KR100623231B1 - Organic Electroluminescence Display Device Comprising Anti-oxidants - Google Patents

Abstract

The present invention relates to an organic electroluminescent device, and more particularly, an organic film layer including a substrate, a first electrode layer formed on the substrate, at least one light emitting layer formed on the first electrode layer, and an upper portion of the organic film layer. The organic electroluminescent device including the second electrode layer formed on the substrate further includes an antioxidant to prevent oxidation and denaturation of the organic film layer generated by oxygen penetrating from the pin-hole or the like formed in the substrate or the electrode layer, thereby providing high reliability. An organic electroluminescent device can be provided.

Organic electroluminescent element, antioxidant film

Description

Organic Electroluminescence Display Device Comprising Anti-oxidants

1 is a cross-sectional structure diagram of an organic electroluminescent device according to a first embodiment of the present invention;

2 is a cross-sectional structural view of an organic electroluminescent device having an antioxidant layer according to the present invention;

3 is a graph showing voltage-luminance characteristics of organic electroluminescent devices manufactured by Experimental Example 1 and Comparative Example 1. FIG.

4 is a graph showing luminance-efficiency characteristics of organic electroluminescent devices manufactured by Experimental Example 1 and Comparative Example 1. FIG.

5 is a graph showing time-life characteristics of organic electroluminescent devices manufactured by Experimental Example 1 and Comparative Example 1. FIG.

(Explanation of symbols for main parts of drawing)

10 substrate 20 first electrode layer

30: hole injection layer 40: hole transport layer

50: light emitting layer 60: hole suppression layer

70: electron transport layer 80: electron injection layer

90 second electrode layer 100 organic layer

200: antioxidant layer

The present invention relates to an organic electroluminescent device, and more particularly, to an organic electroluminescent device comprising an antioxidant in its components.

An organic electroluminescent display (OELD) is an organic (low molecular or polymer) thin film of electrons and holes injected through a cathode and an anode, recombines to form excitons, and emits light of a specific wavelength by energy from the excitons. It refers to a display using the phenomenon.

The organic electroluminescent device has a response speed of more than 30,000 times faster than the current commercially available liquid crystal display (LCD), which enables video to be realized and its own light emitting device has a wide viewing angle and high luminance. Have. The organic EL device has a stacked structure that can realize the highest luminous efficiency possible through recombination of electrons and holes.

In a typical organic electroluminescent device, an anode electrode layer is formed on a substrate, an organic film layer is formed on the substrate, a cathode electrode layer is formed on the organic film layer, and the anode and the cathode electrode layer have a structure connected to a power source.

The organic film layer of the organic electroluminescent device thus constructed is usually composed of three to six thin film layers. Specifically, a light emitting layer should be included and a hole injection layer (HIL), a hole transport layer (HTL), a hole suppression layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), etc., between the anode electrode layer and the cathode electrode layer This can be introduced.

Looking at the driving of the organic EL device having such a structure, first, when a positive voltage is applied to the anode electrode and a negative voltage is applied to the cathode electrode by a power supply, holes are supplied to the organic layer through the anode electrode. The light emitting layer is reached through the hole injection layer and the hole transport layer existing in the organic layer. Then, electrons are supplied from the cathode to the organic layer and reach the light emitting layer through the electron injection layer and the electron transport layer present in the organic layer. In the emission layer of the organic layer, the injected holes and electrons recombine to emit light, and are transmitted to the outside through the substrate.

However, in actual driving, oxygen and moisture, which penetrate inside or outside the device, easily react with the organic layer, thereby degrading the performance of the device and reducing the lifespan. For example, deterioration due to internal factors such as deterioration of the cathode electrode by oxygen, deterioration of the light emitting layer by oxygen from the anode electrode, and deterioration by the reaction between the light emitting layer and the interface occurs. In addition, at the same time, there is a disadvantage in that deterioration is easily caused by external factors such as external moisture, oxygen, ultraviolet rays, and fabrication conditions of the device. In particular, since oxygen and moisture have a fatal effect on the life of the organic EL device, researches on encapsulation of the organic EL device have been conducted in various ways to minimize such effects.

The encapsulation method conventionally used includes an encapsulation method in which an encapsulation substrate or a cap is pressed and adhered to the substrate and then injected by injecting an adhesive to a surface where the substrate contacts; A method of forming a coating film by coating an entire surface of the organic EL device with an inorganic insulating film or an insulating polymer has been performed.

However, even with such a method, it is difficult to completely prevent impurities, oxygen or moisture from penetrating from the outside. In particular, organic materials constituting some organic layers have been proved to be very sensitive to contamination, oxidation, and humidity, and thus researches on new cathode electrode materials, organic layers, and encapsulation methods have been conducted. However, Y. Y. Sato et al., 'Stability of organic electroluminescent diodes', Molecular Crystals and Liquid Crystals, Vol. 253, 1994, pp. 143-150, even with sufficient encapsulation, the pinholes in the metal material constituting the electrode still provide sufficient passage for oxygen and moisture to reach the reactive metal below.

As a result, oxygen and moisture introduced from the outside through the pin-holes in the metal material constituting the electrode diffuse into the organic layer, and the diffused oxygen eventually reacts with the organic layer to cause oxidation and denaturation of the organic layer. As a result, there is a problem that the performance of the organic EL device is degraded.

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide an organic electroluminescent device that prevents oxidation and denaturation of an organic film layer due to oxygen introduced from the outside.                         

It is still another object of the present invention to provide an organic electroluminescent device comprising an antioxidant which can remove oxygen introduced from the outside in its components.

It is another object of the present invention to provide an organic electroluminescent device with increased lifetime and reliability.

In order to achieve the above object, the present invention is:

A substrate, a first electrode layer formed on the substrate, a light emitting layer on the first electrode, and a second electrode layer formed on the light emitting layer, wherein the light emitting layer is doped with an antioxidant. An organic electroluminescent device is provided.

In addition, the present invention:

A substrate, a first electrode layer formed on the substrate, a light emitting layer on the first electrode, a second electrode layer formed on the light emitting layer, and a first electrode and a second electrode It includes an organic film layer having a charge transport capability, the organic film layer is provided with an organic electroluminescent device, characterized in that the doped with an antioxidant.

In addition, the present invention:

A substrate, a first electrode layer formed on the substrate, a light emitting layer located on the first electrode, and a second electrode layer formed on the light emitting layer, and between the first electrode layer and the second electrode layer. It provides an organic electroluminescent device comprising the formed antioxidant layer.

In this case, the organic EL device may further include an organic film layer having charge transport capability between the first electrode layer and the second electrode layer.

Hereinafter, the present invention will be described in more detail.

When the organic EL device is exposed to the external environment, oxygen penetrates through the pin-holes present in the second electrode layer, and the oxygen penetrates rapidly to oxidize the organic layer of the organic EL device to generate radicals. . The generated radical decomposes or denatures the organic material-polymer or low molecule-constituting the organic layer, thereby degrading the characteristics of the organic EL device and shortening the lifespan.

In particular, when a polymer is used as the organic membrane layer, when free radicals are formed in the main chain or the side chain of the polymer, it immediately reacts with oxygen to form a hydroperoxy radical, and the peroxide decomposes itself to form another polymer. So-called Auto Oxidative Reaction occurs. This automatic oxidation reaction continues to occur until a stable compound is produced, and as a result, deterioration of the polymer constituting the organic layer makes it very difficult to obtain characteristics as an element.

Therefore, there is a need for a material that can prevent the physical and chemical degradation caused by oxygen, and such a material is called an antioxidant (酸化 防止 劑). Degradation reaction by oxidation is a radical reaction, which is made by three different chemical reactions: chain initiation, chain propagation, and peroxide degradation reaction. Various methods have been used to suppress and prevent such oxidation-degradation. For example, inhibiting a chain initiation reaction that prevents radical formation, inhibiting a chain growth reaction that captures the generated radicals and inhibits the progress of the radical chain reaction, or does not generate the generated hydroperoxides. Three methods are used, such as the decomposition of peroxides, which decompose into a form that does not.

Among them, the antioxidant which has the effect of inhibiting the chain growth reaction of radicals is called a radical chain inhibitor, and the antioxidant which acts to decompose the produced hydroperoxide into a form that does not generate radicals, It is called peroxides decomposer.

Antioxidants used as the radical chain inhibitors are called primary antioxidants, and include phenolics-, monophenolics-, bisphenolics-, and high molecular weight phenolic antioxidants. There are amine-based antioxidants.

The antioxidant used as the peroxide decomposer is called a secondary antioxidant, and there are phosphoric-based antioxidants and phosphates-based antioxidants.

Specific examples of the antioxidant are as follows.

Primary antioxidants

1. Phenolic Antioxidant

Phenolic antioxidants are classified into phenolic, monophenolic, biphenolic, polyphenolic and thiobisphenolic and hindered phenolics.

Tetrakis (methylene-3.5-di-t-butyl-4-hydroxyphenyl) hydrocinnamate) methane is a high molecular polyphenol-based polytetrafluoroethylene (methylene-3,5-di-t-butyl-4-hydroxyphenylhydrocinnamate) methane. ) And octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate (octadecy-3- (3,5-di-tert-butyl-4-hydroxyphenyl)- propionate).

2. Amine Antioxidant

Amine-based antioxidants play a role of hydrogen donation similar to the phenol-based, and also act as a peroxide decomposer at high temperatures.

For example, as the amine antioxidant, N- of amine of p-phenylene such as alkyl-substituted phenylamine, diaryl-p-phenylene amine or a substituent thereof Substituted reagents such as 6-ethoxy-2,2'-4-trimethyl-1,2-dihydroxynorine (6-ethoxy-2,2'-4-trimethyl-1,2-dihydroxynorine) Substituted piperizines such as nolin, 2,2 ', 6,6'-tetraalkylpiperiazine (2,2', 6,6'-tetralkylpiperazine) are used.

Secondary antioxidant

1. sulfur based antioxidant

The sulfur-based antioxidant is dirauryl 3,3'-thio-dipropionate, dimyristyl 3,3'-thio as an effective peroxide release in the field of long-term heat exposure. Dipropionate (dimiristyl 3,3'-dipropionate, DMTP) is available.

2. Phosphorus-based antioxidant

The phosphorus antioxidant converts hydrogen peroxide to alcohol and then converts itself into phosphites. Such phosphorus antioxidants include trialkylphosphite (alkyl: isodedecyl-, tridecyl-), phenylalkyl-di-phosphite (alkyl: isodedecyl, isoctyl ( isooctyl)), diphenylalkylphosphite (alkyl: isodecyl, isooctyl), triphenylphosphite, phospharasoxide (1,1-biphenyl-4,4'-dil, 1, 1-buphenyl-4,4'-dyl), bistetra (2,4-bis (1,1'-dimethylethyl) phenyl) ester (bis-tetra (bis (1,1'-dimethylethyl) phenyl), 3,5-di-t-butyl-4-hydroxybenzylphosphate diethyl ester (3,5-di-t-butyl-hydroxybenzylphodphate-diethylester), 9,10-dihydro-9-xy-10-phospho Phenanthrene-10-oxide (9,10-dihydro-9-xy-10-phosphonaltrene-10-oxide), sodium bis (4-t-butylphenyl) phosphite, Sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate (sodium-2,2-methylene-b is (4,6-di-t-butylphenyl) phosphate), 1,3-bis (diphenoxyphosphonyloxy) benzene (1,3-bis (diphenoxyphosphonyloxy) benzene), bis (2,6-di-t -Butyl-4-methylphenyl) pentaerythitol phosphite (bis (2,6-di-t-butyl-4-methylphenyl) pentaerystolphodphite), tris (2,4-di-t-butylphenyl) phosphite (2,4-di-t-butylphenyl) phosphite)), 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (2,2-methylene-bis- (4,6- di-t-butylphenyl) octylphosphite).

To use these antioxidants as additives for special purposes, consider their physical form (liquid / solid, melting point), particle size and particle size distribution, thermal stability, interaction with other additives, volatility, compatibility with polymers, etc. To select.

In the present invention, the organic film layer included in the organic electroluminescent device of the present invention is preferably doped with an antioxidant or composed of a layer because it is intended to prevent decomposition or deterioration of the organic film layer by oxygen.

1 is a view showing a cross section of an organic electroluminescent device according to a first embodiment of the present invention.

Referring to FIG. 1, the organic electroluminescent device of the present invention includes a substrate 10, a first electrode layer 20 formed on the substrate 10, and a light emitting layer 50 disposed on the first electrode layer 20. And a second electrode layer 90 formed on the emission layer 50.

The organic electroluminescent device includes a hole injection layer 30, a hole transport layer 40, a hole suppression layer 60, and an electron transport layer 70 having charge transport capability between the first electrode layer 20 and the second electrode layer 90. ) And the electron injection layer 80 may further include one or more layers selected from the group consisting of. In this case, the antioxidant is an organic film layer 100 formed between the first electrode layer 20 and the second electrode layer 90, specifically, a hole injection layer 30, a hole transport layer 40, a light emitting layer 50, a hole It may be doped into one or more layers selected from the group consisting of the suppression layer 60, the electron transport layer 70, and the electron injection layer 80. In addition, the doping of the antioxidant may be performed only in all or some of the organic layer 100, wherein the antioxidant doped in each layer uses the same material as the antioxidant doped in the light emitting layer (50).

The introduction of the antioxidant may be suitably used for top emission or bottom emission type organic electroluminescent devices. Specifically, in the bottom emission organic electroluminescent device, the first electrode layer 20 is a transparent electrode, and the second electrode layer 90 is a reflective electrode. In this case, when the first electrode layer 20 is an anode and the second electrode layer 90 is a cathode, the organic electroluminescent device to be formed includes the first electrode layer 20 (transparent electrode), the hole injection layer 30, The hole transport layer 40, the light emitting layer 50, the hole suppression layer 60, the electron transport layer 70, the electron injection layer 80 and the second electrode layer 90 (the reflective electrode) are sequentially stacked.

In this case, the doping of the antioxidant may be formed on any layer between the first electrode layer 20 and the second electrode layer 90, but the second electrode layer 90 may be the most on the substrate 10 of the organic EL device. It is formed between the light emitting layer 50 and the second electrode layer 90 is formed on the outside, in order to effectively block the oxygen flowing through the pin-hole included in the electrode layer as the electrode layer is formed of a metal material.

Meanwhile, the organic electroluminescent device formed when the first electrode layer 20 is a cathode electrode and the second electrode layer 90 is an anode electrode is formed in the opposite manner to the above structure, and the first electrode layer 20 (transparent electrode), The electron injection layer 80, the electron transport layer 70, the hole suppression layer 60, the light emitting layer 50, the hole transport layer 40, the hole injection layer 30 and the second electrode layer 90 (the reflective electrode) are sequentially It has a laminated structure.

In this case, the doping of the antioxidant may be formed in any layer between the first electrode layer 20 and the second electrode layer 90, but is preferably formed between the light emitting layer 50 and the second electrode layer 90. .

The structure of the layer as described above is formed in the opposite case in the case of top emission, and the doping of the antioxidant introduced can be changed as appropriate.

As described above, in the case where the antioxidant is doped into the organic film layer 100, the organic film layer 100 to which the antioxidant is doped is formed by co-depositing an antioxidant and an organic material at the same time, or a pure organic film layer 100. ) Is formed and co-deposited the constituent material of the organic layer 100 and the antioxidant on the upper layer to form a multilayer of a two-layer structure.

Antioxidants doped in the organic film layer 100 are used at a concentration between 0.1 and 10% by weight, the upper limit of this range is used only in exceptional cases. In this case, when the content of the antioxidant is used less than 0.1% by weight, it is difficult to effectively block the incoming oxygen, and when used in excess of 10% by weight, an undesirable device is obtained such as leakage of current or deterioration of properties.

The antioxidant doping method is a polymer organic electroluminescent device, for example, when introduced into the electron transport layer 70, the electron transport layer 70 on the first electrode layer 20 or the light emitting layer 50 to act as the anode The material forming the film is coated with a thickness of several hundreds of microseconds and the heat treatment is performed after wiping the contact portion of the second electrode layer 90. Subsequently, the material constituting the electron transport layer 70 is blended with the dopant to be coated with a thickness of several hundred microseconds and heat-treated.

In the case of a low molecular organic electroluminescent device, after loading the substrate on which the first electrode layer 20 and the light emitting layer 50 formed as the anode are formed in a deposition chamber, an electron transport layer 70 is formed on the light emitting layer 50. The material and antioxidant are co-deposited and deposited to a thickness of several hundred millimeters.

Hereinafter, another embodiment of the present invention will be described.

Referring to FIG. 2, the organic electroluminescent device of the present invention includes a substrate 10, a first electrode layer 20 formed on the substrate 10, and a light emitting layer 50 disposed on the first electrode layer 20. And an antioxidant layer 200 formed on the light emitting layer 50, and a second electrode layer 90 formed on the antioxidant layer 200.

The organic electroluminescent device includes a hole injection layer 30, a hole transport layer 40, a hole suppression layer 60, and an electron transport layer 70 having charge transport capability between the first electrode layer 20 and the second electrode layer 90. ) And the electron injection layer 80 may further include one or more layers selected from the group consisting of. In this case, the antioxidant layer 200 is an organic layer 100 formed between the first electrode layer 20 and the second electrode layer 90, specifically, a hole injection layer 30, a hole transport layer 40, a light emitting layer ( 50), the hole suppression layer 60, the electron transport layer 70 and the electron injection layer 80 may be formed in part or all between the layer and the layer selected from.

Antioxidant layer 200 formed in the second embodiment of the present invention The materials described above can be used in the same manner as the first embodiment, it is preferable to form a thickness of 1 to 50 kPa. At this time, when the thickness of the antioxidant layer 200 is less than 1 사용 it is difficult to effectively block the incoming oxygen, when used in excess of 50 얻어 it is difficult to inject electrons or deteriorate characteristics such as obtaining an undesirable device Lose.

Unlike the first embodiment, the introduced antioxidant layer 200 forms a layer independently, and an antioxidant to be used is formed by vapor deposition, or dissolved in a solvent, followed by spin coating, spray coating, printing, and dipping. It is formed by a wet method.

The introduction of the antioxidant layer can be suitably used for top emission or bottom emission type organic electroluminescent devices.

Specifically, in the bottom emission organic electroluminescent device, the first electrode layer 20 is a transparent electrode, and the second electrode layer 90 is a reflective electrode. In this case, the organic electroluminescent device formed when the first electrode layer 20 is an anode electrode and the second electrode layer 90 is a cathode electrode includes the first electrode layer 20 (transparent electrode), the hole injection layer 30, and holes. The transport layer 40, the light emitting layer 50, the hole suppression layer 60, the electron transport layer 70, the electron injection layer 80, and the second electrode layer 90 (reflective electrode) are sequentially stacked.

At this time, the antioxidant layer 200 may be formed between any layer between the first electrode layer 20 and the second electrode layer 90, the second electrode layer 90 is the substrate 10 of the organic electroluminescent device In order to effectively block oxygen flowing through the pin-hole included in the electrode layer, the electrode layer is formed on the outermost side with respect to the light emitting layer 50 and the second electrode layer 90. Is done in

Meanwhile, the organic electroluminescent device formed when the first electrode layer 20 is a cathode electrode and the second electrode layer 90 is an anode electrode is formed in the opposite manner to the above structure, and the first electrode layer 20 (transparent electrode), The electron injection layer 80, the electron transport layer 70, the hole suppression layer 60, the light emitting layer 50, the hole transport layer 40, the hole injection layer 30 and the second electrode layer 90 (the reflective electrode) are sequentially It has a laminated structure.

In this case, the antioxidant layer 200 may be formed between any layer between the first electrode layer 20 and the second electrode layer 90, but preferably, the light emitting layer 50 and the second electrode layer 90 are formed. Formed between).

The structure of the above-described layer is formed in the opposite case in the case of top emission, and the position of the antioxidant layer 200 introduced at this time may be appropriately changed.

The organic light emitting display device of the present invention obtained through the first and second embodiments further includes an antioxidant in the organic film layer 100 of the organic electroluminescent device, thereby introducing oxygen introduced from the pin-hole of the second electrode layer. Can be effectively blocked. As a result, oxygen flowing from the outside can be completely blocked, thereby suppressing oxidation or denaturation of the organic layer 100 in the pixel portion, thereby increasing the reliability of the organic light emitting display device and increasing the lifespan.

Introduction of the antioxidant proposed in the present invention is a passive matrix type organic light emitting display device that does not include a thin film transistor and an active matrix type organic field having the thin film transistor as an integrated body. The present invention can also be suitably applied to a light emitting display device.

Hereinafter, experimental examples of the present invention are presented. However, the experimental examples of the present invention are only presented to better understand the present invention, and the present invention is not limited to the following experimental examples.

Experimental Example 1

An organic electroluminescent device was manufactured in which an electron transport layer was doped with an antioxidant based on a bottom emission organic electroluminescent device.

ITO is patterned on the substrate as an anode to define the pixel region, and then UV-O ₃ surface treatment is performed, and then the ITO-deposited substrate is transferred to the evaporator, and then a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode Was deposited sequentially, and sealed using the moisture absorbent and the organic cover.

PEDOT was coated to a thickness of 750 kPa to form the hole injection layer (HIL).

As the light emitting layer, covion red, which is a polymer red light emitting material, was vacuum deposited to form a thickness of 500 mW. Next, Alq3 (soluble) modified with an electron transport layer was formed to a thickness of 100 kW, and the cathode was formed to a thickness of 780 kW / 3000 kW with a double layer electrode of Ca / Ag.

At this time, in order to form an electron transport layer doped with an antioxidant between the electron transport layer and the cathode electrode, poly (1,2-dihydro-2,2,4-trimethyl as an antioxidant in Alq3 (soluble) which is an electron transport layer material. A solution weighted 2% by weight of quinoline) (Poly (1,2-dihydro-2,2,4-trimethylquinoline)) was coated to a thickness of 25 nm under conditions of an appropriate spin rate. Next, the hole injection layer of the cathode contact portion was peeled off and dried at a temperature of 100 ° C. for 60 minutes. Encapsulation was not done separately to see the antioxidant effect.

Comparative Example 1

In order to examine the effect on the characteristics of the organic electroluminescent device when the antioxidant is introduced into the electron transport layer, the electron transport layer (ETL) is the same as in Experimental Example 1 without doping except the electron transport layer doped with the antioxidant The organic electroluminescent device of Comparative Example 1 was prepared.

Luminance and Efficiency Characteristics

In order to determine the voltage-luminance characteristics and the efficiency-luminance characteristics of the organic EL device manufactured in Experimental Example 1 and Comparative Example 1, these results are as shown in Figures 3 and 4.

Referring to FIGS. 3 and 4, even when an electron transport layer doped with an antioxidant is introduced according to the present invention, the luminance and the efficiency of a conventional organic EL device are similar, and thus the voltage-luminance and the efficiency-luminance are doped. It can be seen that there is no change in properties.

Life characteristics

In order to determine the life-time characteristics of the organic EL device manufactured in Experimental Example 1 and Comparative Example 1 was tested, these results are as shown in FIG.

Referring to FIG. 5, when the electron transport layer doped with the antioxidant is introduced according to the present invention, it can be seen that the life characteristics of the device of Comparative Example 1 are deteriorated faster than that of Experimental Example 1. FIG.

As described above, according to the present invention, by introducing an antioxidant into the organic film layer having the charge transporting capacity of the organic electroluminescent device, preferably the electron transporting layer, it is possible to effectively block oxygen penetrating into the device from the outside, thereby preventing the light emitting layer. Deterioration and modification of the organic film layer to be contained can be suppressed. As a result, the organic film layer is stabilized, so that the reliability of the organic EL device is increased and the service life is increased.

While the foregoing has been described with reference to preferred embodiments of the present invention, those skilled in the art will be able to variously modify and change the present invention without departing from the spirit and scope of the invention as set forth in the claims below. It will be appreciated.

Claims (28)

Board; A first electrode layer formed on the substrate; An emission layer doped with an antioxidant having a concentration of 0.1 to 10% by weight on the first electrode layer; And A second electrode formed on the emission layer, The light emitting layer doped with the antioxidant is an organic electroluminescent device, characterized in that it has a laminated structure consisting of a light emitting layer consisting of only a pure light emitting material and the light emitting layer on which the antioxidant and the light emitting material is deposited at the same time. The method of claim 1, The antioxidant is an organic electroluminescent device, characterized in that selected from the group consisting of phenolic, amine, sulfur and phosphorus antioxidant. The method of claim 2, The phenolic antioxidants are tetrakis (methylene-3.5-di-t-butyl-4-hydroxyphenyl) hydrocinnamate (methylene-3,5-di-t-butyl-4-hydroxyphenylhydrocinnamate) methane methane) or octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate (octadecy-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate), The amine antioxidants include N-substituted alkyl-substituted phenylamines, diaryl-p-phenylene amines or amines of p-phenylene amines thereof; Substituted knolins of 6-ethoxy-2,2'-4-trimethyl-1,2-dihydroxynorine; And substituted piperizines of 2,2 ', 6,6'-tetraalkylpiperazine (2,2', 6,6'-tetralkylpiperazine), The sulfur-based antioxidant is dirauryl 3,3'-thio-dipropionate or dimyristyl 3,3'-thio-dipropionate (dimiristyl 3,3 ' -dipropionate, DMTP), The phosphorus antioxidant is trialkylphosphite (trialkylphosphite, alkyl isodecyl-, tridecyl-), phenyldialkylphosphite (phenylalkyl-di-phosphite, alkyl isisodecyl, isococtyl )), Diphenylalkylphosphite (alkyl: isodecyl, isooctyl), triphenylphosphite, phospharasoxide (1,1-biphenyl-4,4'-dil, 1, 1 -buphenyl-4,4'-dyl), bistetra (2,4-bis (1,1'-dimethylethyl) phenyl) ester (bis-tetra (bis (1,1'-dimethylethyl) phenyl), 3 , 5-di-t-butyl-4-hydroxybenzylphosphate diethyl ester (3,5-di-t-butyl-hydroxybenzylphodphate-diethylester), 9,10-dihydro-9-xy-10-phosphofenal Tren-10-oxide (9,10-dihydro-9-xy-10-phosphonaltrene-10-oxide), sodium bis (4-t-butylphenyl) phosphite, sodium -2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate (sodium-2,2-methylene-bis (4,6) -di-t-butylphenyl) phosphate), 1,3-bis (diphenoxyphosphonyloxy) benzene (1,3-bis (diphenoxyphosphonyloxy) benzene), bis (2,6-di-t-butyl-4- Methylphenyl) pentaerythritol phosphite (bis (2,6-di-t-butyl-4-methylphenyl) pentaerystolphodphite), tris (2,4-di-t-butylphenyl) phosphite (tris- (2,4-di) -t-butylphenyl) phosphite)) and 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (2,2-methylene-bis- (4,6-di-t-butylphenyl) An organic electroluminescent device, characterized in that selected from the group consisting of octylphosphite). delete The method of claim 1, The doping of the antioxidant is an organic electroluminescent device, characterized in that formed by co-depositing with the material constituting the light emitting layer. delete The method of claim 1, The organic electroluminescent device according to claim 1, wherein any one of the first electrode layer and the second electrode layer is an anode electrode or a cathode electrode. The method of claim 1, The organic electroluminescent device according to any one of the first electrode layer and the second electrode layer is a reflective electrode or a transparent electrode. Board; A first electrode layer formed on the substrate; A light emitting layer on the first electrode; A second electrode layer formed on the light emitting layer; And An organic film layer having charge transport capability formed between the first electrode and the second electrode, The organic film layer is doped with an antioxidant, and the organic film layer doped with the antioxidant has a laminated structure of an organic film layer composed only of a pure charge transport material and an organic film layer on which an antioxidant and the charge transport material are simultaneously deposited. Organic electroluminescent device. The method of claim 9, The organic layer is an organic electroluminescent device comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, a hole suppression layer, an electron transport layer and an electron injection layer. The method according to claim 9 or 10, The doping of the antioxidant is an organic electroluminescent device, characterized in that formed on all or part of the organic layer. The method according to claim 9 or 10, The doping of the antioxidant is an organic electroluminescent device, characterized in that formed by co-deposition at the same time as the material constituting the organic layer. delete The method of claim 9, The antioxidant is an organic electroluminescent device, characterized in that at least one compound selected from the group consisting of phenolic, amine, sulfur and phosphorus antioxidant. The method of claim 14, The phenolic antioxidants are tetrakis (methylene-3.5-di-t-butyl-4-hydroxyphenyl) hydrocinnamate (methylene-3,5-di-t-butyl-4-hydroxyphenylhydrocinnamate) methane methane) or octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate (octadecy-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate), The amine antioxidants include N-substituted alkyl-substituted phenylamines, diaryl-p-phenylene amines or amines of p-phenylene amines thereof; Substituted knolins of 6-ethoxy-2,2'-4-trimethyl-1,2-dihydroxynorine; And substituted piperizines of 2,2 ', 6,6'-tetraalkylpiperazine (2,2', 6,6'-tetralkylpiperazine), The sulfur-based antioxidant is dirauryl 3,3'-thio-dipropionate or dimyristyl 3,3'-thio-dipropionate (dimiristyl 3,3 ' -dipropionate, DMTP), The phosphorus antioxidant is trialkylphosphite (trialkylphosphite, alkyl isodecyl-, tridecyl-), phenyldialkyl phosphite (phenylalkyl-di-phosphite, alkyl isisodecyl, isococtyl )), Diphenylalkylphosphite (alkyl: isodecyl, isooctyl), triphenylphosphite, phospharasoxide (1,1-biphenyl-4,4'-dil, 1, 1 -buphenyl-4,4'-dyl), bistetra (2,4-bis (1,1'-dimethylethyl) phenyl) ester (bis-tetra (bis (1,1'-dimethylethyl) phenyl), 3 , 5-di-t-butyl-4-hydroxybenzylphosphate diethyl ester (3,5-di-t-butyl-hydroxybenzylphodphate-diethylester), 9,10-dihydro-9-xy-10-phosphofenal Tren-10-oxide (9,10-dihydro-9-xy-10-phosphonaltrene-10-oxide), sodium bis (4-t-butylphenyl) phosphite, sodium -2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate (sodium-2,2-methylene-bis (4, 6-di-t-butylphenyl) phosphate), 1,3-bis (diphenoxyphosphonyloxy) benzene (1,3-bis (diphenoxyphosphonyloxy) benzene), bis (2,6-di-t-butyl-4 -Methylphenyl) pentaerythritol phosphite (bis (2,6-di-t-butyl-4-methylphenyl) pentaerystolphodphite), tris (2,4-di-t-butylphenyl) phosphite (tris- (2,4- di-t-butylphenyl) phosphite)) and 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (2,2-methylene-bis- (4,6-di-t-butylphenyl An organic electroluminescent device, characterized in that selected from the group consisting of octylphosphite). The method of claim 9, The antioxidant is an organic electroluminescent device, characterized in that doped at a concentration of 0.1 to 10% by weight. The method of claim 9, The organic electroluminescent device according to claim 1, wherein any one of the first electrode layer and the second electrode layer is an anode electrode or a cathode electrode. The method of claim 9, The organic electroluminescent device according to any one of the first electrode layer and the second electrode layer is a reflective electrode or a transparent electrode. A substrate, a first electrode layer formed on the substrate, a light emitting layer positioned on the first electrode, and a second electrode layer formed on the light emitting layer, and oxidized between the first electrode layer and the second electrode layer. An organic electroluminescent element comprising an inhibitor layer. The method of claim 19, The antioxidant is an organic electroluminescent device, characterized in that at least one compound selected from the group consisting of phenolic, amine, sulfur and phosphorus antioxidant. The method of claim 20, The phenolic antioxidants are tetrakis (methylene-3.5-di-t-butyl-4-hydroxyphenyl) hydrocinnamate (methylene-3,5-di-t-butyl-4-hydroxyphenylhydrocinnamate) methane methane) or octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate (octadecy-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate), The amine antioxidants include N-substituted alkyl-substituted phenylamines, diaryl-p-phenylene amines or amines of p-phenylene amines thereof; Substituted knolins of 6-ethoxy-2,2'-4-trimethyl-1,2-dihydroxynorine; And substituted piperizines of 2,2 ', 6,6'-tetraalkylpiperazine (2,2', 6,6'-tetralkylpiperazine), The sulfur-based antioxidant is dirauryl 3,3'-thio-dipropionate or dimyristyl 3,3'-thio-dipropionate (dimiristyl 3,3 ' -dipropionate, DMTP), The phosphorus antioxidant is trialkylphosphite (trialkylphosphite, alkyl isodecyl-, tridecyl-), phenyldialkylphosphite (phenylalkyl-di-phosphite, alkyl isisodecyl, isococtyl )), Diphenylalkylphosphite (alkyl: isodecyl, isooctyl), triphenylphosphite, phospharasoxide (1,1-biphenyl-4,4'-dil, 1, 1 -buphenyl-4,4'-dyl), bistetra (2,4-bis (1,1'-dimethylethyl) phenyl) ester (bis-tetra (bis (1,1'-dimethylethyl) phenyl), 3 , 5-di-t-butyl-4-hydroxybenzylphosphate diethyl ester (3,5-di-t-butyl-hydroxybenzylphodphate-diethylester), 9,10-dihydro-9-xy-10-phosphofenal Tren-10-oxide (9,10-dihydro-9-xy-10-phosphonaltrene-10-oxide), sodium bis (4-t-butylphenyl) phosphite, sodium -2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate (sodium-2,2-methylene-bis (4,6) -di-t-butylphenyl) phosphate), 1,3-bis (diphenoxyphosphonyloxy) benzene (1,3-bis (diphenoxyphosphonyloxy) benzene), bis (2,6-di-t-butyl-4- Methylphenyl) pentaerythritol phosphite (bis (2,6-di-t-butyl-4-methylphenyl) pentaerystolphodphite), tris (2,4-di-t-butylphenyl) phosphite (tris- (2,4-di) -t-butylphenyl) phosphite)) and 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (2,2-methylene-bis- (4,6-di-t-butylphenyl) An organic electroluminescent device, characterized in that selected from the group consisting of octylphosphite). The method of claim 19, The antioxidant layer is an organic electroluminescent device, characterized in that formed in a thickness of 1 to 50 kPa. The method of claim 19, The antioxidant layer is an organic electroluminescent device, characterized in that formed by a wet method of spin coating, spray coating, printing and dipping. The method of claim 19, The organic electroluminescent device further comprises an organic film layer between the first electrode layer and the second electrode layer. The method of claim 24, And the organic layer comprises at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, a hole suppression layer, an electron transport layer and an electron injection layer. The method of claim 24 or 25, The antioxidant layer is formed on all or a part of the interlayer of the organic film layer having a charge transport capacity organic electroluminescent device. The method of claim 19, The organic electroluminescent device according to any one of the first electrode layer and the second electrode layer is an anode electrode or a cathode electrode. The method of claim 19, The organic electroluminescent device according to any one of the first electrode layer and the second electrode layer is a reflective electrode or a transparent electrode.

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