JP2013062150A - Organic electroluminescent device and method for manufacturing organic electroluminescent device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an organic EL device capable of preventing deterioration of an organic EL element although a direct film sealing method is used, and also capable of achieving longer life of the organic EL element; and a method for manufacturing the organic EL device.SOLUTION: An organic electroluminescent device 100 comprises an organic electroluminescent element 110 formed on a substrate 101, and has a gas barrier layer 120 on the organic electroluminescent element 110. The gas barrier layer 120 includes at least one of metal and semimetal, and also includes a discharge treatment layer 120b having been subjected to discharge treatment and a non-discharge treatment layer 120a having not been subjected to discharge treatment.

Description

  The present invention relates to an organic electroluminescent device and a method for manufacturing the organic electroluminescent device.

  Organic electroluminescence (EL) devices have been found to be degraded by moisture and oxygen in the atmosphere. Therefore, immediately after the formation of the organic EL element, a barrier film made of an inorganic material such as SiOC or SiON can be directly formed by sputtering or vapor deposition (direct film sealing method), and further laminated with a sealing film. It has been proposed (see, for example, Patent Document 1). However, the direct film sealing method has a problem that when the barrier film is formed, the organic EL element itself is deteriorated by heat or the like, and the luminance is lowered accordingly. Furthermore, there is a problem that the barrier property cannot be sufficiently obtained, and the light emitting area is reduced when stored for a long time (deterioration of element lifetime).

International Publication No. 2007/029586

  Accordingly, the present invention provides an organic EL device capable of preventing the deterioration of the organic EL element and extending the life of the organic EL element despite the direct film sealing method, and a method for manufacturing the same. With the goal.

The organic electroluminescence (EL) device of the present invention is an organic EL device in which an organic electroluminescence (EL) element is formed on a substrate,
A gas barrier layer on the organic EL element;
The gas barrier layer includes at least one of a metal and a metalloid;
The gas barrier layer includes a discharge treatment layer subjected to a discharge treatment and a non-discharge treatment layer not subjected to a discharge treatment.

Moreover, the manufacturing method of the organic EL device of the present invention is a manufacturing method of an organic EL device in which a gas barrier layer is formed on an organic EL element formed on a substrate,
A gas barrier layer forming step of forming a gas barrier layer containing at least one selected from metals and metalloids;
A discharge treatment step in which a part of the gas barrier layer is treated as a discharge treatment layer and another part not subjected to the discharge treatment is treated as a non-discharge treatment layer by performing a discharge treatment on a part of the gas barrier layer. It is characterized by.

  According to the present invention, it is possible to provide an organic EL device capable of preventing the deterioration of the organic EL element and extending the life of the organic EL element, and a method for manufacturing the organic EL element, despite the direct film sealing method. Can do.

FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the organic EL device of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the configuration of the organic EL device of the present invention. FIG. 3 is a schematic diagram showing an example of the configuration of an apparatus for manufacturing the organic EL device of the present invention by a batch production method. FIG. 4 is a schematic diagram showing an example of the configuration of an apparatus for manufacturing the organic EL device of the present invention by a continuous production method. FIG. 5 is a photograph of the initial state and 7 days after the organic EL device of Example 1 and Comparative Example 3 was caused to emit light.

  In the organic EL device of the present invention, it is preferable that a ratio of the density of the discharge treatment layer to the density of the non-discharge treatment layer is in the range of more than 1.0 and 2.0 or less.

  In the organic EL device of the present invention, the ratio of the thickness of the discharge treatment layer to the thickness of the gas barrier layer is preferably in the range of 0.05 to 0.3.

In the organic EL device of the present invention, the gas barrier layer is formed in the order of a non-discharge treatment layer and a discharge treatment layer from the organic EL element side,
It is preferable that a barrier layer is further formed on the discharge treatment layer of the gas barrier layer.

  In the organic EL device of the present invention, at least one of the metal and the metalloid is at least one selected from the group consisting of oxide, nitride, carbide, oxynitride, oxycarbide, nitrided carbide, and oxynitride carbide. It is preferable that

  In the manufacturing method of the organic EL device of the present invention, it is preferable that a part of the gas barrier layer is a surface layer portion of the gas barrier layer.

  In the method for manufacturing an organic EL device according to the present invention, the discharge treatment is preferably performed by plasma beam irradiation or ion beam irradiation.

  The organic EL device according to another aspect of the present invention is preferably manufactured by the method for manufacturing an organic EL device of the present invention.

  Next, the present invention will be described in detail. However, the present invention is not limited by the following description.

  The organic EL element in the present invention has a laminate in which an anode, an organic electroluminescence (EL) layer, and a cathode are provided in this order on a substrate. As the anode, for example, an ITO (Indium Tin Oxide) or IZO (registered trademark, Indium Zinc Oxide) layer that can be used as a transparent electrode layer is formed. The organic EL layer includes, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. As the cathode, an aluminum layer, a magnesium / aluminum layer, a magnesium / silver layer, or the like is also formed as a reflective layer. In order not to expose this laminate to the atmosphere, sealing is performed from above with a gas barrier layer.

  As the substrate of the organic EL element, an insulating substrate such as glass or quartz, a metal substrate provided with an insulating layer, a resin substrate, or the like can be used. It is preferable to use a resin substrate on which a gas barrier layer is formed. Moreover, when the transparent resin film in which the gas barrier layer is formed is used as the substrate, the organic EL element can be reduced in weight, thickness, and flexibility. In this case, the organic EL device as a display becomes flexible and can be used like electronic paper by rolling it.

  The gas barrier layer in the organic EL device of the present invention includes a discharge treatment layer that has been subjected to a discharge treatment and a non-discharge treatment layer that has not been subjected to a discharge treatment.

  The discharge treatment layer and the non-discharge treatment layer contain at least one of a metal and a semimetal. It is preferable that at least one metal or metalloid is at least one selected from the group consisting of oxides, nitrides, carbides, oxynitrides, oxycarbides, nitride carbides, and oxynitride carbides. Examples of the metal include aluminum, titanium, indium, and magnesium. Examples of the metalloid include silicon, bismuth, and germanium. In order to improve the gas barrier property, it is preferable to contain carbon and nitrogen that make the network structure (network structure) in the gas barrier layer dense. Furthermore, in order to improve transparency, it is preferable to contain oxygen.

  The gas barrier layer is formed by a dry process using a vacuum such as vapor deposition, sputtering, or chemical vapor deposition (CVD). Thereby, a very dense thin film having a high gas barrier property can be obtained. Among these, a vapor deposition method is preferable. This is because the vapor deposition method is a process with a very high film formation rate and is a highly productive process, and thus has high production efficiency.

  In the organic EL device of the present invention, the discharge treatment layer is formed by subjecting a part of the gas barrier layer to a discharge treatment. The other part that is not subjected to the discharge treatment is a non-discharge treatment layer. The discharge treatment layer has a higher layer density than the non-discharge treatment layer and has excellent gas barrier properties. It is preferable that a part of the gas barrier layer is a surface layer portion of the gas barrier layer. Since the discharge treatment layer is a layer formed by surface treatment, the layer thickness is thin and the transparency is high. The thickness of the layer varies depending on conditions such as discharge output and processing time, but can be in the range of 2.5 nm to 150 nm, and preferably in the range of 7.5 nm to 105 nm. Examples of the discharge treatment include irradiation with an ionizing active gas such as corona discharge, atmospheric pressure plasma, high frequency plasma, direct current plasma, arc discharge plasma, and ion beam. Among these, arc discharge plasma and ion beam are preferable, and arc discharge plasma is more preferable. Arc discharge plasma has been found to have a very high electron density, unlike normally used glow discharge plasma. By using arc discharge plasma for the vapor deposition method, the reactivity can be increased and a very dense gas barrier layer can be formed.

  The arc discharge plasma can be formed by, for example, a pressure gradient type plasma gun, a direct current discharge plasma generator, a high frequency discharge plasma generator, etc., and the pressure capable of generating a high-density plasma stably even during vapor deposition. It is preferable to use a gradient plasma gun.

  In the discharge treatment, it is preferable to introduce a gas. The gas is not particularly limited, and examples thereof include inert gases such as helium, neon, argon, and xenon, and reactive gases such as oxygen, nitrogen, hydrogen, and hydrocarbons.

The density of the discharge treatment layer is higher than the density of the non-discharge treatment layer, and the ratio of the density of the discharge treatment layer to the density of the non-discharge treatment layer is in the range of more than 1.0 and not more than 2.0. Due to the presence of the high density discharge treatment layer, the gas barrier property can be improved even if the gas barrier layer is thin. However, if the density ratio is greater than 2.0 or less than 1.0, an internal stress difference is generated, cracks are generated, and the gas barrier property is decreased. The density ratio is preferably in the range of 1.2 to 1.8, and more preferably in the range of 1.5 to 1.8. The density of the non-discharge treated layer varies depending on the material, composition, and film forming method. For example, the silicon oxide layer is 1.6 to 2.2 g · cm ⁻³ , and the silicon nitride layer is 2.3 to 2 0.7 g · cm ⁻³ .

  The discharge treatment layer is formed on a part of the gas barrier layer, and a ratio of the thickness of the discharge treatment layer to the thickness of the gas barrier layer is in a range of 0.05 to 0.3. When the thickness ratio is less than 0.05, the gas barrier property is lowered, which is not preferable. On the other hand, when the ratio is larger than 0.3, optical absorption is likely to occur by the discharge treatment layer, and the transparency of the gas barrier layer is lowered, and the production efficiency is lowered due to the time required for the treatment. The thickness ratio is preferably in the range of 0.07 to 0.25, and more preferably in the range of 0.13 to 0.25.

  The thickness of the gas barrier layer is preferably in the range of 50 to 500 nm in consideration of gas barrier properties, transparency, film formation time, and internal stress of the film. More preferably, it is the range of 150 nm-350 nm.

  FIG. 1 is a schematic cross-sectional view of an example of the configuration of the organic EL device of the present invention. As illustrated, the organic EL device 100 has a gas barrier layer 120 on an organic EL element 110 formed on a substrate 101. The organic EL element 110 emits light using the excitation energy generated by the combination of electrons and holes in the organic EL layer 112 by an externally supplied current through the anode 111 and the cathode 113. Light from the organic EL layer 112 is emitted from the anode side or the cathode side depending on the configuration of the substrate 101 and the organic EL element 110. In the gas barrier layer 120, a non-discharge treated layer 120a that has not been subjected to a discharge treatment and a discharge treatment layer 120b that has been subjected to a discharge treatment are formed on the organic EL element 110 in this order. FIG. 2 is a schematic cross-sectional view of another example of the configuration of the organic EL device of the present invention. In the organic EL device 200, a gas barrier layer 220 is formed on the organic EL element 110, and a barrier layer 230 is further formed on the gas barrier layer 220. In the gas barrier layer 220, a non-discharge treatment layer 220a and a discharge treatment layer 220b are formed on the organic EL element 110 in this order. The barrier layer 230 preferably contains at least one of the same metal and semimetal as the gas barrier layer, and can be formed in the same manner as the gas barrier layer and the non-discharge treatment layer in the gas barrier layer.

  In the gas barrier layer, the number and order of formation of the non-discharge treatment layers and the discharge treatment layers are not particularly limited as long as at least one of the layers is formed. The order of the formation can be, for example, the order of non-discharge treatment layer / discharge treatment layer, or the order of non-discharge treatment layer / non-discharge treatment layer / discharge treatment layer. It is preferable to form a non-discharge treatment layer as a barrier layer because gas barrier properties can be effectively expressed.

  In the present invention, when at least one of the metal and the metalloid is selected from the group consisting of oxide, nitride, carbide, oxynitride, oxycarbide, nitrided carbide, and oxynitride carbide, oxide, nitride Oxygen, carbon, or nitrogen contained in carbide, oxynitride, oxycarbide, nitride carbide, oxynitride carbide, for example, generates an arc discharge plasma in the presence of a reaction gas, so that at least the metal and the semimetal It can introduce | transduce by performing 1 type of vapor deposition. A metal oxide or a semi-metal oxide can also be used as a vapor deposition material in the vapor deposition. As the reaction gas, an oxygen-containing gas, a nitrogen-containing gas, a hydrocarbon-containing gas, or a mixed gas thereof can be used.

The oxygen-containing gas is oxygen (O ₂ ), dinitrogen monoxide (N ₂ O), nitric oxide (NO), and the nitrogen-containing gas is nitrogen (N ₂ ), ammonia (NH ₃ ), nitrogen monoxide (NO ), Hydrocarbon-containing gases include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), butane (C ₄ H ₁₀ ), ethylene (C ₂ H ₄ ), acetylene (C ₂ ). H ₂ ).

  As a means for evaporating the vapor deposition material, a method of introducing any one of resistance heating, electron beam, and arc discharge plasma into the vapor deposition material (deposition source) can be used. Among these methods, a method using an electron beam or arc discharge plasma capable of high-speed vapor deposition is preferable. These methods may be used in combination.

  The organic EL device can be manufactured by either a batch production method or a continuous production method. In the case of a continuous production method, for example, a transparent resin film is used as a substrate, and the transparent resin film is continuously conveyed by a roll in a vacuum chamber when forming the organic EL element and the gas barrier layer. The organic EL element and the gas barrier layer are formed on the substrate (Roll-to-roll method).

  FIG. 3 shows an example of the configuration of an apparatus for manufacturing the gas barrier layer of the organic EL device according to the present invention by a batch production method. As shown, the manufacturing apparatus 300 mainly includes a vacuum chamber 1, a pressure gradient plasma gun 2, a reflective electrode 5, a focusing electrode 6, a vapor deposition source 7, a discharge gas supply unit 11, a reaction gas supply unit 12, and a vacuum pump 20. As a component. A substrate heater 13 is disposed in the vacuum chamber 1, and a substrate 3 on which an organic EL element is formed is installed on the substrate heater 13. The vapor deposition source 7 is installed at the bottom of the vacuum chamber 1 so as to face the substrate heater 13. A vapor deposition material 8 is mounted on the upper surface of the vapor deposition source 7. The vacuum pump 20 is disposed on the side wall (right side wall in the figure) of the vacuum chamber 1, whereby the inside of the vacuum chamber 1 can be decompressed. The discharge gas supply means 11 and the reaction gas supply means 12 are arranged on the side wall (right side wall in the figure) of the vacuum chamber 1. The discharge gas supply means 11 is connected to a discharge gas gas cylinder 21, whereby a discharge gas (for example, argon gas) having an appropriate pressure can be supplied into the vacuum chamber 1. Yes. The reaction gas supply means 12 is connected to a reaction gas gas cylinder 22, and thereby supplies a reaction gas (for example, oxygen gas, nitrogen gas, methane gas) having an appropriate pressure into the vacuum chamber 1. Is possible. A temperature control means (not shown) is connected to the substrate heater 13. Thereby, the temperature of the substrate 3 can be set within a predetermined range by adjusting the surface temperature of the substrate heater 13. Examples of the temperature control means include a heat medium circulation device that circulates silicone oil and the like.

An example of the manufacturing process of the gas barrier layer when the manufacturing apparatus shown in FIG. 3 is used is as follows. After evacuating the inside of the vacuum chamber 1 to 10 ⁻³ Pa or less, argon is introduced as a discharge gas from the discharge gas supply means 11 into the pressure gradient plasma gun 2 which is an arc discharge plasma generation source, and a constant voltage is applied. Then, the plasma beam 4 is irradiated toward the reflective electrode 5 so that the organic EL element formed on the substrate 3 is exposed. The plasma beam 4 is controlled by the focusing electrode 6 so as to have a constant shape. The output of the arc discharge plasma is, for example, 1 to 10 kW. On the other hand, the reaction gas is introduced from the reaction gas supply means 12. Moreover, the electron beam 9 is irradiated to the vapor deposition material 8 installed in the vapor deposition source 7 to evaporate the material toward the organic EL element. In the presence of the reaction gas, vapor deposition is performed to form a predetermined gas barrier layer on the organic EL element. The gas barrier layer formation rate (vapor deposition rate) is measured and controlled by a crystal monitor 10 installed in the vicinity of the substrate 3. During the period from the start of evaporation until the deposition rate is stabilized, a shutter (not shown) covering the substrate 3 is closed, and after the deposition rate is stabilized, the shutter is opened to form the gas barrier layer. preferable. When a plurality of layers are stacked as the gas barrier layer, this step is repeated to form a predetermined stacked body. At the time of forming the discharge treatment layer, the substrate 3 (organic EL element) is irradiated with only the arc discharge plasma without irradiating the deposition material 8 placed on the deposition source 7 with the electron beam. The output of the arc discharge plasma at this time is the same as described above. By controlling the output of the discharge plasma and the irradiation time, the density and thickness of the discharge treatment layer can be controlled. When the discharge plasma is set to a high output, the discharge treatment layer can be made dense, and when the irradiation time is made long, the thickness of the discharge treatment layer can be increased. The system pressure at the time of forming each layer is, for example, in the range of 0.01 Pa to 0.1 Pa, and preferably in the range of 0.02 Pa to 0.05 Pa. The substrate temperature is, for example, in the range of 20 ° C to 200 ° C, and preferably in the range of 80 ° C to 150 ° C. The generation of the arc discharge plasma and the introduction of the reaction gas may be performed simultaneously or before and after, the reaction gas introduction and the plasma generation may be performed simultaneously, or the plasma may be generated after the reaction gas introduction, A reactive gas may be introduced after the plasma generation. The reaction gas may be present in the system when the gas barrier layer is formed.

  In FIG. 4, an example of the structure of the apparatus which manufactures the gas barrier layer in the organic EL device of this invention by a continuous production system is shown. In the continuous production method, the gas barrier layer is formed on the organic EL element while the transparent resin film on which the organic EL element is formed is continuously conveyed by a roll in a vacuum chamber when the gas barrier layer is formed. It is. 4, the same parts as those in FIG. 3 are denoted by the same reference numerals. As shown in the drawing, in this manufacturing apparatus 400, in place of the substrate heater 13, an unwinding roll 33a, a can roll 35, a winding roll 33b, and two auxiliary rolls 34a and 34b are arranged in the vacuum chamber 31. Yes. The transparent resin film 32 is stretched over the take-up roll 33a and the take-up roll 33b through the can roll 35 and the two auxiliary rolls 34a and 34b. Except for these, the configuration is the same as in FIG. A temperature control means (not shown) is connected to the can roll 35. Examples of the temperature control means are the same as those for the substrate heater 13.

  In continuous production by this apparatus, a film is continuously introduced into the apparatus, and the film is moved to be exposed to an arc discharge plasma beam in the presence of a reactive gas to perform deposition, thereby continuously forming a gas barrier layer. A predetermined laminate can be formed by switching this reaction gas and target and repeating this process without irradiating the vapor deposition material with an electron beam. Continuous production by this apparatus can be carried out in the same manner as the apparatus manufactured by the batch production method, except that vapor deposition and discharge treatment are performed while moving the film.

  Next, examples of the present invention will be described together with comparative examples. The present invention is not limited or restricted by the following examples and comparative examples. In addition, various properties and physical properties in each example and each comparative example were measured and evaluated by the following methods.

(Thickness of each layer constituting the gas barrier layer)
The thickness d of each layer constituting the gas barrier layer is determined by observing the cross section of the organic EL device with a scanning electron microscope (trade name: JSM-6610) manufactured by JEOL Ltd., and the surface of each layer from the surface of the cathode (aluminum layer). The length up to was measured and calculated.

(Density of each layer constituting the gas barrier layer)
The density ρ of each layer constituting the gas barrier layer was determined by measuring the X-ray reflectivity of each layer constituting the gas barrier layer using an X-ray diffractometer (trade name: Smart Lab) manufactured by Rigaku Corporation, and calculating the density of each layer. .

(Water vapor transmission rate)
For the water vapor transmission rate (WVTR), the same sealing layer as that formed in Examples and Comparative Examples was applied to a transparent resin film (polyethylene naphthalate film manufactured by Teijin DuPont Films (thickness 100 μm, trade name “Teonex”)). It was set as the value measured about what was formed. The water vapor transmission rate (WVTR) was measured in a water vapor transmission rate measurement device (manufactured by MOCON, trade name PERMATRAN) specified in JIS K7126 under an environment of a temperature of 40 ° C. and a humidity of 90% RH. In addition, the measurement range of the said water-vapor-permeability measuring apparatus is 0.005g * m ^<-2 > * day ^{< -1} > or more.

(Initial brightness)
The organic EL devices immediately after fabrication were each driven with a constant voltage of 6 V, and the luminance was measured. The luminance was measured using a luminance orientation characteristic measuring device (trade name: C9920-11) manufactured by Hamamatsu Photonics Co., Ltd.

(Light emission area after 7 days)
The organic EL device after the initial luminance measurement was stored in a non-lighted state under a constant temperature and humidity condition of a temperature of 23 ° C. and a humidity of 40%. Seven days later, the organic EL device was caused to emit light, and the light emission area in the microscopic observation was measured. Observation and light emission area measurement were performed using a digital microscope (trade name: VHX-1000) manufactured by Keyence Corporation.

[Example 1]
[Production of organic EL elements]
A stainless steel (SUS) substrate was prepared as a substrate for producing an organic EL element (SUS304, thickness 50 μm). An insulating smoothing layer (JEM-477 3 μm manufactured by JSR Corporation) was applied on the SUS substrate. On top of that, Al was used as an anode by vacuum deposition, and 100 nm was used as the hole injection layer, LG101 (LG Chemical Co., Ltd.) was 10 nm, and NPB (N, N′-bis (naphthalen-1-yl) -N, N was used as the hole transport layer. '-Bis (phenyl) -benzidine) is 50 nm, Alq (tris (8-quinolinolato) aluminum) is 45 nm as the light emitting layer and the electron transport layer, LiF is 0.5 nm as the electron injection layer, and Mg / Ag is 5/5 as the cathode. 15 nm (co-evaporation) and 60 nm of MoO ₃ as a refractive index adjustment layer were vapor-deposited in this order to produce an organic EL device.

[Production of gas barrier layer]
Next, the organic EL element formed on the SUS substrate was mounted on the manufacturing apparatus shown in FIG. Argon gas 20 sccm (20 × 1.69 × 10 ⁻³ Pa · m ³ / sec) was introduced into the pressure gradient plasma gun, and a discharge output of 5 kW was applied to the plasma gun to generate arc discharge plasma. As a reaction gas, nitrogen (purity 5N: 99.999%) was introduced into the vacuum chamber at a flow rate of 40 sccm (40 × 1.69 × 10 ⁻³ Pa · m ³ / sec). A silicon particle (purity 3N: 99.9%) is irradiated with an electron beam (acceleration voltage 6 kV, applied current 50 mA) and evaporated to a deposition rate of 100 nm / min, and a gas barrier layer is formed on the organic EL element. Was deposited to a thickness of 80 nm. At this time, the system internal pressure was 2.0 × 10 ⁻² Pa, and the substrate heater temperature was 100 ° C.

[Discharge treatment]
Thereafter, the irradiation of the electron beam was stopped, and the evaporation of the silicon grains was stopped. In this state, argon gas was vacuumed at a flow rate of 20 sccm (20 × 1.69 × 10 ⁻³ Pa · m ³ / sec) and nitrogen at a flow rate of 40 sccm (40 × 1.69 × 10 ⁻³ Pa · m ³ / sec). It was introduced into a tank, a discharge output of 5 kW was applied to the plasma gun, an arc discharge plasma was applied to the gas barrier layer for 30 seconds to form a discharge treatment layer, and an organic EL device of this example was obtained. .

About the obtained gas barrier layer, the thickness and density of each layer were analyzed. The thickness of the gas barrier layer was 80 nm, and the density was 2.4 g · cm ⁻³ . The thickness of the discharge treatment layer was 10 nm, and the density was 3.6 g · cm ⁻³ .

[Example 2]
Until the non-discharge treatment layer and the discharge treatment layer are formed, a barrier layer is formed on the discharge treatment layer under the same conditions as in the gas barrier layer formation step. An EL device was obtained.

  When the thickness and density of the obtained gas barrier layer were analyzed, it was the same as in Example 1.

[Example 3]
Except for forming an ITO transparent electrode on an alkali-free glass substrate (manufactured by Matsunami Glass Industrial Co., Ltd., product number: AF-45, thickness: 700 μm) and depositing 100 nm of Al as a cathode, An EL device was obtained.

[Comparative Example 1]
An organic EL device was prepared in the same manner as in Example 1, and a device without a gas barrier layer was used as the organic EL device of this comparative example.

[Comparative Example 2]
An organic EL element was produced in the same manner as in Example 1, a non-discharge treatment layer was formed under the same conditions as in Example 1, and a barrier layer was formed thereon under the same conditions as in the non-discharge treatment layer. The organic EL device of this comparative example was obtained.

[Comparative Example 3]
An organic EL element was produced in the same manner as in Example 3, a non-discharge treatment layer was formed under the same conditions as in Example 3, and a barrier layer was formed thereon under the same conditions as in the non-discharge treatment layer. The organic EL device of this comparative example was obtained.

  For the organic EL devices obtained in Examples 1 to 3 and Comparative Examples 1 to 3, the water vapor transmission rate (WVTR), initial luminance, and light emitting area of the sealing layer (transparent gas barrier layer and barrier layer) were measured. The measurement results are shown in Table 1. Moreover, the initial state of the state which made the organic EL device of Example 1 and Comparative Example 3 light-emit, and the photograph seven days later are shown in FIG.

As shown in Table 1, in the organic EL devices obtained in the examples, the water vapor transmission rate of the sealing layer is 0.01 g · m ⁻² · day ⁻¹ or less and has a good gas barrier property. It can be seen that an organic EL device having a suitable deterioration prevention characteristic with a small reduction rate of the light emitting area after 7 days is obtained. On the other hand, in Comparative Examples 2 and 3 having no discharge treatment layer, the water vapor transmission rate was as high as 0.2 g · m ⁻² · day ⁻¹ and the gas barrier properties were inferior. Therefore, it can be seen that the emission area after 7 days of the organic EL device was significantly reduced, and no significant improvement was made as compared with Comparative Example 1 in which the sealing layer was not formed. As shown in FIG. 5, in the organic EL device of Comparative Example 3, many black spots that did not emit light were observed even in the initial stage (immediately after fabrication). The initial luminance is lower in other examples and comparative examples than in Comparative Example 1 because the light emitting layer is deteriorated during the formation of the sealing layer and the luminance is lowered accordingly. Conceivable. Comparing the examples and the comparative example, it can be seen that the formation of the discharge treatment layer can prevent the deterioration of the organic EL element over time while suppressing the deterioration during the formation of the sealing layer of the light emitting layer. In addition, the example using SUS as the substrate has a higher initial luminance than the example using glass. This is because the thermal conductivity [W / m · K] of the metal (SUS304: 16.7) is higher than that of the glass (0.55 to 0.75), and there is less thermal deterioration during the formation of the sealing layer. It is thought that.

  The organic EL device of the present invention can prevent the deterioration of the organic EL element and can extend the life of the organic EL element. Therefore, according to the present invention, it is possible to improve the luminance, lifetime and reliability of the organic EL device. The organic EL device of the present invention can be used in various fields such as a display device, and its application is not limited.

100, 200 Organic electroluminescence (EL) device 101 Substrate 110 Organic electroluminescence (EL) element 111 Anode 112 Organic electroluminescence (EL) layer 113 Cathode 120, 220 Gas barrier layer 120a, 220a Non-discharge treatment layer 120b, 220b Discharge treatment layer 230 Barrier layers 300 and 400 Manufacturing apparatus 1 and 31 Vacuum chamber 2 Pressure gradient plasma gun (arc discharge plasma generation source)
3 Substrate 4 Plasma beam 5 Reflective electrode 6 Focusing electrode 7 Evaporation source 8 Evaporation material 9 Electron beam 10 Crystal monitor 11 Discharge gas supply means 12 Reaction gas supply means 13 Substrate heater 20 Vacuum pump 21 Gas cylinder for discharge gas 22 Gas cylinder for reaction gas 32 Transparent resin film 33a Unwinding roll 33b Winding rolls 34a, 34b Auxiliary roll 35 Can roll

Claims (8)

An organic electroluminescence device in which an organic electroluminescence element is formed on a substrate,
A gas barrier layer on the organic electroluminescence element;
The gas barrier layer includes at least one of a metal and a metalloid;
The organic electroluminescence device, wherein the gas barrier layer includes a discharge treatment layer that has been subjected to a discharge treatment and a non-discharge treatment layer that has not been subjected to a discharge treatment. 2. The organic electroluminescence device according to claim 1, wherein a ratio of the density of the discharge treatment layer to the density of the non-discharge treatment layer is in a range of more than 1.0 and 2.0 or less. 3. The organic electroluminescence device according to claim 1, wherein a ratio of a thickness of the discharge treatment layer to a thickness of the gas barrier layer is in a range of 0.05 to 0.3. The gas barrier layer is formed in the order of a non-discharge treatment layer and a discharge treatment layer from the organic electroluminescence element side,
The organic electroluminescence device according to any one of claims 1 to 3, wherein a barrier layer is further formed on the discharge treatment layer of the gas barrier layer. At least one of the metal and the metalloid is at least one selected from the group consisting of oxide, nitride, carbide, oxynitride, oxycarbide, nitride carbide, and oxynitride carbide, The organic electroluminescent device according to any one of claims 1 to 4. A method for producing an organic electroluminescent device, wherein a gas barrier layer is formed on an organic electroluminescent element formed on a substrate,
A gas barrier layer forming step of forming a gas barrier layer containing at least one selected from metals and metalloids;
A discharge treatment step in which a part of the gas barrier layer is treated as a discharge treatment layer and another part not subjected to the discharge treatment is treated as a non-discharge treatment layer by performing a discharge treatment on a part of the gas barrier layer. A method for producing an organic electroluminescence device, characterized in that: The method of manufacturing an organic electroluminescence device according to claim 6, wherein a part of the gas barrier layer is a surface layer portion of the gas barrier layer. The method of manufacturing an organic electroluminescent device according to claim 6 or 7, wherein the discharge treatment is performed by plasma beam irradiation or ion beam irradiation.