TWI643370B - Sealed structure, organic electroluminescence display device and sensor - Google Patents

Abstract

The sealing structure 1 of the present invention includes: a first substrate 2 having a main surface 2a; a frame-shaped first metal layer 11 provided on the main surface 2a along an edge of the first substrate 2; and a frame-shaped adhesive layer 12, which is provided on the first metal layer 11, the second substrate 4, which is located above the adhesive layer 12, and has a main surface 4a opposite to the main surface 2a; and the element portion 5, which is on the main surface 2a is provided in a sealed space S surrounded by the first substrate 2, the first metal layer 11, the adhesive layer 12, and the second substrate 4 and sealed. The adhesion layer 12 contains a hydrocarbon resin or a non-polar thermoplastic resin, and the adhesion layer 12 is adhered to the first metal layer 11.

Description

Sealed structure, organic electroluminescence display device and sensor

The invention relates to a sealed structure, an organic electroluminescence display device and a sensor.

In recent years, as a display device, a self-emitting display device using an organic EL element containing an organic EL material (EL: Electro-Luminescence) has attracted much attention. Since the organic EL element is degraded if moisture is infiltrated, some measures are taken to protect the organic EL element from external air. For example, Patent Document 1 described below describes a sealing structure that uses an adhesive made of an ultraviolet-curable resin and a sealing substrate to seal an organic EL element provided on a glass substrate.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-152511.

In the aforementioned Patent Document 1, an epoxy resin is used as an adhesive. When the adhesive is made of a resin having a polar group such as epoxy resin, moisture easily diffuses in the adhesive. For this reason, in the sealing structure of the said patent document 1, there exists a possibility that moisture may infiltrate into the sealed area via an adhesive agent. On the other hand, if an adhesive made of a resin or the like having no polar group is used, depending on the material constituting the substrate, the adhesive may not adhere well to the substrate. In this case, the substrate may be peeled from the adhesive.

An object of the present invention is to provide a sealing structure, an organic EL display device, and a sensor capable of suppressing substrate peeling and moisture intrusion.

A sealing structure according to one aspect of the present invention includes: a first substrate having a first main surface; a frame-shaped first metal layer provided on the first main surface along an edge of the first substrate; a frame A second adhesive layer, which is provided on the first metal layer; a second substrate, which is located above the adhesive layer and has a second main surface opposite to the first main surface; and an element portion, which is located on the first 1 on the main surface, and is provided in a sealed space enclosed by the first substrate, the first metal layer, the adhesive layer, and the second substrate. The adhesive layer contains a hydrocarbon resin or a non-polar thermoplastic resin, and The adhesive layer is adhered to the first metal layer.

In this sealing structure, since the adhesive layer contains a hydrocarbon resin or a non-polar thermoplastic resin which does not have a polar group, it is difficult for water to diffuse in the adhesive layer. Therefore, it is difficult for water to penetrate into the element portion provided in the sealed space enclosed by the first substrate, the first metal layer, the adhesive layer, and the second substrate. The adhesive layer is adhered to the first metal layer. Generally speaking, an adhesion layer made of a hydrocarbon resin or a non-polar thermoplastic resin exhibits good adhesion to metals. Therefore, for example, even when the adhesive layer is difficult to adhere to the first substrate, the adhesive layer can be well adhered to the first metal layer provided on the first main surface, so that the first layer can be suppressed. When the substrate is peeled from the adhesive layer.

The sealing structure may further include a frame-shaped second metal layer provided on the second main surface, and the adhesive layer may be adhered to the second metal layer. At this time, for example, even when the adhesive layer is difficult to adhere to the second substrate, the adhesive layer can be well adhered to the second metal layer provided on the second main surface, so that the first layer can be suppressed. 2 The case where the substrate is peeled from the adhesive layer.

In addition, the second substrate may be a metal substrate, and the adhesive layer is adhered to the second main surface. In this case, since the adhesive layer can adhere well to the second main surface, the second substrate can be prevented from being peeled from the adhesive layer.

The surface of the first metal layer to which the adhesive layer is adhered may be an uneven surface provided with convex portions and concave portions. At this time, the area of the interface between the adhesive layer and the first metal layer becomes larger. Thereby, the distance from the outside to the sealed space via the interface becomes longer. Therefore, it is difficult for water to penetrate into the sealed space through the interface. In addition, since the contact area between the adhesive layer and the first metal layer is increased, the adhesion force of the adhesive layer to the first metal layer is improved.

In addition, the average pitch of the convex portions may be 10 nm or more and 1 μm or less, and the average height of the convex portions with respect to the concave portions may be 50 nm or more and 1 μm or less. At this time, it is more difficult for water to penetrate into the sealed space through the interface.

The adhesive layer is made of a hydrocarbon resin, and the hydrocarbon resin may be an olefin resin.

The adhesive layer is made of a non-polar thermoplastic resin, and the non-polar thermoplastic resin may be a fluorine-based resin.

The first substrate may be a glass substrate, a ceramic substrate, or a semiconductor substrate. At this time, the adhesive layer is difficult to adhere to the first substrate. However, since the adhesive layer can adhere well to the first metal layer provided on the first main surface, it is possible to prevent the first substrate from being peeled from the adhesive layer.

An organic EL display device according to another aspect of the present invention includes the sealing structure described in one of the paragraphs above, and the element portion includes an organic EL element.

In this organic EL display device, since an organic EL element is provided in a sealed structure, and the adhesive layer contains a hydrocarbon resin or a non-polar thermoplastic resin having no polar group, it is difficult for water to diffuse in the adhesive. . Therefore, it is difficult for water to penetrate into the organic EL element provided in a space enclosed by the first substrate, the first metal layer, the adhesive layer, and the second substrate and sealed. The adhesive layer is adhered to the first metal layer. Generally speaking, an adhesion layer made of a hydrocarbon resin or a non-polar thermoplastic resin exhibits good adhesion to metals. Therefore, for example, even when the adhesive layer is difficult to adhere to the first substrate, the adhesive layer can be well adhered to the first metal layer provided on the first main surface, so that the first layer can be suppressed. When the substrate is peeled from the adhesive layer.

The sensor according to another aspect of the present invention has a sealing structure described in one of the above paragraphs, and the element portion has a sensor element.

In this sensor, a sensor element is provided in the sealed structure, and the adhesive layer contains a hydrocarbon resin or a non-polar thermoplastic resin having no polar group, so it is difficult for moisture to diffuse in the adhesive layer. Therefore, it is difficult for water to penetrate into the sensor element provided in the space enclosed by the first substrate, the first metal layer, the adhesive layer, and the second substrate and sealed. The adhesive layer is adhered to the first metal layer. Generally speaking, an adhesion layer made of a hydrocarbon resin or a non-polar thermoplastic resin exhibits good adhesion to metals. Therefore, for example, even when the adhesive layer is difficult to adhere to the first substrate, the adhesive layer can be well adhered to the first metal layer provided on the first main surface, so that the first layer can be suppressed. When the substrate is peeled from the adhesive layer.

According to one aspect of the present invention, it is possible to provide a sealing structure, an organic EL display device, and a sensor that suppress substrate peeling and moisture intrusion.

Hereinafter, an effective embodiment of the present invention will be described in detail with reference to the accompanying drawings. In the following description, the same elements or elements having the same function are denoted by the same reference numerals, and repeated descriptions are omitted.

FIG. 1 is a schematic plan view showing a sealing structure according to an embodiment. FIG. 2 is a cross-sectional view taken along line α-α in FIG. 1. As shown in FIG. 1 and FIG. 2, the sealing structure 1 includes a first substrate 2 having a main surface (first main surface) 2 a, a frame-shaped sealing portion 3 provided on the first substrate 2, and a sealing portion 3. The second substrate 4 above the portion 3 and having a principal surface (second principal surface) 4a opposite to the principal surface 2a is provided and enclosed by the first substrate 2, the sealing portion 3, and the second substrate 4 and sealed The element portion 5 in the sealed space S, and the desiccant 6 provided in the sealed space S.

The first substrate 2 is a substrate having a substantially rectangular shape in a plan view. Therefore, the main surface 2a of the first substrate 2 has a substantially rectangular shape. As the first substrate 2, for example, a glass substrate, a ceramic substrate, or a semiconductor substrate can be used. The first substrate 2 may have translucency, flexibility, and the like. In this embodiment, a glass substrate is used as the first substrate 2.

The sealing portion 3 is a portion where the first substrate 2 and the second substrate 4 are joined. The sealing portion 3 is provided on the main surface 2 a of the first substrate 2 along the edge of the first substrate 2. The sealing portion 3 includes a frame-shaped first metal layer 11 provided on the main surface 2 a, a frame-shaped adhesive layer 12 provided on the first metal layer 11, and the adhesive layer 12 provided on the adhesive layer 12 and The second metal layer 13 is opposed to the first metal layer 11. In the sealing portion 3, the facing surface 11a of the first metal layer 11 facing the second metal layer 13 and the main surface 12a of the adhesive layer 12 facing the first metal layer 11 are closely contacted without gaps. Together. In addition, the facing surface 13 a of the second metal layer 13 facing the first metal layer 11 and the main surface 12 b of the adhesive layer 12 facing the second metal layer 13 are in close contact with each other without a gap.

The first metal layer 11 is provided along the edge of the main surface 2 a of the first substrate 2 and has a frame-like shape. The first metal layer 11 is formed by, for example, patterning a metal film provided on the main surface 2 a into a frame shape. This metal film is formed by, for example, a vacuum evaporation method or a sputtering method. The first metal layer 11 is, for example, various metal layers such as a molybdenum layer, a niobium layer, an aluminum layer, a nickel layer, or a chromium layer. The first metal layer 11 may have a single-layer structure or a laminated structure. The thickness of the first metal layer 11 is, for example, 50 nm or more. The width of the first metal layer 11 is, for example, 1 μm or more and 2 mm or less, and preferably 100 μm or more and 1 mm or less.

The adhesive layer 12 is a frame-shaped layer made of an adhesive that is adhered to the first metal layer 11 and the second metal layer 13. The adhesive contained in the adhesive layer 12 is melted by heating to exert adhesiveness, and contains an organic compound having no polar group such as a hydroxyl group and a carboxyl group. For example, a hydrocarbon resin such as an olefin resin or a non-polar thermoplastic resin such as a fluorine-based resin can be used as the organic compound. In this embodiment, an olefin film is used as the adhesive layer 12. The thickness of the adhesive layer 12 is, for example, 50 μm or more and 300 μm or less. The width of the adhesive layer 12 is, for example, 1 μm or more and 2 mm or less, and preferably 100 μm or more and 1 mm or less.

In this embodiment, the edge of the adhesive layer 12 exceeds the edge of the first metal layer 11 and the edge of the second metal layer 13. However, the edge of the adhesive layer 12 may be the same as the edge of the first metal layer 11 and the first metal layer 11. 2 The edges of the metal layer 13 are aligned. In addition, before the adhesive layer 12 is disposed on the first metal layer 11, the main surface 12 a of the adhesive layer 12 that is in contact with the first metal layer 11 and the main surface 12 b of the second metal layer 13 that is in contact At least one of the main surfaces is treated with an atmospheric piezoelectric slurry. The atmospheric piezoelectric plasma treatment refers to, for example, a treatment in which the adhesive layer 12 is irradiated with plasma-formed gas. For example, helium is used as the plasmatizing gas. By performing an atmospheric piezoelectric slurry treatment on the adhesive layer 12, the surface of the adhesive layer 12 that has been irradiated with the plasma-activated gas is activated. By using the activated surface in the adhesive layer 12 as an adhesive surface, the surface can be firmly bonded to at least one of the first metal layer 11 and the second metal layer 13 by chemical adhesion. The above-mentioned activation refers to the generation of dangling bonds (unsaturated bonds) on the surface or the generation of free radicals on the surface. Alternatively, the adhesive layer 12 may be irradiated with ozone gas instead of the atmospheric piezoelectric slurry treatment.

The second metal layer 13 is provided along the edge of the main surface 4 a of the second substrate 4 and has a frame-like shape. The second metal layer 13 is formed by, for example, patterning a metal film provided on the main surface 4 a into a frame shape. This metal film is formed by, for example, a vacuum evaporation method or a sputtering method. The second metal layer 13 is, for example, various metal layers such as a molybdenum layer, a niobium layer, an aluminum layer, a nickel layer, or a chromium layer. The second metal layer 13 may have a single-layer structure or a laminated structure. The thickness of the second metal layer 13 is, for example, 50 nm or more. The width of the second metal layer 13 is, for example, 1 μm or more and 2 mm or less, and preferably 100 μm or more and 1 mm or less. In this embodiment, the width of the second metal layer 13 is the same as the width of the first metal layer 11, but the width of the second metal layer 13 may be different from the width of the first metal layer 11.

The second substrate 4 is a substrate having a substantially rectangular shape in a plan view. Therefore, the main surface 4a of the second substrate 4 has a substantially rectangular shape. As described above, the main surface 4 a faces the main surface 2 a of the first substrate 2. The shape of the main surface 4a is substantially the same as the shape of the main surface 2a. Therefore, the second metal layer 13 provided on the main surface 4 a is located at a position facing the first metal layer 11 and adhering to the adhesive layer 12. As the second substrate 4, for example, a glass substrate, a ceramic substrate, a plastic substrate, or a metal substrate can be used. The second substrate 4 may have translucency, flexibility, and the like. When the second substrate 4 is a plastic substrate, for example, a polyimide substrate having heat resistance is used. The metal substrate is a substrate containing at least a metal element, and may be a substrate made of an alloy. The metal substrate may be a substrate mainly composed of a metal or an alloy. As the metal substrate, for example, a copper plate, a molybdenum plate, or a stainless steel plate can be used. In this embodiment, a glass substrate is used as the second substrate 4.

The element portion 5 is located in the sealed space S, and includes electrical elements, wiring, electronic circuits, and electronic components formed on the main surface 2 a of the first substrate 2. The electric element is an element that performs certain functions by power supply, and includes, for example, any one of a light emitting element and a sensor element. An electronic circuit is, for example, a circuit that operates to drive electrical components. This electronic circuit is composed of, for example, a resistor, a transistor, and a capacitor formed on the main surface 2a. The electronic component is, for example, an integrated circuit. In this embodiment mode, one or a plurality of organic EL elements are formed in the element portion 5 as elements that are liable to deteriorate due to infiltration of moisture. Therefore, the sealing structure 1 constitutes an organic EL display device.

The desiccant 6 adsorbs moisture in the sealed space S. The desiccant 6 is located in the sealed space S and is formed on the main surface 4 a of the second substrate 4. The desiccant 6 is a solid such as a sheet or powder, or a gel. The desiccant 6 may be an inorganic substance or an organic substance. When the second substrate 4 is translucent, the desiccant 6 may be translucent. A linear or cyclic organometallic compound is used as a light-transmitting drying agent. The organometallic compound includes, for example, any one of aluminum, lanthanum, yttrium, gallium, silicon, and germanium.

According to the sealing structure 1 according to the embodiment described above, the adhesive layer 12 is an olefin film made of a hydrocarbon resin. Thereby, the adhesive layer 12 does not have a polar group, and it is difficult for water to diffuse in the adhesive layer 12. Therefore, it is difficult for moisture to penetrate into the element portion 5 provided in the sealed space S enclosed by the first substrate 2, the sealing portion 3, and the second substrate 4. The sealing portion 3 includes the first metal layer 11. , The adhesion layer 12 and the second metal layer 13. The adhesive layer 12 is adhered to the first metal layer 11 and the second metal layer 13. Generally, the adhesion layer 12 made of a hydrocarbon resin exhibits good adhesion to metals. Therefore, for example, even when the adhesive layer 12 is difficult to adhere to one or both of the first substrate 2 and the second substrate 4, the adhesive layer 12 can adhere well to the main surface 2a. The first metal layer 11 on the surface can prevent the first substrate 2 from being peeled from the adhesive layer 12. In addition, since the adhesive layer 12 can be well adhered to the second metal layer 13 provided on the main surface 4 a, it is possible to suppress the second substrate 4 from being peeled from the adhesive layer 12.

The first substrate 2 may be a glass substrate, a ceramic substrate, or a semiconductor substrate. At this time, the adhesion layer 12 is difficult to adhere to the first substrate 2. However, since the adhesive layer 12 can adhere well to the first metal layer 11 provided on the main surface 2a, it is possible to suppress the first substrate 2 from being peeled from the adhesive layer 12.

In addition, a desiccant 6 may be provided in the sealed space S. At this time, since the moisture in the sealed space S is adsorbed by the desiccant 6, the moisture cannot easily enter the element portion 5.

Hereinafter, the first modification to the third modification of the above-mentioned embodiment will be described. In the description of the first modification to the third modification, the differences from the above-mentioned embodiment are mainly described.

FIG. 3 is a schematic cross-sectional view showing a sealing structure according to a first modification. As shown in FIG. 3, the second substrate 4A of the sealing structure 1A is a metal substrate. The sealing portion 3A includes only the first metal layer 11 and the adhesive layer 12. Therefore, the second metal layer 13 is not provided on the main surface 4 a of the second substrate 4A, and the main surface 4 a is directly adhered to the adhesive layer 12.

According to the first modified example, the adhesive layer 12 exhibits good adhesion to the metal substrate, that is, the second substrate 4A. Therefore, similarly to the above-mentioned embodiment, the effect of suppressing the second substrate 4A from peeling from the adhesive layer 12 can be achieved. In addition, since the sealing portion 3A may not have the second metal layer 13, the sealing portion 3A can be easily formed.

Fig. 4 (a) is a schematic enlarged cross-sectional view showing a sealing portion of a sealing structure according to a second modification. As shown in FIG. 4 (a), in the sealing portion 3 of the sealing structure 1B, the opposing surface 11 a of the first metal layer 11A is an uneven surface provided with a plurality of convex portions 21 and a plurality of concave portions 22. The convex portion 21 and the concave portion 22 are obtained by, for example, wet etching using an etchant such as sulfuric acid-hydrogen peroxide or dry etching such as RIE (Reactive Ion Etching). The height of the convex portions 21 may be the same or different, the depth of the concave portions 22 may be the same or different, and the pitches between the convex portions 21 may be the same or different. In addition, the convex portions 21 and the concave portions 22 may be densely provided in a part of the area of the first metal layer 11A, or the convex portions 21 and the concave portions 22 may be dispersedly provided.

The average pitch P1 between adjacent convex portions 21 is 10 nm or more and 1 μm or less. This average pitch P1 is an average distance in plan view between the vertexes of the adjacent convex portions 21. The average height H1 of the convex portion 21 with respect to the concave portion 22 is 50 nm or more and 1 μm or less. The average height H1 is an average height from the bottom point of the concave portion 22 to the apex of the convex portion 21. The convex portion 21 and the concave portion 22 extend in the width direction of the first metal layer 11A, and the convex portion 21 and the concave portion 22 are determined on the basis of a center line C1 passing through the center of the average height H1. Specifically, in the thickness direction of the first metal layer 11A, the convex portion 21 is positioned on the second substrate 4 side than the center line C1, and the concave portion 22 is positioned on the first substrate 2 side than the center line C1. Hereinafter, the width direction of the first metal layer 11A is simply referred to as the width direction, and the thickness direction of the first metal layer 11A is simply referred to as the thickness direction.

Similar to the first metal layer 11A, the opposing surface 13 a of the second metal layer 13A is an uneven surface provided with a plurality of convex portions 31 and a plurality of concave portions 32. Similar to the convex portion 21 and the concave portion 22, the convex portion 31 and the concave portion 32 are obtained by, for example, wet etching or dry etching. Therefore, the height of the convex portions 31 may be the same or different, the depth of the concave portions 32 may be the same or different, and the pitches between the convex portions 31 may be the same or different. The average pitch P2 between adjacent convex portions 31 is 10 nm or more and 1 μm or less. The average pitch P2 is an average distance in plan view between the vertexes of the adjacent convex portions 31. The average height H2 of the convex portion 31 with respect to the concave portion 32 is 50 nm or more and 1 μm or less. The average height H2 is an average height from the bottom point of the concave portion 32 to the vertex of the convex portion 31. The convex portion 31 and the concave portion 32 extend in the width direction, and the convex portion 31 and the concave portion 32 are determined on the basis of a center line C2 passing through the center of the average height H2. Specifically, in the thickness direction, the first substrate 2 side is positioned as the convex portion 31 and the second substrate 4 side is positioned as the concave portion 32 on the second substrate 4 side than the center line C2.

Also in the above-mentioned second modification, the same effect as that of the above-mentioned embodiment can be obtained. The opposing surface 11 a to which the adhesive layer 12 is adhered is a concave-convex surface in which convex portions 21 and concave portions 22 are alternately provided continuously. Therefore, the area of the interface between the main surface 12 a and the opposing surface 11 a of the adhesive layer 12 is increased. Thereby, the distance from the outside to the sealed space S via the interface becomes longer. Therefore, it is difficult for water to penetrate into the sealed space S through the interface. In addition, since the contact area between the adhesive layer 12 and the first metal layer 11A increases, the adhesion force of the adhesive layer 12 to the first metal layer 11A is improved.

In addition, by setting the average pitch P1 and the average height H1 within the above ranges, it is possible to better prevent moisture from being immersed in the seal through the interface between the main surface 12a of the adhesive layer 12 and the opposing surface 11a of the first metal layer 11A. The situation in space S.

In addition, like the first metal layer 11A, the facing surface 13 a to which the adhesive layer 12 is adhered is an uneven surface in which convex portions 31 and concave portions 32 are alternately provided continuously. Therefore, the area of the interface between the main surface 12 b and the opposing surface 13 a of the adhesive layer 12 is increased. Thereby, the distance from the outside to the sealed space S via the interface becomes longer. Therefore, it is difficult for water to penetrate into the sealed space S through the interface. In addition, since the contact area between the adhesion layer 12 and the second metal layer 13A increases, the adhesion force of the adhesion layer 12 to the second metal layer 13A is improved. In addition, by setting the average pitch P2 and the average height H2 within the above-mentioned ranges, it is possible to better prevent moisture from entering the sealed space S through the interface between the main surface 12b and the opposing surface 13a.

In the second modification, the convex portion 21 and the concave portion 32 face each other, and the concave portion 22 and the convex portion 31 face each other. In this case, unevenness of the adhesive layer 12 can be avoided, and thus the peeling between the first metal layer 11A and the adhesive layer 12 can be suppressed, and the adhesion between the second metal layer 13A and the adhesive layer 12 can be suppressed. Peeling situation. However, the convex portion 21 and the convex portion 31 may be opposed to each other, and the concave portion 22 and the concave portion 32 may be opposed to each other.

FIG. 4 (b) is a schematic enlarged cross-sectional view showing a sealing portion of a sealing structure according to a third modified example. As shown in FIG. 4 (b), the second substrate 4B of the sealing structure 1C is a metal substrate. The sealing portion 3A includes only the first metal layer 11A and the adhesive layer 12. Therefore, the second metal layer 13 is not provided on the main surface 4 a of the second substrate 4A, and the main surface 4 a is directly adhered to the adhesive layer 12.

In the main surface 4 a of the second substrate 4B, a region 4 b to which the adhesive layer 12 is adhered is an uneven surface provided with a plurality of convex portions 41 and a plurality of concave portions 42. Similar to the convex portions 21 and the concave portions 22, the convex portions 41 and the concave portions 42 are obtained by, for example, wet etching or dry etching. Therefore, the height of the convex portions 41 may be the same or different, the depth of the concave portions 42 may be the same or different, and the pitches between the convex portions 41 may be the same or different. The average pitch P3 between the adjacent convex portions 41 is 10 nm or more and 1 μm or less. The average pitch P3 is an average distance in plan view between the vertexes of the adjacent convex portions 41. The average height H3 of the convex portion 41 with respect to the concave portion 42 is 50 nm or more and 1 μm or less. The average height H3 refers to the average height from the bottom point of the concave portion 42 to the apex of the convex portion 41. The convex portion 41 and the concave portion 42 extend in the width direction, and the convex portion 41 and the concave portion 42 are determined on the basis of a center line C3 passing through the center of the average height H3. Specifically, in the thickness direction, the convex portion 41 is positioned on the first substrate 2 side than the center line C3, and the concave portion 42 is positioned on the second substrate 4B side than the center line C3.

In the third modification, the same effects as the second modification can be obtained. Other than that, as in the first modification, in the third modification, the sealing portion 3A does not need to have the second metal layer 13, and thus the sealing portion 3A can be easily formed.

In addition, by setting the average pitch P3 and the average height H3 within the above-mentioned ranges, it is possible to better prevent the moisture from entering the sealed space S via the interface between the main surface 12a of the adhesive layer 12 and the main surface 4a of the second substrate 4B. .

In the third modification, the convex portion 21 and the concave portion 42 face each other, and the concave portion 22 and the convex portion 41 face each other. In this case, unevenness of the adhesive layer 12 can be avoided, and thus, peeling between the first metal layer 11A and the adhesive layer 12 can be suppressed, and peeling between the second substrate 4B and the adhesive layer 12 can be suppressed. situation. However, the convex portion 21 and the convex portion 41 may be opposed to each other, and the concave portion 22 and the concave portion 42 may be opposed to each other.

The sealing structure of the present invention is not limited to the above-mentioned embodiments and modified examples, and various other changes are possible. For example, the element section 5 of the present invention may include a sensor such as a MEMS (Micro Electro Mechanical System) instead of a display element. At this time, the above-mentioned sealing structure becomes a sensor. The element portion 5 may include both a display element and a sensor element, and may include other organic electronic devices (organic semiconductor elements or dye-sensitized solar cells, etc.).

In addition, in the above-mentioned embodiment and the modification, the adhesive layer 12 may not be formed into a frame-shaped film. For example, the adhesive layer 12 may be a member formed by curing a liquid adhesive. In this case, for example, an adhesive may be applied to the first metal layer, the second metal layer may be bonded to the adhesive, and then the adhesive may be cured by heat treatment or the like. In addition to the adhesive, the adhesive layer 12 may contain various additives. Examples of the additives include inorganic fillers and surfactants. In the adhesive layer 12 containing an inorganic filler, it is more difficult for water to diffuse. At the interface between the adhesive layer 12 containing the surfactant and the first metal layer and the interface between the adhesive layer 12 and the second metal layer, it is more difficult for water to penetrate. In addition, when the adhesive layer 12 is composed of a non-polar thermoplastic resin such as a fluorine-based resin, the same effects as those of the above-mentioned embodiment and the above-mentioned modification can be obtained.

In addition, in the second modification, only one of the opposing surface 11 a of the first metal layer 11A and the opposing surface 13 a of the second metal layer 13A may be an uneven surface. Similarly, in the third modified example, only the region 4b of the second substrate 4B may be an uneven surface. The region 4b of the third modified example may be formed on the entire main surface 4a. In other words, the convex portions 41 and the concave portions 42 may be continuously and alternately formed on the entire main surface 4a.

In the second modification, at least one of the average pitches P1 and P2 and the average heights H1 and H2 may be set in the above range. Similarly, in the third modification, at least one of the average pitches P1 and P3 and the average heights H1 and H3 may be set in the above range.

In addition, in the embodiment and the first to third modifications, the first metal layer may be discontinuous. That is, a part of the first metal layer may be interrupted. At this time, a lead wire or the like connected to the element portion 5 may be provided on a portion of the first substrate where the first metal layer is not provided.

[Examples] Hereinafter, the present invention will be described in more detail through the following examples, but the present invention is not limited to these examples.

Embodiment 1 FIG. 5 is a schematic cross-sectional view showing a sealing structure according to an embodiment. As shown in FIG. 5, a sealing structure 101 in which a first substrate 2A and a second substrate 4 are adhered by a frame-shaped sealing portion 3 is prepared, and the first substrate 2A is at the center of the main surface 2 a A depression 51 is provided, and the second substrate 4 has a main surface 4 facing the depression 51. A method of manufacturing the sealing structure 101 will be described below.

First, a first substrate 2A and a second substrate 4 are prepared, wherein the first substrate 2A is provided with a recess 51 in a central portion of the main surface 2a, and the second substrate 4 has a main surface 4a opposite to the recess 51. Next, a metal film made of molybdenum is formed on the main surface 2a, and a metal film made of molybdenum is formed on the main surface 4a. Next, each of the metal films is patterned to form a frame-like first metal layer 11 along the edge of the main surface 2a, and a frame-like second metal layer 13 is formed along the edge of the main surface 4a. Next, the first substrate 2A was immersed in 50% aq of sulfuric acid-hydrogen peroxide for 10 minutes, thereby forming a first metal layer 11A whose opposed surface 11a was an uneven surface. Similarly, the second substrate 4 is immersed in 50% aq of sulfuric acid-hydrogen peroxide for 10 minutes, thereby forming a second metal layer 13A whose facing surface 13 a is an uneven surface. Next, in a hand mode operation box with a dew point of -70 ° C, about 100 mg of a desiccant 52, which is flake calcium oxide (CaO), is filled in the depression 51. Next, the first substrate 2A and the second substrate 4 are temporarily fixed using a film-shaped adhesive layer 12 formed by molding a cycloolefin polymer (ZEONOR, a registered trademark) manufactured by Nippon Ryo Co., Ltd. into a frame shape. At this time, the adhesive layer 12 is sandwiched between the opposing surface 11 a of the first metal layer 11A and the opposing surface 13 a of the second metal layer 13A. Then, heat treatment is performed in an inert gas at a temperature of 160 ° C or higher. Thereby, the adhesive layer 12 is welded to the first metal layer 11A and the second metal layer 13A to obtain a sealing structure 101.

(Example 2) A sealed structure was prepared by the same method as in Example 1, except that the film-shaped adhesive layer 12 was previously subjected to atmospheric piezoelectric slurry treatment. In the atmospheric piezoelectric slurry treatment, first, an alternating voltage of 10 kV at a frequency of 10 kHz is applied to helium, thereby plasmatizing the helium. Next, the plasma-converted helium gas is sprayed into the atmosphere to irradiate the surface of the adhesive layer 12.

(Comparative Example) An epoxy-based adhesive (XNR5516 manufactured by Nagase ChemteX Co., Ltd.) was used instead of the sealing portion 3 to bond the first substrate 2A and the second substrate 4 to obtain a sealed structure. In this comparative example, the first metal layer 11 is not formed on the main surface 2 a of the first substrate 2A, and the second metal layer 13 is not formed on the main surface 4 a of the second substrate 4. Therefore, in this comparative example, the first substrate 2A and the second substrate 4 were not immersed in sulfuric acid-hydrogen peroxide.

(High-temperature and high-humidity test) The high-temperature and high-humidity test was performed on the sealing structure 101 of Example 1, the sealing structure of Example 2, and the sealing structure of the comparative example, and the weight change of the desiccant filled in each sealing structure was measured. In the high-temperature and high-humidity test, each sealed structure was left standing for 300 hours under conditions of a temperature of 85 ° C and a humidity of 85%.

Fig. 6 is a graph showing changes in weight of the desiccant in Examples 1, 2 and Comparative Examples. In Fig. 6, the vertical axis indicates the amount of moisture increase of the desiccant, and the horizontal axis indicates the test time. In addition, the curve 61 shows the measurement result of Example 1, the curve 62 shows the measurement result of Example 2, and the curve 63 shows the measurement result of the comparative example. In the comparative example, the weight of the desiccant was increased by about 0.00025 g (0.25 mg) after the high temperature and high humidity test for 300 hours. In contrast, in Example 1, the weight of the desiccant was increased by about 0.0001 g (0.1 mg). Moreover, in Example 2, no increase in the weight of the desiccant was confirmed. Therefore, it was confirmed that in the sealing structure of Example 2 using the adhesive layer 12 after being subjected to the atmospheric piezoelectric paste treatment, it is most difficult for water to penetrate into the sealed space S.

1‧‧‧sealed structure

1A‧‧‧Sealed structure

1B‧‧‧Sealed structure

1C‧‧‧Sealed structure

2‧‧‧ the first substrate

2a ‧ ‧ main surface (first main surface)

2A‧‧‧The first substrate

3‧‧‧Sealing Department

3A‧‧‧Sealing Department

4‧‧‧ 2nd substrate

4a ‧ ‧ main surface (second main surface)

4A‧‧‧The second substrate

4B‧‧‧The second substrate

5‧‧‧Element Department

6‧‧‧ Desiccant

11‧‧‧ 1st metal layer

11a‧‧‧ Opposite side

11A‧‧‧The first metal layer

12‧‧‧ Adhesive layer

12a‧‧‧Main face

12b‧‧‧ main face

13‧‧‧Second metal layer

13a‧‧‧ Opposite side

13A‧‧‧Second metal layer

21‧‧‧ convex

22‧‧‧ Recess

31‧‧‧ convex

32‧‧‧ recess

41‧‧‧ convex

42‧‧‧ Recess

51‧‧‧ Depression

52‧‧‧ Desiccant

61‧‧‧ curve

62‧‧‧ curve

63‧‧‧ curve

101‧‧‧sealed structure

C1‧‧‧ Centerline

C2‧‧‧ Centerline

C3‧‧‧ Centerline

H1‧‧‧ average height

H2‧‧‧ average height

H3‧‧‧ average height

P‧‧‧average pitch

P1‧‧‧average pitch

P2‧‧‧average pitch

P3‧‧‧average pitch

S‧‧‧Sealed space

FIG. 1 is a schematic plan view showing a sealing structure according to an embodiment. FIG. 2 is a cross-sectional view taken along line α-α in FIG. 1. FIG. 3 is a schematic cross-sectional view showing a sealing structure according to a first modification. FIG. 4 (a) is a schematic enlarged cross-sectional view showing a sealing portion of a sealing structure according to a second modified example, and FIG. 4 (b) is a schematic enlarged cross-sectional view showing a sealing portion of a sealing structure according to a third modified example. Fig. 5 is a schematic cross-sectional view showing a sealing structure according to the embodiment. Fig. 6 is a graph showing changes in weight of the desiccant in Examples 1, 2 and Comparative Examples.

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Claims (8)

A sealing structure includes a first substrate having a first main surface, a frame-shaped first metal layer provided on the first main surface along an edge of the first substrate, and a frame-shaped adhesive layer. Is disposed on the first metal layer; the second substrate is located above the adhesive layer and has a second main surface facing the first main surface; and the element portion is disposed on the first 1 on the main surface and provided in a sealed space enclosed by the first substrate, the first metal layer, the adhesive layer, and the second substrate and sealed; wherein the adhesive layer contains a hydrocarbon resin Or a non-polar thermoplastic resin, and the adhesive layer is adhered to the first metal layer; a surface to which the adhesive layer in the first metal layer is adhered is a concave-convex surface provided with convex portions and concave portions; the convex portion The average pitch of P is 10 nm or more and 1 μm or less; and the average height of the convex portion with respect to the concave portion is 50 nm or more and 1 μm or less. The sealing structure according to claim 1, further comprising: a frame-shaped second metal layer provided on the second main surface; and the adhesive layer is adhered to the second metal layer. The sealing structure according to claim 1, wherein: the second substrate is a metal substrate; and the adhesive layer is adhered to the second main surface. The sealing structure according to any one of claims 1 to 3, wherein: the adhesive layer is made of the hydrocarbon resin; and the hydrocarbon resin is an olefin resin. The sealing structure according to any one of claims 1 to 3, wherein the adhesive layer is made of the non-polar thermoplastic resin, and the non-polar thermoplastic resin is a fluorine-based resin. The sealing structure according to any one of claims 1 to 3, wherein the first substrate is a glass substrate, a ceramic substrate, or a semiconductor substrate. An organic electroluminescence display device comprising the sealing structure according to any one of claims 1 to 6; and the element portion includes an organic electroluminescence element. A sensor including the sealing structure according to any one of claims 1 to 6; and the element portion includes a sensor element.