126 Green Organic Light Emitting Diode (light emitting auxiliary layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, a hole injection layer was formed by vacuum depositing 2-TNATA with a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate, and then a NPD was vacuum deposited with a thickness of 60 nm on the hole injection layer to form a hole transport layer. . Subsequently, Compound 1-1 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. Subsequently, the light emitting auxiliary layer was doped at a weight ratio of 95: 5 with CBP as a host and Ir (ppy) ₃ as a dopant to form a light emitting layer by vacuum deposition at a thickness of 30 nm. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm on the light emitting 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. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Example 127] to [Example 195] Green organic electroluminescent device (light emitting auxiliary layer)

Instead of compound 1-1 of the present invention as a light emitting auxiliary layer material, compounds 1-2 to 1-10, 2-1 to 2-10, 3-1 to 3-10, and 4-1 to 1-1 of the present invention shown in Table 6 below. An organic light emitting diode was manufactured according to the same method as Example 126 except for using 4-10, 5-1 to 5-10, 6-1 to 6-10, and 7-1 to 7-10.

Comparative Example 8

An organic electroluminescent device was manufactured in the same manner as in Example 126, except that an emission auxiliary layer was not formed.

Comparative Example 9

An organic electroluminescent device was manufactured in the same manner as in Example 126, except that Comparative Compound A was used instead of Compound 1-1 of the present invention as a light emitting auxiliary layer material.

Comparative Example 10

An organic electroluminescent device was manufactured in the same manner as in Example 126, except that Comparative Compound B was used instead of Compound 1-1 of the present invention as a light emitting auxiliary layer material.

Comparative Example 11

An organic electroluminescent device was manufactured in the same manner as in Example 126, except that Comparative Compound C was used instead of Compound 1-1 of the present invention.

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples 126 to 195 and Comparative Examples 8 to 11 of the present invention The T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at a luminance of 5000 cd / m 2, and the measurement results are shown in Table 6 below.

TABLE 6

Example 196 Blue Organic Electroluminescent Device (Emitting Auxiliary Layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, a hole injection layer was formed by vacuum depositing 2-TNATA with a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate, and then a NPD was vacuum deposited with a thickness of 60 nm on the hole injection layer to form a hole transport layer. . Subsequently, Compound 1-1 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. Thereafter, 9,10-di (naphthalen-2-yl) anthracene was used as a host on the light emitting auxiliary layer, and BD-052X (manufactured by Idemitsukosan) was used as a dopant in a weight ratio of 93: 7 to vacuum-deposit to a thickness of 30 nm. Formed. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm on the light emitting 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. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Example 197] to [Example 265] Blue organic electroluminescent device (light emitting auxiliary layer)

Instead of compound 1-1 of the present invention as a light emitting auxiliary layer material, compounds 1-2 to 1-10, 2-1 to 2-10, 3-1 to 3-10, and 4-1 to 1-1 of the present invention shown in Table 7 below. An organic electroluminescent device was manufactured in the same manner as in Example 196, except that 4-10, 5-1 to 5-10, 6-1 to 6-10, 7-1 to 7-10 were used.

Comparative Example 12

An organic electroluminescent device was manufactured in the same manner as in Example 196, except that an emission auxiliary layer was not formed.

Comparative Example 13

An organic electroluminescent device was manufactured in the same manner as in Example 196, except that Comparative Compound A was used instead of Compound 1-1 of the present invention as a light emitting auxiliary layer material.

Comparative Example 14

An organic electroluminescent device was manufactured in the same manner as in Example 196, except that Comparative Compound B was used instead of Compound 1-1 of the present invention as a light emitting auxiliary layer material.

Comparative Example 15

An organic electroluminescent device was manufactured in the same manner as in Example 196, except that Comparative Compound C was used instead of Compound 1-1 of the present invention as a light emitting auxiliary layer material.

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples 196 to 265 and Comparative Examples 12 to 15 of the present invention The T95 life was measured using the life measurement equipment manufactured by McScience Inc. at a luminance of 500 cd / m 2, and the measurement results are shown in Table 7 below.

TABLE 7

As can be seen from the results of Table 5, Table 6, and Table 7, the organic electroluminescent device using the compound of the present invention as a material of the light emitting auxiliary layer has a luminous efficiency and The service life is significantly improved.

This is because, as described in Table 4 of Example 1, the amine groups are connected in a non-linear type to have a deep HOMO energy level and a high T1 value, thereby facilitating the transport of holes to the light emitting layer and blocking electrons. It is believed that the efficiency and lifespan are improved by improving. In addition, a bulky substituent called dibenzofuran or dibenzothiophene is introduced into the nitrogen of carbazole to lower the packing density between materials in the light emitting auxiliary layer, thereby lowering the hole mobility. This makes it easy to achieve a charge balance in the light emitting layer, and consequently, it is considered that the luminous efficiency and lifetime are significantly improved.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application claims priority under Patent Application No. 10-2013-0138149, filed with Korea on November 14, 2013, under Section 119 (a) (35 USC § 119 (a)). All content is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims (9)

1. Compound represented by the following formula (1):

   <Formula 1>

   

   In Chemical Formula 1,

   Ar ¹ and Ar ² are each independently a C ₆ -C ₆₀ aryl group; Or a fluorenyl group;

   L is

   

   

   

   It is selected from the group consisting of (mark * means a bond with nitrogen (N) of Formula 1),

   X is O or S,

   m and p are independently of each other an integer from 0 to 3,

   n and o are each independently an integer from 0 to 4,

   R ¹ to R ⁴ are i) independently of each other deuterium; halogen; C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; C ₆ -C ₃₀ aryloxy group; And -L'-N (R ') (R "); or ii) neighboring groups combine with each other to form at least one ring,

   L 'is a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P, wherein R ′ and R ″ are independently of each other. C ₆ -C ₆₀ aryl group; fluorenyl group; C ₃ -C ₆₀ aliphatic ring and C ₆ -C ₆₀ aromatic ring group; and O, N, S, Si and P selected from the group consisting of C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom; selected from the group consisting of,

   Here, in the case where the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, fluorenylene group is further substituted with one or more substituents, respectively heavy hydrogen; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R ') (R "); Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Of C ₆ -C ₂₀ Aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; And an arylalkenyl group of C ₈ -C _20. It may be further substituted with one or more substituents selected from the group consisting of.
2. The method of claim 1,

   Compound represented by the following formula (2) to (8):

   <Formula 2>

   

   <Formula 3>

   

   <Formula 4>

   

   <Formula 5>

   

   <Formula 6>

   

   <Formula 7>

   

   <Formula 8>

   

   In Formulas 2 to 8, Ar ¹ , Ar ² , X, R ¹ to R ⁴ , m, n, o and p are the same as defined in claim 1.
3. The method of claim 1,

   Compounds characterized in that one of the following compounds:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

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4. A first electrode; Second electrode; And an organic material layer positioned between the first electrode and the second electrode.

   The organic material layer is an organic electroluminescent device comprising the compound of claim 1.
5. The method of claim 4, wherein

   The compound is an organic electric device, characterized in that contained in at least one layer of a hole injection layer, a hole transport layer, a light emitting auxiliary layer or a light emitting layer of the organic material layer.
6. The method of claim 4, wherein

   And an optical efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.
7. The method of claim 4, wherein

   The organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process.
8. Claim 4 display device comprising the organic electroluminescent element; And

   And a controller for driving the display device.
9. The method of claim 8,

   The organic electronic device is at least one of an organic electroluminescent device, an organic solar cell, an organic photosensitive member, an organic transistor, and a device for monochrome or white illumination.

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