WO2015046883A1 - Compound for organic electrical element, organic electrical element using same and electronic device therewith - Google Patents

Abstract

The present invention relates to a novel compound that can improve the light-emitting efficiency, the stability and the lifespan of an element, to an organic electrical element using same, and to an electronic device therewith.

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 electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, a cathode and an organic material layer therebetween. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electroluminescent 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 electroluminescent device may be classified into a hole injection material, a hole transport material, a light emitting 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, these efficiency and life problems must be solved. Efficiency, lifespan, and driving voltage are related to each other, and as the efficiency increases, the driving voltage is relatively decreased, and as the result, the crystallization of organic materials due to Joule heating generated during driving decreases as the driving voltage decreases. It shows a tendency to increase the 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 and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved. to be.

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, holes move faster than electrons, and excitons generated in the emission layer are transferred to the electron transport layer, resulting in charge unbalance in the emission layer, thereby emitting light at the electron transport layer interface. When emitting light at the interface of the electron transport layer, there is a problem that the color purity and efficiency of the organic electroluminescent device is deteriorated, and in particular, when the organic electroluminescent device is manufactured, the temperature of the organic electroluminescent device is shortened due to low temperature stability. . Therefore, it is time to develop an electron transport material having high temperature stability, high T1 value, and fast and efficient hole blocking ability.

On the other hand, while delaying the penetration of the 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 electroluminescent device, a material forming 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. Supported by an efficient material should be preceded, but development of a stable and efficient organic material layer for an organic electroluminescent device has not been made yet. Therefore, the development of new materials continues to be required, and in particular, the development of material combinations such as a hole transport layer and an electron transport layer is urgently required.

In recent years, in addition to the study of improving the device characteristics by changing the performance of each material, as well as improving the color purity and efficiency by the optical thickness optimized between the anode and the cathode in the top device of the resonant structure This is one of the important factors in improving device performance. Compared with the bottom device structure of the non-resonant structure, the top device structure has a large optical energy loss due to the surface plasmon polariton (SPP) because the formed light is reflected by the anode, which is a reflecting film, and comes out toward the cathode. Therefore, one of the important methods for improving the shape and efficiency of the EL spectrum is to use a capping layer on the top cathode. In general, electron emission is mainly performed by four metals of Al, Pt, Ag, Au, and surface plasmon is generated on the surface of the metal electrode. For example, when the cathode is used as Ag, the light emitted by the Ag of the cathode is quenched by SPP (light energy loss due to Ag), thereby reducing efficiency. On the other hand, when the capping layer is used, SPP occurs at the interface between the MgAg electrode and the high refractive organic material, among which TE polarized light is dissipated from the CPL plane in the vertical direction by evanescent wave. In addition, the transverse magnetic polarized light traveling along the cathode and the capping layer causes wavelength amplification by surface plasma resonance, thereby increasing the intensity of the peak. As a result, high efficiency and effective color purity control are possible.

The organic electroluminescent device and its electronic device having high efficiency, high lifetime and high color purity are developed through the development of a compound having high electron mobility and high temperature stability and more efficient hole blocking ability at high T1 value. It is for the purpose of providing.

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.

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 specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, 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.

Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. 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 -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 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.

Also, unless stated otherwise, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is 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, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Group, germanium group, and C ₂ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.

Also, unless otherwise stated, the formulas used in the present invention apply equally to the definitions of substituents based on the exponential definition of the following formulas.

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 Can be used as a material.

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.

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

<Formula 1>

In Formula 1, R ¹ to R ¹² are I) hydrogen independently of each other; heavy hydrogen; C ₆ -C ₂₄ aryl group; C ₂ ~ C ₂₄ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; selected from the group consisting of, or II) R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² may combine with each other to form a ring. Here, the 'ring' refers to a fused ring composed of C ₃ ~ C ₆₀ aliphatic ring, C ₆ ~ C ₆₀ aromatic ring, C ₂ ~ C ₆₀ hetero ring or a combination thereof, and includes a saturated or unsaturated ring do.

L ¹ to L ³ are each independently a single bond; C ₆ ~ C ₂₄ arylene group; It may be selected from the group consisting of fluorenylene group.

In addition, L ³ is a linker whose valence may vary depending on n, and when n is 1, it may be a divalent linking group, and when n is 2, it may be a trivalent linking group. For example, L ³ is C ₆ ~ 2 or trivalent aryl of C _60; Divalent or trivalent fluorene; It may be selected from the group consisting of, further L ³ may be a single bond. Provided that when n is 2, L ³ may not be a single bond.

n is an integer of 1 or 2, and Het is a C ₂ ~ C ₆₀ heterocyclic group containing at least one nitrogen (except indazole, benzoimidazole, Indole, Carbazole below). By way of example, Het may be pyridyl, pyrimidinyl, triazine, quinazolinyl, and the like.

Wherein the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, fluorenylene group are each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -LN (R _a ) (R _b ); C ₁ ~ C ₂₀ of the import alkylthio; C ₁ -C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to 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; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; And C ₈ ~ C ₂₀ An aryl alkenyl group; It may be further substituted with one or more substituents selected from the group consisting of, and these substituents may be bonded to each other to form a ring, wherein the 'ring' is C ₃ ~ It refers to a fused ring consisting of C ₆₀ aliphatic ring, C ₆ ~ C ₆₀ aromatic ring, C ₂ ~ C ₆₀ hetero ring or a combination thereof, and includes a saturated or unsaturated ring.

L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P.

R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P.

Specifically, the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 2 or Chemical Formula 3.

<Formula 2> <Formula 3>

In Formulas 2 and 3, R ¹ to R ¹² , L ¹ to L ³ and Het are the same as defined in Formula 1, Het ¹ and Het ² are defined the same as Het in Formula 1.

Specifically, Het of Formula 1 may be represented as follows.

In the above formula, X ₁ to X ₃ are independently of each other CR or N, at least one is N.

R is hydrogen; heavy hydrogen; C ₆ -C ₂₄ aryl group; may be selected from the group consisting of.

Ar ¹ and Ar ² are C ₆ -C ₂₄ aryl groups.

X ₄ and X ₅ are independently of each other CR ′ or N and at least one is N.

R 'is hydrogen; heavy hydrogen; C ₆ -C ₂₄ aryl group; may be selected from the group consisting of.

Ar ³ is an aryl group of C ₆ -C ₂₄ ; It may be selected from the group consisting of; C ₂ -C ₂₄ heterocyclic group.

X ₆ to X ₉ are each independently CR ″ or N, at least one is CR ″, and all are CR ″.

R ″ represents hydrogen, deuterium, and a bond with the linking group L ³ .

Y ₁ is S or O.

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

In another embodiment of the present invention, the present invention comprises a first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer provides an organic electric device including the compound represented by Chemical Formula 1. Specifically, the present invention provides an organic electric device comprising the compound represented by Formula 2 or Formula 3 in the organic material layer. More specifically, the present invention provides an organic electric device comprising a compound represented by the respective formula in the organic material layer.

In another embodiment of the present invention, the present invention provides an organic electric device comprising at least an electron transport layer in the organic material layer, the compound containing the compound in the electron transport layer.

In another embodiment of the present invention, the present invention is an optical 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 comprising a.

In another embodiment of the present invention, the present invention provides an organic electroluminescent device is formed by any one of the organic layer is spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process and roll-to-roll process do.

In another embodiment of the present invention, the present invention is a display device including an organic electric element comprising the organic material layer; And a controller for driving the display device.

In another embodiment of the present invention, the organic electroluminescent device according to the present invention is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination It can be one.

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

Synthesis of the compound was carried out in the following manner.

I. Synthesis of Formula 1

The compound represented by Formula 1 according to the present invention may be synthesized by the reaction route of Scheme 1 below, but is not limited thereto.

<Scheme 1>

1.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>

(1) Sub 1-2 synthesis

1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole (1 equivalent), 1,3,5-tribromobenzene (1 equivalent), Pd (PPh ₃ ) ₄ (0.03 eq), K ₂ CO ₃ was (3 equiv.) at reflux for I, 24 hours after dissolved in anhydrous THF and a small amount of water. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give 1- (3,5-dibromophenyl) -1H-indole.

(2) Sub 1-4 Synthesis

1- (3,5-dibromophenyl) -1H-indole (1 equiv) and 1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole (1 equiv) ), Pd (PPh ₃ ) ₄ (0.03 equiv) and K ₂ CO ₃ (3 equiv) were dissolved in anhydrous THF and a small amount of water and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give 1,1 '-(5-bromo-1,3-phenylene) bis (1H-indole )

(3) Sub 1 Synthesis

After dissolving 1,1 '-(5-bromo-1,3-phenylene) bis (1H-indole) (1 equiv) in DMF in a round bottom flask, Bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc (3 equiv) were added and stirred at 90 ° C. After the reaction was completed, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallization to obtain 1,1 '-(5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (1H-indole) was obtained.

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

TABLE 1

2.Example of Sub 2

Examples of Sub 2 of Scheme 1 are as follows, but are not limited thereto, and their FD / MS are shown in Table 2 below.

TABLE 2

3. Synthesis of Final Product of Formula 1

Sub 1 (1 equiv) was dissolved in THF, then Sub 2 (1.1 equiv), Pd (PPh ₃ ) ₄ (0.03 equiv), NaOH (3 equiv), and water were added followed by stirring under reflux. 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 final product.

(1) 1-1 synthesis

<Scheme 3>

1,1 '-(5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (1H-indole) (8.7g, 20mmol) After dissolving in THF, 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5 g, 24 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (2.4 g, 60 mmol) ), And water was added, followed by stirring under reflux. 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 8.0g (yield: 74%) of the final product.

(2) 1-15 synthetic

<Scheme 4>

1,1 '-(5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (2,3-dimethyl-1H-indole) (9.8 g, 20 mmol) in THF, followed by 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (9.3 g, 24 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (2.4 g, 60 mmol) and water were added, followed by stirring under reflux. 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 9.7 g (yield: 72%) of the final product.

(3) 1-24 synthesis

Scheme 5

1,1 '-(5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (2-phenyl-1H-indole) (11.7 g, 20 mmol) in THF, followed by 2,2 '-(5-bromo-1,3-phenylene) dipyridine (7.5 g, 24 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH ( 2.4 g, 60 mmol) and water were added, followed by stirring under reflux. 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 substance was purified by silicagel column and recrystallized to obtain 10.4 g (yield: 75%) of the final product.

(4) 1-30 synthetic

<Scheme 6>

1,1 '-(5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (1H-indole) (8.7g, 20mmol) After dissolving in THF, 2-chloro-4-phenylquinazoline (5.8g, 24mmol), Pd (PPh ₃ ) ₄ (0.7g, 0.6mmol), NaOH (2.4g, 60mmol) and water were added, followed by stirring under reflux. 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 purified by silicagel column and recrystallized to obtain 8.0g (yield: 78%) of the final product.

(5) 1-59 synthetic

Scheme 7

1,1 '-(5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (2-phenyl-1H-indole) (11.7 g, 20 mmol) in THF, and then 4-([1,1'-biphenyl] -4-yl) -2- (4-bromophenyl) quinazoline (10.5 g, 24 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (2.4 g, 60 mmol) and water were added, followed by stirring under reflux. 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 substance was purified by silicagel column and recrystallized to obtain 12.3 g (yield: 75%) of the final product.

On the other hand, the FD-MS value of the final product of the formula (1) prepared according to the synthesis examples as described above are shown in Table 3.

TABLE 3

Manufacturing Evaluation of Organic Electrical Device

Experimental Example Green Organic Electroluminescent Device (electron transport layer)

First, 4,4 ', 4 "-Tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as 2-TNATA) is vacuum deposited to a thickness of 60 nm on the ITO layer (anode) formed on the glass substrate. After forming the layer, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as NPD) was vacuum deposited to a thickness of 60 nm on the hole injection layer. A transport layer was formed on the hole transport layer, followed by 4,4'-N, N'-dicarbazole-biphenyl (hereinafter abbreviated as CBP) as a host and tris (2-phenylpyridine) -iridium (hereinafter, Ir). (ppy, abbreviated as ₃ ) as a dopant, and a mixture doped at 95: 5 weight was vacuum deposited to a thickness of 30 nm to form a light emitting layer, followed by (1,1'-bisphenyl) -4- on the light emitting layer. Oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm to form a hole blocking layer, and is represented by Formula 1 of the present invention on the hole blocking layer felled One of the compounds was vacuum-deposited to a thickness of 40 nm to form an electron transport layer, and then an electron injection layer was formed by depositing LiF, which is a halogenated alkali metal, to a thickness of 0.2 nm on the electron transport layer, followed by Al to 150 nm thickness. An organic electroluminescent device was manufactured by forming a cathode by vapor deposition.

[Comparative Example]

Comparative Example (1)

An organic electric device was manufactured in the same manner as in Experimental Example 1, except that Comparative Compound 1 was used instead of the compound represented by Formula 1 of the present invention as an electron transport layer material.

<Comparative Compound 1> Alq ₃

Comparative Example (2)

An organic electric device was manufactured according to the same method as the Experimental Example except that Comparative Compound 2 was used instead of the compound represented by Formula 1 of the present invention as an electron transport layer material.

Comparative Compound 2

Comparative Example (3)

An organic electric device was manufactured according to the same method as the Experimental Example except that Comparative Compound 3 was used instead of the compound represented by Formula 1 of the present invention as an electron transport layer material.

Comparative Compound 3

Comparative Example (4)

An organic electroluminescent device was manufactured in the same manner as in Experimental Example except that Comparative Compound 4 was used instead of the compound represented by Formula 1 of the present invention as an electron transport layer material.

 Comparative Compound 4

Comparative Example (5)

An organic electric device was manufactured according to the same method as the Experimental Example except that Comparative Compound 5 was used instead of the compound represented by Formula 1 of the present invention as an electron transport layer material.

Comparative Compound 5

Thus, the forward bias DC voltage was applied to the organic electroluminescent devices according to the experimental examples (Experimental Example (1) to (59)) and Comparative Example (Comparative Example (1) to Comparative Example (5) prepared as described above. The electroluminescence (EL) characteristics were measured with a PR-650 from Research Inc., and the T95 lifetime was measured using a life-time measurement device manufactured by McScience Inc. at a luminance of 5000 cd / m 2.

[Table 4] shows the device fabrication for the experimental example (Experimental Example (1) to Experimental Example (59)) and the comparative example (Comparative Example (1) to Comparative Example (5)) to which the compound according to the present invention is applied and its The evaluation result is shown.

TABLE 4

As can be seen from the results of Table 4, the organic electroluminescent device (OLED) using the compounds of the present invention is used as an electron transport layer material, the driving voltage and higher efficiency and higher than the conventional compound 1 Alq ₃ widely used Lifespan. This is the case of the compounds of the hand, indicate the dopant T ₁ value (2.0 eV) of the Alq ₃ is significantly lower T ₁ values using as an electron transporting layer than the Ir (ppy) ₃ of the T ₁ value (2.4 eV) used in the light emitting layer invention, It exhibits a T ₁ value (2.5 ev to 2.6 ev) that is generally higher than the T ₁ value of Ir (ppy) ₃ (2.4 eV), thereby improving hole blocking ability as well as excitons in the light emitting layer. This is because the relative probability of staying well increases.

Subsequently, comparing the results of the organic electroluminescent device of the compounds of the present invention and Comparative Compounds 2 to 5, the efficiency and lifespan of Comparative Compounds 2 to 5 in which Het comprises a five-membered ring is a compound of the present invention. It can be seen that it is lower. In addition, comparable compound 3, which has a carbazole structure, was higher in lifespan than comparable compound 2, which was an indole structure. It was confirmed that the low life. This means that the compound containing the five-membered ring in Het has a relatively low thermal stability, and the T1 value is relatively low, resulting in a decrease in hole blocking ability, thereby reducing the lifespan.

In addition, when using the compounds of the present invention it was confirmed that a significant improvement in the relatively low driving voltage and efficiency and life. It is believed that the compounds of the present invention have better charge balance of holes and electrons in the emission layer than Comparative Compounds 2 to 5, thereby improving the performance of the device and reducing thermal damage, thereby increasing the lifespan.

In addition, the evaluation results of the above-described device fabrication described the device characteristics from the viewpoint of the electron transport layer, but materials commonly used as the electron transport layer include organic electrons such as the electron injection layer, the hole injection layer, the hole transport layer, the light emitting auxiliary layer, and the light emitting layer. The organic layer of the device can be used in combination with a single or other material. Therefore, the compounds of the present invention can be used in a single or other materials in addition to the electron transport layer, for example, other organic material layers, for example, electron injection layer, hole injection layer, hole transport layer, light emitting auxiliary layer and light emitting layer.

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 No. 119 (a) (35 USC § 119 (a)) of the US Patent Act No. 10-2013-0113331, filed with South Korea on September 24, 2013. 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 (10)

1. A compound represented by the following formula (1).

   <Formula 1>

   

   [In Formula 1,

   R ¹ to R ¹² are I) independently of each other hydrogen; heavy hydrogen; C ₆ -C ₂₄ aryl group; C ₂ ~ C ₂₄ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; selected from the group consisting of, or II) R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² may combine with each other to form a ring,

   L ¹ to L ³ are each independently a single bond; C ₆ ~ C ₂₄ arylene group; Fluorenylene group; selected from the group consisting of,

   Het is a C ₂ ~ C ₆₀ heterocyclic group containing at least one nitrogen,

   

   ,

   

   ,

   

   ,

   

   ),

   n is an integer of 1 or 2.

   Wherein the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, fluorenylene group are each deuterium; halogen; silane group; siloxane group Boron group, germanium group, cyano group, nitro group, -LN (R _a ) (R _b ); C ₁ ~ C ₂₀ of the import alkylthio; C ₁ -C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to 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; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; And C ₈ ~ C ₂₀ An arylalkenyl group; It may be further substituted with one or more substituents selected from the group consisting of, wherein L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And O, N, S, Si, and a C ₂ ~ C ₆₀ containing at least one hetero atom of the P heterocyclic group; is selected from the group consisting of, wherein R _a and R _b are independently C ₆ ~ C with each other An aryl group of ₆₀ ; Fluorenyl group; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P.]
2. The method of claim 1,

   Compound represented by the following formula (2) or formula (3).

   <Formula 2> <Formula 3>

   

   [In Formula 2 and Formula 3,

   R ¹ to R ¹² , L ¹ to L ³ and Het are the same as defined in claim ^1, and Het ¹ and Het ² are defined to be the same as Het as defined in claim 1]
3. The method of claim 1,

   Het of Formula 1 is a compound characterized in that

   

   [In the above formula,

   X ₁ to X ₃ are independently of each other CR or N, at least one is N,

   R is hydrogen; heavy hydrogen; C ₆ -C ₂₄ aryl group; It is selected from the group consisting of,

   Ar ¹ and Ar ² are C ₆ -C ₂₄ aryl groups,

   X ₄ and X ₅ are each independently CR ′ or N, at least one is N,

   R 'is hydrogen; heavy hydrogen; C ₆ -C ₂₄ aryl group; It is selected from the group consisting of,

   Ar ³ is an aryl group of C ₆ -C ₂₄ ; C ₂ -C ₂₄ heterocyclic group; selected from the group consisting of,

   X ₆ to X ₉ independently of each other is CR ″ or N, at least one is CR ″, except that all are CR ″, wherein R ″ represents a bond with hydrogen, deuterium, a linking group L ³ ,

   Y ₁ is S or O.]
4. The method of claim 1,

   Compound which is any one of the following compounds.

   

   
5. 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 any one of claims 1 to 4.
6. The method of claim 5,

   The organic material layer is an organic electronic device, characterized in that it comprises an electron transport layer containing the compound.
7. The method of claim 5,

   And an optical efficiency improvement layer formed on at least one of one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer.
8. The method of claim 5,

   The organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process.
9. A display device comprising the organic electroluminescent element of claim 5; And

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

    The organic electroluminescent device is an electronic device, characterized in that at least one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor and a device for monochrome or white illumination.

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