JP6648752B2 - Sealed structure - Google Patents

Description

  The present invention relates to a sealing structure such as an electronic device.

  Electronic devices such as organic electroluminescent elements (organic EL elements), organic solar cells, organic transistors, inorganic electroluminescent elements, and inorganic solar cells (eg, CIGS solar cells) are sensitive to oxygen and moisture present in the use environment. . For this reason, a number of sealing methods for protecting electronic devices from oxygen and moisture have been proposed, and a sealing structure for sealing using a barrier substrate using glass or metal has been put to practical use. .

  As a method of sealing these base materials, a method of welding the base material and a sealing substrate on which the electronic element body is mounted can be considered, but has not been put into practical use due to a problem of heat resistance of the electronic device and the like. For this reason, a sealing method using an adhesive made of an organic compound (such as an epoxy resin) is generally used. However, such a sealing method using an adhesive has a problem in that sufficient sealing properties cannot be obtained, and it is impossible to completely prevent intrusion of moisture or oxygen from a joint.

  As a solution to such a problem, a method of using a material having low moisture permeability such as a metal or a metal oxide as an adhesive has been proposed. Was not the right way.

  As another solution, a method has been proposed in which the thickness of the joint is made as small as possible to reduce the moisture permeating from the joint as much as possible. For example, Japanese Patent Application Laid-Open No. 2013-218805 discloses a monomolecular layer of two different silane coupling agents that can react with each other on two members to be sealed in order to minimize the size of the adhesive layer at the sealing portion. Are disclosed, and a method of sealing an organic EL device by reacting them is disclosed. However, Japanese Patent Application Laid-Open No. 2013-218805 does not specifically disclose the structure of the electrode portion and the like, and also does not disclose specific effects of the invention.

Furthermore, in recent years, when joining metals and metal oxides, as a technique that enables joining at normal temperature so that the electronic device does not deteriorate, for example, Tadatomo Suga, Takashi Matsuyamae, Yoshishi Matsumoto, Masashi Nakano, “Direct Bond,” of Polymer to Glass Wafers Using Surface Activated Bonding (SAB) Method at Room Temperature, "Proceedings of the 3rd International IEEE."
Works on Low Temperature Bonding for
Room temperature bonding techniques such as 3D Integration, May 22-June 23, 2012 have also been proposed. According to such a normal temperature bonding technique, flat surfaces can be easily bonded to each other without using an adhesive or the like, and the thickness of the bonding portion can be reduced.

Here, according to the study of the present inventor, according to the above-mentioned Japanese Patent Application Laid-Open No. 2013-218805, Tadatomo Suga, Takashi Matsusumae, Yoshishi Matsumoto, Masashi Nakano, "Direct Bonding"
of Polymer to Glass Wafers Using Surface Activated Bonding (SAB) Method at Room
Temperature, "Proceedings of the 3rd International IEEE Works on Low Temperature Bonding for 3D Integration, Where the device was obtained by the technique described in the case where the device was thinned by the technique described in" May 22-June 23, 2012 ". When a strong force acts locally on the device, such as an impact at the time of a drop, it has been found that there is a problem that the joints are separated and the sealing cannot be maintained. As in the case of the lead electrode from the element body in the above, when the unevenness is present in the joint, the problem of separation due to the impact is more remarkably exhibited.

  Therefore, the present invention enables a reliable sealing even when an electronic device or the like is sealed by a technique for thinning a bonding portion, and has a high sealing even when an impact is applied. It is an object to provide a means capable of maintaining performance.

Means for solving the problem

  The present inventor has conducted intensive studies in order to solve the above problems. As a result, the object to be sealed is sealed using the main base material and the sealing base material, and in a sealing structure in which the thickness of the bonding portion is 100 nm or less, the sealing base material is supported. Body, using a gas barrier layer disposed on the sealed body side with respect to the support, further, at least one of the main substrate and the support of the sealing substrate, a specific thickness and It has been found that the above problem can be solved by using a resin film having a Young's modulus, and the present invention has been completed.

  That is, the above object is achieved by the following configurations.

1. Main base material,
An object to be sealed disposed on the main substrate,
A sealing base material that is bonded to the main base material through a bonding portion provided around the sealed body to seal the sealed body,
A sealing structure having
The sealing substrate includes a support, and a gas barrier layer disposed on the sealed body side with respect to the support,
The thickness of the joint is 0.1 to 100 nm,
Wherein at least one of the main substrate and the support is a resin film satisfying the following conditions (A) and (B):
(A) the thickness is 1 μm or more and less than 30 μm;
(B) the Young's modulus at 25 ° C is 1 to 10 GPa;
2. The above-described 1., further comprising a convex lead structure having a thickness of 10 to 500 nm, which is formed so as to be exposed from the object to be sealed, and which is drawn to the outside through the joint portion. A sealing structure according to
3. 1. The sealed body is an electronic element main body of an electronic device, and the convex lead-out structure is an extraction electrode for controlling the electronic element main body. A sealing structure according to
4. The above-mentioned 1., wherein the support is a resin film satisfying the above conditions (A) and (B). ~ 3. The sealing structure according to any one of the above;
5. 3. The thickness of the support is 1 to 15 μm, and the Young's modulus at 25 ° C. of the support is 3 to 5 GPa. A sealing structure according to
6. The above-mentioned 1., wherein the gas barrier layer has an organic layer arranged on the support side and an inorganic layer arranged on the sealed body side. ~ 5. The sealing structure according to any one of the above;
7. 5. The organic layer according to the above item 6, wherein the inorganic layer has a surface roughness (Ra) of 0.1 to 5 nm. A sealing structure according to
8. 6. The elongation percentage of the inorganic layer is 0.5 to 5.0%. Or 7. A sealing structure according to
9. The above-mentioned 1., wherein the bonding portion includes an activation treatment layer obtained by performing a surface activation treatment on each of the bonding surface of the main base material and the bonding surface of the sealing base material. ~ 8. The sealing structure according to any one of the above;
10. The bonding portion includes a metal layer formed on the surface of the main base material and an activation treatment layer obtained by performing a surface activation treatment on each of the metal layers formed on the surface of the sealing base material. And 1. ~ 8. The sealing structure according to any one of the above;
11. The above-mentioned 1., wherein the bonding portion includes an adhesive layer containing a silane coupling agent or a molecular adhesive. ~ 8. The sealing structure according to any one of the above.

12. The electronic device described in 1. above. ~ 11. The sealing structure according to any one of the above,
The sealed body is an electronic element body,
Further comprising an extraction electrode formed to be exposed from the electronic element main body and drawn out to the outside via the bonding portion, for controlling the electronic element main body,
The sealing substrate, a support, disposed on the electronic element body side with respect to the support, a gas barrier layer having an organic layer and an inorganic layer,
A sealing structure, wherein the organic layer has a nanoindentation elastic modulus (at 23 ° C. and 50% RH) of 0.01 to 1 GPa;
13. 12. The bonding device according to the above 12, wherein the bonding portion includes an activation treatment layer obtained by performing a surface activation treatment on each of the bonding surface of the main base material on which the lead electrode is formed and the bonding surface of the sealing base material. . A sealing structure according to
14． The bonding portion is obtained by performing a surface activation treatment on each of the metal layer formed on the surface of the main substrate on which the lead electrode is formed, and the metal layer formed on the surface of the sealing substrate. 12. The method as described in the above item 12. 3. The sealing structure according to 1.

FIG. 1A is a schematic sectional view of an organic EL device according to one embodiment of the present invention. FIG. 1B is a diagram schematically illustrating a cross section taken along line 1b-1b in FIG. 1A. It is explanatory drawing for demonstrating the technique of measuring the elongation rate of the inorganic barrier layer in a sealing base material. FIG. 2 is a schematic cross-sectional view illustrating an example of a room-temperature bonding apparatus that can be used for manufacturing an electronic device according to the present invention. FIG. 3 is a schematic cross-sectional view showing a pressurized state for room temperature bonding in a room temperature bonding apparatus that can be used for manufacturing an electronic device according to the present invention. FIG. 3 is an explanatory diagram for explaining a layout of a lead electrode and a magnesium layer on a main substrate in a simulated electronic device manufactured in an example.

According to one embodiment of the present invention, a main base, a sealed body disposed on the main base, and the main base via a bonding portion provided around the sealed body. A sealing structure having a sealing base material that seals the sealed body by bonding, wherein the sealing base material is provided on a side of the sealed body with respect to the support and the support. A resin having a gas barrier layer disposed therein, wherein the thickness of the bonding portion is 0.1 to 100 nm, and at least one of the main substrate and the support satisfies the following conditions (A) and (B): A sealing structure is provided, characterized in that it is a film:
(A) the thickness is 1 μm or more and less than 30 μm;
(B) The Young's modulus at 25 ° C. is 1 to 10 GPa.

  The sealing structure according to one embodiment of the present invention is characterized in that at least one of the main substrate and the support forming the sealing substrate is formed of a resin film having a predetermined thickness and a Young's modulus. is there. As a result, even if the object to be sealed is sealed by the technique of reducing the thickness of the joint, reliable sealing is possible and high sealing performance even when an impact is applied. Can be maintained. In the present invention, as a mechanism for achieving such an effect, when a resin film having the above-described predetermined Young's modulus is used, the resin film has a Young's modulus of 10 GPa or less. The durability against local forces due to the above is improved, while the Young's modulus is 1 GPa or more, so that the film is less susceptible to tension and the like during film formation, so that the stress remaining in the film is reduced. it is conceivable that. Further, since the resin film has the above-mentioned predetermined thickness, the concentration of the stress acting on the joint due to the impact at the time of dropping can be reduced, and as a result, the joint is less likely to be broken even when subjected to an impact or the like. It is presumed that the sealing performance of the joint is improved and the impact resistance is also improved. In the conventional technical common sense, it was considered that the larger the thickness of the support constituting the main base material and the sealing base material, the higher the impact resistance of the sealing structure. According to the study of the present inventor, when the thickness of the resin film is large, the impact resistance is rather deteriorated, and the relatively thin resin film is used as the main base or the sealing base after controlling the Young's modulus. It has been found that there is a fact contrary to the above-mentioned conventional general knowledge that the impact resistance of the sealing structure is improved.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. Note that the present invention is not limited to only the following embodiments. The dimensional ratios in the drawings are exaggerated for the sake of explanation and may differ from the actual ratios.

  The sealing structure according to one embodiment of the present invention is, for example, an electronic device such as an organic electroluminescence (EL) device. In the following description, a case where the sealing structure according to the present invention is an organic EL device, which is one type of electronic device, will be described as a typical embodiment, but the technical scope of the present invention is as follows. It is not limited only to the form.

  FIG. 1A is a schematic sectional view of an organic EL device 10 according to one embodiment of the present invention. That is, the organic EL device 10 shown in FIG. 1 has a main substrate 11, a sealing substrate 12, and an organic EL element body 13 located between the main substrate 11 and the sealing substrate 12. The sealing substrate 12 is formed of a laminate of a support 12a, an undercoat layer 12b, and an inorganic barrier layer 12c, and is disposed so that the inorganic barrier layer 12c faces the organic EL element body 13. Here, the undercoat layer 12b and the inorganic barrier layer 12c in the sealing base material 12 together form a gas barrier layer, whereby the sealing base material 12 is a gas barrier film. In the present embodiment, a protective layer 15 is provided on the upper part of the electronic element main body 13 so as to cover a part of the organic EL element main body 13. A lead electrode 14 for controlling the organic EL element body 13 from the outside is formed on the main substrate 11, and a joint 16 is formed between the main substrate 11 and the lead electrode 14. ing. The organic EL element main body 13 is sealed by joining the main substrate 11 and the sealing substrate 12 via the joint 16. That is, the joining portion 16 is formed at the interface between the extraction electrode 14 formed on the main substrate 11 and the inorganic barrier layer 12 c constituting the sealing substrate 12, and the main substrate 11 and the sealing substrate are interposed therebetween. The material 12 is joined.

  In the embodiment shown in FIG. 1A, the electronic element main body 13 is an organic EL element main 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. (Cathode) 21 is formed by laminating on the main substrate 11 in this order. However, in the sealing structure according to the present invention, an electronic element main body (sealed body) such as the organic EL element main body 13 is formed on a sealing base material together with a protective layer as necessary, and is formed via a bonding portion. The sealing with the main base material may be performed.

  FIG. 1B is a diagram schematically illustrating a cross section taken along line 1b-1b in FIG. 1A. As shown in FIG. 1B, a lead electrode 14 is formed on the main base 11, and the inorganic barrier layer 12 c of the sealing base 12 is connected to the main base 11 via the joining portion 16. It is joined to the electrode 14.

  Hereinafter, members constituting the sealing structure according to the present embodiment will be described in detail.

[Main substrate]
The main base material is a substrate for forming a sealed 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 include a glass substrate, a metal foil, a resin film, a gas barrier film having a support (resin film) and a gas barrier layer.

The water vapor permeability (WVTR; measured by a method specified in Examples described later) of the main substrate according to the present invention is preferably 5 × 10 ⁻³ g / m ² · day or less, and preferably 5 × 10 ^−4. g / m ² · day or less, more preferably 5 × 10 ⁻⁵ g / m ² · day or less.

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

  When the main substrate is composed of a resin film, as the constituent material, the materials listed as a support of the sealing substrate described later can be similarly employed. In addition, when the main substrate is formed of a gas barrier film, the description of the sealing substrate described below applies to the configuration of the gas barrier film in the same manner.

In the sealing structure according to the present invention, the main base material and a sealing base material described later preferably have flexibility. As used herein, “flexible” refers to the property of being flexible and deforming by applying a force but returning to its original shape when the force is removed. Quantitatively expressing this flexibility, the bending elastic modulus specified in JIS K7171: 2008 for the main base material and the sealing base material is, for example, 1.0 × 10 ^{3 to} 4.5 × 10 ³ [ N / mm ² ].

[Sealing base material]
The sealing base material is bonded to the main base material via a bonding portion provided around a sealed body (for example, an electronic element body such as the organic EL element body 13 shown in FIG. 1A). It has a function of sealing an object to be sealed. In the present invention, the sealing substrate includes a support and a gas barrier layer. Here, the gas barrier layer is disposed on the electronic element body side with respect to the support. The gas barrier layer preferably has an organic layer and an inorganic layer. In this case, the organic layer is usually disposed on the support side and functions as an undercoat layer (smoothing layer). Is disposed on the sealed body side as an inorganic barrier layer and exhibits a main gas barrier property.

<Support>
The support is long and can hold a gas barrier layer having a gas barrier property described below (also simply referred to as “barrier property”), and is formed of the following material. It is not particularly limited to these.

  Examples of the support include polyacrylate, polymethacrylate, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, and polyvinyl chloride (PVC). , Polyethylene (PE), polypropylene (PP), cycloolefin polymer (COP), cycloolefin copolymer (COC), triacetate cellulose (TAC), styrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, Polysulfone, polyethersulfone, polyimide, films of each resin such as polyetherimide, heat-resistant transparent film based on silsesquioxane having an organic-inorganic hybrid structure (for example, (Product name: Sila-DEC; manufactured by Chisso Corporation, and product name: Silplus (registered trademark); manufactured by Nippon Steel Chemical Co., Ltd.), and a resin film formed by laminating two or more layers of the resin. it can.

  From the viewpoint of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), and the like are preferably used. TAC, COC, COP, PC, etc., which are produced by a method, are preferably used. In terms of optical transparency, heat resistance, and adhesion to a gas barrier layer, silsesquioxane having an organic-inorganic hybrid structure is used. A heat-resistant transparent film having a basic skeleton is preferably used.

  Preferably, the support is transparent. The term “transparent support” as used herein means that the light transmittance of visible light (400 to 700 nm) is 80% or more. Since the support is transparent and the gas barrier layer formed on the support is also transparent, a transparent gas barrier film can be obtained, so that a transparent substrate such as an organic EL device can be used. There is an advantage. Before forming the gas barrier layer on the support, the surface thereof may be subjected to a surface treatment such as a corona treatment.

  When a gas barrier layer to be described later is formed of an inorganic barrier layer and the inorganic barrier layer is formed on a support, the surface roughness of the support may be a 10-point average roughness (Rz specified in JIS B0601: 2001). ) Is preferably in the range of 1 to 500 nm, more preferably in the range of 5 to 400 nm, and even more preferably in the range of 300 to 350 nm. In this case, the center line average surface roughness (Ra) of the support surface defined by JIS B0601: 2001 is preferably 12 nm or less, more preferably 8 nm or less, further preferably 5 nm or less, particularly preferably 5 nm or less. Preferably it is 2 nm or less. The lower limit of Ra is not particularly limited, but is usually 0.1 nm or more. In the sealing structure according to the present invention in which the thickness of the bonding portion is extremely thin, it is very important that the surface on which the inorganic barrier layer is formed (for example, the surface of the support) is flat. , Ra are preferably in the above-mentioned range, since an inorganic barrier layer can be formed on a surface having extremely high flatness. A method of setting the surface roughness of the surface of the support to a value within the above-described range is conventionally known.For example, the support is manufactured using a method that can obtain a flattened resin film such as a casting method. Or the amount of filler added to the support may be reduced.

(Thickness and Young's modulus of main substrate and support)
In the sealing structure according to the present invention, at least one of the “main base material” and the “support forming the sealing base material” is a resin film satisfying the following conditions (A) and (B). There is a feature in the point. Hereinafter, a resin film satisfying the following conditions (A) and (B) is also referred to as “resin film of the present invention”:
(A) the thickness is 1 μm or more and less than 30 μm;
(B) The Young's modulus at 25 ° C. is 1 to 10 GPa.

  Here, when the main base material is the “resin film of the present invention”, the thickness of the main base material is preferably 1 to 15 μm, and more preferably 3 to 10 μm. In this case, the main base material preferably has a Young's modulus of 3 to 5 GPa. On the other hand, when the main substrate is not the “resin film of the present invention”, the main substrate may be a glass substrate or a metal foil as described above, or a resin film that is not the “resin film of the present invention”. It may be. Here, when the main substrate is a resin film other than the “resin film of the present invention”, the thickness is preferably 30 to 500 μm, and more preferably 30 to 250 μm.

  When the main base material has a configuration of a gas barrier film having a support and a gas barrier layer in the same manner as the sealing base material, the support forming the main base material is a “resin film of the present invention”. If there is, the main substrate is assumed to be the “resin film of the present invention”.

  Further, when the support constituting the sealing substrate is the “resin film of the present invention”, the thickness of the support is preferably 1 to 15 μm, more preferably 3 to 10 μm. In this case, the support preferably has a Young's modulus of 3 to 5 GPa. On the other hand, when the support constituting the sealing substrate is not the “resin film of the present invention”, the support may be a resin film that is not the “resin film of the present invention”. Here, when the support constituting the sealing substrate is a resin film other than the “resin film of the present invention”, the thickness is preferably 30 to 500 μm, and more preferably 30 to 250 μm.

  In addition, about the "Young's modulus at 25 degreeC" of a resin film, the value measured by the method prescribed | regulated to ASTM-D-882 and JIS-7127 shall be employ | adopted.

<Gas barrier layer>
The sealing substrate has a gas barrier layer. Further, the gas barrier layer preferably includes at least two layers of an organic layer and an inorganic layer. Therefore, hereinafter, a case where the gas barrier layer is composed of two layers of an organic layer (undercoat layer) and an inorganic layer (inorganic barrier layer) will be described as an example, but is limited to only such an embodiment. Do not mean. In FIGS. 1A and 1B, the organic layer (undercoat layer 12b) is disposed on the support 12a side, and the inorganic layer (inorganic barrier layer 12c) is disposed on the electronic element body (organic EL element body 13) side. However, a configuration in which the organic layer and the inorganic layer are arranged in reverse may be adopted. However, as shown in FIG. 1, it is more preferable that the organic layer is disposed on the support side and the inorganic layer is disposed on the electronic element body side.

  The gas barrier layer is a layer that exhibits a barrier property against water vapor and oxygen by being disposed on a support. Measured by the method specified in Examples described later) is 5 × 10^-3g / m²-When it is less than or equal to day, it has "gas barrier properties". This WVTR is 5 × 10^-3g / m ²It is preferably 5 days or less.^-4g / m²It is more preferably 5 days or less.^-5g / m²-It is more preferable that it is day or less.

(Inorganic layer)
The inorganic layer constituting the gas barrier layer is not particularly limited as long as it is a layer containing an inorganic compound, but typically is a conventionally known barrier layer containing an inorganic compound (inorganic barrier layer).

  The material constituting the inorganic barrier layer 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 A simple substance of at least one metal selected from the group consisting of tantalum (Ta), and a metal compound such as an oxide, a nitride, a carbide, an oxynitride or an oxycarbide of the above-mentioned metal are exemplified.

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 oxide boride, titanium oxide boride, and composites thereof And inorganic barrier materials such as metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxide borides, 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.

  The method for forming the inorganic barrier layer is not particularly limited. For example, a sputtering method (for example, magnetron cathode sputtering, flat plate magnetron sputtering, two-pole AC flat-plate magnetron sputtering, two-pole AC rotating magnetron sputtering, etc.), a vapor deposition method (for example, resistance Heat evaporation, electron beam evaporation, ion beam evaporation, plasma assisted evaporation, etc.), thermal CVD, catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD (CCP-CVD), photo CVD, plasma CVD Method (PE-CVD), an epitaxial growth method, an atomic layer growth method, and a chemical vapor deposition method such as a reactive sputtering method.

  Further, after a coating solution containing an inorganic precursor such as polysilazane or tetraethyl orthosilicate (TEOS) is wet-coated on a support (or an organic layer (that is, an undercoat layer) on the support), irradiation with vacuum ultraviolet light is performed. A method of forming an inorganic barrier layer by performing a reforming treatment by using, for example, metal plating on a support (or an organic layer (that is, an undercoat layer) on the support), The inorganic barrier layer can also be formed by a film metallization technique such as bonding a layer (that is, an undercoat layer) and a metal foil.

  The inorganic barrier layer may be a single layer or a laminated structure of two or more layers. In the case of a laminated structure of two or more layers, the material of each layer may be the same or different. In addition, the thickness of the inorganic layer is preferably 3 to 1000 nm, and more preferably 10 to 300 nm.

  The elongation percentage of the inorganic layer (inorganic barrier layer) is preferably greater than 0.2%. In addition, the value of the elongation percentage of the inorganic layer is a value measured by the following method, more preferably 0.5% to 6.0%, and more preferably 0.5% to 5.0%. More preferably, it is particularly preferably 1.0 to 5.0%.

(Method of measuring elongation)
As shown in FIG. 2, the sealing base material is curved and fixed between two parallel plates 70 so that the inorganic barrier layer of the sealing base material is located outside, and fixed at room temperature for 24 hours. Save time. Then, at the same room temperature, the curved portion is observed with a microscope to check whether cracks have occurred. If no crack has occurred, the same operation is repeated with the distance d between the two plates 70 smaller than the previous time. When a crack occurs, the radius of curvature r of the curved portion of the inorganic barrier layer is calculated from the distance d between the two plates at the time of the operation immediately before the crack did not occur and the thickness of the support of the sealing base material according to the following equation. Ask for.

Radius of curvature r = (distance d-thickness of support) / 2
From the obtained radius of curvature r, the elongation percentage of the inorganic barrier layer is obtained by the following equation.

Elongation (%) = (thickness of support / 2r) × 100
The elongation percentage of the inorganic layer can be controlled by adjusting the composition of the inorganic layer. For example, when the inorganic layer is an inorganic barrier layer and the composition of the inorganic barrier layer is mainly composed of SiO ₂ , the elongation rate is increased by introducing an Al element or a C element into the composition. The value can be controlled. Specifically, it is preferable to contain 1 to 30 atomic% of Al atoms with respect to Si atoms. Further, the content of C atoms is preferably 3 to 30% with respect to Si atoms. On the other hand, when the inorganic barrier layer has a composition containing an N element (for example, SiON or SiN), when the composition is SiO _x N _y , the value of 2x + 3y is 3.5 or less when the elongation rate is less than 3.5. Although preferable from the viewpoint, the value of 2x + 3y is preferably 2.0 or more from the viewpoint of durability of the barrier property.

  In the gas barrier layer, when the inorganic layer (inorganic barrier layer) is disposed on the side of a sealed body such as an electronic element body, the surface roughness of the inorganic layer (inorganic barrier layer) is specified in JIS B0601: 2001. The center line average surface roughness (Ra) is preferably 3 nm or less, more preferably in the range of 0.1 to 2.0 nm.

(Organic layer)
When the gas barrier layer contains an organic layer, any layer containing an organic compound can be used as the organic layer.

  The organic layer constituting the gas barrier layer is not particularly limited. For example, an organic monomer or an organic oligomer is applied to a support to form a coating film, and then, for example, an electron beam device, a UV light source, a discharge device, or other Formed by polymerization and, if necessary, crosslinking using a suitable apparatus. Examples of the constituent material of the organic layer include an ethylene-vinyl acetate copolymer (EVA resin), an acrylic resin, a urethane resin, a polyolefin resin, a rubber resin, a polyester resin, and the like.

  Alternatively, the organic layer may be formed, for example, by depositing an organic monomer or an organic oligomer capable of flash evaporation and radiation crosslinking, and then forming a polymer from the organic monomer or the organic oligomer. Coating efficiency can be improved by cooling the support. Examples of the method for applying the organic monomer or the organic oligomer include roll coating (for example, gravure roll coating) and spray coating (for example, electrostatic spray coating).

  The thickness of the organic layer is preferably 100 nm to 100 μm, more preferably 1 μm to 50 μm.

  Here, when the gas barrier layer is composed of an organic layer disposed on the support side and an inorganic layer (inorganic barrier layer) disposed on the sealed body side, and the inorganic barrier layer is formed on the organic layer As for the surface roughness of the organic layer, the 10-point average roughness (Rz) defined in JIS B0601: 2001 described above for the support is preferably in the range of 0.1 to 50 nm. It is more preferably in the range of 0.5 to 40 nm, and even more preferably in the range of 1.0 to 30 nm. In this case, the center line average surface roughness (Ra) of the support surface defined by JIS B0601: 2001 is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 2 nm or less. . In addition, Ra of the organic layer is preferably 0.1 nm or more. It is preferable that the Ra of the surface of the organic layer is within the above-described range, since the inorganic barrier layer can be formed on a surface having extremely high flatness. A method for adjusting the surface roughness of the surface of the organic layer to a value within the above-mentioned range is conventionally known. However, the roughness can be obtained by flattening the unevenness of the support by wet coating the organic layer.

(Bleed-out prevention layer)
A bleed-out prevention layer may be disposed on the surface of the support constituting the sealing substrate on the side opposite to the surface on which the gas barrier layer is provided. The bleed-out prevention layer is provided for the purpose of suppressing the phenomenon in which unreacted oligomers and the like migrate from the support to the surface when the film having the organic layer or the like is heated and contaminate the contact surface. The bleed-out prevention layer may have the same configuration as the organic layer as long as it has this function.

[Drawer electrode]
The sealing structure (for example, an electronic device such as an organic EL device) according to the present invention is formed so as to be exposed from an object to be sealed, such as the extraction electrode 14 in the organic EL device 10 shown in FIG. It is preferable to further have a convex draw-out structure drawn out to the outside through the portion. The thickness of the convex drawing structure is usually about 10 to 500 nm, and preferably 50 to 300 nm. In the organic EL device 10 shown in FIG. 1, the provision of the extraction electrode 14 enables the organic EL element body 13 to be controlled from the outside.

When the convex lead-out structure is a lead-out electrode, as a constituent material of the lead-out electrode, for example, indium tin oxide (ITO), AZO (aluminum-doped zinc oxide), FTO (fluorine-doped tin oxide), SnO ₂ , ZnO , A transparent metal oxide such as titanium oxide, a metal such as Ag, Al, Au, Pt, Cu, Rh, In, Ni, Pd, and Mo, a metal nanowire, a nanowire such as a carbon nanotube, and a nanoparticle. . An electrode having a structure in which two or more kinds of metals are stacked may be used.

  The extraction electrode can be manufactured by forming these electrode substances into a thin film by a method such as evaporation or sputtering.

  There is no particular limitation on a method of forming an electrode having a stripe shape or the like, and a conventionally known method can be used. For example, a lead electrode having a desired shape can be produced by forming a thin film on the main substrate by a method such as vapor deposition or sputtering and then etching the film using a known photolithography method.

Here, in order to drive and control the electronic device, it is necessary to take out the signal lines and electrodes from the electronic element body to the outside, and these usually have a thickness of 100 nm or more due to problems such as resistance. This is one of the causes of unevenness at the joint. According to the study of the present inventor, if such unevenness exists on the bonding surface, the above-mentioned Japanese Patent Application Laid-Open No. 2013-218805, Tadatomo Suga, Takashi Matsuyamae, Yoshishi Matsumoto, Masashi Nakano, "Direct Bonding Bonding" Glass Wafers using Surface
Activated Bonding (SAB) Method at Room Temperature, "Procedings of the 3rd International IEEE IEEE Workshop on Low-Temp. It has been found that it is difficult to reliably seal the portion, and that the durability of the electronic device is reduced due to the intrusion of moisture or the like from the joint portion. As a result, the thickness of the bonding portion was set to 100 nm or less, as described later, and as shown in FIG. A gas barrier layer having an organic layer and an inorganic layer disposed on the electronic element body side with respect to the body, and furthermore, the nanoindentation elastic modulus (at 23 ° C. and 50% RH condition) of the organic layer is determined by a predetermined value. It has been found that the above-mentioned problem that occurs when the bonding surface has irregularities can be solved by controlling the value to be within the range, that is, a preferred embodiment of the sealing structure according to the present invention is the above-described covering structure. The sealing device is an electronic device main body, which is an electronic device further formed with an extraction electrode for controlling the electronic element main body, which is formed so as to be exposed from the electronic element main body, and which is drawn out to the outside through a bonding portion. The sealing base material is provided with a support, a gas barrier layer having an organic layer and an inorganic layer disposed on the electronic element body side with respect to the support, and It has been found that the above problem can be solved if the organic layer has a nanoindentation elastic modulus (at 23 ° C. and 50% RH) of 0.01 to 1 GPa. As a mechanism of achieving the effect, the presence of an organic layer having a predetermined elastic modulus relatively smaller than that of the conventional technology allows the gas barrier layer to follow irregularities and the elastic modulus of this region. As a result, it becomes possible to form a stable inorganic layer (inorganic barrier layer) adjacent to the organic layer having the organic compound, and as a result, the bonding portion is reliably sealed, which contributes to the improvement of the durability of the electronic device. The value of the nanoindentation elastic modulus of the organic layer is a value measured by the method described in the section of Examples described later, and is preferably 0.05 to 1.0 GPa. Is preferably 0.1 to 0.5 Pa.

  In a preferred embodiment of the present invention in which the value of the nanoindentation elastic modulus of the organic layer is controlled to a value within the above-described preferred range, the organic layer constituting the gas barrier layer satisfies the above-described definition of the nanoindentation elasticity. Although not particularly limited as long as, for example, an organic monomer or an organic oligomer is applied to a support to form a coating film, and then, for example, an electron beam device, a UV light source, a discharge device, or another suitable device is used. It is formed by polymerization and, if necessary, crosslinking. Examples of the constituent material of the organic layer include an ethylene-vinyl acetate copolymer (EVA resin), an acrylic resin, a urethane resin, a polyolefin resin, a rubber resin, a polyester resin, and the like. A person skilled in the art can control the nanoindentation elastic modulus of the organic layer by adjusting the copolymer composition and the weight average molecular weight (Mw) of these copolymers / resins.

  Further, for example, the organic layer in this embodiment can also be formed by forming a polymer from the organic monomer or the organic oligomer after vapor-depositing an organic monomer or an organic oligomer capable of flash evaporation and radiation crosslinking. Coating efficiency can be improved by cooling the support. Examples of the method for applying the organic monomer or the organic oligomer include roll coating (for example, gravure roll coating) and spray coating (for example, electrostatic spray coating).

  In addition, as a constituent material of the organic layer used in the present embodiment, a thermoplastic resin whose elastic modulus is reduced by increasing the temperature during bonding is preferably used. In this case, a resin having an elastic modulus of 0.001 to 0.1 GPa at the bonding temperature is preferable.

  As such a resin, a so-called hot melt resin is preferably used. Specific examples include a rubber-based hot melt resin, a polyolefin resin-based hot melt resin, and a polyester resin-based hot melt resin. Among these, polyolefin resin-based hot melt resins and polyester resin-based hot melt resins are preferred from the viewpoints of adhesive strength, chemical resistance, and the like. The softening point of the hot melt resin is preferably from 60 to 150 ° C, more preferably from 70 to 120 ° C. When the softening point of the hot melt adhesive is within the above range, it is preferable from the viewpoint of the durability of the device, the manufacturing process and the working process of the adherend.

  Further, a rubber-based resin, a polyolefin resin, a polyester resin, or the like can also be used. Specific examples of the rubber-based resin include a styrene-isopropylene-styrene block copolymer and a resin obtained by adding a petroleum resin to a styrene-butadiene-styrene block copolymer. Specific examples of the polyolefin resin include a copolymer of propylene, ethylene and butene-1, and an ethylene-vinyl acetate copolymer. Commercially available polyolefin resin-based hot melt resins include, for example, “MORESCOMELT EP-167” manufactured by MORESCO Corporation, “Nucrel (registered trademark)”, “Himilan (registered trademark)” manufactured by DuPont Mitsui Polychemicals, Inc. Is mentioned. Specific examples of the polyester resin include a polycondensate of a dicarboxylic acid component and a diol component. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, lower alkyl esters thereof, malonic acid, succinic acid, adipic acid, sebacic acid and the like. The diol component includes ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and cyclohexanediene. Examples include methanol, neopentyl glycol, and polytetramethylene glycol. A polyester resin-based hot melt resin can be obtained using at least one of each of these dicarboxylic acid components and diol components. Commercially available polyester resins include, for example, "ER series" manufactured by Toyo Adre and "Nichigo Polyester (registered trademark) series" ("Polyester SP-165") manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can be

[Joint]
As shown in FIG. 1, the bonding portion is provided around a sealed body (for example, an electronic element body such as the organic EL element body 13) and exists between the main base material and the sealing base material. I do. The present invention is characterized in that the thickness of the bonding portion is made smaller than that in the case where a general adhesive is used, and specifically, is in the range of 0.1 to 100 nm. If the thickness of the joining portion is 0.1 nm or more, the joining between the main base material and the sealing base material is sufficiently performed, and the object to be sealed is securely sealed between the main base material and the sealing base material. It is possible to stop. On the other hand, when the thickness of the joint is 100 nm or less, intrusion of moisture, oxygen, or the like from the joint can be reduced, and deterioration of the sealed body due to the intrusion can be suppressed. Become. The thickness of the joint can be determined by taking a tomographic photograph of the joint between the main base and the sealing base and measuring the distance between the main base and the sealing base. In addition, the thickness of the bonding portion is preferably 0.1 to 80 nm, more preferably 1 to 50 nm.

There is no particular limitation on the method of sealing such that the thickness of the bonding portion is 0.1 to 100 nm, and conventionally known knowledge can be appropriately referred to. For example, Tadatomo Suga, Takashi Matsumae, Yoshishi Matsumoto,
Masashi Nakano, "Direct Bonding of Polymer to Glass Wafers using Surface Activated Bonding (SAB) Method at Room Temperature," Proceedings of the 3rd International IEEE Workshop on Low Temperature Bonding for 3D Integration, are disclosed in May 22- June 23, 2012 For example, there is a method of performing bonding using a so-called room-temperature bonding technique. When bonding is performed using this room temperature bonding technique, there is no risk of exposing the resin material forming the main base material and the sealing base material to high temperatures, and thus there is an advantage that the deterioration of the resin material can be prevented. Hereinafter, a method of bonding the main base material and the sealing base material using the room temperature bonding technique will be described in detail with reference to FIGS.

  First, bonding margins for joining the main base material and the sealing base material are formed on the peripheral portions of the main base material and the sealing base material.

  Here, FIG. 3 is a schematic sectional view showing an example of a room-temperature bonding apparatus that can be used for manufacturing the 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. As the vacuum pump, there is a turbo-molecular pump in which a plurality of metal blades inside exhaust air by blowing off gas molecules. The degree of vacuum in the vacuum chamber 131 can be adjusted to a predetermined degree 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 sealing base material 12, and attracts and fixes the sealing base material 12 to the dielectric layer by electrostatic force. Similarly, the target stage 134 adsorbs and fixes the substrate 11 via the dielectric layer.

  The target stage 133 can be formed in the shape of a column, a cube, or the like, and can move in parallel with the vacuum chamber 131 in the vertical direction. The parallel movement is performed by a pressing mechanism (not shown) provided on the target stage 133.

  The target stage 134 can be translated in a vertical direction with respect to the vacuum chamber 131, and can also be rotated around a rotation axis parallel to the vertical direction. The translation and rotation are performed by a transfer mechanism (not shown) provided on the target stage 134.

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

  Upon receiving the irradiation of the charged particles, the metal is sputtered from the target stages 133 and 134 in the apparatus, and is sputtered on desired portions of the base material 11 and the sealing base material 12, and is bonded to the desired portions to form a metal film. To form The range of the desired portion can be determined by a known metal mask technique or the like. For example, when encapsulating the electronic device according to one embodiment of the present invention, the metal portion with respect to the electronic element body is sealed. By masking (not shown), a first bonding margin is formed around the non-metal masked electronic element body on the base material, and the first metal sheet is formed on the unsealed portion of the sealing base material. A second joining margin is formed at the periphery.

  After the metal sputtering, the irradiation conditions of the charged particles are changed by adjusting the operation parameters of the ion gun 132, and activation for bonding the respective bonding margins is performed. Then, after the irradiation of the charged particles is completed and the metal mask is removed, the pressing mechanism of the target stage 1 is operated to lower the target stage 133 in the vertical direction, and as shown in FIG. The stop substrate 12 is brought into contact. By joining at room temperature in this manner, the first joining margin of the base material 11 and the second joining margin of the sealing base material 12 are joined together, and joined to the interface 127 between the base material 11 and the sealing base material 12. A part 16 is formed. Thereby, the electronic element body can be sealed. The joining conditions are not particularly limited, and the joining can be carried out even under normal temperature and no pressure in vacuum. However, from the viewpoint of more firm joining, it is preferable to apply a pressure of 1 to 100 MPa for 1 to 10 minutes.

In addition, before forming the bonding margin, it is preferable to clean each bonding margin forming portion from the viewpoint of removing impurities, an adsorbed gas, an oxide film, and the like attached to the surface. The cleaning and subsequent steps are preferably performed in a vacuum in order to prevent moisture, oxygen, and the like from being contained in the sealed electronic element body. The cleaning is preferably performed in an environment having a degree of vacuum of 10 ⁻⁶ to 10 ⁻⁴ Pa.

  The cleaning can be performed by a known method, and examples thereof include reverse sputtering, ion beam, and ion beam sputtering. Reverse sputtering as an example for performing cleaning can be performed as follows. Using an inert gas such as argon, the accelerating voltage is set to 0.1 to 10 kV, preferably 0.5 to 5 kV, and the current value is set to 10 to 1000 mA, preferably 100 to 500 mA, for 1 to 30 minutes, preferably 1 to 30 minutes. The irradiation can be performed for up to 5 minutes.

  As described above, the method of performing the joining using the room temperature joining technique and sealing the electronic element body (“joining method I-1” and “joining method I-2” in Examples described later) has been described. As long as the thickness can be set in the above range (0.1 to 100 nm), the bonding may be performed using another method.

As a bonding method other than the cold bonding technology, for example, the following methods can be mentioned:
-Using a metal mask similar to that of the bonding method I, a bonding margin between the main substrate and the sealing substrate is subjected to a surface activation treatment using a plasma dry cleaner or the like (plasma discharge treatment in an oxygen atmosphere under reduced pressure). I do. Next, after removing the metal mask, each of the main substrate and the sealing substrate is exposed to a high humidity (for example, 80% RH) environment, and the respective bonding margins are brought into contact using a vacuum laminator. A method of joining the main base material and the sealing base material by applying a pressure and heat treatment to the region (“Joining method II-1” and “Joining method II-2” in Examples described later);
Using a metal mask similar to the bonding methods I-1 and I-2, a bonding margin between the main substrate and the sealing substrate is subjected to a surface activation treatment using a plasma dry cleaner or the like (under an oxygen atmosphere under reduced pressure. Plasma discharge treatment). Next, a sealing base (or main base) metal-masked with a saturated vapor of a first silane coupling agent (for example, KBM-903 (3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)). To form an adhesive layer made of a silane coupling agent on the periphery of the sealing base material (or main base material). On the other hand, the saturated vapor of the second silane coupling agent (for example, KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.)) that can react with the first silane coupling agent is added to the metal. The masked main substrate (or sealing substrate) is exposed to form an adhesive layer made of a second silane coupling agent on the periphery of the main substrate (or sealing substrate). Then, after removing the metal mask, the respective bonding margins are brought into contact with each other using a vacuum laminator, and the main base material and the sealing base material are subjected to pressure and heat treatment on the bonding margin areas. Joining method ("joining method III-1" and "joining method III-2" in Examples described later; for details of this method, JP-A-2013-218805 can be referred to);
-Remove the thickeners, fillers, and the like, which are the large particle size components that have been conventionally blended, from the components of the conventionally known ultraviolet-curing adhesive or thermosetting adhesive, and use the resulting adhesive to form the main base. A method of joining the peripheral portions of the material and the sealing base material ("joining method V-1" and "joining method V-2" in examples described later);
Using a metal mask similar to that of the bonding method I-1 and the bonding method I-2, the bonding margin between the main base material and the sealing base material is subjected to a surface activation treatment using a plasma dry cleaner or the like (under reduced pressure, oxygen Plasma discharge treatment in an atmosphere). Next, a molecular adhesive such as 6- (3-triethoxysilyl) propylamino) -1,3,5-triazine-2,4-dithiol monosodium (hereinafter also referred to as “TES”) is placed in an aqueous ethanol solution. , The sealing substrate (or main substrate) covered with a metal mask is immersed, heated and then subjected to a washing and drying treatment, so that an adhesive layer made of a molecular adhesive is applied to the joint of the sealing substrate (or main substrate). To form Then, after removing the metal mask, the respective bonding margins are brought into contact with each other using a vacuum laminator, and the main base material and the sealing base material are subjected to pressure and heat treatment on the bonding margin areas. Joining method ("Joining method VI-2" in Examples described later); For details of this method, see JP-A-2010-254793, and Monthly Display, Vol. 16, No. 8, pp. 70-77. Can be referenced);
In the present invention, each of the bonding surface of the main substrate on which the extraction electrode is formed and the bonding surface of the sealing substrate are surface-active, like the bonding portion formed by the bonding method I to III or VI described above. It is preferable to include an activation treatment layer obtained by the activation treatment. Further, in some cases, a metal layer is formed on each of the surfaces of the main base material and the sealing base material on which the extraction electrodes are formed, and the activation treatment layer is formed by performing a surface activation treatment on each of the formed metal layers. They may be formed and joined. Further, a mode in which the bonding portion includes an adhesive layer containing a silane coupling agent or a molecular adhesive as in the bonding method III and the bonding method VI described above is another preferred embodiment of the present invention.

[Sealed object]
In the sealing structure according to the present invention, there is no particular limitation on the specific configuration of the sealed body sealed by the main base and the sealing base, and shielding from moisture and oxygen is required. Conventionally known materials can be used without particular limitation as the object to be sealed. One example of the object to be sealed is a main body of an electronic device (electronic element main body), such as the organic EL element main body 13 shown in FIG. The electronic device is not limited to the 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 (LCD), an electronic paper, Examples include a thin film transistor and a touch panel. The configuration of the main body of these electronic devices is not particularly limited, and may have a known configuration.

  In the embodiment shown in FIG. 1, an object to be sealed (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, and a second electrode (cathode) 21. Etc. 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 device, the hole injection layer, the hole transport layer 18, the electron transport layer 20, and the electron injection layer are optional layers provided as needed.

  Hereinafter, an organic EL element, which is one type of electronic device, will be described as an example of a specific configuration of a sealed body.

(First electrode: anode)
As the first electrode (anode), a metal, an alloy, an electrically conductive compound, or a mixture thereof having a large work function (4 eV or more) as an electrode material 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 an electrode and an organic layer for lowering a driving voltage and improving emission luminance.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes. 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 particular limitation on the stacking order when the light emitting layers are stacked, and a non-light emitting intermediate layer may be provided 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. The electron injection layer is a layer provided between an electrode and an organic layer for lowering driving voltage and improving 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. The electron injection layer is a layer provided between an electrode and an organic layer for lowering driving voltage and improving light emission luminance.

(Second electrode: cathode)
As the second electrode (cathode), a material having a low 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 object to be sealed according to the present invention is an electronic device such as an organic EL device, a protective layer 15 is provided on the object to be sealed (electronic element body) as necessary. Is also good. The protective layer has a function of preventing a substance that promotes the deterioration of the sealed body (electronic element body) such as moisture or oxygen from entering the element, and a function of the sealed body ( It has a function of insulating an electronic element body) or the like, or a function of eliminating a step due to an object to be sealed (electronic element body). The protective layer may be a single layer or a laminate of a plurality of layers.

  In the present invention, in particular, when the support constituting the sealing base material is the “resin film of the present invention”, the unevenness of the electronic element main body, which is the object to be sealed, is the unevenness of the sealing structure. Various effects (eg, adverse effects on optical homogeneity) may be exerted on components provided outside. For this reason, the surface (exposed surface) of the sealing base material on the side opposite to the side where the object to be sealed is sealed is an optical resin (OCR; Optical Clear Resin) or an optical adhesive (OCA; Optical Clear Adhesive). ) Is preferably adjacent to another component (for example, an optical member) via the layer according to the above.

  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 examples, “parts” or “%” is used, and unless otherwise specified, it means “parts by mass” or “% by mass”.

<Example 1>
[Production of sealing base material 1]
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 0.7 μm (Young's modulus @ 25 ° C: 4.2 GPa) was prepared as a support.

One surface of the support was subjected to a surface activation treatment by corona discharge. Further, propylene glycol monomethyl ether (PGME) was added to UV-curable resin Opstar (registered trademark) Z7527 (manufactured by JSR Corporation) to prepare a coating solution such that the solid content concentration was 30% by mass. This coating solution was applied to the surface of the support that had been subjected to the surface activation treatment by an extrusion coater so that the film thickness after drying was 0.2 μm. After the coating film was dried at a temperature of 80 ° C. for 3 minutes, it was cured by irradiating ultraviolet light having an integrated light amount of 0.5 J / cm ^{2 with} a high-pressure mercury lamp to form an undercoat layer (organic layer). With respect to the undercoat layer (organic layer) thus formed, the center line average surface roughness (Ra) defined by JIS B0601: 2001 was 1.7 nm.

  Subsequently, a type 01 inorganic barrier layer (inorganic layer) is formed on the exposed surface of the undercoat layer (organic layer) by the following procedure, and the undercoat layer (organic layer) and the inorganic barrier layer (inorganic layer) are formed. A sealing substrate 1 in which a gas barrier layer made of was formed on one surface of a support was produced. The inorganic barrier layer is composed of two layers.

(Method of forming type 01 inorganic barrier layer)
First, in a deposition apparatus using a PECVD method, a mixed gas of hexamethyldisiloxane (HMDSO) and oxygen gas was supplied into a chamber. Thereafter, the support with an undercoat layer was transported to a discharge region where plasma was generated by applying a voltage, and a first inorganic barrier layer was formed on the undercoat layer. The thickness of the first inorganic barrier layer was 80 nm.

  Here, specific conditions for forming the first inorganic barrier layer are as follows.

(Deposition conditions)
Mixing ratio of gas: hexamethyldisiloxane / oxygen = 100/1000 (unit of supply amount of each source gas is sccm)
Vacuum degree: 1.5Pa
Supply power of power supply for plasma generation: 1 kW
Frequency of power supply for plasma generation: 80 kHz
Conveyance speed of support: 5 m / min
Next, a dibutyl ether solution NAX120-20 containing 1% by mass of N, N, N ', N'-tetramethyl-1,6-diaminohexane and 19% by mass of perhydropolysilazane as an amine catalyst (AZ Electronic Materials Co., Ltd.) (10 g) was added to 0.5 g of aluminum ethyl acetoacetate diisopropylate, stirred at 80 ° C. for 1 hour, and allowed to cool to prepare a coating liquid for the second inorganic barrier layer.

The coating liquid for the second inorganic barrier layer prepared above was dried on the first inorganic barrier layer formed above in an atmosphere of air, at a temperature of 23 ° C., and a relative humidity of 50% RH. Was applied by an extrusion coater so as to be 150 nm. After drying at room temperature for 10 minutes, a vacuum ultraviolet ray having a wavelength of 172 nm and an integrated light quantity of 1.5 J / cm ² was irradiated at 80 ° C. in a nitrogen atmosphere in which the oxygen concentration was adjusted within a range of 0.01 to 0.10% by volume. Thus, a second inorganic barrier layer was formed.

Here, the obtained sealing base material 1 was measured for water vapor transmission rate (WVTR) at 40 ° C. and 90% RH using a film permeability evaluation device (API-BA90 manufactured by Nippon API Co., Ltd.). × 10 ⁻³ g / m ² · day.

[Production of sealing base materials 2 to 11]
Except that the thickness of the biaxially stretched PET film as the support was changed as shown in Table 1 below, the sealing base materials 2 to 11 were respectively prepared in the same manner as in the production of the sealing base material 1 described above. Produced. The thickness of the support constituting the sealing base materials 1 to 11, the surface roughness (Ra) of the undercoat layer (organic layer), and the gas barrier property (water vapor transmission rate (WVTR)) of the sealing base material are as follows. Is shown in Table 1.

  As is clear from Table 1, as the thickness of the PET film as the support constituting the sealing substrate increases, the surface roughness of the undercoat layer (organic layer) decreases. When the thickness of the support is less than 1 μm, the water vapor transmission rate (WVTR) increases, and the barrier performance deteriorates.

[Production of Simulated Electronic Device 101]
After an aluminum film was formed on a main substrate (a glass substrate having a thickness of 0.7 mm) by a sputtering method, the aluminum film was formed into a stripe shape by a photolithography method to form 1,000 lead electrodes. In addition, a magnesium layer was formed by vapor deposition at the center of the main base on the side where the extraction electrode was formed, instead of the main unit.

  Here, FIG. 5A shows a layout of a lead electrode and a magnesium layer on the main base material. As shown in FIG. 5A, the main base material 81 had a size of 50 mm × 50 mm and a thickness of 0.7 mm. The magnesium layer 83 had a size of 30 mm × 30 mm and a thickness of 100 nm. The 1000 lead electrodes 82 were formed at equal intervals at positions 5 mm apart from both ends of the main substrate 81. As shown in FIG. 5B, each extraction electrode 82 had a trapezoidal cross section, an upper side width of 18 μm, a lower side width of 20 μm, and a thickness of 300 nm. The distance between the extraction electrodes 82 was 20 μm, and the distance between the centers in the width direction was 40 μm.

  The simulated electronic device 101 was produced by joining the main substrate on which the magnesium layer was formed and the sealing substrate 1 produced above by the following joining method I-1. As shown in FIG. 5A, the margin 84 between the main base 81 and the sealing base 1 has a width 2 mm away from the end of the main base 81 or the sealing base 1 by 2.0 mm. It is an area of 0.0 mm.

(Joining method I-1)
A 50 mm × 50 mm main substrate on which a magnesium layer is formed, and a sealing substrate 1 cut out to a size of 50 mm × 50 mm, the magnesium layer on the main substrate and the gas barrier layer of the sealing substrate 1 face each other. In this way, they were set on the holders of the target stage 1 (133) and the target stage 2 (134) of the room temperature bonding apparatus 130 shown in FIG. Further, a metal mask was arranged on each of the opposing surfaces of the main substrate and the sealing substrate. The metal mask had a slit in a region corresponding to the bonding margin.

After disposing the mask, reverse bonding is performed by the ion gun 132 under a vacuum pressure of 1 × 10 ⁻⁶ Pa in the room-temperature bonding apparatus 130 to clean and bond the area between the main base and the sealing base to the bonding margin. Treatment. In this reverse sputtering, Ar ion irradiation was performed for 1 to 10 minutes with an acceleration voltage in the range of 0.1 to 2 kV and a current value in the range of 1 to 20 mA.

  Next, sputtering was performed using silicon (Si) as a target, and a silicon (Si) film having a thickness of 20 nm was formed in a region to be joined. This sputtering was performed at an acceleration voltage of 1.5 kV and a current value of 100 mA for 3 minutes. Furthermore, surface activation treatment was performed by reverse sputtering on the silicon (Si) film. The processing conditions for reverse sputtering are the same as the processing conditions for reverse sputtering for the main substrate and the sealing base material described above.

After the metal mask was removed and the degree of vacuum was adjusted to 1 × 10 ⁻⁷ Pa, the bonding margin between the main base material and the sealing base material was brought into contact, and bonding was performed by applying a pressure of 20 MPa for 3 minutes.

  A tomographic photograph of the junction between the main substrate and the sealing substrate was taken, and the total thickness of the silicon (Si) film between the main substrate and the sealing substrate was measured as the thickness of the junction. However, it was 50.0 nm.

[Production of Simulated Electronic Devices 102 to 126]
In the fabrication of the simulated electronic device 101, the sealing base materials shown in Table 2 below were used, and the bonding between the peripheral portions of the main base material and the sealing base material was performed by the bonding method I-1 or the following bonding method. Simulated electronic devices 102 to 126 were produced in the same manner except that the method was performed by any one of the methods II-1 to V-1.

(Joining method II-1)
Using the same metal mask as in the bonding method I-1, the bonding margin between the main substrate on which the magnesium layer is formed and the sealing substrate 1 is surfaced using a plasma dry cleaner Model PC-300 (manufactured by SAMCO Corporation). Activation treatment was performed. The surface activation treatment was performed under the conditions of a vacuum degree of 30 Pa, an oxygen flow rate of 10 ml / min, a discharge power of 100 W, and a treatment time of 5 minutes. The metal mask was removed, and each of the main substrate and the sealing substrate was exposed to an environment of a temperature of 25 ° C. and a relative humidity of 80% RH for 3 minutes. Using a vacuum laminator, each joining margin is brought into contact, and by applying a pressure of 0.5 MPa and heating at 80 ° C. for 5 minutes to a region of the joining margin, the main base material and the sealing base material are separated. Joined.

  A tomographic photograph of the joint between the main substrate and the sealing substrate was taken, and the distance between the main substrate and the sealing substrate was measured as the thickness of the joint.

(Joining method III-1)
Using the same metal mask as in the bonding method I-1, the bonding margin between the main substrate on which the magnesium layer is formed and the sealing substrate 1 is surfaced using a plasma dry cleaner Model PC-300 (manufactured by SAMCO Corporation). Activation treatment was performed. The surface activation treatment was performed under the conditions of a vacuum degree of 30 Pa, an oxygen flow rate of 10 ml / min, a discharge power of 100 W, and a treatment time of 5 minutes.

  Next, the metal-masked sealing base material was exposed to saturated steam of a silane coupling agent KBM-903 (3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) at a temperature of 23 ° C. for 3 minutes to perform sealing. An adhesive layer made of the silane coupling agent KBM-903 was formed on the periphery of the base material. On the other hand, the metal-masked main substrate was exposed to saturated steam of a silane coupling agent KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.) at a temperature of 23 ° C. for 3 minutes. An adhesive layer made of a silane coupling agent KBM-403 was formed on the periphery of the substrate.

  After removing the metal mask, the respective bonding margins are brought into contact with each other using a vacuum laminator, and a pressure of 0.5 MPa and a heating of 80 ° C. are applied to a region of the bonding margins for 5 minutes, whereby the main base material is formed. And the sealing substrate.

  When a tomographic photograph of a bonding portion between the main base material and the sealing base material was taken and the thickness of the adhesive layer between the main base material and the sealing base material was measured as the thickness of the bonding portion, 1.0 nm was obtained. Met.

(Joining method IV-1)
The following adhesive components are mixed and heated to 80 ° C., and then uniformly stirred and mixed at a stirring speed of 3000 rpm using a homomixer L-type (manufactured by Primix), with an epoxy resin as a main component. An adhesive was obtained.

(Adhesive component)
Epoxy resin YL983U (bisphenol F type epoxy resin liquid at ordinary temperature, manufactured by Mitsubishi Chemical Corporation): 50 parts by mass Celloxide (registered trademark) 2021P (alicyclic epoxy resin (3 ', 4'-epoxycyclohexylmethyl-liquid at ordinary temperature) 3,4-epoxycyclohexanecarboxylate), manufactured by Daicel Corporation): 20 parts by mass Epoxy resin jER1001 (bisphenol A type epoxy resin solid at room temperature, manufactured by Mitsubishi Chemical Corporation): 30 parts by mass Gelling agent Zefiac (registered trademark) F351 (Acrylic core-shell particles, manufactured by Ganz Chemical Co., Ltd.): 20 parts by mass Nanoace (registered trademark) D-600 (talc having a volume average particle diameter of 0.6 μm, manufactured by Nippon Talc): 10 parts by mass Photocationic polymerization initiator CPI (Registered trademark) -210S (manufactured by San Apro): 2 parts by mass silane coupling agent Agent KBM-403 (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.): 1 part by mass The obtained adhesive was discharged at a discharge rate of 2 mg / cm using a dispenser to form a sealing base material. It was applied to the area of the adhesion margin. Using a vacuum laminator, the sealing substrate coated with the adhesive was brought into contact with the main substrate, and a pressure of 0.1 MPa was applied. Thereafter, ultraviolet light having an integrated light amount of ² J / cm ² was irradiated at a temperature of 80 ° C. using a high-pressure mercury lamp, and a curing treatment was performed for 30 minutes to join the main substrate and the sealing substrate.

  When a tomographic photograph of a bonding portion between the main base material and the sealing base material was taken and the thickness of the adhesive layer between the main base material and the sealing base material was measured as the thickness of the bonding portion, 1000.0 nm Met.

(Joining method V-1)
The joining was performed in the same manner as the joining method IV-1, except that Nanoace (registered trademark) D-600 was removed from the adhesive component in the joining method IV-1.

  When a tomographic photograph of a joint portion between the main base material and the sealing base material was taken, and the thickness of the adhesive layer between the main base material and the sealing base material was measured as the thickness of the bonding portion, 100.0 nm Met.

[Evaluation]
(Sealing performance before and after resistance test)
First, each of the simulated electronic devices 101 to 126 produced above was placed in a high-temperature and high-humidity environment without undergoing a durability test, and the sealing performance (sealing performance before the resistance test) was determined by the following method. ) Was evaluated.

  In addition, as a durability test, a drop test was performed 100 times from a height of 10 cm, and then the device was placed in a high-temperature and high-humidity environment to evaluate sealing performance (sealing performance after a resistance test). The results are shown in Table 2 below.

(Evaluation method of sealing performance)
After leaving the simulated electronic device in an environment of a temperature of 85 ° C. and a relative humidity of 85% RH for 500 hours, corrosion of the magnesium layer was observed. The ratio of the area of the corroded portion to the entire magnesium layer was determined, and the ratio (%) of the area of the corroded portion was evaluated as the sealing performance according to the following criteria:
：: No corrosion was observed, and the sealing performance was very high. ：: There was corrosion, but the ratio of the area of the corroded portion was less than 0.5%, and the sealing performance was high. The ratio of the area of the portion is 0.5% or more and less than 1.5%, which is a practical sealing performance. X: The ratio of the area of the corroded portion is 1.5% or more, and the sealing performance is low.

  As is clear from the results shown in Table 2, the organic EL devices 109 to 111, 116 to 117, and 119 using the sealing bases 9 to 11 in which the thickness of the support constituting the sealing base is 30 μm or more. , 126, when the thickness of the joining portion was small, the sealing performance after the durability test was inferior. On the other hand, in the organic EL device 101 using the sealing substrate 1 in which the thickness of the support constituting the sealing substrate is less than 1 μm, the sealing is performed not only after the durability test but also before the durability test. The stopping performance was inferior.

  On the other hand, in the organic EL device using the sealing substrates 2 to 8 in which the thickness of the support constituting the sealing substrate is 1 μm or more and less than 30 μm, when the thickness of the bonding portion is reduced (organic EL The devices 102 to 108, 112 to 113, 115, and 120 to 125) showed excellent sealing performance both before the durability test and after the durability test. On the other hand, even when using the sealing base material 5 in which the thickness of the support constituting the sealing base material is 1 μm or more and less than 30 μm, when the thickness of the joining portion is more than 100 nm (joining method IV- In 1), the sealing performance after the durability test was poor. It is considered that this is because the organic EL element was deteriorated as a result of the penetration of moisture from the junction due to the thickness of the junction.

<Example 2>
[Production of sealing base materials 12 to 15]
Sealing base materials 12 to 15 were produced in the same manner as the sealing base material 1 described above, except that the following resin film was used as a support instead of the PET film described above.

Sealing substrate 12: Zeonor Film (registered trademark) ZF-14, a cycloolefin polymer (abbreviation: COP) film manufactured by Zeon Corporation, Young's modulus 2.2 GPa, thickness 25 μm
Sealing substrate 13: Upilex (registered trademark) 25SGA, polyimide (abbreviation: PI) film manufactured by Ube Industries, Young's modulus 9.2 GPa, thickness 25 μm
Sealing substrate 14: LL linear low density polyethylene film LL-XHT, low density polyethylene (LDPE) film manufactured by Futamura Chemical Co., Young's modulus 0.7 GPa, thickness 25 μm
Sealing base material 15: Unstretched polypropylene film FG-LTH, unstretched polypropylene (CPP) film manufactured by Futamura Chemical Co., Young's modulus 1.1 GPa, thickness 25 μm
[Production of Simulated Electronic Devices 201 to 204]
Except for using any of the sealing base materials 12 to 15 instead of the sealing base material 1 as the sealing base material, the simulated electronic devices 201 to 204 were prepared in the same manner as in the production of the simulated electronic device 108 described above. Produced.

[Evaluation]
For the simulated electronic devices 201 to 204 produced above, the sealing performance before and after the durability test was evaluated in the same manner as described above. The results are shown in Table 3 below.

  As is clear from the results shown in Table 3, when the Young's modulus of the support constituting the sealing base material is less than 1 GPa (when the sealing base material 14 is used), the thickness of the bonding portion is small. And the sealing performance after the durability test was inferior. On the other hand, when the Young's modulus of the support constituting the sealing base material was 1 to 10 GPa, excellent sealing performance before and after the durability test was achieved.

<Example 3>
[Production of sealing base materials 16 to 19]
The sealing base material was formed in the same manner as the sealing base material 1 described above, except that the thickness of the undercoat layer (organic layer) formed on the surface of the support was changed as shown in Table 4 below. Nos. 16 to 19 were produced.

[Production of Simulated Electronic Devices 301 to 304]
Except for using any one of the sealing base materials 16 to 19 instead of the sealing base material 1 as the sealing base material, the simulated electronic devices 301 to 304 were manufactured in the same manner as in the production of the simulated electronic device 108 described above. Produced.

[Evaluation]
For the simulated electronic devices 301 to 304 produced above, the sealing performance before and after the durability test was evaluated in the same manner as described above. The results are shown in Table 4 below.

  From the results shown in Table 4, the sealing performance was improved as the surface roughness (Ra) of the undercoat layer (organic layer) constituting the gas barrier layer on the inorganic barrier layer side was smaller.

<Example 4>
[Production of organic EL device 401]
A polyimide U-Varnish-S (manufactured by Ube Industries, Ltd.) is cast into a film on a glass substrate having a thickness of 0.7 mm and baked at 350 ° C. for 30 minutes to form a polyimide film having a thickness of 25 μm. Was prepared. A pixel portion composed of 640 pixels × 480 pixels and a driving circuit portion were provided on the polyimide film of the main substrate formed as described above. Then, 50 nm of molybdenum / 200 nm of aluminum / 50 nm of molybdenum were sequentially laminated so as to be in contact with the pixel portion and the drive circuit portion, and then formed into an electrode shape by photolithography to form a lead electrode. The cross-sectional shape of the extraction electrode was trapezoidal, the length of the bottom was 150 μm, the length of the top was 145 μm, and the thickness was 300 nm. Then, so as to cover the Shumoto material entirely except for the end portions of the anode and cathode, to form a SiO ₂ film of 200nm as a protective layer by a PECVD method, thereby constructing an organic EL element body.

  Subsequently, the sealing base material 8 produced as described above is cut into a size of 50 mm × 50 mm, and the peripheral portion of the main substrate (where the extraction electrode is present) and the peripheral portion of the sealing substrate are joined by the bonding method I-1 described above. And sealing was performed, and finally, the polyimide film as the main base material was peeled off from the glass substrate to manufacture the organic EL device 401. The Young's modulus of the polyimide film thus formed was 9.4 GPa.

[Production of Organic EL Devices 402 to 424]
In the production of the organic EL device 401, the thickness of the main substrate (polyimide film), the type of the sealing substrate, and the method of joining the main substrate and the sealing substrate were changed as shown in Table 5 below. Except for this, organic EL devices 402 to 424 were produced in the same manner.

[Evaluation]
With respect to the simulated electronic devices 401 to 424 manufactured as described above, before and after the same durability test as above, the sealing performance after the durability test was evaluated using the following method. The results are shown in Table 5 below.

(Evaluation method of sealing performance)
The organic EL device was stored under an environment of a temperature of 40 ° C. and a relative humidity of 50% RH for 250 hours while applying a current of 10 mA / cm ² . Thereafter, an emission image obtained by applying a current of 1 mA / cm ² to the organic EL device at room temperature was taken, and the ratio (%) of the area of the dark spot to the entire area of the obtained image was calculated. The ratio of the area of this dark spot was evaluated as the sealing performance according to the following criteria:
：: The ratio of the area of the dark spot is 0% and the sealing performance is very high. ：: The ratio of the area of the dark spot is more than 0% and 0.2% or less and the sealing performance is high. Δ: Dark The ratio of the area of the spot is more than 0.2% and 0.5% or less, and the sealing performance is of a practical level. ×: The ratio of the area of the dark spot is more than 0.5% and the sealing performance is low. .

  From the results shown in Table 5, when the polyimide (PI) film having a thickness of 25 μm was used as the main substrate, excellent sealing performance was achieved regardless of the thickness of the support constituting the sealing substrate. You can see that it was done. On the other hand, when the thickness of the PI film, which is the main substrate, is 50 μm, excellent sealing performance can be achieved when the thickness of the support constituting the sealing substrate is 1 μm or more and less than 30 μm. In the device 413 in which the thickness of the support is less than 1 μm and in the devices 421 to 423 in which the thickness is 30 μm or more, the sealing performance after the durability test was inferior.

<Example 5>
[Production of sealing base material 20]
A 50 μm-thick cycloolefin copolymer (abbreviation: COP) film ZF-14 50 μm (manufactured by Zeon Corporation) was prepared as a support.

One surface of the support was subjected to a surface activation treatment by corona discharge. Further, propylene glycol monomethyl ether (PGME) was added to UV-curable resin Opstar (registered trademark) Z7527 (manufactured by JSR Corporation) to prepare a coating solution such that the solid content concentration was 30% by mass. This coating solution was applied to the surface of the support which had been subjected to the surface activation treatment by an extrusion coater so that the film thickness after drying was 3 μm. After the coating film was dried at a temperature of 80 ° C. for 3 minutes, it was cured by irradiating ultraviolet light having an integrated light amount of 0.5 J / cm ^{2 with} a high-pressure mercury lamp to form an undercoat layer (organic layer). The undercoat layer (organic layer) thus formed was measured for nanoindentation elastic modulus (23 ° C., 50% RH) by the following measurement method, and was 5.5 GPa.

(Method of measuring nanoindentation elastic modulus)
The measurement was performed using a scanning probe microscope SPA400, Nano Navi II manufactured by SII Nanotechnology. For the measurement, a triangular pyramid-shaped diamond indenter called Cube corner Tip (tip angle 90 °) was used as an indenter. A triangular pyramid-shaped indenter was applied at right angles to the sample surface, and a load was gradually applied until the maximum depth reached 15 nm. After reaching the maximum load, the load was gradually returned to zero. Both loading and unloading were performed in 5 seconds.

  The nanoindentation elastic modulus (GPa) was calculated using the following equation, where the slope of the unloading curve was S (μN / nm).

In the formula, A (μm ² ) represents the projected area of the indenter contact portion, and π represents the pi. In addition, as a standard sample, the apparatus was calibrated in advance so that the hardness obtained as a result of pushing the attached fused quartz was 9.5 ± 1.5 GPa and measured.

  Subsequently, a type 01 inorganic barrier layer (inorganic layer) is formed on the exposed surface of the undercoat layer (organic layer) by the following procedure, and the undercoat layer (organic layer) and the inorganic barrier layer (inorganic layer) are formed. The sealing base material 20 in which the gas barrier layer made of was formed on one surface of the support was produced. The inorganic barrier layer is composed of two layers.

(Method of forming type 01 inorganic barrier layer)
First, in a deposition apparatus using a PECVD method, a mixed gas of hexamethyldisiloxane (HMDSO) and oxygen gas was supplied into a chamber. Thereafter, the support with an undercoat layer was transported to a discharge region where plasma was generated by applying a voltage, and a first inorganic barrier layer was formed on the undercoat layer. The thickness of the first inorganic barrier layer was 80 nm.

  Here, specific conditions for forming the first inorganic barrier layer are as follows.

(Deposition conditions)
Mixing ratio of gas: hexamethyldisiloxane / oxygen = 100/1000 (unit of supply amount of each source gas is sccm)
Vacuum degree: 1.5Pa
Supply power of power supply for plasma generation: 1 kW
Frequency of power supply for plasma generation: 80 kHz
Conveyance speed of support: 5 m / min
Next, a dibutyl ether solution NAX120-20 containing 1% by mass of N, N, N ', N'-tetramethyl-1,6-diaminohexane and 19% by mass of perhydropolysilazane as an amine catalyst (AZ Electronic Materials Co., Ltd.) (10 g) was added to 0.5 g of aluminum ethyl acetoacetate diisopropylate, stirred at 80 ° C. for 1 hour, and allowed to cool to prepare a coating liquid for the second inorganic barrier layer.

The coating liquid for the second inorganic barrier layer prepared above was dried on the first inorganic barrier layer formed above in an atmosphere of air, at a temperature of 23 ° C., and a relative humidity of 50% RH. Was applied by an extrusion coater so as to be 150 nm. After drying at room temperature for 10 minutes, a vacuum ultraviolet ray having a wavelength of 172 nm and an integrated light quantity of ² J / cm ² was irradiated at 80 ° C. in a nitrogen atmosphere in which the oxygen concentration was adjusted within the range of 0.01 to 0.10% by volume. A second inorganic barrier layer was formed.

Here, the obtained sealing base material 20 was measured for water vapor transmission rate (WVTR) at 40 ° C. and 90% RH using a film permeability evaluation apparatus (API-BA90 manufactured by Nippon API Co., Ltd.). 0.0 × 10 ⁻⁵ g / m ² · day.

[Production of sealing base materials 21 to 27]
Ethylene-vinyl acetate copolymers (EVA resins) having different vinyl acetate content, weight average molecular weight (Mw), and nanoindentation elasticity (23 ° C., 50% RH) were prepared (see Table 6 below). ), Except that an undercoat layer (organic layer) was formed by coating by a melt extrusion method so that the film thickness after application was 5 μm, in the same manner as in the production of the sealing base material 20 described above. Stopping base materials 21 to 27 were respectively produced. Table 6 below shows the structures and gas barrier properties (water vapor transmission rate (WVTR)) of the sealing base materials 20 to 27.

  As is clear from Table 6, undercoat layers (organic layers) having different nanoindentation elastic moduli were formed using ethylene-vinyl acetate copolymers (EVA resins) having different compositions and weight average molecular weights. It is understood that when the elastic modulus is less than 0.01 GPa (sealing base material 21), the gas barrier properties of the sealing base material cannot be sufficiently realized.

[Production of Organic EL Device 501]
A polyimide U-Varnish-S (manufactured by Ube Industries, Ltd.) is cast into a film on a glass substrate having a thickness of 0.7 mm and baked at 350 ° C. for 30 minutes to form a polyimide film having a thickness of 25 μm. Was prepared. A pixel portion composed of 640 pixels × 480 pixels and a drive circuit portion were provided on the thus formed main substrate polyimide film (Young's modulus of a single layer at 25 ° C .: 9.8 GPa). Then, 50 nm of molybdenum / 200 nm of aluminum / 50 nm of molybdenum were sequentially laminated so as to be in contact with the pixel portion and the drive circuit portion, and then formed into an electrode shape by photolithography to form a lead electrode. The cross-sectional shape of this extraction electrode was trapezoidal, the bottom length was 20 μm, the top length was 18 μm, and the thickness was 300 nm. Thereafter, a 100-nm SiN film was formed as a protective layer by PECVD so as to cover the entire surface of the main substrate except for the end portions of the anode and the cathode, thereby producing an organic EL device body.

  Subsequently, the sealing base material 20 prepared as described above is cut into a size of 50 mm × 50 mm, and the peripheral portion of the main base material (where the extraction electrode is present) and the peripheral portion of the sealing base material are joined in the following joining method I-2. And sealing was performed, and finally, the polyimide film as the main base material was peeled off from the glass substrate to produce an organic EL device 501.

(Joining method I-2)
The main substrate on which the sealing substrate 20 and the organic EL element main body are formed is placed on the target stage 1 (FIG. 2) of the room temperature bonding apparatus 130 shown in FIG. 2 so that the gas barrier layer of the sealing substrate 20 faces the organic EL element main body. 133) and the target stage 2 (134). Further, a metal mask was arranged on each of the opposing surfaces of the main substrate and the sealing substrate. The metal mask had a slit in a region corresponding to the bonding margin.

After disposing the mask, reverse bonding is performed by the ion gun 132 under a vacuum pressure of 1 × 10 ⁻⁶ Pa in the room-temperature bonding apparatus 130 to clean and bond the area between the main base and the sealing base to the bonding margin. Treatment. In this reverse sputtering, Ar ion irradiation was performed for 1 to 10 minutes with an acceleration voltage in the range of 0.1 to 2 kV and a current value in the range of 1 to 20 mA.

  Next, sputtering was performed using silicon (Si) as a target, and a silicon (Si) film having a thickness of 20 nm was formed in a region to be joined. This sputtering was performed at an acceleration voltage of 1.5 kV and a current value of 100 mA for 3 minutes. Furthermore, surface activation treatment was performed by reverse sputtering on the silicon (Si) film. The processing conditions for reverse sputtering are the same as the processing conditions for reverse sputtering for the main substrate and the sealing base material described above.

After the metal mask was removed and the degree of vacuum was adjusted to 1 × 10 ⁻⁷ Pa, the bonding margin between the main base material and the sealing base material was brought into contact, and bonding was performed by applying a pressure of 20 MPa for 3 minutes.

  A tomographic photograph of the junction between the main substrate and the sealing substrate was taken, and the total thickness of the silicon (Si) film between the main substrate and the sealing substrate was measured as the thickness of the junction. However, it was 50.0 nm.

[Production of Organic EL Device 502]
An organic EL device 502 was produced in the same manner as the production of the organic EL device 501, except that the peripheral portions of the main substrate and the sealing substrate were joined by the following joining method II-2.

(Joining method II-2)
Using a metal mask similar to the bonding method I-2, a bonding margin between the main base material and the sealing base material was subjected to a surface activation treatment using a plasma dry cleaner Model PC-300 (manufactured by SAMCO Corporation). The surface activation treatment was performed under the conditions of a vacuum degree of 30 Pa, an oxygen flow rate of 10 ml / min, a discharge power of 100 W, and a treatment time of 5 minutes. The metal mask was removed, and each of the main substrate and the sealing substrate was exposed to an environment of a temperature of 25 ° C. and a relative humidity of 80% RH for 3 minutes. Using a vacuum laminator, each joining margin is brought into contact, and by applying a pressure of 0.5 MPa and heating at 80 ° C. for 5 minutes to a region of the joining margin, the main base material and the sealing base material are separated. Joined.

  A tomographic photograph of the joint between the main substrate and the sealing substrate was taken, and the distance between the main substrate and the sealing substrate was measured as the thickness of the joint.

[Production of Organic EL Device 503]
An organic EL device 503 was produced in the same manner as the production of the organic EL device 501, except that the peripheral portions of the main substrate and the sealing substrate were joined by the following joining method III-2.

(Joining method III-2)
Using a metal mask similar to the bonding method I-2, a bonding margin between the main base material and the sealing base material was subjected to a surface activation treatment using a plasma dry cleaner Model PC-300 (manufactured by SAMCO Corporation). The surface activation treatment was performed under the conditions of a vacuum degree of 30 Pa, an oxygen flow rate of 10 ml / min, a discharge power of 100 W, and a treatment time of 5 minutes.

  Next, the sealing substrate covered with the metal mask was exposed to saturated steam at a temperature of 23 ° C. of a silane coupling agent KBM-903 (3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) for 3 minutes to perform sealing. An adhesive layer made of the silane coupling agent KBM-903 was formed on the periphery of the base material. On the other hand, the organic EL element covered with the metal mask was exposed to saturated vapor of a silane coupling agent KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.) at a temperature of 23 ° C. for 3 minutes, and the main base material was exposed. An adhesive layer made of a silane coupling agent KBM-403 was formed on the periphery of the substrate.

  After removing the metal mask, the respective bonding margins are brought into contact with each other using a vacuum laminator, and a pressure of 0.5 MPa and a heating of 80 ° C. are applied to a region of the bonding margins for 5 minutes, whereby the main base material is formed. And the sealing substrate.

  When a tomographic photograph of a bonding portion between the main base material and the sealing base material was taken and the thickness of the adhesive layer between the main base material and the sealing base material was measured as the thickness of the bonding portion, 1.0 nm was obtained. Met.

[Production of Organic EL Device 504]
An organic EL device 504 was produced in the same manner as in the production of the organic EL device 501, except that the peripheral portions of the main substrate and the sealing substrate were joined by the following joining method VI-2.

(Joining method VI-2)
Using a metal mask similar to the bonding method I-2, a bonding margin between the main base material and the sealing base material was subjected to a surface activation treatment using a plasma dry cleaner Model PC-300 (manufactured by SAMCO Corporation). The surface activation treatment was performed under the conditions of a vacuum degree of 30 Pa, an oxygen flow rate of 10 ml / min, a discharge power of 100 W, and a treatment time of 5 minutes.

  Next, as a molecular adhesive, 6- (3-triethoxysilyl) propylamino) -1,3,5-triazine-2,4-dithiol monosodium (TES) using a 5% by mass aqueous solution of ethanol as a solvent. Was prepared at a concentration of 0.2% by mass. With the metal mask placed in a region other than the bonding margin of the sealing base material, the substrate was immersed in the solution prepared above and heated in an oven at a temperature of 100 ° C. for 15 minutes. Further, the sealing base material was washed with ethanol and dried with a drier to form an adhesive layer made of TES between the sealing base materials.

  After removing the metal mask from the sealing base material, the respective bonding margins are brought into contact with each other using a vacuum laminator, and a pressure of 0.5 MPa and a heating of 80 ° C. are performed on the bonding margin area for 5 minutes. Thereby, the main substrate and the sealing substrate were joined.

  When a tomographic photograph of a bonding portion between the main base material and the sealing base material was taken and the thickness of the adhesive layer between the main base material and the sealing base material was measured as the thickness of the bonding portion, 10.0 nm Met.

[Production of Organic EL Device 505]
An organic EL device 506 was produced in the same manner as in the production of the organic EL device 501, except that the peripheral portions of the main substrate and the sealing substrate were joined by the following joining method V-2.

(Joining method V-2)
The following adhesive components are mixed and heated to 80 ° C., and then uniformly stirred and mixed at a stirring speed of 3000 rpm using a homomixer L-type (manufactured by Primix), with an epoxy resin as a main component. An adhesive was obtained.

(Adhesive component)
Epoxy resin YL983U (bisphenol F type epoxy resin liquid at ordinary temperature, manufactured by Mitsubishi Chemical Corporation): 50 parts by mass Celloxide (registered trademark) 2021P (alicyclic epoxy resin (3 ', 4'-epoxycyclohexylmethyl-liquid at ordinary temperature) 3,4-epoxycyclohexanecarboxylate), manufactured by Daicel Corporation): 20 parts by mass Epoxy resin jER1001 (bisphenol A type epoxy resin solid at room temperature, manufactured by Mitsubishi Chemical Corporation): 30 parts by mass Gelling agent Zefiac (registered trademark) F351 (Acrylic core-shell particles, manufactured by Ganz Kasei Co., Ltd.): 20 parts by mass Photo-cationic polymerization initiator CPI (registered trademark) -210S (manufactured by San Apro): 2 parts by mass Silane coupling agent KBM-403 (γ-glycidoxypropyl) Trimethoxysilane, manufactured by Shin-Etsu Silicone Co.): 1 part by mass The obtained adhesive was discharged at a discharge amount of 2 mg / cm using a dispenser, and was applied to an area of the sealing base material where bonding was allowed. Using a vacuum laminator, the sealing substrate coated with the adhesive was brought into contact with the main substrate, and a pressure of 0.1 MPa was applied. Thereafter, ultraviolet light having an integrated light amount of ² J / cm ² was irradiated at a temperature of 80 ° C. using a high-pressure mercury lamp, and a curing treatment was performed for 30 minutes to join the main substrate and the sealing substrate.

  When a tomographic photograph of a joint portion between the main base material and the sealing base material was taken, and the thickness of the adhesive layer between the main base material and the sealing base material was measured as the thickness of the bonding portion, 100.0 nm Met.

[Production of Organic EL Devices 506 to 525]
Any one of the sealing bases 21 to 27 instead of the sealing base 20 as the sealing base and any of the bonding methods I-2 to VI-2 as the bonding method are used in combinations shown in Table 7 below. Organic EL devices 506 to 525 were produced in the same manner as in the production of the organic EL device 501 described above, except for the fact that the organic EL device 501 was used.

[Evaluation]
(Sealing performance after resistance test)
With respect to the organic EL devices 501 to 525 manufactured as described above, before and after the same durability test as in Example 4, the sealing performance after the durability test was evaluated using the following method. The results are shown in Table 7 below.

The organic EL device was stored under an environment of a temperature of 40 ° C. and a relative humidity of 50% RH for 250 hours while applying a current of 10 mA / cm ² . Thereafter, an emission image obtained by applying a current of 1 mA / cm ² to the organic EL device at room temperature was taken, and the ratio (%) of the area of the dark spot to the entire area of the obtained image was calculated. The ratio of the area of the dark spot was evaluated as sealing performance according to the following criteria. The results are shown in Table 7 below:
：: The ratio of the area of the dark spot is 0% and the sealing performance is very high. ：: The ratio of the area of the dark spot is more than 0% and 0.2% or less and the sealing performance is high. Δ: Dark The ratio of the area of the spot is more than 0.2% and 0.5% or less, and the sealing performance is of a practical level. ×: The ratio of the area of the dark spot is more than 0.5% and the sealing performance is low. .

(Sealing performance after high humidity resistance test)
The organic EL devices 501 to 525 prepared as described above were stored for 250 hours while passing a current of 10 mA / cm ² under an environment of a temperature of 40 ° C. and a relative humidity of 90% RH. Thereafter, an emission image obtained by applying a current of 1 mA / cm ² to the organic EL device at room temperature was taken, and the ratio (%) of the area of the dark spot to the entire area of the obtained image was calculated. The ratio of the area of the dark spot was evaluated as sealing performance according to the same standard as above. The results are shown in Table 7 below.

(Sealing performance after bending test)
A bending test was performed in which the organic EL devices 501 to 525 produced above were wound on a cylinder having a diameter of 10 mmφ for 1 second, and then unwound for 1 second and returned to a flat surface for 100,000 cycles.

  Furthermore, after storing for 250 hours in an environment of a temperature of 85 ° C. and a relative humidity of 85% RH, the sealing performance after the bending test was evaluated in the same manner as the evaluation of the sealing performance after the high humidity resistance test. The results are shown in Table 7 below.

(Sealing performance after temperature and humidity cycle test)
After performing the following steps (1) to (3) for 100 cycles as a temperature and humidity cycle test, the sealing performance after the temperature and humidity cycle test was evaluated in the same manner as the evaluation of the sealing performance after the high humidity resistance test. The results are shown in Table 7 below.
(1) After placing each organic EL device in an environment of a temperature of 25 ° C. and a relative humidity of 20% RH, the temperature was raised to 85 ° C. over 1 hour. Further, the relative humidity was raised to 85% RH over 1 hour, and the temperature was kept at 85 ° C. and the relative humidity was 85% RH for 1 hour.
(2) The relative humidity was reduced to 20% RH over 1 hour, and the temperature was lowered to −35 ° C. over 2 hours, and kept at an environment of −35 ° C. and 20% RH for 1 hour.
(3) The temperature was raised to 25 ° C. over 1 hour, and the temperature was returned to an environment of 25 ° C. and a relative humidity of 20% RH.

  As is clear from the results shown in Table 7, even in the sealing structure according to the present invention, the sealing substrate 21 having a nanoindentation elastic modulus of the undercoat layer (organic layer) of less than 0.01 GPa is used. In the organic EL devices 506 to 507, the sealing performance after the durability test was somewhat excellent before and after the durability test, but the gas barrier property of the sealing base material itself was slightly inferior. When the thickness was reduced, the sealing performance after the high humidity resistance test, the sealing performance after the bending test, and the sealing performance after the temperature / humidity cycle test were all insufficient. Further, the organic EL devices 501 to 505 using the sealing base material 20 having a nanoindentation elastic modulus of the undercoat layer (organic layer) of more than 1.0 GPa, and the organic EL devices 521 to 521 using the sealing base material 27. 525 had excellent sealing performance after the durability test before and after the durability test. However, despite the fact that the gas barrier properties of the sealing substrate itself were sufficient, when the thickness of the joint was reduced, the sealing performance after the bending test and the sealing performance after the temperature-humidity cycle test were sufficient. Not the result. This is presumed to be due to the fact that the nanoindentation elastic modulus of the undercoat layer (organic layer) is too large, so that the gas barrier layer cannot sufficiently follow the unevenness of the joint.

  On the other hand, the organic EL devices 508 to 520 using the sealing base materials 22 to 26 having the nanoindentation elastic modulus of the undercoat layer (organic layer) of 0.01 to 1.0 GPa before and after the durability test. In addition to the excellent sealing performance after the resistance test, when the thickness of the joint is reduced, the sealing performance after the resistance test, the sealing performance after the bending test, and the sealing after the temperature / humidity cycle test All of the performances showed excellent performance.

<Example 6>
[Production of sealing base materials 28 to 32]
The sealing substrates 28 to 32 were produced in the same manner as the above-mentioned production of the sealing substrates 21 to 27 except that the following resin was used instead of the EVA resin.

Sealing base material 28: Nucrel (registered trademark) AN4228C (manufactured by Du Pont-Mitsui Polychemicals, ethylene-methacrylic acid copolymer resin, nanoindentation elastic modulus of undercoat layer (organic layer): 0.09 GPa)
Sealing base material 29: Nucrel (registered trademark) AN4214C (manufactured by DuPont-Mitsui Polychemicals, ethylene-methacrylic acid copolymer resin, nanoindentation elastic modulus of undercoat layer (organic layer): 0.2 GPa)
Sealing base material 30: NUC8452D (manufactured by NUC Corporation, ethylene-vinyl acetate copolymer resin, nanoindentation elastic modulus of undercoat layer (organic layer): 0.07 GPa)
Sealing base material 31: Primalloy (registered trademark) CP300 (manufactured by Mitsubishi Chemical Corporation, polyester elastomer, nanoindentation elastic modulus of undercoat layer (organic layer): 0.3 GPa)
Sealing base material 32: Primalloy (registered trademark) CP200 (manufactured by Mitsubishi Chemical Corporation, polyester elastomer, nanoindentation elastic modulus of undercoat layer (organic layer): 1.1 GPa)
[Production of Organic EL Devices 601 to 605]
Except for using any one of the sealing base materials 28 to 32 in place of the sealing base material 20 as the sealing base material, the organic EL devices 601 to 605 were prepared in the same manner as in the production of the organic EL device 501 described above. Produced.

[Evaluation]
For the organic EL devices 601 to 605 prepared above, sealing performance after a durability test before and after a durability test, sealing performance after a high humidity resistance test, sealing performance after a bending test, and The sealing performance after the temperature / humidity cycle test was evaluated. The results are shown in Table 8 below.

  As is evident from the results shown in Table 8, the organic EL device 205 using the sealing substrate 32 having a nanoindentation elastic modulus of the undercoat layer (organic layer) of more than 1.0 GPa before and after the durability test. The sealing performance after the resistance test was excellent. However, the gas barrier properties of the sealing substrate itself are sufficient, and the sealing performance after the bending test and the sealing performance after the temperature / humidity cycle test are not sufficient despite the reduced thickness of the joint. It became. This is presumed to be due to the fact that the nanoindentation elastic modulus of the undercoat layer (organic layer) is too large, so that the gas barrier layer cannot sufficiently follow the unevenness of the joint.

  On the other hand, the organic EL devices 601 to 604 using the sealing base materials 28 to 31 having the nanoindentation elastic modulus of the undercoat layer (organic layer) of 0.01 to 1.0 GPa before and after the durability test. In addition to being excellent in the sealing performance after the resistance test, all of the sealing performance after the resistance test, the sealing performance after the bending test, and the sealing performance after the temperature / humidity cycle test were excellent.

  This application is based on Japanese Patent Application No. 2015-028931 and Japanese Patent Application No. 2015-028932 filed on February 17, 2015, the disclosures of which are incorporated by reference in their entirety. .

10 electronic devices,
11, 81 main base material,
12 sealing base material,
12a support 12b undercoat layer (organic layer)
12c Inorganic barrier layer (inorganic layer)
13 Organic EL element body,
14, 82 extraction electrodes,
15 protective layer,
16 joints,
17 first electrode (anode),
18 hole transport layer,
19 light-emitting layer,
20 electron transport layer,
21 second electrode (cathode),
70 boards,
83 magnesium layer,
84 Join,
127 Interface between main base material and sealing base material 130 Room temperature bonding device,
131 vacuum chamber,
132 ion gun (sputtering source),
133 target stage 1,
134 Target stage 2.

Claims (12)

Main base material,
An object to be sealed disposed on the main substrate,
A sealing base material that is bonded to the main base material through a bonding portion provided around the sealed body to seal the sealed body,
A sealing structure having
The sealing substrate includes a support, and a gas barrier layer disposed on the sealed body side with respect to the support,
The thickness of the joint is 0.1 to 100 nm,
Wherein at least one of the main substrate and the support is a resin film satisfying the following conditions (A) and (B):
(A) the thickness is 1 μm or more and less than 30 μm;
(B) The Young's modulus at 25 ° C. is 1 to 10 GPa.   2. The sealing structure according to claim 1, further comprising a convex lead structure having a thickness of 10 to 500 nm formed so as to be exposed from the object to be sealed and pulled out to the outside through the joint.   The sealing structure according to claim 2, wherein the object to be sealed is an electronic element main body of an electronic device, and the protruding lead structure is an extraction electrode for controlling the electronic element main body.   The sealing structure according to any one of claims 1 to 3, wherein the support is a resin film satisfying the conditions (A) and (B).   The sealing structure according to claim 4, wherein the thickness of the support is 1 to 15 m, and the Young's modulus of the support at 25C is 3 to 5 GPa.   The sealing structure according to any one of claims 1 to 5, wherein the gas barrier layer has an organic layer disposed on the support side and an inorganic layer disposed on the sealing target side.   The sealing structure according to claim 6, wherein the surface roughness (Ra) of the organic layer on the inorganic layer side is 0.1 to 5 nm.   The sealing structure according to claim 6, wherein an elongation percentage of the inorganic layer is 0.5% to 5.0%.   The bonding part according to any one of claims 1 to 8, wherein the bonding part includes an activation treatment layer obtained by performing a surface activation treatment on each of the bonding surface of the main base material and the bonding surface of the sealing base material. Item 7. The sealing structure according to Item 1.   The bonding portion includes a metal layer formed on the surface of the main base material and an activation treatment layer obtained by performing a surface activation treatment on each of the metal layers formed on the surface of the sealing base material. The sealing structure according to any one of claims 1 to 8.   The sealing structure according to any one of claims 1 to 8, wherein the bonding portion includes an adhesive layer including a silane coupling agent or a molecular adhesive. It is an electronic device, the sealing structure according to any one of claims 1 to 11,
The sealed body is an electronic element body,
Further comprising an extraction electrode formed to be exposed from the electronic element main body and drawn out to the outside via the bonding portion, for controlling the electronic element main body,
The sealing substrate, a support, disposed on the electronic element body side with respect to the support, a gas barrier layer having an organic layer and an inorganic layer,
The sealing structure, wherein the organic layer has a nanoindentation elastic modulus (at 23 ° C. and 50% RH) of 0.01 to 1 GPa.