JP2003017244A - Organic electroluminescent element and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electroluminescent element that prevents deterioration by water or oxygen and is capable of improving reliability, and its manufacturing method. SOLUTION: The element part 10 on the substrate is covered by a barrier layer 20 at its surface. The barrier layer 20 seals the element part 10 and an organic layer P and an inorganic layer I are laminated alternately so as to shut off infiltration of water and oxygen. The inorganic layer I performs the function of mainly preventing transmission of water and oxygen and the organic layer P has sufficient elasticity and performs the function of suppressing stress by being provided between the inorganic layers I so that the inorganic layers I may not contact each other. When the barrier layer 20 is made multi-layered by thinning the thickness of one layer, the occurrence of cracks is prevented and the barrier performance is improved and flexibility for enduring deformation such as bending is provided. These organic layer P and inorganic layer I are formed by the vacuum dry process such as vacuum evaporation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device suitable for use in an ultra-thin organic electroluminescent (EL) display and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a liquid crystal display has been the mainstream as a flat panel display, but in recent years, an organic EL display has been attracting attention as one that achieves further thinning and a larger screen. For its practical use, it is required to have a shape processability capable of forming a curved shape as well as a reduction in weight and thickness, and it has been proposed to use a substrate made of a flexible material such as a polymer film. (For example, Japanese Patent Laid-Open Nos. 2-251449 and 2-124785).

This organic EL display has a strip-shaped electrode layer (anode) made of a transparent conductive film on a transparent substrate and a strip-shaped electrode layer (cathode) made of a metal thin film and orthogonal to the anode.
And a large number of element body portions having an organic electroluminescent layer are provided between and. Further, the anode and the cathode are in a matrix, and a voltage is applied between the selected electrodes to cause the organic electroluminescent layer at a predetermined position to emit light. Such a light emitting portion corresponds to each organic EL element, that is, constitutes a pixel on the display.

[0004]

By the way, it is known that the organic EL material is easily and significantly deteriorated by moisture and oxygen, and the organic EL display has a practically great problem that the brightness is lowered. Is left. Conventionally, in order to prevent moisture and oxygen from entering the element body of an organic EL display, a metal lid or glass lid is UV-cured so as to cover the element body from the side opposite to the display surface (transparent substrate side). A method of attaching with an adhesive such as resin has been adopted. However, such a method has a limit in reducing the thickness and weight of the display. In addition, for a flexible display using a polymer film as a substrate, this method cannot fully utilize the degree of freedom in shape.

On the other hand, a method of protecting the element body from moisture and oxygen by forming an inorganic thin film of silicon nitride or the like on the element body, and further applying a resin by spin coating or dipping on it. Has also been proposed (Japanese Patent Laid-Open No. 2000-223264). In this method, the solvent contained in the resin paste may attack the organic electroluminescent layer, so that the inorganic thin film is first formed and then the resin is laminated. This inorganic thin film must be dense and thick enough to have sufficient barrier properties.
For this reason, cracks are likely to occur due to an increase in stress and the barrier properties are rather deteriorated. Further, since the organic electroluminescent layer does not have high adhesion to the transparent electrode layer such as ITO (indium tin oxide), the organic electroluminescent layer may peel off from the transparent electrode layer if the internal stress of the inorganic thin film is high. There is. In addition, since there is a possibility that water may enter the underlying film during the application of the resin, or water or oxygen may be adsorbed at the interface between the film to be formed and the underlying film, the inorganic thin film is thin or the film quality is poor. However, there is a possibility that moisture or oxygen may penetrate the inorganic thin film to reach the organic electroluminescent layer and deteriorate it. As described above, conventionally, it has been difficult to improve the reliability of the element by sealing the organic EL element with a thin film having a high barrier property.

The present invention has been made in view of the above problems, and an object thereof is to provide an organic electroluminescent device capable of preventing deterioration due to water and oxygen and enhancing reliability, and a method for manufacturing the same. It is in.

[0007]

An organic electroluminescent device according to the present invention has an organic electroluminescent layer between a substrate and a first electrode layer and a second electrode layer and is in contact with one surface side of the substrate. The device body has a structure in which an organic layer and an inorganic layer are alternately deposited and laminated, and includes a barrier layer in contact with the surface of the device body opposite to the substrate. This barrier layer prevents the permeation of moisture and oxygen.

In the method for manufacturing an organic electroluminescent device according to the present invention, the first electrode layer, the organic electroluminescent layer and the second electrode layer are sequentially formed on one surface of the substrate to form the device body. And a step of alternately forming an organic layer and an inorganic layer in vacuum on the element body to form a barrier layer.

In the organic electroluminescent device and the method of manufacturing the same according to the present invention, the barrier layer does not contain water or oxygen inside when it is formed, and at the same time, the barrier layer is formed while sandwiching the organic layer. Stresses in the barrier layer are suppressed without compromising flexibility.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic diagram showing an organic EL device according to an embodiment of the present invention. This organic EL device is configured such that the device body 10 is provided on the substrate 1 and the surface thereof is covered with the barrier layer 20 and the protective layer 30.

The substrate 1 is preferably made of a transparent and flexible material, and here, polyethylene (Terephthalate) (PET) is used.
e)) is used. In addition, polycarbonate (P
C: Poly Carbonate), polyolefin (PO: PolyOlef)
in), polyether sulfone (PES; PolyEter Sulph)
One can be preferably used as a high molecular polymer material, and thin film glass may be used.

The element body 10 is a portion having a function as an organic EL element, and the transparent electrode layer 2 from the substrate 1 side,
The organic EL layer 3 and the metal electrode layer 4 are laminated in this order. Here, the transparent electrode layer 2 is a strip-shaped electrode layer (anode) provided to inject holes into the organic EL layer 3. The transparent electrode layer 2 is preferably made of a material having a light-transmitting property in order to extract light from the substrate 1 side. It is preferable that ITO is used as such a material, and tin oxide (SnO ₂ ) and zinc oxide (Z
nO) or the like is used.

The organic EL layer 3 is formed on the transparent electrode layer 2, and the hole transport layer,
A light emitting layer and an electron transporting layer (neither shown) are laminated. The hole transport layer is for transporting holes injected from the transparent electrode layer 2 to the light emitting layer, and its material is, for example, benzine, styrylamine,
Triphenylamine, porphyrin, triazole, imidazole, oxadiazole, polyarylalkane, phenylenediamine, arylamine, oxazole, anthracene, fluorenone, hydrazone, stilbene, or derivatives thereof, or polysilane compounds, vinylcarbazole compounds, A heterocyclic conjugated monomer, oligomer or polymer such as a thiophene compound or an aniline compound can be used. Specifically, for example, α-naphthylphenyldiamine, porphyrin, metal tetraphenylporphyrin, metal naphthalocyanine, 4,4,4-tris (3-
Methylphenylphenylamino) triphenylamine)
Triphenylamine, N, N, N, N-tetrakis (p
-Tolyl) p-phenylenediamine, N, N, N, N-
Examples thereof include tetraphenyl 4,4-diaminobiphenyl, N-phenylcarbazole, 4-di-p-tolylaminostilbene, poly (paraphenylenevinylene), poly (thiophenvinylene), poly (2,2-thienylpyrrole), and the like. .

The light emitting layer is a region in which electrons and holes are injected from the metal electrode layer 4 and the transparent electrode layer 2 when a voltage is applied, and these electrons and holes are recombined. The light emitting layer is made of a material having a high luminous efficiency, for example, an organic material such as a low molecular weight fluorescent dye, a fluorescent polymer, and a metal complex. Such materials include, for example:
Anthracene, naphthalene, phenanthrene, pyrene,
Examples include chrysene, perylene, butadiene, coumarin, acridine, stilbene, tris (8-quinolinolato) aluminum complex, bis (benzoquinolinolato) beryllium complex, and tri (dibenzoylmethyl) phenanthroline europium complex ditoluyl vinylbiphenyl.

The electron transport layer is for transporting electrons injected from the metal electrode layer 4 to the light emitting layer. Examples of the material for the electron transport layer include quinoline, perylene, bisstyryl, pyrazine, and derivatives thereof. Specifically, 8-hydroxyquinoline aluminum, anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene, butadiene, coumarin, acridine, stilbene, or derivatives thereof are used.

A metal electrode layer 4 is provided on the organic EL layer 3. The metal electrode layer 4 is a strip-shaped electrode layer (cathode) provided to inject electrons into the organic EL layer 3, and is formed in a direction orthogonal to the transparent electrode layer 2. Examples of the metal electrode layer 4 include aluminum (Al), indium (In), magnesium (Mg), and silver (A).
g), calcium (Ca), barium (Ba), lithium (Li) and the like are used. Note that these metals may be used alone or may be alloyed with other metals.

The barrier layer 20 seals the element body 10 in order to block intrusion of moisture and oxygen into the element body 10, and is formed by alternately stacking organic layers P and inorganic layers I. It was done. In the present embodiment, the barrier layer 20
From the element body 10 side to the organic layer P1, the inorganic layer I1 ,.
.., starting from the organic layer P, the organic layer Pn, the inorganic layer In, and n layers (n ≧ 2) are laminated.

In this barrier layer 20, the inorganic layer I mainly has a function of preventing permeation of moisture and oxygen, and the organic layer P is generally rich in elasticity and is provided between the inorganic layers I so that they do not come into contact with each other. This has the function of suppressing stress at the interface between the layers. Note that the first layer is the organic layer P1 here because the organic layer P having such a function is also present between the metal electrode layer 4 and the inorganic layer I so that the stress generated at the interface between the two is also present. This is because it is reduced.

The barrier property of the barrier layer 20 against moisture and oxygen is determined by the total thickness of the inorganic layer I. Therefore,
In the present embodiment, the number of layers n is set to be appropriately large with respect to the predetermined total thickness of the inorganic layer I that provides sufficient barrier properties. Therefore, the thickness of each layer is relatively thin, so that the barrier layer 20 has a reduced stress to prevent the occurrence of cracks, and also has flexibility to withstand deformation such as bending. As described above, the thickness of the barrier layer 20 and the number of layers n are appropriately selected in consideration of the relationship between the barrier property and the total thickness, the materials of the organic layer P and the inorganic layer I, and the like. As for the barrier layer 20, it is desirable that the thickness of one layer is made thin to form a multilayer.

The organic layer P and the inorganic layer I are formed by a vacuum film forming method. The vacuum film forming method refers to a film forming method that is performed in a container that has been evacuated to a high vacuum in advance, whereby the organic layer P and the inorganic layer I contain almost no water or oxygen at the interfaces or insides of the layers. . As the vacuum film forming method, for example, a vacuum vapor deposition method, a sputtering method or C
The VD (Chemical Vapor Deposition) method is used.
In the conventional barrier layer, the solvent contained in the organic film raw material is organic E
Although there is a possibility that the barrier layer 20 may penetrate to the L layer, since these are a dry process in which film formation is performed without using a solution or solvent containing water, the barrier layer 20 contains water inside when it is formed. Is prevented and the barrier property is high.

The organic layer P is preferably made of an organic material that can be formed into a film by a film forming process in vacuum and has low water permeability and water absorption. As such a material, for example, cycloolefin polymer, polyethylene, polytetrafluoroethylene, nylon, polymethylmethacrylate (PMMA) can be used, but the material is not limited thereto. In addition, the same barrier layer 20
In the above, it is not necessary to limit the organic layers P1, ..., Pn to one kind of material, and the organic layers P may be two or more kinds. Further, the organic layer P can be composed of a laminated film of two or more layers. For example, a laminated film in which nylon that functions as a moisture absorbent is provided between cycloolefin polymers having low water permeability and low water absorption may be used.

The inorganic layer I can be formed by a film forming process in vacuum and is made of an inorganic material having low water permeability and water absorption and low oxygen permeability. As such a material, for example, silicon nitride (Si
N _x ), silicon oxide (SiO _x ), aluminum oxide (AlO _x ), and metals such as aluminum are included, but are not limited thereto.

The protective layer 30 is for preventing the organic EL element from being damaged from the outside, and is made of, for example, an ultraviolet curable resin. When the outermost layer of the barrier layer 20 is the inorganic layer In, it may also serve as the protective layer 30 depending on the material of the inorganic layer.

Next, a method of manufacturing the organic EL device having such a structure will be described.

First, the element body 10 is formed. For example, a strip-shaped substrate 1 made of PET having a thickness of 188 μm is prepared, and the following layers are sequentially formed thereon. That is, for example, the transparent electrode layer 2 made of ITO and having a thickness of 150 nm is formed by reactive DC sputtering. Then
An organic EL is formed on the transparent electrode layer 2 by, for example, a vacuum deposition method.
As the layer 3, a hole transport layer, a light emitting layer and an electron transport layer are formed in this order. At this time, for example, as the hole transport layer, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphene is used.
ylamine (m-MTDATA), 4,4 'as the light emitting layer
-bis [N- (1-naphtyl) -N-phenylamino] biphenyl) (α-N
PD), as an electron transport layer, tris (8-hydroxyquinolin
e) A film is formed using aluminum (Alq ₃ ).
The total thickness of the organic EL layer 3 is, eg, 150 nm.
Next, on the organic EL layer 3, Al is formed by, for example, a vacuum deposition method.
A metal electrode layer 4 made of a Li alloy and having a thickness of 100 nm is formed.

Next, the barrier layer 20 is formed. Figure 2
It is a block diagram which shows the outline of the film-forming apparatus used for film-forming of the barrier layer 20 of an organic EL element in this Embodiment. The film forming apparatus 100 forms a film on the film-shaped substrate 1 by a so-called roll coating method in which the film is processed while being fed from one roll to the other roll.

The film forming apparatus 100 shuts off outside air by, for example, an exhaust valve 42 connected to a vacuum pump (not shown) and a vacuum chamber 41 provided with a gas introduction valve 43 for introducing a reaction gas. It is possible to do. Inside the vacuum chamber 41, there are provided a feed roll 44 for continuously feeding the film-shaped substrate 1, a guide roll 45, and a winding roll 46 for winding the fed-out substrate 1. Can rolls 47a to 47e for forming a traveling path of the substrate 1 between the rolls are appropriately arranged. Furthermore, the substrate 1
A plasma electrode 48 for cleaning the surface thereof, and a vapor deposition source 49A and a vapor deposition source 49B for forming a thin film on the surface are provided on the one surface side. Here, it is assumed that the vapor deposition source 49A deposits the organic layer P by vapor deposition, and the vapor deposition source 49B deposits the inorganic layer I by sputtering. The vapor deposition source 49A uses the organic layer P as an evaporation material.
The material is stored in the vapor deposition source 49B, and the vapor deposition source 49B is provided with a target according to the material of the inorganic layer I. For example, a cycloolefin polymer is used as the material of the organic layer P, and a Si target is used when the inorganic layer I is, for example, silicon nitride. A monitor for confirming the film quality and thickness of the formed thin film may be provided in the vacuum chamber 41.

In this film forming apparatus 100, the feed roll 44
When the substrate 1 is rotated and the substrate 1 wound around it is delivered, the take-up roll 46 is rotated to wind the substrate 1 following the path shown in the figure. At that time, by adjusting the rotation speeds of the feed roll 44 and the take-up roll 46, the traveling speed of the substrate 1 between them can be controlled. Further, the substrate 1 once fed from the feed roll 44, the can rolls 47a to 47c, the guide roll 4
5, winding roll 4 through can rolls 47d and 47e
Take up to 6. In this traveling route, the substrate 1 is sequentially subjected to the following processing on its one surface side.

First, the surface is cleaned by the plasma discharge generated by the plasma electrode 48, and when the position of the guide roll 45 facing the vapor deposition source 49A is reached,
Here, the organic layer P is vacuum-deposited by the vapor deposition source 49A.
Is formed. Further, the evaporation source 49B of the guide roll 45
When it reaches a position facing with, the inorganic layer I is deposited here by sputtering by the vapor deposition source 49B. In this way, the organic layer P and the inorganic layer I are sequentially formed on the substrate 1. By performing this while rotating the feed roll 44 and the winding roll 46, the organic layer P and the inorganic layer I are formed on the substrate 1. I can be continuously formed into a film.

Next, the procedure of film formation will be described. First, the strip-shaped substrate 1 on which the element body 10 is formed is formed into a film forming apparatus 10
The substrate 1 is wound around the 0 feed roll 44 and adjusted so that the substrate 1 travels to the take-up roll 46 along the above-described path. Further, the vacuum chamber 41 is hermetically sealed, and the inside thereof is evacuated through the exhaust valve 42.

Subsequently, plasma discharge is generated in the plasma electrode 48, and vapor deposition is started in the vapor deposition sources 49A and 49B respectively. In this state, the feed roll 44 and the take-up roll 46 are rotated to feed the feed roll 44. At the same time as the substrate 1 wound on the
Try to wind it up with. At that time, the input power to the vapor deposition sources 49A and 49B is (to determine the vapor deposition rate):
The travel speed of the substrate 1 is adjusted appropriately.

As a result, the substrate 1 is moved to the can roll 47.
When traveling between a and 47b, the surface is plasma-cleaned, and when it reaches a position facing the vapor deposition source 49A of the guide roll 45 via the can roll 47c, the organic layer P is formed on the surface by vacuum vapor deposition. . Further, the guide roll 45
When reaching a position facing the vapor deposition source 49B, the inorganic layer I is formed on the organic layer P by sputtering. After that, the substrate 1 is wound around the winding roll 46 via the can rolls 47d and 47e. The substrate 1 to be housed has the element body portion 10, the organic layer P, and the inorganic layer I in that order on one surface side. It has been formed into a film.

At this time, the organic layer P provided between the element body 10 and the inorganic layer I buffers the stress and prevents its influence. Therefore, in the formed substrate 1, the organic EL layer 3 is less likely to be peeled off or the inorganic layer I is cracked even if the substrate 1 is wound by a roll and bent or subjected to tension.

After the film formation on the substrate 1 having a predetermined length is completed, the plasma electrode 48, the vapor deposition source 49A and the vapor deposition source 49B are once stopped, and the substrate 1 is rewound on the feed roll 44. The feed roll 44 and the take-up roll 46 may be made compatible with each other, and the take-up roll 46 removed after winding may be attached to the position of the feed roll 44. Next, the plasma electrode 48, the vapor deposition source 49A and the vapor deposition source 49
B is operated again, and the organic layer P and the inorganic layer I are formed on the substrate 1 in the same manner as the above steps. Thus, by repeating the step of forming the organic layer P and the inorganic layer I at one time,
The organic layer P and the inorganic layer I can be easily laminated periodically in a desired number of layers.

As a result, the barrier layer 20 in which two or more organic layers P and inorganic layers I are alternately laminated is formed on the surface of the element body 10. Here, since the organic layer P and the inorganic layer I are continuously formed by a dry process without being exposed to the atmosphere, the risk of water or oxygen being taken in at the film interface or in the film is prevented. It

Finally, for example, an ultraviolet curable resin is spin-coated to form a protective layer 30 having a thickness of 10 μm so as to cover the barrier layer 20 from above. Thus, organic E
The L element is manufactured.

As described above, in this embodiment, since the barrier layer 20 provided on the element body 10 is laminated between the inorganic layers I with the organic layer P interposed therebetween, the inside of the barrier layer 20 is formed. Is reduced, and the occurrence of cracks in the inorganic layer I is prevented. Further, since the barrier layer 20 is configured to achieve a desired total thickness by stacking a large number of thin layers, the stress is reduced and the cracks are generated even when the thickness of the inorganic layer I per layer is reduced. It will be difficult. Therefore, it becomes possible to form the inorganic layer I to a desired total thickness while preventing the occurrence of cracks, and the barrier layer 20 can have a sufficient barrier property. This allows organic EL
The element is resistant to deterioration and has high reliability.

At the same time, a glass lid or the like is conventionally used to seal the element body, but the organic EL element can be made thinner by replacing the barrier layer 20 made of a thin film. Further, the organic layer P and the inorganic layer I are multi-layered, so that the organic EL element has flexibility that can follow the deformation of the substrate 1.

Further, since the barrier layer 20 uses the organic layer P1 as the first layer, the inorganic layer I and the metal electrode layer 4 of the element body 10 are
The stress generated between and is also reduced, cracks generated in the inorganic layer I can be further prevented, and peeling of the organic EL layer 3 and the like can also be prevented.

Furthermore, since the organic layer P and the inorganic layer I are formed continuously by the vacuum evaporation method in the same apparatus, the barrier layer 2 containing neither moisture nor oxygen in the film or at the film interface is used.
It is possible to obtain an organic EL element that is resistant to deterioration because 0 is formed, and it is possible to simplify the manufacturing process and reduce the manufacturing cost. Here, since the belt-shaped polymer substrate is used as the substrate 1, roll coating by the film forming apparatus 100 is possible, and mass productivity is dramatically improved.

[0042]

EXAMPLES Next, examples of the present invention will be described. In the present embodiment, the same elements as those in the above-described embodiment are designated by the same reference numerals and described.

Example 1 One layer each of the organic layer P and the inorganic layer I was laminated on the surface of the element body 10 on the substrate 1 to form a barrier layer. The film forming apparatus used is an apparatus for vacuum film forming, in which both an evaporation source for vacuum evaporation and an evaporation source (target) for sputtering are provided in one container.

First, the substrate 1 on which the element body 10 is formed
Was installed in the device, and a cycloolefin polymer was formed as a 100 nm-thick organic layer P on the surface of the element body 10 side by vacuum deposition. At that time, the cycloolefin polymer was pulverized and the tantalum (T
a) It was placed in a boat made by evaporation and vapor deposition was performed by resistance heating.
In addition, F was added to the formed cycloolefin polymer layer.
When T-IR measurement was performed, it became clear that the structure was the same as that of the evaporation material before film formation. From this, it was confirmed that the vapor deposition method can be used for the film formation of the cycloolefin polymer.

Subsequently, a 200 nm thick silicon nitride film was formed as an inorganic layer I on the cycloolefin polymer film by sputtering. The film forming conditions at that time were as follows: Si was used as a target, the flow rate ratio of argon gas and nitrogen gas was 88:12, and the gas was introduced into the apparatus at a gas pressure of 0.4 P.
a, RF power was 1.5 kW. No crack was found in the silicon nitride layer of the barrier layer thus formed.

After forming the barrier layer, the organic EL device was left in an atmosphere of 40 ° C. and a relative humidity of 90% for 60 hours or more, but no deterioration of the device body 10 was observed. Therefore, it is understood that the formed barrier layer has excellent barrier properties.

Example 2 On the surface of the element body 10 on the substrate 1, an inorganic layer I1 was formed as a first barrier layer by using silicon nitride. The film forming conditions were the same as in Example 1, and the thickness was 100 nm. No cracks were found in this silicon nitride layer. Further, when the refractive index of the deposited silicon nitride was measured using light with a wavelength of 633 nm, the value was 2.0, and it is considered that a film with high density was obtained. Therefore, it is understood that a barrier layer without cracks can be formed by alternately depositing the same silicon nitride layer and the organic layer P.

(Comparative Example) On the surface of the element body 10 on the substrate 1, an inorganic layer I1 was formed as a first barrier layer by silicon nitride. The film forming conditions were the same as in Example 1, and the thickness was 200 nm. Generation of cracks was observed in this silicon nitride layer.

From Example 1 and Comparative Example, it is considered that in Example 1, the stress generated in the silicon nitride layer was suppressed by providing the cycloolefin polymer layer with the element body 10. Further, according to Examples 1, 2 and Comparative Example, when the inorganic layer I is formed as the first layer as the barrier layer, cracks are more likely to occur than when the organic layer P is the first layer, It is suggested that the thickness needs to be set thinner.

Although the present invention has been described with reference to the embodiments and examples, the present invention is not limited to the above-described embodiments and examples, and various modifications can be made. For example, in the above-described embodiment, the barrier layer 20 includes the organic layers P1, the inorganic layers I1, ... 2) The barrier layer 20 is assumed to be laminated.
The first layer and the outermost layer may be either the organic layer P or the inorganic layer I, and the number of the organic layers P and the inorganic layers I is not the same, and either one may be more than one layer.

Further, in the above embodiment, the film forming apparatus 10
In the description of 0, the vapor deposition sources 49A and 49B are provided and two layers are formed by one roll coating, but the number and type of the vapor deposition sources 49 can be arbitrarily selected. Further, it goes without saying that the film formation of each layer does not necessarily have to be performed by the roll coating method. As a modification of such a film forming apparatus, for example, one vacuum chamber 3
A plurality of vapor deposition sources 49 may be provided in one to form a multilayer during one roll coating or one cycle of the substrate. Further, one vacuum chamber may be partitioned into several areas, and the substrate 1 may be run between them. In any case, any structure may be used as long as the organic layer P and the inorganic layer I can be continuously formed without exposure to the atmosphere. Furthermore, not only the organic layer P and the inorganic layer I but also the vapor deposition source 49 is provided not only for the element body 10 or the protective film 30.
It may be formed by roll coating in the film forming apparatus 100.

Further, the structure of the element body is not limited to the structure shown in the above-mentioned embodiment, and any structure can be used as long as it can be configured as an organic EL element using an organic compound in the light emitting layer.

[0053]

As described above, according to the organic electroluminescent element of any one of claims 1 to 6, an organic layer and an inorganic layer are alternately deposited and laminated. As well as having a barrier layer in contact with the surface of the element body portion opposite to the substrate, it contains almost no moisture or oxygen and is sufficient to block moisture or oxygen by suppressing the occurrence of cracks. The element body portion is protected by the barrier layer having a good barrier property and its deterioration is prevented.
Therefore, the reliability of the element can be improved. Further, the barrier layer in which the organic layer is interposed between the inorganic layers is resistant to bending, and the element itself can be provided with flexibility. Furthermore, the barrier layer can be made thinner than a glass lid or the like that has been conventionally used for sealing.

Further, according to the method of manufacturing an organic electroluminescence device according to any one of claims 7 to 13,
Since a step of forming a barrier layer by alternately vacuum-depositing an organic layer and an inorganic layer on the element body is included, the element body is sealed with a barrier layer containing almost no water or oxygen. Thus, it is possible to obtain an organic electroluminescence device in which deterioration is prevented. Further, the organic layer and the inorganic layer can be continuously formed, and the manufacturing process can be simplified and the manufacturing cost can be reduced.

[Brief description of drawings]

FIG. 1 is a schematic view of an organic EL element according to an embodiment of the present invention.

FIG. 2 is a schematic view of a film forming apparatus according to an embodiment of the present invention as seen from a side surface.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Transparent electrode layer, 3 ... Organic EL layer, 4 ... Metal electrode layer, 10 ... Element body part, 20 ... Barrier layer, 30 ... Protective layer, 41 ... Vacuum chamber, 42 ... Exhaust valve, 43 ...
Gas introduction valve, 44 ... Feed roll, 45 ... Guide roll, 46 ... Winding roll, 47 ... Can roll, 48 ... Plasma electrode, 49A, 49B ... Vapor deposition source, 100 ... Film forming apparatus, P ... Organic layer, I ... Inorganic layer

Continued front page    (72) Inventor Masato Kobayashi             6-735 Kita-Shinagawa, Shinagawa-ku, Tokyo Soni             -Inside the corporation F-term (reference) 3K007 AB11 AB13 AB15 AB18 BA07                       BB00 CA06 CB01 DA01 DB03                       EA01 EA04 EB00 FA01 FA02

Claims (13)

[Claims] 1. A substrate, an element main body portion having an organic electroluminescent layer between the first electrode layer and the second electrode layer, which is in contact with one surface side of the substrate, and an organic layer and an inorganic layer. An organic electroluminescence device having a structure in which films are alternately formed and stacked, and a barrier layer in contact with a surface of the device body opposite to the substrate. 2. The organic electroluminescent device according to claim 1, wherein the organic layer and the inorganic layer are formed by a vacuum film forming method. 3. The organic electroluminescent device according to claim 2, wherein the organic layer and the inorganic layer are formed by any one of a vapor deposition method, a sputtering method and a CVD method. 4. The organic electroluminescent device according to claim 1, wherein a layer of the barrier layer that is in contact with the device body is an organic layer. 5. The organic electroluminescent device according to claim 1, wherein the substrate is made of a flexible material. 6. The organic electroluminescent device according to claim 5, wherein the substrate is made of a polymer material. 7. A step of sequentially forming a first electrode layer, an organic electroluminescent layer, and a second electrode layer on one surface side of the substrate to form an element body portion; and, on the element body portion, And a step of forming a barrier layer by alternately vacuum-depositing an organic layer and an inorganic layer. 8. The method of manufacturing an organic electroluminescence device according to claim 7, wherein the organic layer and the inorganic layer are continuously formed. 9. The method of manufacturing an organic electroluminescent device according to claim 8, wherein at least a part of the process of forming the device body is continuously performed with the process of forming the barrier layer. 10. The method for manufacturing an organic electroluminescence device according to claim 7, wherein the organic layer and the inorganic layer are formed by any one of a vapor deposition method, a sputtering method and a CVD method. 11. The method of manufacturing an organic electroluminescent device according to claim 7, wherein in the step of forming the barrier layer, an organic layer is first formed immediately above the device body. 12. The method of manufacturing an organic electroluminescent device according to claim 7, wherein a flexible substrate is used as the substrate. 13. The method of manufacturing an organic electroluminescent device according to claim 12, wherein a polymer substrate is used as the substrate.