KR100707482B1 - Arylphosphine oxide compounds, arylphosphine sulfide compounds or arylphosphine selenide compounds and organic electroluminescence devices using the same - Google Patents

Abstract

A new structure of aryl phosphine oxide based compounds is provided. The organic EL device including the arylphosphine oxide compound in the electron transport layer, the light emitting layer, or the light emitting / electron transport layer can be driven at low power, and the luminous efficiency is maintained even during long time driving to achieve long life of the organic EL device. .

Description

Aryl phosphine oxide compounds, aryl phosphine sulfide compounds or aryl phosphine selenide compounds and organic electroluminescent devices using the same {Arylphosphine oxide compounds, arylphosphine sulfide compounds or arylphosphine selenide compounds and organic electroluminescence devices using the same}

1 shows a cross-sectional structure of an organic EL device according to an embodiment of the present invention.

2 is a graph showing the correlation between the voltage and the luminance of the organic EL device using the compound (18) obtained in Example 12 and the organic EL device of the comparative example corresponding to the conventional example.

3 is a graph showing the correlation between the voltage and current of the organic EL device using the compound (18) obtained in Example 12 and the organic EL device of Comparative Example corresponding to the conventional example.

4 is a graph showing a relationship between time and efficiency during constant voltage driving of the organic EL device using the compound (18) obtained in Example 12 and the organic EL device of the comparative example corresponding to the conventional example.

The present invention relates to an aryl phosphine oxide compound, an aryl phosphine sulfide compound or an aryl phosphine selenide compound, and an organic electroluminescent device (hereinafter referred to as an organic EL device) using the same, and more particularly, to an aryl having a new structure. The present invention relates to a phosphine oxide compound and an organic EL device capable of driving low power using the same and achieving long-term lifespan of an organic EL device by maintaining light emission efficiency even during long time driving.

In the field of flat panel displays, LCD devices are increasingly being used in various fields because of low driving voltage, low power consumption, and little flickering phenomenon. However, the LCD device has a disadvantage in that the contrast changes according to the viewing angle, that is, the viewing angle is narrow and the backlight consumes a large power consumption.

Organic EL devices have recently attracted attention as high-brightness flat panel display devices that can overcome the disadvantages of such LCD devices. An organic EL device is a light emitting device that expresses an image by using luminescence by fluorescence or phosphorescence of an organic light emitting material and has a structure in which an organic light emitting layer made of an organic light emitting material is inserted between a cathode and an anode. The organic EL device may include some or all of an electron transport layer, a hole transport layer, an electron injection layer, and a hole injection layer in order to improve the efficiency of the light emitting layer, and if necessary, a hole blocking layer, And further including an electron blocking layer or a hole blocking / electron transport layer (meaning a layer that simultaneously performs two functions of hole blocking and electron transport. That is, in the present specification, / means and). Can be.

The organic EL device emits light by the following mechanism. That is, a voltage is applied between the cathode and the anode, holes are supplied through the anode, electrons are supplied to the light emitting layer through the cathode, and holes and electrons are combined to bring the light emitting material into an excited state. When the excited luminescent material returns to the ground state, the emitted light emits energy corresponding to the energy difference between the excited state and the ground state in the form of light. The organic EL device can control the light emission color by appropriately selecting a host light emitting material in the light emitting layer and a guest light emitting material used therewith.

In order to fundamentally improve the efficiency of the organic EL device, it is essential to develop a light emitting material having a high luminous efficiency, a high efficiency electron transport material, and a hole transport material. These light emitting materials, electron transporting materials and the like should have high stability and high workability as well as high efficiency.

As a representative example of a light emitting material for an organic EL device (also sometimes acting as an electron transporting material), green light emitting material and electron transporting material AlQ3 [tris- (8-hydroxy quinoline) aluminum], and a blue light emitting material 4,4 ' -Bis (2,2'-diphenyl vinyl) -1,1'-biphenyl (DPVBi), 4- (dicyanomethylene) -2-t-butyl-6- (1,1,7) , 7-tetramethyljulolidyl-9-enyl) 4H-pyran (DCJTB) etc. are mentioned.

However, such an organic light emitting material is insufficient in luminance, heat resistance, etc. in large-area organic EL devices, and many studies have been made to overcome them.

Many studies have been made on hole transport materials. As the hole transport materials, arylamine derivatives are basically used, and various types of derivatives have been developed to have high stability and efficiency.

In the case of electron transport materials, AlQ3 has been used continuously until now since Tang and Van Slyke (Appl. Phys. Lett. 1987, 51, 913) announced organic EL devices. Examples of electron transport materials other than AlQ3 include 2,5-diaryl silol derivatives (PyPySPyPy), perfluorinated compounds (PF-6P), Octasubstituted cyclooctatetraene compounds (COTs), and the like. Although these compounds are partially superior to AlQ3, there is a need for improvement in terms of overall efficiency and economics. AlQ3 is known to provide excellent electron molility and long life time of organic EL devices, but it is known that AlQ3 is decomposed by hole injection due to chemical instability.

Accordingly, it is an object of the present invention to provide an aryl phosphine oxide compound, an arylphosphine sulfide compound and an arylphosphine selenide compound having a novel molecular structure which is also useful as an electron transport material and in some cases a light emitting material.

Another object of the present invention is to provide an organic EL device in which the luminous efficiency is drastically improved by using the above-described aryl phosphine oxide compound, aryl phosphine sulfide compound or aryl phosphine selenide compound.

In order to achieve the above object, an embodiment of the present invention,

An aryl phosphine oxide compound, an aryl phosphine sulfide compound, or an aryl phosphine selenide compound represented by the following Chemical Formula 1 (hereinafter, sometimes referred to simply as "aryl phosphine oxide compound") is provided:

[Formula 1]

Here, X ₁ is a substituted or unsubstituted arylene group of C6 to C18 or a substituted or unsubstituted divalent heterocyclic group of C4 to C18,

Y is oxygen, sulfur or selenium,

n represents the integer of 0-5.

Ar ₁ is a substituted or unsubstituted aromatic group of C18 to C60 represented by the following formula.

Wherein Ar ₄ and Ar ₅ may be the same as or different from C6 to C30 substituted or unsubstituted aryl group or C4 to C30 substituted or unsubstituted heterocyclic group, C4 to C30 substituted or unsubstituted arylamino group or C4 to C30 is a substituted or heterocyclicamino group.

Ar ₂ and Ar ₃ may be the same or different and are a C6 to C30 substituted or unsubstituted aryl group or a C4 to C30 substituted or unsubstituted heterocyclic group.

In order to achieve the above object, another embodiment of the present invention,

It provides an aryl phosphine oxide compound represented by the formula (2):

[Formula 2]

Here, Ar ₆ , Ar ₇ , Ar ₈ , and Ar ₉ mean the same as Ar ₂ and Ar ₃ , which may be the same or different, and X ₂ and X ₃ mean the same as X ₁ , which may be the same or different. When X ₂ and X ₃ are substituted at positions 9 and 10 of the anthracene moiety, m and n are integers of 1 to 5, and an aryl group, a heterocyclic group, When an arylamino group or heterocyclic amino group is substituted, m and n are integers of 0-5.

In order to achieve the above another object, the present invention provides an organic EL device comprising an aryl phosphine oxide compound represented by the formula (1) or 2 in an electron transport layer, a light emitting layer, or a light emitting / electron transport layer.

The aryl phosphine oxide compound of the novel structure represented by Formula 1 or 2 according to the present invention is useful as an electron transport material or a light emitting material. This compound is particularly useful as an electron transport material. The organic EL device of the present invention including this compound in the electron transport layer or the light emitting layer can be driven at low power, and the luminous efficiency is maintained even during long driving, thereby achieving long life of the organic EL device.

An organic electroluminescent device comprising an aryl phosphine oxide compound according to the present invention in an electron transport layer, a light emitting layer, or a light emitting / electron transport layer may be used in fields such as flat panel display devices and lighting equipment.

Hereinafter, the aryl phosphine oxide compound and the organic EL device including the same according to the present invention will be described in detail.

An aryl phosphine oxide compound according to one embodiment of the present invention is represented by the following formula (1).

[Formula 1]

Here, X ₁ is a substituted or unsubstituted arylene group of C6 to C18 or a substituted or unsubstituted divalent heterocyclic group of C4 to C18,

Y is oxygen, sulfur or selenium,

n represents the integer of 0-5.

Preferred examples of X ₁ include the following arylene groups or divalent heterocyclic groups:

In addition, Ar ₁ is a substituted or unsubstituted aromatic group of C18 to C60 represented by the following formula.

Wherein Ar ₄ and Ar ₅ may be the same as or different from C6 to C30 substituted or unsubstituted aryl group or C4 to C30 substituted or unsubstituted heterocyclic group, C4 to C30 substituted or unsubstituted arylamino group or C4 to C30 is a substituted or heterocyclicamino group. Herein, the arylamino group or heterocyclic amino group means that at least one, preferably both, of the hydrogen atoms of the amino group represented by -NH ₂ are substituted with the aryl group or heterocyclic group described above.

Preferred examples of Ar ₄ and Ar ₅ include the following aryl groups, heterocyclic groups, arylamino groups or heterocyclic amino groups.

Also, Ar ₂ and Ar ₃ may be the same or different and are a substituted or unsubstituted aryl group of C6 to C30 or a substituted or unsubstituted heterocyclic group of C4 to C30.

Preferred examples of Ar ₂ and Ar ₃ include the following aryl group or heterocyclic group.

An aryl phosphine oxide compound according to another embodiment of the present invention is represented by the following formula (2).

[Formula 2]

Here, Ar ₆ , Ar ₇ , Ar ₈ , and Ar ₉ mean the same as Ar ₂ and Ar ₃ , which may be the same or different, and X ₂ and X ₃ may be the same or different and equal to X ₁ When X ₂ and X ₃ are substituted at positions 9 and 10 of the anthracene moiety, m and n are integers of 1 to 5, and an aryl group and a complex at positions 9 and 10 of the anthracene moiety. When the ventilating, arylamino group or heterocyclic amino group is substituted, m and n are integers of 0-5.

Examples of the substituent in the case where Ar ₁ to Ar ₉ and X ₁ to X ₃ are substituted include, but are not limited to, an alkyl group, an alkoxy group, thioalkoxy, and the like.

The aryl phosphine oxide compound represented by the formula (1) or (2) according to the present invention is useful as an electron transport material and / or a luminescent material as will be apparent from the following examples. The organic EL device of the present invention comprising this compound in an electron transport layer or a light emitting layer can be driven with low power and can achieve long life of the organic EL device.

The aryl phosphine oxide compound represented by Formula 1 or 2 according to the present invention can be easily molded into a uniform amorphous film by vacuum deposition. Therefore, by using this compound, an organic EL device can be easily produced at low cost. In addition, since the compound generally has a high melting point, the organic EL device manufactured using the compound is thermally stable, and thus can exhibit an excellent durability.

Specific examples of the arylphosphine oxide compound of Formula 1 include the following.

,

,

   (Compound 1) (Compound 2)

,

,

    (Compound 3) (Compound 4)

,

,

       (Compound 5) (Compound 6)

,

,

       (Compound 7) (Compound 8)

,

      (Compound 9) (Compound 10)

,

,

      (Compound 11) (Compound 12)

,

,

       (Compound 13) (Compound 14)

,

,

       (Compound 15) (Compound 16)

,

,

      (Compound 17) (Compound 18)

                      (Compound 19)

Specific examples of the arylphosphine oxide compound of Formula 2 include the following.

                         (Compound 20)

                         (Compound 21)

                        (Compound 22)

                         (Compound 23)

                         (Compound 24)

                         (Compound 25)

,

,

         (Compound 26) (Compound 27)

,

,

         (Compound 28) (Compound 29)

Next, a method for preparing an arylphosphine oxide compound of Formula 1 or 2 according to the present invention having the above structure will be described in detail.

The arylphosphine oxide compound of Formula 1 or 2 may be obtained through the following four step reaction.

That is, referring to Scheme 1, in the first step, the primary arylamine is reacted with copper bromide and tert-butyl nitrite by a bromination reaction and a Sandmeyer reaction to obtain an aryl halogen compound.

In the second step, the substituted aryl halogen compound is subjected to lithium substitution using basic n-butyllithium, followed by ketone addition and hydrolysis to obtain a dialcohol compound. Next, this dialcohol compound is dehydrated to obtain an anthracene halide derivative having an aryl substituent.

In the third step, the anthracene halide derivative is reacted with aryl force by 1) lithium substitution with basic n-butyllithium and with chlorodiphenylphosphine or 2) with diphenylphosphine boronic acid compound under Pd-based catalyst. Pin compounds can be obtained.

Scheme 1

First step:

2nd step:

3rd step:

In the fourth step, the aryl phosphine compound is oxidized with hydrogen peroxide (H ₂ O ₂ ), sulfur (S), or selenium (Se) as an oxidizing agent, and then the desired aryl phosphine oxide compound, arylphosphine sulfide compound, or aryl A phosphine selenide type compound can be obtained.

Alternatively, the arylphosphine oxide compound of Formula 1 or 2 according to the present invention can also be obtained through the following three step reaction.

That is, referring to Scheme 2, the aryl halogen compound substituted in the first step is subjected to lithium substitution using basic n-butyllithium, followed by ketone addition and hydrolysis to form a dialcohol compound. The dealcohol compound is then dehydrated to obtain an anthracene compound with an aryl substituent.

In the second step, anthracene compound having an aryl substituent is reacted with 1) lithium substitution with basic n-butyllithium and chlorodiphenylphosphine or 2) lithium substitution with 2 moles of n-butyllithium By reacting with 2 moles of chlorodiphenylphosphine, an asymmetric or symmetrical aryl phosphine compound can be obtained.

Scheme 2

First step:

Second step:

In the third step, the aryl phosphine compound obtained in the previous step is oxidized with hydrogen peroxide (H ₂ O ₂ ), sulfur (S), or selenium (Se), which is the desired aryl phosphine oxide compound, aryl phosphine sulfide type A compound or an aryl phosphine selenide type compound can be obtained.

Ar in Schemes 1 and 2 represents an aryl group or a heterocyclic group, preferably a substituted or unsubstituted aryl group of C6 to C30 or a substituted or unsubstituted heterocyclic group of C4 to C30. In addition to the synthetic route, the compound of Formula 1 or 2 may be obtained by appropriately changing the synthesis step and method according to the reactants.

On the other hand, the organic EL device using the aryl phosphine oxide compound represented by the formula (1) or 2 can be realized in various structures. Basically, as shown in FIG. 1, the organic EL device 50 according to the exemplary embodiment of the present invention includes a light emitting layer 7, a hole transport layer 9, and an anode between the anode 3 and the cathode 5. The electron transport layer 11 has a structure inserted. The compound of Formula 1 or 2 of the present invention is used in the electron transport layer 11 and / or the light emitting layer (7). Further, in addition to the light emitting layer 7 and the hole transport layer 9, an electron injection layer, a hole injection layer, a hole blocking layer, and / or an electron blocking layer may be separately stacked to improve the luminous efficiency of the organic EL device.

The organic EL device having the above structure is preferably supported by a transparent substrate (1 in FIG. 1). The material of the transparent substrate is not particularly limited as long as it has good mechanical strength, thermal stability and transparency. For example, glass, a transparent plastic film, etc. can be used.

As the anode material of the organic EL device of the present invention, a metal, an alloy, an electrically conductive compound having a work function of 4 eV or more, or a mixture thereof can be used. Specifically, transparent conductive materials such as Au or CuI, ITO (indium tin oxide), SnO ₂ and ZnO which are metals are mentioned. The thickness of the positive electrode film may be about 10-200 nm.

As the negative electrode material of the organic EL device of the present invention, a metal, an alloy, an electrically conductive compound or a mixture thereof having a work function of less than 4 eV can be used. Specifically, Na, Na-K alloy, calcium, magnesium, lithium, lithium alloy, indium, aluminum, magnesium alloy, aluminum alloy is mentioned. In addition, aluminum / AlO ₂ , aluminum / lithium, magnesium / silver or magnesium / indium may be used. The thickness of the negative electrode film may be about 10-200 nm.

In order to increase the luminous efficiency of the organic EL device, at least one electrode should preferably have a light transmittance of 10% or more. The sheet resistance of the electrode is preferably several hundreds of mm 3 / mm or less. The thickness of the electrode is 10 nm to 1 탆, preferably 10 to 400 nm. Such an electrode may be manufactured by forming the above electrode material into a thin film through vapor deposition or sputtering such as chemical vapor deposition (CVD), physical vapor deposition (PVD), or the like.

As the hole transport material and the hole injection material, any of those materials commonly used as the hole transport material in the photoconductive material and a known material used for forming the hole transport layer or the hole injection layer of the organic EL device can be used. For example, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (hereinafter referred to as TPD), N, N'-diphenyl-N , N'- dinaphthyl-4,4'-diaminobiphenyl, N, N, N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl, N, N, N'N '-Tetraphenyl-4,4'-diaminobiphenyl; Porphyrin compound derivatives such as Copper (II) 1,10,15,20-tetraphenyl-21H, 23H-porphyrin and the like; Polymers having an aromatic tertiary amine in the main or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N-tri (p-tolyl) amine, 4, 4 ', Triarylamine derivatives such as 4'-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine; Carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; Phthalocyanine derivatives such as metal phthalocyanine and copper phthalocyanine; Starburst amine derivatives; Enamine stilbene derivatives; Derivatives of aromatic tertiary amines and styryl amine compounds; And polysilanes.

In addition to the compound of Formula 1 or 2 of the present invention, the electron transport layer may be a known electron transport material, for example, AlQ3, 2,5-diaryl silol derivative (PyPySPyPy), perfluorinated compound (PF-6P), Octasubstituted cyclooctatetraene Compounds (COTs) and the like can be mixed.

In the organic EL device of the present invention, the hole injection layer and / or the hole transport layer may be formed of a single layer containing one or more kinds of the above-described compounds, or may be formed of a plurality of layers containing different kinds of compounds stacked on each other. Can be configured.

As other light emitting materials used in the organic EL device of the present invention, known light emitting materials such as photoluminescent fluorescent materials, fluorescent brighteners, laser dyes, organic scintillators, and reagents for fluorescence analysis can be used. Specific examples include polyaromatic compounds such as AlQ 3, anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone; Oligophenylene compounds such as quiterphenyl; 1,4-bis (2-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-methyl-5-phenyl-2-oxazolyl) benzene, 1 , 4-bis (5-phenyl-2-oxazolyl) benzene, 2,5-bis (5-t-butyl-2-benzoxazolyl) thiophene, 1,4-diphenyl-1,3-butadiene, Scintillators for liquid scintillation such as 1,6-diphenyl-1,3,5-hexatriene, 1,1,4,4-tetraphenyl-1,3-butadiene; Metal complexes of auxin derivatives; Coumarin pigments; Dicyano methylene pyran pigment; Dicyano methylenethiopyran pigments; Polymethine pigments; Oxobenzanthracene pigment; Xanthene pigments; Carbostyryl pigments; Perylene pigments; Oxazine compounds; Stilbene derivatives; Spiro compounds; An oxadiazole compound etc. are mentioned.

Each layer constituting the organic EL device of the present invention can be formed into a thin film through a known method such as vacuum deposition, spin coating or casting, or can be produced using a material used in each layer. There is no particular limitation on the film thickness of each layer, and may be appropriately selected depending on the properties of the material, but can usually be determined in the range of 2nm to 5000nm.

Since the compounds of Formulas 1 and 2 according to the embodiments of the present invention and other embodiments can be formed by vacuum deposition, the thin film forming process is simple and can be easily obtained as a homogeneous thin film having little pin holes. There is an advantage. When the compounds of the formulas (1) and (2) are formed into thin films by vacuum deposition, the preferred deposition conditions are boat heating temperatures of 50 to 400 ° C., depending on the type of the compound and the crystal structure and the associative structure of the desired molecular accumulation film. Vacuum degrees of ⁻⁷ to 10 ⁻⁴ torr, deposition rates of 0.01 to 5 nm / sec, substrate temperatures of 0 to 100 ° C., and film thicknesses of 10 nm to 200 nm are preferred.

The organic EL device formed of the above-described anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode using the compound represented by any one of Formulas 1 or 2 of the present invention will be described below. same.

First, a hole injection layer is formed using a hole injection material on an ITO transparent substrate having a thickness of 1 μm or less, preferably 10-200 nm. Subsequently, a hole transport layer is formed so as to cover the hole injection layer with any one of the above hole transport materials. Subsequently, the light emitting layer is formed so as to cover the hole transport layer with any one of the above light emitting materials. Subsequently, an electron transport layer is formed on the light emitting layer by using the compound of Formula 1 or 2. Finally, an organic EL element can be obtained by coating the above-mentioned negative electrode material on the electron transport layer with a film thickness of usually 1 mu m or less to form a negative electrode. When a DC voltage is applied to the organic EL device obtained by using the positive electrode as the positive electrode and the negative electrode as the negative electrode, light emission can be observed through a transparent or opaque electrode (either positive or negative electrode, or both electrodes). .

The organic electroluminescent device including the aryl phosphine oxide compound according to the present invention described above in an electron transport layer, a light emitting layer or a light emitting / electron transport layer can be used in the field of flat panel display devices, lighting equipment and the like.

Hereinafter, a method of manufacturing an arylphosphine oxide compound and an organic EL device according to the present invention will be described in more detail with reference to Examples. However, this is for illustrative purposes and the scope of the present invention is not limited thereby.

Example 1 Synthesis of Aryl Phosphine Oxide Compounds of Compound (8)

First Step Reaction: 2-Bromoanthraquinone Synthesis

Copper bromide (CuBr ₂ , 55.5 g, 0.249 mol) was dissolved in 300 ml of acetonitrile in a 2000 ml three-necked flask equipped with a reflux condenser, and t-butyl nitrite (t-BuONO, 30 ml, 0.252 mol) was added thereto. 2-aminoanthraquinone (24.03 g, 0.124 mol) was dissolved in 400 ml of THF at 25 ° C. in the flask, and stirred for 20 hours after 30 minutes of addition.

After completion of the reaction, the reaction mixture was distilled, dried and water was added to pulverize the solid, followed by stirring for 30 minutes to obtain a solid. The solid was dissolved in dichloromethane, filtered and the filtrate was concentrated, and then purified by column with hexane / dichloromethane solution to give 30.4 g (85.4%) of light yellow pure 2-bromoanthraquinone.

Second Step Reaction: 2-bromo [9,10-di (α-naphthyl)] anthracene synthesis

1-bromonaphthalene (11.4 g, 55 mmol) was added to a 500 ml three-necked flask equipped with a reflux condenser, dissolved in 250 ml of THF under an argon atmosphere, and n-butyllithium (1.6 M, 33 ml, 53 mmol hexane solution) was added slowly, followed by stirring for 1 hour. Here, 2-bromoanthraquinone (7.23 g, 25 mmol) obtained in the first step was dissolved in 150 ml of THF, and then slowly added at the same temperature. After removing the cooling vessel and stirred for 5 hours at room temperature. A saturated ammonium chloride solution was added to the reaction mixture, followed by extraction with dichloromethane, followed by drying and recrystallization with petroleum ether to obtain 12.6 g (yield 92.8%) of a solid naphthyl alcohol compound. In a nitrogen atmosphere, dinaphthyl alcohol compound (12.6 g, 23.2 mmol) was dispersed in 250 ml of acetic acid, followed by potassium iodine (41.5 g, 250 mmol) and sodium hypophosphite hydrate (NaH ₂ PO ₂ H ₂ O 44 g, 500 mmol). It was refluxed for 4 hours after the addition. After cooling to room temperature, filtered, washed with water and dried to obtain 9.6 g of pale yellow 2-bromo [9,10-di (α-naphthyl)] anthracene (yield 81.4%).

Third Step Reaction: Synthesis of Compound (8)

After replacing the inside of a 500 ml three-necked flask equipped with a reflux condenser with argon, the flask was subjected to 2-bromo [9,10-di (α-naphthyl)] anthracene (15.2) obtained in the second step reaction. g, 30 mmol), dissolved in 250 ml of THF, and n-butyllithium (1.6 M, 20 ml, 32 mmol hexane solution) was slowly added at a temperature of −78 ° C. and stirred for 1 hour. Chloro diphenyl phosphine (6.62 g 30 mmol) was diluted in 100 ml of THF and added slowly at the same temperature. After removing the cooling vessel was stirred for 5 hours at room temperature. A saturated ammonium chloride solution was added to the reaction mixture, followed by extraction with dichloromethane. The dried material was dissolved in 200 ml of acetone, and 30% hydrogen peroxide (4.1 ml, 40 mmol) was added thereto, followed by stirring for 1 hour. The mixture was dried and column purified using a hexane / ethyl acetate / methanol mixed solution as an eluent to obtain 13.2 g of an aryl phosphine oxide compound of compound (8) (yield: 69.5%). The melting point of the obtained crystal was 318 ~ 320 ℃, NMR spectroscopic data was as follows.

NMR- ¹ H (400 MHz, CDCl ₃ ; ppm): δ = 7.09-7.24 (m, 9H), 7.30-7.59 (m, 16H), 7.63-7.75 (m, 1H), 7.68-7.73 (m, 1H) , 7.93-7.96 (t, 2H), 8.00-8.03 (q, 1H), 8.06-8.08 (d, 1H).

NMR- ³¹ P (400 MHz, CDCl ₃ ; ppm): δ = 31.26 (s).

Ms [M + H] = 631. .

Example 2 Synthesis of Aryl Phosphine Oxide Compounds of Compound (9)

First Step Reaction: 2-bromo [9,10-di (β-naphthyl)] anthracene synthesis

2-bromonaphthalene (5.17g, 25mmol) was added to a 500ml three-necked flask equipped with a reflux condenser, dissolved in 150ml of THF under argon atmosphere, and n-butyllithium (1.6M, 14.4ml) was used at a temperature of -78 ° C or lower. , 23 mmol hexane solution) was added slowly, and stirred for 1 hour. Here, 2-bromoanthraquinone (2.9 g, 10 mmol) obtained in the first step was dissolved in 100 ml of THF, and then slowly added at the same temperature. After removing the cooling vessel was stirred for 5 hours at room temperature. A saturated ammonium chloride solution was added to the reaction mixture, followed by extraction with dichloromethane, followed by drying. The dinaphthyl alcohol compound (15 g, 9.2 mmol) was dispersed in 120 ml of acetic acid under nitrogen atmosphere, followed by potassium iodine (16.6 g, 100 mmol) and sodium hypophosphite hydrate (NaH ₂ PO ₂ H ₂ O 17.6 g 200 mmol). It was refluxed for 4 hours after the addition. The reaction mixture was cooled to room temperature, filtered, washed with water and dried to obtain 3.5 g (yield 74.5%) of pale yellow 2-bromo [9,10-di (β-naphthyl)] anthracene.

Second Step Reaction: Synthesis of Compound (9)

After replacing the inside of a 500 ml three-necked flask equipped with a reflux condenser with argon, the flask was subjected to 2-bromo [9,10-di (β-naphthyl)] obtained in the first step reaction of Example 1. Anthracene (5.1 g 10 mmol) was added thereto, dissolved in 150 mL of THF, and n-butyllithium (1.6 M, 7.5 mL, 12 mmol hexane solution) was slowly added at a temperature of −78 ° C., followed by further stirring for 1 hour. Chloro diphenyl phosphine (2.2 g, 10 mmol) was diluted in 50 ml of THF and added slowly at the same temperature. After removing the cooling vessel was stirred for 5 hours at room temperature. Saturated ammonium chloride solution was added to the reaction mixture, followed by extraction with dichloromethane, and the dried material was dissolved in 200 ml of acetone. Then, 30% hydrogen peroxide (1.5 ml, 15 mmol) was added, followed by stirring for 1 hour. The reaction mixture was dried and column purified using a hexane / ethyl acetate / methanol mixture as eluent to obtain 5 g (yield 79.4%) of pure yellow compound (9). The melting point of the obtained crystal was 188 ~ 189 ℃, NMR spectroscopic data was as follows.

NMR- ¹ H (400 MHz, CDCl ₃ ; ppm): δ = 7.18-7.19 (m, 5H), 7.25-7.27 (m, 1H), 7.34-7.42 (m, 3H), 7.49-7.54 (m, 4H) , 7.56 ~ 7.60 (m, 6H), 7.67 ~ 7.71 (m, 1H), 7.76 ~ 7.83 (m, 5H), 7.87 ~ 7.89 (d, 1H), 7.94 ~ 7.93 (m, 1H), 7.96 ~ 7.98 ( m, 2H), 8.00-8.01 (m, 1H), 8.01-8.02 (d, 1H).

NMR- ³¹ P (400 MHz, CDCl ₃ ; ppm): δ = 31.73 (s).

Ms [M + H] = 631.

Example 3 Synthesis of Aryl Phosphine Oxide Compounds of Compound (10)

First Step Reaction: Synthesis of 2-formyl [9,10-di (α-naphthyl)] anthracene

After replacing the inside of a 250 ml three-necked flask equipped with a reflux condenser with argon, the flask was subjected to 2-bromo [9,10-di (α-naphthyl)] obtained in the second step reaction of Example 1. Anthracene (5.1 g 10 mmol) was added thereto, dissolved in 150 mL of THF, and n-butyllithium (1.6 M, 7.5 mL, 12 mmol hexane solution) was slowly added at a temperature of −78 ° C., followed by further stirring for 1 hour. To this was added DMF (1.1 g, 15 mmol) slowly at the same temperature. After removing the cooling vessel, the mixture was further stirred at room temperature for 5 hours. Saturated ammonium chloride solution was added to the reaction mixture, followed by extraction with dichloromethane. The dried material was purified by column purification using a mixture of hexane / dichloromethane as eluent to obtain pure yellow 2-formyl [9,10-di (α- Naphthyl)] anthracene 2.5 g (yield 54.6%).

Second Step Reaction: Synthesis of 4-bromomethylphenyl diphenylphosphine oxide

After replacing the inside of a 250 ml three-necked flask equipped with a reflux condenser with argon, 4-methylphenyl diphenylphosphine oxide (5.8 g, 20 mmol) and N-Bromosuccinimide (NBS) (3.9 g, 22 mmol) were added to the flask. , 0.6 g of AIBN, and 60 ml of CCl ₄ were added and then refluxed for 3 hours with stirring. The reaction mixture was cooled to room temperature, extracted with dichloromethane, and dried. The obtained material was purified by column purification using a hexane / dichloromethane mixed solution as an eluent. Pure light brown 4-bromomethylphenyl diphenylphosphine oxide 6.5g (yield 87.8 %) Was obtained.

Third Step Reaction: Synthesis of Compound (10)

Into a 100 ml three-necked flask equipped with a reflux condenser, 4-bromomethylphenyl diphenylphosphine oxide (0.78 g, 2.1 mmol) was added triethylphosphite (0.4 g, 2.3 mmol) under an argon atmosphere and stirred for 4 hours. Heated to reflux. Excess triethylphosphite and byproduct ethyl bromide were then removed by distillation under reduced pressure. The residue was cooled to give 0.88 g of phosphonate compound crystals (yield 97.8%).

After replacing the inside of a 100 ml three-necked flask equipped with a reflux condenser with argon, the flask was subjected to 2-formyl [9,10-di (α-naphthyl)] anthracene (0.9, 2 mmol) and the above force. 0.88 g of phonate compound was added thereto, dissolved in 60 ml of THF, and t-BuOK (0.34 g, 0.3 mmol) was added thereto, followed by stirring for 10 hours while refluxing. Saturated ammonium chloride solution was added to the reaction mixture, followed by extraction with dichloromethane and drying. The obtained material was purified by column purification using hexane / ethyl acetate / methanol mixed solution as eluent to obtain 1 g (yield 68%) of pure yellow compound (10). Got it. The melting point of the obtained crystal was 182 ~ 183 ℃, NMR spectroscopic data was as follows.

NMR- ¹ H (400 MHz, DMSO; ppm): δ = 7.03-7.06 (d, 1H), 7.15-7.18 (d, 1H), 7.22-7.37 (m, 9H), 7.43-7.59 (m, 17H), 7.67-7.69 (m, 3H), 7.72-7.86 (m, 3H), 8.15-8.25 (q, 3H).

NMR- ³¹ P (400 MHz, CDCl ₃ ; ppm): δ = 31.20 (s)

Example 4 Synthesis of Aryl Phosphine Oxide Compounds of Compound (20)

First stage reaction: 9,10-di (4-bromophenyl) anthracene

1,4-dibromobenzene (6 g, 25 mmol) was added to a 250 ml three-necked flask equipped with a reflux condenser, dissolved in 100 ml of THF under an argon atmosphere, and n-butyllithium (1.6M, 15.6 ml, 25 mmol hexane solution) was added slowly and stirred for 1 hour. Anthraquinone (2.08 g, 10 mmol) was dissolved in 100 ml of THF and added slowly at the same temperature. After removing the cooling vessel, the mixture was further stirred at room temperature for 5 hours. A saturated ammonium chloride solution was added to the reaction mixture, followed by extraction with dichloromethane, drying and recrystallization with petroleum ether to obtain 4.8 g of a dialcohol compound (yield 92.3%). After dispersing the dialcohol compound in 150 ml of acetic acid under nitrogen atmosphere, potassium iodine (16.6 g, 100 mmol) and sodium hypophosphite hydrate (NaH ₂ PO ₂ H ₂ O 17.6 g 200 mmol) were added and refluxed for 4 hours. After cooling to room temperature, filtered, washed with water and dried to give 3.8g (yield 84.4%) of a pale yellow compound.

Second Step Reaction: Synthesis of Compound (20)

After replacing the inside of a 250 ml three-necked flask equipped with a reflux condenser with argon, the flask was subjected to 9,10-di (4-bromophenyl) anthracene (2 g, 4 mmol) obtained in the first step reaction of Example 4. ) Was dissolved in 100 ml of THF, n-butyllithium (1.6 M, 6.25 ml, 10 mmol hexane solution) was slowly added at a temperature of −78 ° C. and stirred for 1 hour. Chloro diphenyl phosphine (1.77 g, 8 mmol) was diluted in 50 ml of THF and added slowly at the same temperature. After removing the cooling vessel, the mixture was further stirred at room temperature for 5 hours. Saturated ammonium chloride solution was added to the reaction mixture, followed by extraction with dichloromethane. The dried material was dissolved in 100 ml of acetone. Then, 30% hydrogen peroxide (1 ml, 10 mmol) was added, followed by stirring for 1 hour. The reaction mixture was dried and column purified using a hexane / ethyl acetate / methanol mixed solution as eluent to obtain 1.8 g (yield: 62.1%) of aryl phosphine oxide compound of pure yellow compound (20). The melting point of the obtained crystal was 372 ~ 374 ℃, NMR spectroscopic data were as follows.

NMR- ¹ H (400 MHz, DMSO; ppm): δ = 7.46-7.48 (q, 4H), 7.55-7.57 (q, 4H), 7.64-7.70 (m, 18H), 7.78-7.79 (d, 2H), 7.80-7.81 (m, 4H), 7.83 (s, 1H), 7.86-7.91 (q, 3H).

NMR- ³¹ P (400 MHz, CDCl ₃ ; ppm): δ = 30.48 (s)

Ms [M + H] = 731.

Example 5: Synthesis of Compound (22)

First Step Reaction: Synthesis of 9,10-di (5-bromothienyl) anthracene

2,5-dibromothiophene (6.1 g, 25 mmol) was added to a 250 ml three-necked flask equipped with a reflux condenser, dissolved in 100 ml of THF under an argon atmosphere, and n-butyllithium (1.6M) was used at a temperature of -78 ° C or lower. , 15.6ml, 25mmol hexane solution) was added slowly and stirred for 1 hour. Anthraquinone (2.08 g, 10 mmol) was dissolved in 100 ml of THF, and then slowly added at the same temperature. After removing the cooling vessel and stirred for 5 hours at room temperature. A saturated ammonium chloride solution was added to the reaction mixture, followed by extraction with dichloromethane, followed by drying and recrystallization with petroleum ether to obtain a solid compound. 4.8 g (yield 90.6%) of obtained dial alcohol compound was obtained. Dialcohol compounds (4.8 g, 9 mmol) were dispersed in 150 ml of acetic acid under nitrogen atmosphere, followed by adding potassium iodine (16.6 g, 100 mmol) and sodium hypophosphite hydrate (NaH ₂ PO ₂ H ₂ O, 17.6 g, 200 mmol). It was then refluxed for 4 hours. The reaction mixture was cooled to room temperature, filtered, washed with water and dried to yield 3.6 g (yield 86.7%) of a pale yellow compound.

Second Step Reaction: Synthesis of Compound (22)

After replacing the inside of a 250 ml three-necked flask equipped with a reflux condenser with argon, the flask was subjected to 9,10-di (5-bromothienyl) anthracene ( 2 g, 4 mmol) was dissolved in 100 ml of THF, and n-butyllithium (1.6 M, 6.25 ml, 10 mmol hexane solution) was slowly added at a temperature of −78 ° C., followed by stirring for 1 hour. Chloro diphenyl phosphine (1.77 g, 8 mmol) was diluted in 50 ml of THF and added slowly at the same temperature. After removing the cooling vessel was stirred for 5 hours at room temperature. A saturated ammonium chloride solution was added to the reaction mixture, followed by extraction with dichloromethane, and the dried material was dissolved in 100 ml of acetone. Then, 30% hydrogen peroxide (1 ml, 10 mmol) was added, followed by stirring for 1 hour. The reaction mixture was dried and the column was purified using a hexane / ethyl acetate / methanol mixture as an eluent to obtain 2 g of an aryl phosphine oxide compound (yield: 68.9%) of pure yellow compound (22). The melting point of the obtained crystal was 352 ~ 353 ℃, NMR spectroscopic data was as follows.

NMR- ¹ H (400 MHz, DMSO; ppm): δ = 7.50-7.52 (q, 2H), 7.57-7.60 (q, 5H), 7.62-7.62 (m, 9H), 7.68-7.71 (m, 6H), 7.74 to 7.77 (q, 3H), 7.82 to 7.87 (m, 7H).

NMR- ³¹ P (400 MHz, CDCl ₃ ; ppm): δ = 22.57 (s).

Ms [M + H] = 743.

Example 6: Synthesis of Compound (11)

First Step Reaction: Synthesis of Diphenylphosphino Phenyl-4-boronic Acid

After replacing the inside of a 100 ml three-necked flask with argon, 1.0 g of 4-bromophenyldiphenylphosphine was added to the flask and dissolved in 15 ml of distilled THF. After cooling to −78 ° C., 2.53 ml of n-butyllithium (1.6M hexane solution) was added, and stirring was continued at the same temperature for 1 hour. 1.0 ml of trimethylborate was slowly added thereto, followed by stirring at room temperature for 2 hours. 5 ml of 2N hydrochloric acid solution was added to the above solution, stirred, extracted with diethyl ether, and the solvent was removed and recrystallized to obtain 0.8 g (yield 80%) of diphenylphosphino phenyl-4-boronic acid.

Second Step Reaction: Synthesis of Compound (11)

After replacing the inside of a 100 ml three-necked flask equipped with a reflux condenser with argon, 0.4 g of 2-bromo [9,10-di (β-naphthyl)] anthracene obtained in step 1 of Example 2 and 92 mg of Pd (PPh ₃ ) ₄ was added thereto, dissolved in 30 ml of toluene, and stirred for 20 minutes. To this was added 0.32 g of diphenylphosphino phenyl-4-boronic acid obtained above and 10 ml of 2N sodium carbonate, followed by stirring while refluxing for 48 hours. The reaction was terminated by raising the temperature to room temperature, the toluene layer was extracted with methylene chloride, and the solvent was removed. 30% hydrogen peroxide solution was mixed with this solution for oxidation, and column purification was performed to obtain 0.19 g (yield 34%) of the solid as pale yellow compound (11). Melting | fusing point (mp) of the obtained crystal | crystallization was 215 degreeC, and NMR spectroscopy data were as follows.

NMR- ¹ H (400 MHz, DMSO; ppm): δ = 7.41-7.44 (m, 2H), 7.50-7.52 (m, 4H), 7.57-7.62 (m, 18H), 7.76 (s, 2H), 7.92 ( s, 1H), 8.04-8.06 (d, 2H), 8.10-8.13 (m, 4H), 8.20-8.23 (q, 2H).

NMR- ³¹ P (400 MHz, CDCl ₃ ; ppm): δ = 30.18 (s)

Ms [M + H] = 707.

Example 7: Synthesis of Compound (12)

First Step Reaction: Synthesis of Diphenylphosphino-2-thiophene

After replacing the inside of a 100 ml three-necked flask equipped with a reflux condenser with argon, 3.2 ml of thiophene was added thereto and dissolved in 20 ml of a mixed solvent of ethyl ether / THF (3: 1). The reaction solution was cooled to 0 ° C., and then 25 ml of n-butyllithium (1.6 M hexane solution) was added, followed by reaction at that temperature for 1 hour and refluxed for 5 hours. Subsequently, the reaction solution was cooled to −60 ° C., and then a mixed solution of 7.1 ml of chlorodiphenylphosphine and 20 ml of a mixed solvent of ethyl ether / THF (3: 1) was slowly added thereto, followed by stirring at room temperature. At the end of the reaction, an aqueous ammonium chloride solution was added, extraction was performed with ethyl ether, and the solvent was removed to obtain 5.7 g (yield 67%) of a pale yellow solid.

Second Step Reaction: Synthesis of Diphenylphosphino-2-thionyl-5-boronic acid

After replacing the inside of a 100 ml three-necked flask equipped with a reflux condenser with argon, 6 g of diphenylphosphino-2-thiophene obtained above was added thereto and dissolved in 160 ml of a mixed solvent of ethyl ether / THF (2: 1). . The reaction solution was cooled to 0 ° C., and then 14.3 ml of n-butyllithium (1.6M hexane solution) was added thereto, followed by 20 minutes of reaction at the above temperature, and refluxed for 3 hours. 7.7 ml of trimethyl borate was slowly added thereto, followed by stirring at room temperature for 2 hours. 150 ml of 2N hydrochloric acid was added to the above solution, stirred, extracted with diethyl ether, and the solvent was removed and recrystallized to obtain 3.57 g (yield 50%) of a pale yellow solid.

Third Step Reaction: Synthesis of Compound (12)

Yellow crystals were reacted in the same manner as in the second step of Example 1, except that 0.29 g of diphenylphosphino-2-thionyl-5-boronic acid was used instead of diphenylphosphino phenyl-4-boronic acid. 0.2 g (yield: 38%) of Compound (12) was obtained. Melting | fusing point (m.p) of the obtained crystal | crystallization was 223 degreeC, and NMR spectroscopy data were as follows.

NMR- ¹ H (400 MHz, DMSO; ppm): δ = 7.30-7.40 (m, 6H), 7.45-7.55 (m, 9H), 7.62-7.72 (m, 9H), 7.90-7.74 (d, 1H), 7.98 (s, 2H), 8.01-8.03 (d, 1H), 8.08-8.12 (t, 4H), 8.17-8.20 (d, 1H).

MR- ³¹ P (400 MHz, CDCl ₃ ; ppm): δ = 31.64 (s).

Ms [M + H] = 713.

Example 8: Synthesis of Compound (13)

First Step Reaction: Synthesis of 5-diphenylphosphino-2,2'-bithionyl-5'-boronic acid

After replacing the inside of a 250 ml three-necked flask with argon, 1 g of 2,2'-bithiophene was added to the flask, dissolved in 50 ml of hexane, and cooled to 0 ° C. 2.26 ml of TMEDA (N, N, N, N-tetramethylethylenediamine) was added thereto, and 9.37 ml of n-butyllithium was added thereto, followed by stirring for 1 hour. In another flask, a solution of 1 ml of chlorodiphenylphosphine and 75 ml of THF was added and cooled to −60 ° C., followed by addition of the reaction solution substituted with lithium. After the mixture was stirred at room temperature for 1 hour, it was cooled to -60 ° C again, 1.24 g of trimethyl borate was added, and then reacted at room temperature for 3 hours. 2N hydrochloric acid solution was added thereto and extracted with methylene chloride. After drying over anhydrous magnesium sulfate, the solvent was removed, and the column was purified to obtain 0.8 g of a solid (34.7% yield).

Second Step Reaction: Synthesis of Compound (13)

Same as the second stage reaction of Example 1, except that 0.32 g of 5-diphenylphosphino-2,2'-bithionyl-5'-boronic acid was used instead of diphenylphosphino phenyl-4-boronic acid The reaction was carried out to obtain 0.17 g (yield: 38%) of compound (13) as yellow crystals. Melting | fusing point (m.p) of the obtained crystal | crystallization was 117 degreeC, and NMR spectroscopy data were as follows.

NMR- ¹ H (400 MHz, DMSO; ppm): δ = 7.11-7.13 (q, 1H), 7.27-7.45 (m, 7H), 7.56-7.70 (m, 20H), 7.84-7.88 (m, 1H), 8.05-8.17 (m, 4H), 8.21-8.32 (m, 2H).

Ms [M + H] = 765.

Example 9: Synthesis of Compound (16)

First Step Reaction: Synthesis of 9,10-bis-5- (2,2'-bithionyl) anthracene

After replacing the inside of a 250 ml one-necked flask with argon, 10 g of 2,2'-bithiophene was added to the flask, dissolved in 200 ml of hexane, and cooled to 0 ° C. 9 g of TMEDA was added thereto, and 48.7 ml of n-butyllithium (1.6 M hexane solution) was added thereto, followed by stirring for 1 hour. Another 500 ml three-necked flask was replaced with argon, 4.37 g of anthraquinone was added, dissolved in 200 ml of THF, cooled to 0 ° C., and a solution substituted with stomach lithium was added to the reaction vessel. After removing the cooler and stirring at room temperature for 3 hours, the solution was poured into an aqueous ammonium chloride solution and extracted with ethyl ether. The extract was dried over anhydrous magnesium sulfate, the solvent was removed, and recrystallization gave 6.9 g (yield 60.7%) of a pale green solid.

In a three-necked flask equipped with a reflux condenser, argon was substituted, 3.4 g of a dialcohol compound was dispersed in 80 ml of acetic acid, and 10.45 g of potassium iodine and 12 g of sodium hypophosphite hydrate were added thereto. After stirring for 4 hours under reflux, the mixture was cooled to room temperature and the resulting solid was filtered and washed with water and methanol to obtain 2.16 g (yield 67.7%) of a green solid.

Second Step Reaction: Synthesis of Compound (16)

After replacing the inside of a 100 ml three-necked flask equipped with a reflux condenser with argon, 2.1 g of 9,10-bis-5- (2,2'-bithionyl) anthracene was added to the flask and dissolved in 70 ml THF. . The solution was cooled to 0 ° C. and then 3.1 ml of n-butyllithium was added, followed by 20 minutes of reaction at the above temperature, stirred at 60 ° C. for 2 hours, and then cooled to 0 ° C. again. Then, 0.74 ml of chlorodiphenylphosphine was added to the reaction solution, and the mixture was stirred at room temperature. At the end of the reaction, the solid formed by adding water was filtered, dried and purified by column to remove starting materials. 30% hydrogen peroxide was added to the resultant solid, followed by oxidation, and column purification to obtain 1.88 g (yield 64.8%) of compound (16) as a yellow solid. Melting | fusing point (m.p) of the obtained crystal | crystallization was 304 degreeC, and NMR spectroscopy data were as follows.

NMR- ¹ H (400 MHz, DMSO; ppm): δ = 7.33-7.74 (d, 1H), 7.43-7.45 (q, 1H), 7.56-7.63 (m, 10H), 7.67-7.70 (m, 3H), 7.73-77.7 (m, 8H), 7.87-7.90 (q, 4H).

NMR- ³¹ P (400 MHz, CDCl ₃ ; ppm): δ = 22.757 (s)

Ms [M + H] = 706. .

Example 11 Fabrication of Organic EL Device Using Compound (8)

This embodiment is for explaining the fabrication of an organic EL device using the compound (8) synthesized in the previous embodiment as an electron transporting material of the electron transporting layer.

First, an ITO (indium-tin oxide) substrate having a thickness of 150 nm and a surface resistance of 10 μs / □ was ultrasonically washed sequentially using a mixed solution of isopropyl alcohol and pure water, pure water, and isopropyl alcohol solution, and then inert. Dry with gas. TPD was vacuum deposited on the washed ITO under a vacuum of 2 × 10 ⁻⁶ torr at a rate of 0.2˜2.0 μs / sec to form a hole transport layer having a thickness of 70 nm. AlQ3 was vacuum-deposited thereon to form a light emitting layer having a thickness of 35 nm. Subsequently, Compound (8) was vacuum-deposited on the light emitting layer at a rate of 0.2 to 2.0 mW / sec under a vacuum of 2 × 10 ⁻⁶ torr to form an electron transport layer having a thickness of 35 nm. Subsequently, LiF was vacuum-deposited thereon to form an electron injection layer of 1.0 nm, and then Al was vacuum-deposited thereon to form a 200 nm cathode layer to complete the organic EL device. The completed organic EL device had a current density of 50 mA / cm ² at a driving voltage of 6.26 volts, and the luminance was 410 cd / m ² . Maximum emission wavelength was 530 nm.

Example 12 Fabrication of Organic EL Device Using Compound (18)

This example is for explaining the fabrication of an organic EL device using the compound (18) synthesized in Example 4 as an electron transporting material of the electron transporting layer. That is, the organic EL device was manufactured in the same manner as in Example 11, except that Compound (18) was used as the electron transporting material. The completed organic EL device showed a current density of 50 mA / cm ² at a driving voltage of 7 volts, and the luminance was 565 cd / m ² . Maximum emission wavelength was 530 nm.

Example 13 Fabrication of Organic EL Device Using Compound (12)

This example is for explaining the fabrication of an organic EL device using the compound (12) synthesized in Example (7) as an electron transporting material of the electron transporting layer. That is, the organic EL device was manufactured in the same manner as in Example 11, except that Compound (12) was used as the electron transporting material. The completed organic EL device had a current density of 50 mA / cm ² at a driving voltage of 6.42 volts, and the luminance at this time was 655 cd / m ² . Maximum emission wavelength was 530 nm.

Example 14 Fabrication of Organic EL Device Using Compound (8)

This embodiment is intended to explain the fabrication of an organic EL device using the compound (8) synthesized in the previous embodiment simultaneously as a light emitting material of the light emitting layer and an electron transporting material of the electron transporting layer. That is, an organic EL device was manufactured in the same manner as in Example 11, except that Compound (8) was used as a light emitting material and an electron transporting material. The completed organic EL device showed a current density of 50 mA / cm ² at a driving voltage of 6.16 volts, and the luminance was 360 cd / m ² . Maximum emission wavelength was 502 nm.

Example 15 Fabrication of Organic EL Device Using Compound (11)

This embodiment is intended to explain the fabrication of an organic EL device using the compound (11) synthesized in Example 6 simultaneously as a light emitting material of the light emitting layer and an electron transporting material of the electron transporting layer. That is, an organic EL device was manufactured in the same manner as in Example 11, except that Compound (11) was used as a light emitting material and an electron transporting material. The completed organic EL device showed a current density of 50 mA / cm ² at a driving voltage of 5.76 volts, and the luminance was 210 cd / m ² . Maximum emission wavelength was 477 nm.

Comparative Example 1 Fabrication of Organic EL Device Using AlQ3

An organic EL device was manufactured in the same manner as in Example 11, except that AlQ3 was used as both a light emitting layer and an electron transporting layer. The completed organic EL device had a current density of 50 mA / cm ² at a driving voltage of 7.66 volts, and the luminance at this time was 570 cd / m ² . Maximum emission wavelength was 530 nm.

2 is a graph showing the correlation between the voltage and the luminance of the organic EL device using the compound (18) obtained in Example 12 and the organic EL device of the comparative example corresponding to the conventional example.

3 is a graph showing the correlation between the voltage and current of the organic EL device using the compound (18) obtained in Example 12 and the organic EL device of Comparative Example corresponding to the conventional example. 2 and 3, the unit of the voltage on the horizontal axis is volts (V).

4 is a graph showing a relationship between time and efficiency during constant voltage driving of an organic EL device using a compound (18) obtained in Example 12 and an organic EL device of a comparative example corresponding to the conventional example.

2, 3 and 4, an organic EL device manufactured by using an arylphosphine oxide compound corresponding to the present invention as an electron transport material or a light emitting material is AlQ3, which is a typical representative electron transport material and / or a light emitting material. It can be seen that low-power driving is possible and has a long life compared to the organic EL device manufactured by using a.

As described above, the organic EL device manufactured using the arylphosphine oxide compound according to the present invention as an electron transport material and / or a light emitting material can be driven with low power and can achieve long life of the organic EL device.

Claims (8)

An aryl phosphine oxide compound represented by Formula 1 below: [Formula 1]

Here, X ₁ is a substituted or unsubstituted arylene group of C6 to C18 or a substituted or unsubstituted divalent heterocyclic group of C4 to C18, Y is oxygen, sulfur or selenium, n represents an integer of 0 to 5, Ar ₁ is a substituted or unsubstituted aromatic group of C18 to C60 represented by the following formula,

Ar ₂ and Ar ₃ may be the same or different, a substituted or unsubstituted aryl group of C6 to C30 or a substituted or unsubstituted heterocyclic group of C4 to C30, Ar ₄ and Ar ₅ may be the same or different and are a substituted or unsubstituted aryl group of C6 to C30 or a substituted or unsubstituted heterocyclic group of C4 to C30, or a substituted or unsubstituted arylamino group of C4 to C30. The aryl phosphine oxide compound according to claim 1, wherein X ₁ is an arylene group or a divalent heterocyclic group represented by:

. The aryl phosphine oxide compound of claim 1, wherein Ar ₂ and Ar ₃ are an aryl group or a heterocyclic group as follows:

. The aryl phosphine oxide compound of claim 1, wherein Ar ₄ and Ar ₅ are an aryl group, a heterocyclic group, an arylamino group, or a heterocyclic amino group represented by the following.

. An aryl phosphine oxide compound, characterized in that represented by the formula (2): [Formula 2]

Here, Ar ₆ , Ar ₇ , Ar ₈ , and Ar ₉ mean the same as Ar ₂ and Ar ₃ , which may be the same or different, and X ₂ and X ₃ mean the same as X ₁ , which may be the same or different. When X ₂ and X ₃ are substituted at positions 9 and 10 of the anthracene moiety, m and n are integers of 1 to 5, and an aryl group, a heterocyclic group, When an arylamino group or heterocyclic amino group is substituted, m and n are integers of 0-5. An organic electroluminescent device comprising the aryl phosphine oxide compound according to any one of claims 1 to 5 in an electron transport layer, a light emitting layer, or a light emitting / electron transport layer. A flat panel display comprising an organic electroluminescent device comprising the aryl phosphine oxide compound according to any one of claims 1 to 5 in an electron transport layer, a light emitting layer, or a light emitting / electron transport layer. A lighting device comprising an organic electroluminescent device comprising the aryl phosphine oxide compound according to any one of claims 1 to 5 in an electron transport layer, a light emitting layer, or a light emitting / electron transport layer.

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