JP2016171038A - Method for manufacturing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an electronic device that is excellent in bending durability.SOLUTION: A method for manufacturing an electronic device includes the steps of: subjecting the surface of a gas barrier film that includes a base material, a gas barrier layer and a transition metal compound-containing layer and the surface of a main base material to activation treatment, and then forming a joining margin on each of the surface of the gas barrier film and the surface of the main base material; and bringing the joining margins into contact to each other and sealing an electronic element body by normal temperature joining.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing an electronic device, including a step of room-temperature bonding of an electronic element body using a gas barrier film including a transition metal compound-containing layer.

  Electronic devices such as organic electroluminescent elements (organic EL devices), organic solar cells, organic transistors, inorganic electroluminescent elements, inorganic solar cells (for example, CIGS solar cells) are sensitive to oxygen and moisture present in the environment of use. . For example, when a display or a lighting device is configured using an organic EL device, the organic material itself is deteriorated by oxygen or moisture (including water vapor etc.), the luminance is lowered, and as a result, there is a drawback in that it does not emit light. is there.

  As a means for protecting an electronic device from oxygen and moisture, for example, Patent Document 1 describes an invention relating to an organic EL device in which the periphery of a display unit is sealed at room temperature using a base substrate and a sealing substrate. Has been.

  Furthermore, in recent years, development of flexible electronic devices such as a display that can be bent and folded or wound can be expected.

JP 2004-152663 A

  Room temperature bonding is advantageous for the manufacture of electronic devices because the thickness of the bonded portion can be extremely reduced compared to when bonded by a sealing material such as an adhesive, and damage to the device due to heating during bonding can be prevented. is there. However, in an electronic device as described in Patent Document 1, when repeated bending under practical conditions, that is, when repeated bending is performed with a small bending radius, the gas barrier property and the light emission intensity are lowered, so that the bending durability is low. The inventor has found that this is insufficient.

  Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a method for manufacturing an electronic device having excellent bending durability.

  The present inventors have intensively studied to solve the above problems. As a result, the surface of the gas barrier film including the base material, the gas barrier layer and the transition metal compound-containing layer and the surface of the main base material are activated and bonded to the surface of the gas barrier film and the surface of the main base material, respectively. And a step of forming a margin; and a step of bringing the joining margins into contact with each other and sealing the electronic element body by room temperature bonding. It came to.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the electronic device excellent in bending durability can be provided.

Fig.1 (a) is a schematic cross section of the electronic device obtained by one Embodiment of the manufacturing method concerning this invention. FIG.1 (b) is the figure which represented typically the 1b-1b cross section in Fig.1 (a). It is a typical top view showing an electronic device obtained by one embodiment of a manufacturing method concerning the present invention. 1 is a schematic cross-sectional view showing an example of a room temperature bonding apparatus that can be used in the present invention. It is a cross-sectional schematic diagram which shows the pressurization state for normal temperature joining in the normal temperature joining apparatus which can be used for this invention.

  In one embodiment of the present invention, the surface of the gas barrier film including the base material, the gas barrier layer and the transition metal compound-containing layer and the surface of the main base material are activated, and the surface of the gas barrier film and the main base material A method of manufacturing an electronic device, comprising: forming a bonding margin on each of the surfaces; and contacting the bonding margins and sealing an electronic element body by room temperature bonding. The electronic device manufactured by such a manufacturing method is excellent in bending durability. Although it does not restrict | limit the technical scope of this invention, it is estimated that this is based on the following mechanisms.

  In sealing an electronic device by room temperature bonding, a rigid sealing material such as an adhesive is not required, so that flexibility can be imparted to the electronic device. Here, when the electronic device is repeatedly bent with a small radius of curvature, stress is applied in a direction in which the interface of the joint formed during sealing peels off. When bending is repeated, it is considered that the joint part peels off when the joint part cannot withstand this stress. On the other hand, the inventor has surprisingly improved the bending resistance of electronic devices by using a gas barrier film containing a transition metal compound-containing layer as a member used for sealing an electronic element body by room temperature bonding. I found. Although the detailed mechanism is unknown, since the transition metal compound (for example, Group 5 element) can have a plurality of valences, the transition metal compound-containing layer is a compound having various intermolecular distances. Can exist. Thereby, it is presumed that the gas barrier film has a flexible structure and functions to relieve stress applied to the joint portion of the electronic device.

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

  In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

  In the present specification, “a gas barrier film including a base material, a gas barrier layer and a transition metal compound-containing layer” is also referred to as “a gas barrier film according to the present invention”.

  FIG. 1A is a schematic cross-sectional view of an electronic device 10 manufactured by a manufacturing method according to an embodiment of the present invention. That is, the electronic device 10 shown in FIG. 1 has a main substrate 11, a gas barrier film 12, and an organic EL element body 13 positioned between the main substrate 11 and the gas barrier film 12. The gas barrier film 12 is composed of a laminate of a base material 12a, a gas barrier layer 12b, and a transition metal compound-containing layer 12c, and is arranged so that the transition metal compound-containing layer 12c faces the organic EL element body 13. Yes. The gas barrier film 12 includes a gas barrier layer 12b formed on the base material 12a and a transition metal compound-containing layer 12c formed on the gas barrier layer 12b. The gas barrier film according to the present invention has this configuration. It is not limited, For example, the structure which has the transition metal compound containing layer formed on the base material and the gas barrier layer formed on the said transition metal compound containing layer may be sufficient.

  In the present embodiment, a protective layer 15 is provided on the organic EL element body 13 so as to cover a part of the organic EL element body 13. An extraction electrode 14 for controlling the organic EL element main body 13 from the outside is formed on the main base material 11, and the main base material 11 (and the extraction electrode 14) is disposed between the gas barrier film 12. A silicon film 16 is formed. The organic EL element body 13 is sealed by bonding the main substrate 11 and the gas barrier film 12 via the silicon film 16. That is, at the interface between the main base material 11 and the extraction electrode 14 formed on the main base material 11 and the transition metal compound-containing layer 12 c constituting the gas barrier film 12, the main base material 11 is interposed via the silicon film 16. (And the extraction electrode 14) and the gas barrier film 12 are joined. In the electronic device 10, the transition metal compound-containing layer 12 c is disposed so as to face the organic EL element body 13. However, the base material 12 a and the organic EL element body 13 may be disposed so as to face each other. In this case, at the interface between the lead electrode formed on the main substrate and the substrate constituting the gas barrier film, the main substrate and the gas barrier film are bonded via a silicon film formed as necessary. Will be. In addition, although the silicon film 16 is formed between the main base material 11 and the gas barrier film 12, in the manufacturing method according to the present invention, the main base material and the gas barrier film are formed without forming the silicon film. The electronic element body may be sealed with.

  In the embodiment shown in FIG. 1A, the organic EL element body 13 is an electronic element body, and includes a first electrode (anode) 17, a hole transport layer 18, a light emitting layer 19, an electron transport layer 20, and a second electrode. A (cathode) 21 is formed by being laminated on the main base material 11 in this order. In the electronic device manufactured by the manufacturing method according to the present invention, the main substrate 11 may be the gas barrier film according to the present invention.

  FIG.1 (b) is the figure which represented typically the 1b-1b cross section in Fig.1 (a). As shown in FIG. 1 (b), an extraction electrode 14 is formed on the main substrate 11, and the transition metal compound-containing layer 12 c of the gas barrier film 12 is interposed between the main substrate 11 ( And the extraction electrode 14).

  FIG. 2 is a schematic plan view showing an electronic device obtained by an embodiment of the manufacturing method according to the present invention. In FIG. 2, an organic EL element body 203 is provided on a main substrate 201, and a first joining margin is formed around the organic EL element body 203. Further, the gas barrier film 202 is formed with a second joining margin at a portion corresponding to the first joining margin on the surface to be joined to the main base material 201. The organic EL element body 203 is sealed so as to be sandwiched between the main base material 201 and the gas barrier film 202 by bringing the first and second joining margins into contact with each other and performing normal temperature joining. Here, the “periphery” of the organic EL element body 203 is a periphery having a predetermined distance d from the periphery of the organic EL element body 203 as shown in FIG.

  Hereafter, each process of the manufacturing method which concerns on this invention is demonstrated in detail.

[Gas barrier film including substrate, gas barrier layer and transition metal compound-containing layer]
In the production method according to the present invention, a gas barrier film (gas barrier film according to the present invention) including a base material, a gas barrier layer and a transition metal compound-containing layer is used. In addition, the number of each of the gas barrier layer and the transition metal compound-containing layer included in the gas barrier film may be one layer or a plurality of layers. Preferably, the number of gas barrier layers is 1 to 10, more preferably 1 to 3. Moreover, the number of layers of a transition metal compound content layer becomes like this. Preferably it is 1-10 layers, More preferably, it is 1-3 layers. The gas barrier layer and the transition metal compound-containing layer may be formed on one side of the substrate or may be formed on both sides, but from the viewpoint of production efficiency of the gas barrier film, the gas barrier layer is preferably formed on one side of the substrate. A gas barrier film comprising a layer and a transition metal compound-containing layer is used.

  In the gas barrier film according to the present invention, the order in which the gas barrier layer and the transition metal compound-containing layer are laminated on the substrate is not particularly limited. Examples of the order in which the gas barrier layer and the transition metal compound-containing layer are laminated are illustrated below, but are not limited thereto.

(1) Base material / gas barrier layer / transition metal compound-containing layer (2) Base material / transition metal compound-containing layer / gas barrier layer (3) Base material / transition metal compound-containing layer / gas barrier layer / transition metal compound-containing layer (4) ) Base material / gas barrier layer / transition metal compound-containing layer / gas barrier layer Preferably, the outermost gas barrier layer is a base material rather than the outermost transition metal compound-containing layer, as in (1) and (3) above. Preferably it is formed on the side. That is, in the process for producing the gas barrier film according to the present invention, it is preferable to include at least one step of forming a transition metal compound-containing layer on the gas barrier layer after the step of forming the gas barrier layer. Thus, when sealing the electronic device body, as shown in FIG. 1, when the transition metal compound-containing layer and the electronic device body are arranged so as to face each other, the transition metal compound-containing layer and the layered electronic device body are The distance can be reduced. The “outermost gas barrier layer” and “outermost transition metal compound-containing layer” mean a gas barrier layer and a transition metal compound-containing layer provided at positions farthest from the substrate. The above “on the gas barrier layer” includes an aspect in which the transition metal compound-containing layer is directly formed on the surface of the gas barrier layer and an aspect in which another functional layer is included between the gas barrier layer and the transition metal compound-containing layer. However, preferably, the transition metal compound-containing layer is formed directly on the surface of the gas barrier layer. Use a gas barrier film in which the outermost gas barrier layer is formed on the substrate side of the outermost transition metal compound-containing layer (that is, the distance between the transition metal compound-containing layer and the multilayer electronic device body is reduced). Thereby, the bending durability of the electronic device can be improved. This is considered to be due to the effect that the transition metal compound-containing layer absorbs the stress load applied to the joint interface becoming larger. In one embodiment of the present invention, the gas barrier film includes a base material, a gas barrier layer, and a transition metal compound-containing layer in this order, and forms a bonding margin on the surface on which the transition metal compound-containing layer is disposed. An electronic device manufacturing method is provided.

  Moreover, as a gas barrier film used for the manufacturing method which concerns on this invention, what the gas barrier layer and the transition metal compound content layer were arrange | positioned adjacently is preferable. In one embodiment of the present invention, an electronic device manufacturing method using a gas barrier film in which a gas barrier layer and a transition metal compound-containing layer are disposed adjacent to each other is provided. By using such a gas barrier film, the bending durability of the electronic device can be further improved. Although it does not restrict | limit the technical scope of this invention, it is estimated that this is based on the following mechanisms. That is, when the electronic device is repeatedly bent with a small radius of curvature, stress is applied not only to the joint formed at the time of sealing but also to the gas barrier layer. As described above, since the transition metal compound-containing layer is considered to have stress relaxation properties, in the gas barrier film in which the gas barrier layer and the transition metal compound-containing layer are arranged adjacent to each other, the gas barrier is formed by the transition metal compound-containing layer. It is considered that the stress applied to the layer may be particularly effectively alleviated. From the viewpoint of stress relaxation of the gas barrier layer, the gas barrier film according to the present invention further has at least one transition metal compound-containing layer on the substrate side, further than the gas barrier layer formed on the most substrate side. preferable. More preferably, the gas barrier film according to the present invention includes a base material, a first transition metal compound-containing layer, a gas barrier layer, and a second transition metal compound-containing layer in this order. In a certain embodiment, the manufacturing method which concerns on this invention forms a joining margin on the surface by which the said 2nd transition metal compound content layer is arrange | positioned.

<Base material>
The base material used for the gas barrier film is a long one, and can hold a gas barrier layer having a gas barrier property (also simply referred to as “barrier property”) described below. However, it is not particularly limited to these.

  Examples of the substrate include, for example, polyacrylate ester, polymethacrylate ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC). , Polyethylene (PE), polypropylene (PP), cycloolefin polymer (COP), cycloolefin copolymer (COC), triacetate cellulose (TAC), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, Resin films such as polysulfone, polyethersulfone, polyimide, polyetherimide, and heat-resistant transparent film having silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton (for example, Product name Sila-DEC; manufactured by Chisso Corporation, and product name Sylplus (registered trademark); manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and further, a resin film constituted by laminating two or more layers of the resin. it can.

  In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), etc. are preferably used, and are cast because of their optical transparency and low birefringence. TAC, COC, COP, PC, etc. produced by the above method are preferably used, and silsesquioxane having an organic-inorganic hybrid structure in terms of optical transparency, heat resistance, and adhesion to the gas barrier layer A heat-resistant transparent film is preferably used.

  On the other hand, for example, when a gas barrier film is used for a functional element of a flexible display, the process temperature may exceed 200 ° C. in the array manufacturing process. In the case of manufacturing by roll-to-roll, since a certain amount of tension is always applied to the base material, when the base material temperature rises when the base material is placed under high temperature, the base material temperature exceeds the glass transition point. There is a concern that the elastic modulus of the base material is drastically lowered and the base material is stretched by tension, thereby damaging the gas barrier layer. Therefore, in such applications, it is preferable to use a heat-resistant material having a glass transition point of 150 ° C. or higher as the base material. That is, it is preferable to use a heat-resistant transparent film having polyimide, polyetherimide, or silsesquioxane having an organic / inorganic hybrid structure as a basic skeleton. However, since the heat-resistant resin represented by these is non-crystalline, the water absorption rate is larger than that of crystalline PET or PEN, and the dimensional change of the base material due to humidity becomes larger, which makes it a gas barrier layer. There is a concern of damaging it. However, even when these heat-resistant materials are used as a base material, by forming a gas barrier layer on both sides, dimensional changes due to moisture absorption and desorption of the base film itself under severe conditions of high temperature and high humidity are suppressed. And damage to the gas barrier layer can be suppressed. Therefore, it is one of the more preferable embodiments to use a heat-resistant material as a base material and to form a gas barrier layer on both surfaces. Moreover, in order to reduce the expansion and contraction of the base material at a high temperature, a base material containing glass fiber, cellulose or the like is also preferably used.

  The thickness of the substrate is preferably about 5 to 500 μm, more preferably 10 to 250 μm.

  Moreover, it is preferable that a base material is transparent. The term “transparent” as used herein means that the light transmittance of visible light (light wavelength range of 400 to 700 nm) is 80% or more.

  Since the base material is transparent and the gas barrier layer formed on the base material is also transparent, a transparent gas barrier film can be obtained. Therefore, a transparent substrate such as an organic EL element can be obtained. Because.

  In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

  The base material used for the gas barrier film according to the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.

  Further, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis).

  The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction. Furthermore, in order to improve the dimensional stability of the substrate in the stretched film, it is preferable to perform a relaxation treatment after stretching.

  Moreover, in the base material which concerns on this invention, before forming a gas barrier layer, you may give the corona treatment to the surface.

  As the surface roughness of the substrate used in the present invention, the 10-point average roughness Rz defined by JIS B0601: 2001 is preferably in the range of 1 to 500 nm, and more preferably in the range of 5 to 400 nm. Preferably, it exists in the range of 300-350 nm.

  Moreover, it is preferable that the centerline average surface roughness (Ra) prescribed | regulated by JISB0601: 2001 is in the range of 0.5-12 nm in the base-material surface, and it is more preferable that it exists in the range of 1-8 nm.

<Gas barrier layer>
The material for the gas barrier layer used in the present invention is not particularly limited, and various inorganic barrier materials can be used. Examples of inorganic barrier materials include, for example, silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), titanium (Ti), copper (Cu), cerium (Ce) and Examples include at least one metal selected from the group consisting of tantalum (Ta), and metal compounds such as oxides, nitrides, carbides, oxynitrides, and oxycarbides of the above metals.

More specific examples of the metal compound include silicon oxide, aluminum oxide, titanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), tantalum oxide, zirconium oxide, niobium oxide, aluminum silicate (SiAlO _x ), Boron carbide, tungsten carbide, silicon carbide, oxygen-containing silicon carbide, aluminum nitride, silicon nitride, boron nitride, aluminum oxynitride, silicon oxynitride, boron oxynitride, zirconium boride, titanium boride, and composites thereof And inorganic barrier materials such as metal oxides such as metal nitrides, metal carbides, metal oxynitrides, metal oxyborides, diamond-like carbon (DLC), and combinations thereof. Indium tin oxide (ITO), silicon oxide, aluminum oxide, aluminum silicate (SiAlO _x ), silicon nitride, silicon oxynitride and combinations thereof are particularly preferred inorganic barrier materials. ITO is an example of a special member of ceramic material that can be made conductive by appropriately selecting the respective elemental components.

  The metal compound is preferably a silicon compound such as silicon oxide, silicon carbide, oxygen-containing silicon carbide, silicon nitride, and silicon oxynitride because of its high gas barrier property. In one embodiment of the present invention, a method for manufacturing an electronic device is provided, wherein the gas barrier layer comprises a silicon compound.

  The gas barrier layer may include an organic layer containing an organic polymer. That is, the gas barrier layer may be a laminate of an inorganic barrier layer containing the inorganic barrier material and an organic layer.

  The organic layer is, for example, applied with an organic monomer or organic oligomer to the substrate, followed by polymerization and optionally cross-linking using, for example, an electron beam device, UV light source, discharge device or other suitable device. Can be formed. The organic layer can also be formed, for example, by depositing an organic monomer or organic oligomer that can be flash evaporated and radiation cross-linked, and then forming a polymer from the organic monomer or organic oligomer. Coating efficiency can be improved by cooling the substrate. Examples of the method for applying the organic monomer or organic oligomer include roll coating (for example, gravure roll coating), spray coating (for example, electrostatic spray coating), and the like. Moreover, as an example of the laminated body of an inorganic barrier layer and an organic layer, the laminated body as described in international publication 2012/003198, international publication 2011/013341, etc. is mentioned, for example.

  The gas barrier film according to the present invention may have a single gas barrier layer, or may have two or more similar gas barrier layers or different gas barrier layers laminated. When two or more gas barrier layers are stacked, the gas barrier layers may be formed by the same formation method or may be formed by different formation methods.

  The thickness of the gas barrier layer (in the case of a laminated body, the total thickness) is preferably in the range of 10 nm to 10 μm, more preferably 15 nm to 1 μm. If the thickness of the gas barrier layer is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 μm or less, high light transmittance can be realized.

  Further, the surface center line average roughness (Ra) of the gas barrier layer is not particularly limited, but it is preferable to flatten the bonding surface as much as possible in order to seal the electronic element body described later. Therefore, the surface center line average roughness (Ra) of the gas barrier layer is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 2 nm or less.

The method for forming the gas barrier layer is not particularly limited, but vapor phase film formation such as physical vapor deposition (PVD), sputtering, chemical vapor deposition (CVD), or atomic layer deposition (ALD) is used. Or a coating solution formed by applying a coating solution containing an inorganic compound, preferably a coating solution containing a polysilazane compound (hereinafter also simply referred to as “coating method”). . Further, the coating method has an advantage that the surface center line average roughness (Ra) of the gas barrier layer can be easily controlled. The vapor deposition method and coating method will be described below (vapor deposition method).
The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum deposition method, and an ion plating method.

In the sputtering method, a target is placed in a vacuum chamber, and a rare gas (usually argon) ionized by applying a high voltage is collided with a target such as silicon oxide (SiO _x ) to eject atoms on the target surface. This is a method of attaching to a substrate. At this time, a reactive sputtering method may be used in which an inorganic layer is formed by causing nitrogen and oxygen gas to flow into the chamber to react an element ejected from the target with argon gas and nitrogen or oxygen. .

  The chemical vapor deposition (CVD) method is a method of depositing a film by a chemical reaction on the surface of the substrate or in the vapor phase by supplying a raw material gas containing a target thin film component onto the substrate. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. Examples include methods. Although not particularly limited, it is preferable to apply a plasma CVD method such as a vacuum plasma CVD method or an atmospheric pressure plasma CVD method from the viewpoint of a film forming speed and a processing area.

  An atomic layer deposition (ALD method) is a method that uses chemisorption and chemical reaction of a plurality of low energy gases on a substrate surface. Sputtering and CVD methods use high-energy particles to cause pinholes and damage to the thin film produced. This method uses multiple low-energy gases, so pinholes and damage There is an advantage that a high-density monoatomic film is obtained (Japanese Patent Laid-Open No. 2003-347042, Japanese Translation of PCT International Publication No. 2004-535514, International Publication No. 2004/105149).

(Coating method)
In the present invention, the gas barrier layer is formed by a coating method by drying a coating film (polysilazane-containing coating film) formed by coating a coating liquid containing a polysilazane compound (polysilazane-containing coating liquid). The gas barrier layer formed by the coating method may be obtained by further modifying the polysilazane-containing coating film. When a gas barrier film having a gas barrier layer formed by drying a polysilazane-containing coating film is used for sealing an electronic device, the bending durability of the electronic device is particularly excellent. This is because the gas barrier layer formed by the polysilazane coating film is closer to an amorphous molecular structure such as silicon constituting the gas barrier layer than the silicon oxide film formed by sputtering or the like, and stress is easily relaxed. it is conceivable that. In one embodiment of the present invention, a method for producing an electronic device is provided in which the gas barrier layer is formed by drying a polysilazane-containing coating film.

In the present invention, the polysilazane compound is a polymer having a silicon-nitrogen bond. Specifically, ceramic precursors having bonds such as Si—N, Si—H, and N—H in the molecular structure, such as SiO ₂ , Si ₃ N ₄ and intermediate solid solutions thereof (SiO _x N _y ). It is an inorganic polymer. In the present specification, “polysilazane compound” is also abbreviated as “polysilazane”.

  More specifically, the polysilazane compound preferably has a structure represented by the following general formula (I).

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R ₁ , R ₂ and R ₃ may be the same or different.

  In the general formula (I), n is an integer, and the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. preferable.

In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

  Alternatively, polysilazane has a structure represented by the following general formula (II).

In the general formula (II), R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} may be the same or different.

  In the general formula (II), n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that Note that n ′ and p may be the same or different.

Among the polysilazanes of the above general formula (II), R _{1 ′} , R _{3 ′} and R _{6 ′} each represent a hydrogen atom, and R _{2 ′} , R _{4 ′} and R _{5 ′} each represent a methyl group; R _{1 '} , R _3' and R _{6 '} each represents a hydrogen atom, R _2' , R _{4 '} each represents a methyl group, and R _5' represents a vinyl group; R _{1 '} , R _3' , R ₄ A compound in which _' and R _6' each represent a hydrogen atom and R _{2 '} and R _5' each represents a methyl group is preferred.

  Alternatively, polysilazane has a structure represented by the following general formula (III).

In the general formula (III), R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} may be the same or different.

  In the general formula (III), n ″, p ″ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ″, p ″, and q may be the same or different.

Of the polysilazanes of the above general formula (III), R _{1 ″} , R _{3 ″} and R _{6 ″} each represent a hydrogen atom, and R _{2 ″} , R _{4 ″} , R _{5 ″} and R _{8 ″} each represent a methyl group. , R _{9 ″} represents a (triethoxysilyl) propyl group, and R _{7 ″} represents an alkyl group or a hydrogen atom.

  On the other hand, organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group has an alkyl group such as a methyl group, so that adhesion to the base material as a base is improved and ceramic The film can be toughened, and there is an advantage that generation of cracks can be suppressed even when the (average) film thickness is increased. For this reason, perhydropolysilazane and organopolysilazane may be selected as appropriate according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

  The polysilazane compound is commercially available in the form of a solution dissolved in an organic solvent. Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, manufactured by AZ Electronic Materials Co., Ltd. NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140 etc. are mentioned.

  Another example of the polysilazane compound that can be used in the present invention is not limited to the following. For example, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with the above polysilazane (Japanese Patent Laid-Open No. 5-238827) and glycidol are reacted. Glycidol-added polysilazane (JP-A-6-122852) obtained by reaction, alcohol-added polysilazane (JP-A-6-240208) obtained by reacting an alcohol, and metal carboxylic acid obtained by reacting a metal carboxylate Obtained by adding a salt-added polysilazane (JP-A-6-299118), an acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, and metal fine particles. Metal fine particle added Such as silazane (JP-A-7-196986), and a polysilazane compound to a ceramic at low temperatures.

  The solvent (solvent) for preparing the coating liquid containing polysilazane (polysilazane-containing coating liquid) is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups that easily react with polysilazane. An organic solvent that does not contain (for example, hydroxyl group or amine group) and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable. Specifically, as a solvent for preparing a polysilazane-containing coating solution, an aprotic solvent; for example, fats such as pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, and taven Hydrocarbon solvents such as aromatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons; halogen hydrocarbon solvents such as methylene chloride and trichloroethane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone And ethers such as dibutyl ether, dioxane, tetrahydrofuran, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. These solvents are selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  In the present invention, the surface centerline average roughness (Ra) of the gas barrier layer described above can be controlled within a suitable range by lowering the viscosity of the polysilazane-containing coating solution. Of course, there is a balance with the type of solvent to be used, but the polysilazane concentration in the polysilazane-containing coating solution is preferably 0.2 to 35% by mass, more preferably 2 to 20% by mass, More preferably, it is 15 mass%.

  The polysilazane-containing coating solution preferably contains a catalyst together with polysilazane in order to promote modification to silicon oxynitride. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on polysilazane. By setting the addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects, and the like.

  In the polysilazane-containing coating solution according to the present invention, the following additives can be used as necessary. For example, cellulose ethers, cellulose esters; natural resins such as ethyl cellulose, nitrocellulose, cellulose acetate, and cellulose acetobutyrate; synthetic resins such as rubber and rosin resin; and condensation resins such as polymer resins; Aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

  As a method of applying the polysilazane-containing coating solution, a conventionally known appropriate wet coating method can be employed. Specific examples include spin coating method, die coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, gravure printing method and the like. It is done.

  The coating thickness can be appropriately set according to the purpose. For example, the coating thickness is preferably about 10 nm to 10 μm after drying, more preferably 15 nm to 1 μm, and even more preferably 20 to 500 nm. If the thickness of the polysilazane layer is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 μm or less, stable coating properties can be obtained when forming the polysilazane layer, and high light transmittance can be realized.

  The coating film obtained by applying the polysilazane-containing coating solution may optionally include a step of removing moisture. The step of removing moisture may be performed during application of energy. As a method for removing moisture, a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. The preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), the more preferable dew point temperature is −5 ° C. or lower (temperature 25 ° C./humidity 10%), and the maintaining time depends on the film thickness of the gas barrier layer. It is preferable to set appropriately. Under the condition that the film thickness of the gas barrier layer is 1.0 μm or less, it is preferable that the dew point temperature is −5 ° C. or less and the maintaining time is 1 minute or more. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher and preferably −40 ° C. or higher.

  After coating the coating solution, the coating film is dried. By drying the coating film, the organic solvent contained in the coating film can be reduced or removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable gas barrier layer can be obtained.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 50-200 degreeC. The drying temperature is preferably set to 150 ° C. or lower in consideration of deformation of the substrate due to heat. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

The gas barrier layer may be one obtained by applying energy to the above-mentioned dried polysilazane coating film and modifying the polysilazane. The modification treatment of polysilazane refers to a reaction in which part or all of polysilazane is converted into silicon oxide or silicon oxynitride. By the modification treatment, the barrier property of the gas barrier layer can be improved to a water vapor transmission rate of about 1 × 10 ⁻³ g / m ² · day or less at 40 ° C. and 90% RH. From the viewpoint of improving flexibility, the gas barrier film according to the present invention preferably contains a gas barrier layer formed by modifying a polysilazane compound.

  For the modification treatment, a known method based on a conversion reaction from polysilazane to silicon oxide or silicon oxynitride can be appropriately selected and applied. For example, plasma treatment, heat treatment, active energy ray irradiation treatment (for example, vacuum ultraviolet ray treatment), etc. Is mentioned. In the present invention, from the viewpoint of applying the gas barrier film as a sealing substrate for an electronic device, a reforming treatment by vacuum ultraviolet ray treatment capable of a conversion reaction at a lower temperature is more preferable.

In vacuum ultraviolet ray irradiation treatment (excimer irradiation treatment), it is preferable that the illuminance of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is in the range of 30~300mW / cm ^2, in the range of 50~200mW / cm ² More preferably. When it is 30 mW / cm ² or more, there is no concern that the reforming efficiency is lowered, and when it is 200 mW / cm ² or less, the coating film is not ablated and the base material is not damaged.

  The irradiation time of the vacuum ultraviolet ray on the polysilazane coating surface is, for example, 1 to 400 seconds, and preferably 3 to 200 seconds.

Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably in the range of 200~10000mJ / cm ^2, and more preferably in the range of 500~7000mJ / cm ^2. If it is this range, there will be no crack generation or thermal deformation of the substrate.

  As the vacuum ultraviolet light source, a rare gas excimer lamp such as Xe, Kr, Ar, or Ne is preferably used.

  Among these, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process is likely to decrease. For this reason, it is preferable to perform the irradiation with vacuum ultraviolet rays in a state where the oxygen concentration and the water vapor concentration are as low as possible. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably in the range of 1 to 10000 volume ppm, more preferably in the range of 3 to 5000 volume ppm, and still more preferably in the range of 5 to 4000 volume ppm.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

<Transition metal compound-containing layer>
The gas barrier film according to the present invention has a transition metal compound-containing layer. The transition metal compound-containing layer contains a transition metal compound as a main component. Since transition metal compounds, particularly Group 5 elements, can have a plurality of valences, they can exist in the transition metal compound-containing layer as a mixture of compounds having various intermolecular distances. Thereby, it is presumed that the gas barrier film having the transition metal compound-containing layer has a flexible structure, and the stress applied to the joint portion of the electronic device is relieved.

  The transition metal compound has a low oxidation-reduction potential. For example, when the gas barrier layer contains silicon, it is oxidized prior to the gas barrier layer in a high temperature and high humidity environment. Therefore, it is considered that the effect of suppressing oxidation on the surface of the gas barrier layer is exhibited, and the spot-like gas barrier property is hardly reduced. Therefore, the gas barrier film of the present invention provided with the transition metal compound-containing layer is also excellent in durability in a high temperature and high humidity environment.

  Here, “including a transition metal compound as a main component” means that the content of the transition metal compound is 50% by mass or more based on the total mass of the transition metal compound-containing layer. The content is more preferably 80% by mass or more, further preferably 95% by mass or more, particularly preferably 98% by mass or more, and 100% by mass (that is, containing a transition metal compound). Most preferably, the layer comprises a transition metal compound).

  The transition metal compound contained in the transition metal compound-containing layer is not particularly limited, and examples thereof include transition metal oxides, nitrides, carbides, oxynitrides, and oxycarbides. Among these, from the viewpoint of more effectively suppressing oxidation of the gas barrier layer, the transition metal compound is preferably a transition metal oxide. The transition metal compounds may be used alone or in combination of two or more.

The transition metal compound-containing layer preferably includes a metal oxide MO _x1 where x1 <x2 where M is the transition metal and MO _x2 is the stoichiometrically obtained transition metal oxide. By including such a metal oxide, the gas barrier performance of the gas barrier film is improved, and high gas barrier performance is maintained even under high temperature and high humidity conditions. By including the metal oxide MO _x1 where x1 <x2, there is a region with a lower degree of oxidation than the stoichiometric degree of oxidation, that is, a region with room for further oxidation, which is higher. It is thought that gas barrier performance is exhibited.

For example, taking the oxide of Nb (niobium) as an example, the Nb stoichiometric oxide is niobium pentoxide, which is NbO _2.5 , so x2 = 2.5. is there. Nb can take the composition of niobium trioxide, but x2 in the present invention means x2 of a stoichiometric compound having the highest degree of oxidation. The inclusion of the metal oxide MO _x1 where x1 <x2 means that when a composition profile in the thickness direction is measured by a composition analysis method such as XPS, a measurement point where x1 <x2 is obtained, in the case of Nb Means that a measurement point where x1 <2.5 is obtained. Even when the transition metal compound-containing layer contains a plurality of types of transition metals, the stoichiometric x2 can be calculated from the ratio of each transition metal and the total thereof.

  Expressing the relationship of x1 <x2 as an index of the degree of oxidation as an x1 / x2 ratio, the x1 / x2 ratio is preferably 0.99 or less because the gas barrier performance under high temperature and high humidity is further improved. It is more preferably 0.9 or less, and further preferably 0.8 or less. The smaller the x1 / x2 ratio, the higher the oxidation suppression effect, but the higher the absorption with visible light. Accordingly, when used in applications where transparency is desired, it is preferably 0.2 or more. .3 or more is more preferable.

  The x1 / x2 ratio can be adjusted by, for example, forming a transition metal compound-containing layer by sputtering, using a metal or a transition metal oxide that is stoichiometrically deficient in oxygen as a target. This can be done by appropriately adjusting the amount of oxygen introduced.

x1 can be determined by the atomic ratio of O to M using XPS analysis in the thickness direction. If the minimum value of x1 is x1 <x2, it can be said that the metal oxide MO _x1 where x1 <x2 is included.

<< XPS analysis conditions >>
・ Device: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Measurement area: Si2p, C1s, N1s, O1s, etc., set by a regular method according to the metal to be measured.
Depth profile: repeats measurement after sputtering for a certain time. In one measurement, the sputtering time is adjusted so that the thickness is about 2.5 nm in terms of SiO _2.・ Quantification: The background is obtained by the Shirley method, and the relative sensitivity coefficient method is calculated from the obtained peak area. And quantified. Data processing uses MultiPak manufactured by ULVAC-PHI.

  A transition metal atom refers to a Group 3 element to a Group 12 element, and examples of the transition metal include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, and Mo. , Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir , Pt, and Au.

  Among these, the transition metal in the transition metal compound is preferably a metal having a lower redox potential than silicon. By forming a layer containing a transition metal compound having a lower oxidation-reduction potential than silicon, better barrier properties can be obtained. Specific examples of the metal having a lower redox potential than silicon include niobium, tantalum, barium, zirconium, titanium, hafnium, yttrium, lanthanum, cerium, and the like. These metals may be used alone or in combination of two or more. Of these, niobium, tantalum, and vanadium, which are Group 5 elements, can be preferably used because they have a high effect of suppressing oxidation of the gas barrier layer. Further, from the viewpoint of optical properties, the transition metal in the transition metal compound is more preferably niobium or tantalum from which a compound with good transparency can be obtained.

  The standard redox potentials and x2 for the major metals are shown in the table below.

  As the transition metal compound, niobium oxide or tantalum oxide is preferable from the viewpoint of bending durability, and niobium oxide is particularly preferable. That is, in one embodiment of the present invention, a method for manufacturing an electronic device is provided in which the transition metal compound is niobium oxide.

  The method for forming the transition metal compound-containing layer is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, and ion plating, plasma CVD (chemical vapor deposition), and ALD (Atomic Layer). Chemical vapor deposition methods such as Deposition). Among them, it is preferable to form by sputtering because it has high productivity and can be formed on the gas barrier layer without damaging the lower layer.

  For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used. In addition, a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used. By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable. For example, when performing DC sputtering or DMS sputtering, a transition metal oxide thin film can be formed by using a transition metal for the target and introducing oxygen into the process gas. In addition, when a film is formed by an RF (high frequency) sputtering method, for example, a transition metal oxide target can be used. As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a transition metal compound thin film such as a transition metal oxide, nitride, nitride oxide, or carbonate can be formed. When a mixed gas of an inert gas such as Ar and a reactive gas such as oxygen is used as the process gas, for example, the partial pressure of the reactive gas is reduced with respect to the entire process gas so as to become a transition metal compound having a target composition. adjust. For example, when oxygen is used as the reactive gas, the oxygen composition in the transition metal oxide can be increased by increasing the oxygen partial pressure.

  Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, film material, film thickness, and the like. A sputtering method using a transition metal or a transition metal compound as a target is preferable because it has a higher film formation rate and higher productivity. Among these, the sputtering method using a transition metal oxide as a target is more preferable because it has a higher film formation rate and higher productivity.

  The transition metal compound-containing layer may be a single layer or a laminated structure of two or more layers. When the transition metal compound-containing layer has a laminated structure of two or more layers, the transition metal compounds contained in the transition metal compound-containing layer may be the same or different.

  The transition metal compound-containing layer can be effective even in a relatively thin layer. Specifically, the thickness of the transition metal compound-containing layer (the total thickness in the case of a laminated structure of two or more layers) is preferably 0.1 nm to 150 nm from the viewpoint of bending durability. It is more preferably 5 nm to 50 nm, and further preferably 1 nm to 15 nm. In one embodiment of the present invention, an electronic device manufacturing method is provided in which the layer thickness of the transition metal compound-containing layer is 1 nm to 15 nm.

<Other functional layers>
(Middle layer)
In the present invention, an intermediate layer may be further formed between the gas barrier film substrate and the gas barrier layer. The intermediate layer preferably has a function of improving the adhesion between the substrate surface and the gas barrier layer. A commercially available substrate with an easy-adhesion layer can also be preferably used.

(Smooth layer)
In the gas barrier film according to the present invention, the intermediate layer may be a smooth layer. The smooth layer used in the present invention is provided in order to flatten the rough surface of the substrate on which protrusions and the like exist, or to fill in and flatten the irregularities and pinholes generated in the gas barrier layer by the protrusions existing on the substrate. It is done. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

(Bleed-out prevention layer)
The gas barrier film according to the present invention may have a bleed-out preventing layer on the base material surface opposite to the surface on which the gas barrier layer is provided. A bleed-out prevention layer can be provided. The bleed-out prevention layer is used for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the film base material to the surface when the film having the smooth layer is heated and contaminate the contact surface. It is provided on the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

[Main substrate]
The main base material is a substrate for forming an electronic element body (for example, an electronic element body such as the organic EL element body 13 shown in FIG. 1A), but the configuration is not particularly limited. Examples thereof include a glass substrate, a metal foil, a resin film, a gas barrier film having a base material (resin film) and a gas barrier layer, and a composite of these. Using the gas barrier film according to the present invention as a main base material is also one of the preferred embodiments. For example, in FIG. 1A, the main base material 11 may be a gas barrier film according to the present invention. In this case, the main substrate 11 and the gas barrier film 12 may be the same film or different.

Water vapor permeability (Water Vapor Transmission Rate, WVTR, moisture permeability measuring device (AQUATRAN model 1, manufactured by MOCON, USA) of the gas barrier film according to the present invention described above was used at 38 ° C. and relative humidity of 100%. (Measured in the atmosphere) is preferably 5 × 10 ⁻³ g / m ² · day or less, more preferably 5 × 10 ⁻⁴ g / m ² · day or less, and more preferably 5 × 10 ⁻⁵ g / day. More preferably, it is not more than m ² · day.

  Examples of the glass substrate include a quartz glass substrate, a borosilicate glass substrate, a soda glass substrate, and a non-alkali glass substrate. As the metal foil, aluminum (Al), gold (Au), silver (Ag), chromium (Cr), iron (Fe), nickel (Ni), cobalt (Co), copper (Cu), indium (In), Examples of the metal foil include tin (Sn), lead (Pb), titanium (Ti), and alloys thereof.

  When the main base material is composed of a resin film, as the constituent material, materials listed as the base material of the above-described gas barrier film can be similarly employed.

In the electronic device manufactured by the manufacturing method according to the present invention, the main base material and the gas barrier film described above preferably have flexibility. In this specification, “flexibility” refers to a property that is flexible and deforms when a force is applied, but returns to its original shape when the force is removed. When this flexibility is expressed quantitatively, the flexural modulus defined in JIS K7171: 2008 is, for example, 1.0 × 10 ^{3 to} 4.5 × 10 ³ [N for the main base material and the gas barrier film. / Mm ² ].

  From the viewpoint of ensuring flexibility and gas barrier properties, the thickness of the main base material (in the case of a laminate) is, for example, 5 to 500 μm, and preferably 10 to 200 μm.

[Electronic element body]
In the production method according to the present invention, there is no particular limitation on the specific configuration of the electronic element body sealed by the main base material and the gas barrier film, and a conventionally known one that needs to be shielded from moisture and oxygen. A thing without particular restriction is used. An example of the electronic element body is the organic EL element body 13 shown in FIG. The electronic device is not limited to an organic EL device, and may be a known electronic device to which sealing with a gas barrier film can be applied. For example, a solar cell (PV), a liquid crystal display element (LCD), electronic paper, A thin film transistor, a touch panel, etc. are mentioned. There is no restriction | limiting in particular also about the structure of the main body of these electronic devices, It can have a well-known structure.

  1, the electronic element body (organic EL element body) 13 includes a first electrode (anode) 17, a hole transport layer 18, a light emitting layer 19, an electron transport layer 20, a second electrode (cathode) 21, and the like. Have In addition, if necessary, a hole injection layer may be provided between the first electrode 17 and the hole transport layer 18, or an electron injection layer may be provided between the electron transport layer 20 and the second electrode 21. May be provided. In the organic EL element, the hole injection layer, the hole transport layer 18, the electron transport layer 20, and the electron injection layer are arbitrary layers provided as necessary.

  Hereinafter, an organic EL element body will be described as an example of a specific configuration of the electronic element body.

(First electrode: anode)
As the first electrode (anode), an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used.

(Hole injection layer: anode buffer layer)
A hole injection layer (anode buffer layer) may be present between the first electrode (anode) and the light emitting layer or the hole transport layer. The hole injection layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the light emission luminance.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

(Light emitting layer)
The light emitting layer refers to a blue light emitting layer, a green light emitting layer, and a red light emitting layer. There is no restriction | limiting in particular as a lamination order in the case of laminating | stacking a light emitting layer, You may have a nonluminous intermediate | middle layer between each light emitting layer.

(Electron transport layer)
The electron transport layer is made of a material having a function of transporting electrons and is included in the electron transport layer in a broad sense. An electron injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.

(Electron injection layer: cathode buffer layer)
The electron injection layer (cathode buffer layer) formed in the electron injection layer forming step is made of a material having a function of transporting electrons and is included in the electron transport layer in a broad sense. An electron injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.

(Second electrode: cathode)
As the second electrode (cathode), a material having a small work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof is used.

(Protective layer)
As shown in FIG. 1, when the electronic device is an organic EL device or the like, a protective layer 15 may be provided on the electronic element body as necessary. The protective layer has a function of preventing moisture, oxygen, and the like that promote deterioration of the electronic device body from entering the device, a function of insulating the electronic device body disposed on the main substrate 11, or the like. It has a function to eliminate the step due to the element body. The protective layer may be a single layer or a laminate of a plurality of layers.

[Step of forming a joining margin, step of sealing the electronic element body by room temperature bonding]
The production method according to the present invention includes a step of activating the surface of the gas barrier film and the surface of the main substrate, forming a bonding margin on each of the surface of the gas barrier film and the surface of the main substrate, and the bonding margins. And the step of sealing the electronic element body by room temperature bonding. The joining margin can be formed by a room temperature joining apparatus as shown in FIG. 3, for example. When bonding is performed using a room temperature bonding technique, there is no possibility that the resin material constituting the main base material or the gas barrier film is exposed to a high temperature, and thus there is an advantage that deterioration of the resin material can be prevented.

  As shown in FIG. 2, the joining margin 204 exists at a distance d from the periphery of the electronic element body (organic EL element body 203). The interval d may have the same value or different values on each side of the periphery of the electronic element body. Moreover, although the value of the distance d depends on the size of the electronic device, it is preferably d ≧ 100 nm, more preferably d ≧ 10 μm, and further preferably d ≧ 100 μm. The upper limit is not particularly limited, but d ≦ 10 cm, for example.

  Furthermore, although the width h of the joining depends on the size of the electronic device, it is preferably 10 to 2000 μm and more preferably 50 to 1000 μm from the viewpoint of joining stability and flexibility.

  FIG. 3 is a schematic cross-sectional view showing an example of a room temperature bonding apparatus that can be used in the method of manufacturing an electronic device according to the present invention. The room temperature bonding apparatus 130 includes a vacuum chamber 131, an ion gun (sputtering source) 132, a target stage 1 (133), and a target stage 2 (134).

  The vacuum chamber 131 is a container that seals the inside from the environment, and further includes a vacuum pump (not shown) for discharging gas from the inside of the vacuum chamber 131 and a gate that connects the outside and the inside of the vacuum chamber 131. A lid (not shown) for opening and closing is provided. Examples of the vacuum pump include a turbo molecular pump that exhausts gas blades by blowing a plurality of metal blades inside. The degree of vacuum in the vacuum chamber 131 can be adjusted by a vacuum pump.

  The target stages 133 and 134 as metal emitters are arranged so as to face each other, and have a dielectric layer on each facing surface. The target stage 133 applies a voltage between the dielectric layer and the gas barrier film 12, and adsorbs and fixes the gas barrier film 12 to the dielectric layer by electrostatic force. Similarly, the target stage 134 adsorbs and fixes the main substrate 11 via a dielectric layer. Although the electronic element body is not shown in FIG. 3, the electronic element body is sealed by using a main substrate on which the electronic element body (for example, an organic EL element body) is formed. It fixes on the target stage 134 so that the surface of the done side may oppose the gas barrier film 12.

  When a gas barrier film (for example, the gas barrier film 12 in FIG. 1) in which the outermost gas barrier layer is formed on the substrate side of the outermost transition metal compound-containing layer is used, the outermost transition metal compound is used. It is preferable to fix the containing layer so as to face the main substrate (that is, adsorb the substrate 12a toward the target stage 133). Thereby, a bonding margin can be formed on the surface of the gas barrier film on which the transition metal compound-containing layer is disposed, and the distance between the transition metal compound-containing layer and the layered electronic device body can be reduced. In one embodiment of the present invention, the gas barrier film includes a base material, a gas barrier layer, and a transition metal compound-containing layer in this order, and forms a bonding margin on the surface on which the transition metal compound-containing layer is disposed. An electronic device manufacturing method is provided.

  The target stage 133 can have a cylindrical shape or a cubic shape, and can be translated in the vertical direction with respect to the vacuum chamber 131. The parallel movement is performed by a pressure contact mechanism (not shown) provided in the target stage 133. Further, the target stage 133 can be formed from a material (for example, silicon) to be sputtered on the main substrate 11.

  The target stage 134 can be translated in the vertical direction with respect to the vacuum chamber 131 and can be rotated around a rotation axis parallel to the vertical direction. The parallel movement and rotation are performed by a transfer mechanism (not shown) provided in the target stage 134. Further, the target stage 134 can be formed of a material (for example, silicon) desired to be sputtered on the gas barrier film 12.

  An ion gun (also referred to as “sputtering source”) 132 is directed to the main substrate 11 and the gas barrier film 12. The ion gun 132 emits charged particles accelerated in the direction in which the ion gun 132 is directed. Examples of charged particles include rare gas ions such as argon ions. Further, an electron gun may be provided in the vacuum chamber 131 (not shown) in order to neutralize the object that is positively charged by the charged particles emitted by the ion gun 132.

  The bonding margin is formed by activating each surface of the main base material 11 and the gas barrier film 12 by a conventionally known method such as reverse sputtering, ion beam, ion beam sputtering or the like. As a result, a bond is generated in the portion where the activation process has been performed, and the joining margins can be brought into contact with each other to perform room temperature joining. Reverse sputtering as an example for performing the activation treatment can be performed as follows. Using an inert gas such as argon, the acceleration voltage is 0.02 to 10 kV, preferably 0.1 to 5 kV, the current value is 0.2 to 100 mA, preferably 0.5 to 500 mA, 0.1 to The irradiation can be performed for 30 minutes, preferably 1 to 5 minutes. In addition, reverse sputtering means that sputtering is caused by irradiating a certain target object with some energy beam, and as a result, the irradiated portion is physically scraped.

  In FIG. 2, the distance d and the bonding width h can be arbitrarily set by a known metal mask technique or the like. For example, when the electronic device is sealed, a metal mask is applied to the portion of the electronic element body (not shown), so that the first peripheral portion of the electronic element body on the main base material that is not metal-masked A second joining margin is formed around the portion of the gas barrier film where the metal mask is not formed.

Room temperature bonding (activation treatment, and optionally laminating of the silicon film and activation treatment of the silicon film thereafter) prevents the inside of the sealed electronic element body from containing moisture, oxygen, and the like. Therefore, it is preferable to carry out in a vacuum. The room temperature bonding is performed, for example, in a vacuum environment with a degree of vacuum of 10 ⁻⁷ to 10 ⁻⁴ Pa.

The joining margin may be formed by laminating a film (inorganic element film) containing an inorganic element such as silicon, germanium and / or tin, preferably a film containing silicon, in the activated region. Good. As in the silicon film 16 included in the electronic device 10 of FIG. 1A, the bonding property including the inorganic element film can be further strengthened. In one embodiment of the present invention, there is provided a method for manufacturing an electronic device in which a bonding margin is formed by laminating a silicon film on at least one of the surface of an activated gas barrier film and the surface of a main substrate. . The formation of the inorganic element film is, in terms of area, 80% or more, preferably 90% or more, more preferably 100% of the region where the activation process has been performed (that is, the entire region where the activation process has been performed). ). In one embodiment, the width d _{1 of} the region subjected to the activation treatment and the width d ₂ of the inorganic element film have a relationship of d ₁ ≧ d ₂ . The silicon film may be formed on either the surface of the activated gas barrier film or the surface of the main substrate, but it is formed on both the surface of the gas barrier film and the surface of the main substrate. It is preferable to do. A metal film containing at least one selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum may be further formed on the silicon film.

  An inorganic element film containing an inorganic element such as silicon, germanium, and / or tin can be formed by sputtering using the inorganic element as a target, for example, sputtering of a silicon target.

  Upon irradiation with charged particles, metal is released from the target stages 133 and 134 in the apparatus by sputtering, and sputtering is performed on desired portions of the main base material 11 and the gas barrier film 12, and a part of the bond to the desired portions is joined. As a result, a silicon film is formed. The range of the desired portion can be determined by a known metal mask technique or the like.

  The thickness of the inorganic element film such as a silicon film is not particularly limited as long as the effect of the present invention is not impaired, and is preferably 1 to 50 nm, and more preferably 5 to 30 nm. The thickness of the arbitrarily formed metal film is not particularly limited as long as the effect of the present invention is not impaired, and is preferably 0.1 to 10 nm, and more preferably 1 to 5 nm.

  After the sputtering of the inorganic element film or metal film, the irradiation conditions of the charged particles are changed by adjusting the operating parameters of the ion gun 132. For example, the activity of the inorganic element film or metal film by reverse sputtering, ion beam, ion beam sputtering, etc. Processing may be performed. In one embodiment of the present invention, there is provided a method for manufacturing an electronic device in which a bonding margin is formed by activating a silicon film. At this time, the activation of the inorganic element film or the metal film may be performed simultaneously with the film formation by using an argon ion beam not incident on the target or after the film formation. From the viewpoint, it is more preferable to carry out after film formation. In addition, the magnitude | size of the effect | action of film formation and activation can be adjusted by setting suitably the arrangement | positioning of a target, the strength of the energy beam from the sputtering source 132, etc. FIG. Of course, no adjustment is made to produce a reverse sputtering effect over deposition. In the case of activating the inorganic element film or the metal film by reverse sputtering, for example, the conditions such as the acceleration voltage, current value, and irradiation time described for the reverse sputtering can be applied.

Thereafter, the irradiation of the charged particles is terminated, the metal mask is removed, the pressure contact mechanism of the target stage 133 is operated, the target stage 133 is lowered in the vertical direction, and as shown in FIG. The gas barrier film 12 is brought into contact. Thus, by joining at room temperature, the first joining margin formed on the main base material 11 and the second joining margin formed on the gas barrier film 12 are joined, and the main base material 11 and the gas barrier film 12 are joined. The interface 127 is joined. When an inorganic element film such as a silicon film is formed at the joining margin, the silicon film 16 exists at the interface 127 as shown in FIG. As a result, the electronic element body can be sealed. There is no particular limitation on the bonding conditions, and bonding is possible even at room temperature and no pressure in vacuum, but it is preferable to apply a pressure of 1 to 100 MPa for 1 to 10 minutes from the viewpoint of bonding more firmly. The contact is preferably performed in a vacuum environment having a degree of vacuum of about 10 ⁻⁸ to 10 ⁻⁵ Pa from the viewpoint of bonding strength.

<Bending test method>
In this specification, as a method for evaluating flexibility, a method for evaluating durability against repeated bending with a radius of curvature fixed is adopted. According to this method, it is possible to determine whether or not bending can be performed at a predetermined curvature radius, and to evaluate durability of flexibility. Specifically, the repeated bending test method defined in the mechanical stress test (IEC62715-6-1 Ed.1) of a flexible display element is mentioned. This can be bent repeatedly by repeatedly sliding both ends of the functional element back and forth when the functional element is bent into a U shape so as to have a constant radius of curvature. An example of the apparatus is a U-shaped folding tester manufactured by Yuasa System Equipment Co., Ltd. Other test conditions include bending speed, but in the present invention, the test is performed at a repetition rate of 60 times per minute in consideration of the test period and the actual use site.

  The determination of whether or not it is possible to bend at a radius of curvature of 2.0 mm, and the durability of the flexibility, after being subjected to the above test, are left in an environment of, for example, 85 ° C. and 85% RH for 24 hours. By performing a light emission test, the sealing performance can be evaluated.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. In the following operations, unless otherwise specified, the measurement of the operation and physical properties is performed under conditions of room temperature (25 ° C.) and relative humidity of 50%.

<< Manufacture of gas barrier film 1 >>
[Gas barrier layer 1]
A PET base material (75 μm thick) with a clear hard coat layer manufactured by Kimoto Co., Ltd. is used with a magnetron sputtering apparatus, a SiO ₂ target as a target, and a process gas having a film thickness of 300 nm by DC sputtering using Ar as a process gas. A silicon oxide film (SiO ₂ ) was formed to produce a gas barrier film 1 having a gas barrier layer 1.

<< Manufacture of gas barrier film 2 >>
Using a PET base material (75 μm thick) with a clear hard coat layer manufactured by Kimoto Co., Ltd., using a Ta ₂ O ₅ target as a target and Ar and O _{2 as} process gases in a magnetron sputtering apparatus. The film was formed by RF sputtering, and the film thickness was 10 nm. The transition metal compound-containing layer 1 was formed by adjusting the oxygen partial pressure so that the film composition was Ta ₂ O ₃ .

  Subsequently, in the same manner as in the production of the gas barrier film 1, the gas barrier layer 1 was formed on the transition metal compound-containing layer 1, and the gas barrier film 2 was produced.

<< Manufacture of gas barrier film 3 >>
A gas barrier layer 1 was formed in the same manner as the gas barrier film 1. Thereafter, the transition metal compound-containing layer 1 was formed on the gas barrier layer 1 in the same manner as the gas barrier film 2, and the gas barrier film 3 was produced.

<< Manufacture of gas barrier film 4 >>
In the same manner as the gas barrier film 2, a transition metal compound-containing layer 1 and a gas barrier layer 1 were formed. Thereafter, the transition metal compound-containing layer 1 was formed on the gas barrier layer 1 in the same manner as the gas barrier film 3, and the gas barrier film 4 was produced.

<< Manufacture of gas barrier film 5 >>
A gas barrier film 5 was produced in the same manner as the gas barrier film 3 except that the gas barrier layer 1 was changed to the following gas barrier layer 2.

[Gas barrier layer 2]
Dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NN120-20) and 5% by mass of amine catalyst (N, N, N ′, N′-tetramethyl) -1,6-diaminohexane (TMDAH)) perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) 4: 1 (mass ratio) ) To prepare a polysilazane stock solution. Further, the polysilazane stock solution is diluted with a diluting solvent mixed so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, and a polysilazane-containing coating solution having a solid content of 5% by mass is obtained. Prepared.

The coating solution obtained above was applied on a PET substrate (75 μm thickness) with a clear hard coat layer manufactured by Kimoto Co., Ltd. by spin coating so that the thickness after drying was 300 nm, and contained polysilazane. A coating film was formed. The substrate on which the polysilazane-containing coating film was formed was allowed to stand at room temperature (25 ° C.) and a relative humidity of 10% for 2 minutes, and then heat-treated for 1 minute on an 80 ° C. hot plate to dry the polysilazane-containing coating film. The dried polysilazane-containing coating film was subjected to irradiation treatment of 6000 mJ / cm ² (200 mW / cm ² , 30 seconds) with a Xe excimer lamp (172 nm) in a nitrogen atmosphere (oxygen concentration: 5 volume ppm) to improve the polysilazane. The gas barrier layer 2 was formed.

<< Manufacture of gas barrier film 6 >>
In the method for producing the gas barrier film 5, the target used when forming the transition metal compound-containing layer 1 is changed to an oxygen-deficient Nb ₂ O ₅ target, and the film is formed by DC sputtering using Ar and O _{2 as} process gases. The film thickness was 30 nm. The oxygen partial pressure was adjusted so that the film composition was Nb ₂ O _3, and a gas barrier film 6 was produced.

<< Production of Gas Barrier Films 7 to 10 >>
In the method for producing the gas barrier film 6, the film thickness of the transition metal compound-containing layer 2 was changed to 15 nm, 10 nm, 2 nm, and 1 nm, respectively, and gas barrier films 7 to 10 were produced.

<< Production of electronic devices >>
An organic EL device was produced as an example of an electronic device.

[Production of Organic EL Device 1]
(Formation of the first electrode)
On a main base material (50 mm × 100 mm) in which a thin film glass of 30 μm thickness and a PET film of 50 μm thickness are combined, a rectangular ITO of 40 mm × 30 mm and a thickness of 150 nm is formed by sputtering. Then, patterning was performed by a photolithography method to form a first electrode.

(Formation of hole transport layer)
The cleaning surface modification treatment of the resin substrate on which the first electrode was formed was performed using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm ² and a distance of 10 mm. The charge removal treatment was performed using a static eliminator with weak X-rays.

  Polyethylenedioxythiophene / polystyrene sulfonate (PEDOT / PSS, H.C. Starck Baytron (registered trademark) P AI 4083) diluted to 65% by mass with pure water and then diluted to 5% by mass with methanol Was prepared as a coating solution for forming a hole transport layer.

  On the first electrode of the resin substrate on which the first electrode was formed, the above hole transport layer forming coating solution was applied with a spin coater in an environment of 25 ° C. and 50% RH. The coating solution for forming the hole transport layer was applied so that the thickness after drying was 50 nm. Then, after removing the solvent by blowing air at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., heat transfer from the back surface at a temperature of 150 ° C. using a heat treatment apparatus. The hole transport layer was formed by heat treatment of the system.

(Formation of light emitting layer)
1.0 g of a compound represented by the following chemical formula HA as a host material, 100 mg of a compound represented by the following chemical formula DA as a luminescent dopant, 0.2 mg of a compound represented by the following chemical formula DB as a luminescent dopant, and As a luminescent dopant, 0.2 mg of a compound represented by the following chemical formula DC was dissolved in 100 g of toluene to prepare a coating solution for forming a white luminescent layer.

  A white light-emitting layer-forming coating solution was applied onto the hole transport layer with a spin coater under an atmosphere having a nitrogen gas concentration of 99% or more and a coating temperature of 25 ° C. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm. Then, after removing the solvent by blowing at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., heat treatment is performed at a temperature of 130 ° C. Formed.

(Formation of electron transport layer)
A compound represented by the following chemical formula EA was dissolved in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution, which was used as an electron transport layer forming coating solution.

  In an atmosphere having a nitrogen gas concentration of 99% or more, an electron transport layer forming coating solution (25 ° C.) was applied on the light emitting layer formed above by a spin coater. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm. Then, after removing the solvent by blowing at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., the substrate is subsequently heated at a temperature of 200 ° C. in the heat treatment section. Processing was performed to form an electron transport layer.

(Formation of electron injection layer)
An electron injection layer was formed on the electron transport layer formed above. First, the substrate was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. Cesium fluoride prepared in advance was heated in a tantalum vapor deposition boat in a vacuum chamber, and an electron injection layer having a thickness of 3 nm was formed by vapor deposition.

(Formation of second electrode)
A second electrode having a thickness of 100 nm is stacked on the electron injection layer formed as described above by depositing the first electrode on the portion other than the portion serving as the extraction electrode so as to have the extraction electrode. did. For the film formation, aluminum was used as a forming material, and a mask pattern was formed under a vacuum of 5 × 10 ⁻⁴ Pa so that the light emission area was a rectangle of 40 mm × 30 mm. Thus, an electronic element body (organic EL element body) formed on the main substrate was prepared.

(Sealing with sealing material)
The gas barrier film 1 was cut into 50 mm × 100 mm and used. A thermosetting adhesive (sealing material) was uniformly applied with a thickness of 20 μm on the gas barrier layer side of the gas barrier film using a dispenser to form an adhesive layer.

At this time, as the thermosetting adhesive, an epoxy adhesive in which the following (A) to (C) were mixed at a mass ratio of 85/10/5 was used;
(A) Bisphenol A diglycidyl ether (DGEBA)
(B) Dicyandiamide (DICY)
(C) Epoxy adduct curing accelerator.

  The gas barrier film on which the adhesive layer was formed was adhered and disposed so that the adhesive layer side of the gas barrier film was directed to the electronic element body so as to cover the electronic element portion. The electronic element body was tightly sealed using a pressure roller (pressure roller temperature 120 ° C., pressure 0.5 MPa, apparatus speed 0.3 m / min). Thus, the organic EL device 1 was produced.

[Production of organic EL devices 2 to 11]
Using the gas barrier films 1 to 10, the sealing step in the production of the organic EL device 1 was changed to room temperature bonding, and organic EL devices 2 to 11 were produced.

(Sealing by room temperature bonding)
The main base material on which the organic EL element body was formed was placed on the target stage 134 of the bonding apparatus as shown in FIG. Further, a gas barrier film was fixed to the target stage 133. At this time, the surface of the main substrate on the side where the electronic element is formed is arranged so that the outermost layer surface of the gas barrier film (the surface opposite to the substrate, the gas barrier layer or the transition metal compound-containing layer) is opposed to the surface. did. The outermost layer surface (gas barrier layer or transition metal compound-containing layer) of the gas barrier film and the surface of the main base material (side on which the electronic element was formed) were respectively cleaned with an Ar ion gun under a vacuum of 1 × 10 ⁻⁶ Pa. Activation treatment was performed by reverse sputtering. Reverse sputtering was performed for 5 minutes at an acceleration voltage of 1 kV and a current value of 10 mA. Note that, using a metal mask, the distance d between the electronic device body and the joining margin was 500 μm, and the joining width h was 100 μm.

  After the activation treatment, while maintaining the degree of vacuum, silicon was sputtered for 3 minutes under the conditions of an acceleration voltage of 1.5 kV and a current value of 100 mA in accordance with the method described in Japanese Patent Application Laid-Open No. 2008-62267. A silicon film having a thickness of 20 nm was laminated on the surface of the film and the surface of the main substrate. Under the conditions of an acceleration voltage of 1 kV and a current value of 10 mA, the silicon film was reverse-sputtered with an Ar ion gun for 5 minutes to activate the silicon film surface and form a bonding margin.

Next, the degree of vacuum is reduced to 1 × 10 ⁻⁷ Pa, the second joining margin on the surface of the gas barrier film and the first joining margin on the surface of the main substrate are brought into contact, and the joining margins are added at 20 MPa for 3 minutes. Pressurized and vacuum bonded at room temperature to seal the electronic device body. Thereafter, the electronic element body was taken out into the atmosphere.

[Evaluation of bending resistance]
The bending resistance of the organic EL devices 1 to 11 produced above was evaluated in accordance with a mechanical stress test (IEC62715-6-1 Ed. 1) of a flexible display element. Specifically, using a U-shaped folding tester manufactured by Yuasa System Equipment Co., Ltd. in an environment of 23 ° C. and 50% RH, set the curvature radius to be 2.0 mm and the sealing film side to the outside, and the bending speed Bending was repeated at 60 times / min.

  Thereafter, the sample was left in an environment of 85 ° C. and 85% RH for 24 hours, and the maximum number of bendings was obtained. The durability was determined by determining that the bendability was lost when the light emission intensity at a constant voltage (10 V) before the stress test was less than 50% after the test, and using the number of bends as a measure. In addition, when it was possible to bend 10,000 times or more, the emission intensity was measured every 10,000 times.

10 electronic devices,
11, 201 Main base material,
12, 202 Gas barrier film,
12a substrate,
12b gas barrier layer,
12c transition metal compound-containing layer,
13, 203 Organic EL element body,
14 Extraction electrode,
16 silicon film,
17 First electrode (anode),
18 hole transport layer,
19 light emitting layer,
20 electron transport layer,
21 Second electrode (cathode),
130 Room temperature bonding equipment,
131 vacuum chamber,
132 ion gun (sputtering source),
133 Target stage 1,
134 Target stage 2,
204 Join.

Claims (9)

The surface of the gas barrier film including the base material, the gas barrier layer and the transition metal compound-containing layer and the surface of the main base material are activated to form bonding margins on the surface of the gas barrier film and the surface of the main base material, respectively. And a step of bringing the bonding margins into contact with each other and sealing the electronic element body by room temperature bonding;
A method for manufacturing an electronic device, comprising:   The method for manufacturing an electronic device according to claim 1, wherein the transition metal compound is niobium oxide.   The gas barrier film includes the base material, the gas barrier layer, and the transition metal compound-containing layer in this order, and forms the joining margin on the surface on which the transition metal compound-containing layer is disposed. 3. A method for manufacturing an electronic device according to 1 or 2.   The manufacturing method of the electronic device of any one of Claims 1-3 using the gas barrier film in which the said gas barrier layer and the said transition metal compound content layer are arrange | positioned adjacently.   The manufacturing method of the electronic device of any one of Claims 1-4 whose layer thickness of the said transition metal compound content layer is 1 nm-15 nm.   The method for manufacturing an electronic device according to claim 1, wherein the gas barrier layer includes a silicon compound.   The method for manufacturing an electronic device according to claim 1, wherein the gas barrier layer is formed by drying a polysilazane-containing coating film.   The electron according to any one of claims 1 to 7, wherein the joining margin is formed by laminating a silicon film on at least one of the surface of the activated gas barrier film and the surface of the main substrate. Device manufacturing method.   The method of manufacturing an electronic device according to claim 8, wherein the bonding margin is formed by activating the silicon film.