Cover member with sealing base film and method for producing the same, cover member with sealing material, hermetically sealed package, and device

Abstract

To provide a cover member with a sealing base film which has a high airtight sealing property, does not deteriorate devices to be installed in a hermetically sealed package, is low-cost and has excellent mass-producibility.SOLUTION: A cover member with a sealing base film in which a sealing base film is formed in a partial region of the cover member is made of an inorganic material, the cover member has a flat-plate shape with a pair of opposing main surfaces, or has a specific sectional inverted concave shape, the sealing base film is formed in a frame-like shape on a specific outer edge portion of the cover member, the sealing base film includes, in order from the cover member side, a glass layer and a metal matrix layer, an average thickness of the glass layer is more than 0 μm and 10 μm or less, the metal matrix layer includes a metal phase and a glass phase, and the metal constituting the metal phase is at least one kind selected from the group consisting of gold, tin, antimony, silver, and copper.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a cover member with a sealing base film and a manufacturing method thereof.The present invention also relates to a cover member with a sealing material, a hermetically sealed package, and a device, each including the cover member with a sealing base film. [Background technology]

[0002] Devices using light-emitting diodes (LEDs) are used in a wide range of applications, such as backlights for mobile phones and large LCD TVs, and for lighting purposes. For example, in the case of a light-emitting device that uses a light-emitting diode that emits visible light (visible light LED), a commonly used configuration is to place an LED chip on a flat substrate such as aluminum nitride and seal it using a resin-based material.

[0003] In contrast, light-emitting devices that use ultraviolet light-emitting diodes (UV-LEDs), semiconductor lasers (laser diodes, LDs), vertical-cavity surface-emitting lasers (VCSELs), etc. require airtight sealing. VCSELs also require a diffusion plate. For this reason, these light-emitting devices may require a cover glass with an outer frame as a cover member.

[0004] Not only the light emitting device, but also light receiving devices such as sensors may require airtight sealing. For example, there is a device called MEMS (Micro Electro Mechanical Systems), which is a device in which an electric circuit and a fine mechanical structure are integrated on a single substrate. An example of a substrate used in MEMS is a silicon substrate. As with light emitting devices, light receiving devices may require a cover member with an outer frame.

[0005] Furthermore, in addition to the electronic components described above, all-solid-state batteries may also require airtight sealing. This is because high water resistance is required for both oxide solid electrolytes and sulfide solid electrolytes, which are mainly used in all-solid-state batteries. Furthermore, sulfide solid electrolytes generate toxic gases when they react with water, so higher airtight sealing is required.

[0006] When such high airtight sealing is required, for example, Patent Document 1 discloses a method for joining glass materials by applying high temperature to cause welding. In the case where the substrate and the cover member are made of materials with different thermal expansion coefficients, for example, Patent Document 2 discloses that a highly reliable sealing structure can be obtained by arranging the first metal layer, the second metal layer, and the metal bonding portion to be in specific positions. Patent Document 3 discloses the use of a metal-based bonding material containing metal particles with a specific particle size. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2013-222522 A [Patent Document 2] JP 2018-037581 A [Patent Document 3] International Publication No. 2021 / 261356 Summary of the Invention [Problem to be solved by the invention]

[0008] However, there are concerns that high-temperature welding as described in Patent Document 1 may cause deterioration in performance and reliability due to heat in devices installed in hermetically sealed packages. In addition, it is difficult to apply this method to joining materials other than glass. In addition, when joining different materials, direct joining is not possible, and when sealing is performed via a metal layer as described in Patent Document 2 and Patent Document 3, metallization is required, such as providing a base film for sealing that contains the metal that constitutes the metal layer. The base film for the metallization needs to be formed by a sputtering method, which is expensive and difficult to mass-produce.

[0009] Therefore, the present invention aims to provide a cover member with a sealing base film that has high airtight sealing properties, does not deteriorate a device installed in the hermetically sealed package, and is low-cost and excellent in mass productivity, a manufacturing method thereof, and a cover member with a sealing material further formed thereon. Another aim is to provide a hermetically sealed package and device using the cover member with a sealing base film. [Means for solving the problem]

[0010] In order to solve the above problems, the present inventors have conducted research on the premise of hermetic sealing via a metal layer in order to prevent deterioration of a device installed in a hermetically sealed package. In order to achieve hermetic sealing via a metal layer, they have decided to form a sealing base film by a coating method such as a printing method, which is less expensive and more suitable for mass production than a sputtering method. After further investigation, the inventors found that by adding glass powder in addition to the metal and forming a sealing base film using a coating method, the resulting sealing base film has a structure including a metal matrix layer containing a metal phase and a glass phase, and a glass layer. This sealing base film realizes high airtight sealing. Thus, the inventors have completed the present invention.

[0011] That is, one aspect of the present invention relates to the following [1] to

[21] . [1] A cover member with a sealing base film, in which a sealing base film is formed in a partial area of ​​a cover member, The cover member is made of an inorganic material, The cover member is a flat plate having a pair of opposing main surfaces, the sealing base film is formed in a frame shape on one outer edge portion of the main surface; the sealing base film includes, in order from the cover member side, a glass layer and a metal matrix layer, The average thickness of the glass layer is more than 0 μm and 10 μm or less, the metal matrix layer includes a metal phase and a glass phase; A cover member with a sealing underlayer, wherein the metal constituting the metal phase is at least one metal selected from the group consisting of gold, tin, antimony, silver and copper.

[0012] [2] A cover member with a sealing base film, in which a sealing base film is formed in a partial region of the cover member, The cover member is made of an inorganic material, The cover member has an inverted concave cross section having an upper wall portion, a side wall portion, and a lower opening portion, the sealing base film is formed in a frame shape on at least an outer edge portion of the bottom surface of the side wall portion, the sealing base film includes, in order from the cover member side, a glass layer and a metal matrix layer, The average thickness of the glass layer is more than 0 μm and 10 μm or less, the metal matrix layer includes a metal phase and a glass phase; A cover member with a sealing underlayer, wherein the metal constituting the metal phase is at least one metal selected from the group consisting of gold, tin, antimony, silver and copper.

[0013] [3] The cover member with a sealing base film according to [1] or [2], wherein the average area ratio of the glass phase in the metal matrix layer is 15% or less. [4] The inorganic material is a glass material; The cover member with a sealing underlayer according to any one of [1] to [3] above, wherein the glass transition temperatures of the glass in the glass layer and the glass phase are lower than the glass transition temperature of the glass material. [5] The cover member with a sealing base film according to [4], wherein the glass material has a glass transition temperature of 700° C. or higher. [6] The cover member with a sealing base film according to [4] or [5], wherein the composition of the glass material, based on oxides, satisfies: SiO2: 50-75%, Al2O3: 0-25%, B2O3: 0-20%, MgO: 0-20%, CaO: 0-20%, SrO: 0-20%, and MgO+CaO+SrO: 5-40%. [7] The cover member with a sealing base film according to any one of [1] to [6] above, wherein the glass layer and the glass of the glass phase have a glass transition temperature of 450° C. or lower. [8] The cover member with a sealing underlayer according to any one of the above [1] to [7], wherein the metal constituting the metal phase is gold. [9] The cover member with a sealing underlayer according to any one of [1] to [8], wherein the glass layer and the glass of the glass phase have a composition based on oxides of Bi2O3: 50 to 90 mass %.

[10] The cover member with a sealing underlayer according to [9], wherein the glass layer and the glass of the glass phase have a composition based on oxides of 70 to 90 mass % Bi2O3, 1 to 20 mass % ZnO, and 2 to 12 mass % B2O3.

[11] The cover member with a sealing underlayer according to any one of [1] to

[10] above, wherein the inorganic material is a ceramic material, quartz, or sapphire.

[12] The cover member with a sealing underlayer according to any one of [1] to

[11] above, wherein the inorganic material is a light-transmitting inorganic material.

[13] The cover member with a sealing underlayer according to any one of the above [1] to

[12] , wherein the metal matrix layer has a thickness of 5 to 30 μm.

[0014]

[14] A cover member with a sealing material, in which a sealing material containing a metal is formed in a frame shape on a surface of the sealing base film opposite to the side in contact with the cover member in the cover member with a sealing base film described in any one of [1] to

[13] .

[15] A hermetically sealed package comprising a cover member with a sealing base film according to any one of [1] to

[13] above and a substrate, which are integrated via a sealing material containing a metal.

[16] A device comprising the hermetically sealed package according to

[15] above, wherein an electronic component or an all-solid-state battery is provided on the substrate and hermetically sealed.

[0015]

[17] A method for manufacturing a cover member with a sealing base film, in which a sealing base film is formed in a partial region of a cover member and the cover member is hermetically sealed to a substrate via a sealing material containing a metal, comprising: As the cover member, a flat plate-shaped inorganic material having a pair of opposing main surfaces or an inverted concave cross-sectional shape having an upper wall portion, a side wall portion and a lower opening portion is prepared; and applying a metal paste in a frame shape to at least a region of the inorganic material that is to be in contact with the sealing material containing the metal, and firing the metal paste to form a sealing base film; The metal paste contains at least one metal selected from the group consisting of gold, tin, antimony, silver, and copper, glass powder, and a vehicle; In the metal paste, the content of the glass powder with respect to the total content of the metal and the glass powder is 1 to 40 mass %, The method for producing a cover member with a sealing base film, wherein the firing is carried out at a temperature 150° C. or more higher than the glass transition temperature of the glass powder.

[18] The method for manufacturing a cover member with a sealing underlayer according to

[17] , wherein the glass powder in the metal paste has a glass transition temperature of 450°C or lower.

[19] The method for producing a cover member with a sealing underlayer according to

[17] or

[18] , wherein the glass powder in the metal paste has a composition based on oxides that satisfies Bi2O3: 50 to 90 mass %.

[20] The method for manufacturing a cover member with a sealing underlayer according to

[19] , wherein the glass powder in the metal paste has a composition based on oxides satisfying: Bi2O3: 70 to 90 mass %, ZnO: 1 to 20 mass %, and B2O3: 2 to 12 mass %.

[21] The method for producing a cover member with a sealing underlayer according to any one of

[17] to

[20] above, wherein the metal in the metal paste is gold. Effect of the Invention

[0016] According to the present invention, since the sealing base film can be formed by a coating method, a cover member with a sealing base film can be obtained at low cost and with excellent mass productivity. In addition, airtight sealing can be achieved using a metal layer as a sealing material via the sealing base film. This does not require welding at high temperatures, and therefore high airtight sealing can be achieved without deteriorating the device installed in the hermetically sealed package. The present invention also provides a cover member with a sealing material, in which a sealing material is formed on the cover member with the sealing base film, and also provides a hermetically sealed package and device using the cover member and the sealing base film. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 shows one embodiment of a cover member with a sealing base film according to this embodiment, in which the cover member is flat, with (a) of FIG. 1 being a schematic cross-sectional view of the cover member with a sealing base film, and (b) of FIG. 1 being a schematic bottom view of the cover member with a sealing base film. [Diagram 2] FIG. 2 shows one embodiment of a cover member with a sealing base film according to this embodiment, in which the cover member has an inverted concave cross-sectional shape, where (a) of FIG. 2 is a schematic cross-sectional view of the cover member with the sealing base film, and (b) of FIG. 2 is a schematic bottom view of the cover member with the sealing base film. [Diagram 3] FIG. 3 is an enlarged schematic cross-sectional view of a sealing base film in a cover member with a sealing base film according to this embodiment. [Figure 4] FIG. 4 is an explanatory diagram of a method for determining the average area ratio of the glass phase in the metal matrix layer, in which (a) in FIG. 4 is a cross-sectional SEM image of the metal matrix layer, and (b) in FIG. 4 is a cross-sectional SEM image obtained by subjecting the cross-sectional SEM image of (a) in FIG. 4 to binarization and inversion processing. [Diagram 5] FIG. 5 is an explanatory diagram of a method for determining the average area ratio occupied by the glass phase in the metal matrix layer, in which FIG. 5(a) is a first histogram obtained from FIG. 4(a), and FIG. 5(b) is a second histogram obtained from FIG. 4(b). [Figure 6] FIG. 6 is a schematic cross-sectional view showing one aspect of the cover member with sealing material according to the present embodiment. [Figure 7] FIG. 7 is a schematic cross-sectional view showing one aspect of the cover member with sealing material according to the present embodiment. [Figure 8] FIG. 8 is a schematic cross-sectional view showing one embodiment of the hermetically sealed package according to the present embodiment. [Figure 9] FIG. 9 is a schematic cross-sectional view showing one embodiment of the hermetically sealed package according to the present embodiment. [Figure 10] FIG. 10 is an SEM image of a cross section of the cover member with the sealing base film obtained in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be modified in any manner without departing from the gist of the present invention. In this specification, the use of "to" indicating a numerical range means that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, the term "coefficient of thermal expansion" refers to a value measured as the average rate of elongation per 1°C when heated in the range of 50 to 350°C.

[0019] <Cover material with sealing base film> In the cover member 10 with a sealing base film according to this embodiment, a sealing base film 2 is formed in a partial region of a cover member 1.

[0020] In the first aspect of this embodiment, the cover member 1' is made of an inorganic material and is a flat cover member 1' having a pair of opposing main surfaces as shown in (a) of Fig. 1. As shown in (b) of Fig. 1, a sealing base film 2' is formed in a frame shape on the outer edge of one of the main surfaces of the cover member 1'. As shown in (a) of Fig. 1, the sealing base film 2' includes, in order from the cover member 1' side, a glass layer 21' and a metal matrix layer 22'.

[0021] The average thickness of the glass layer 21' is greater than 0 μm and equal to or less than 10 μm. In this specification, the average thickness of the glass layer is a value measured using a scanning electron microscope (SEM) image of a cross section of a cover member with a sealing base film. Specifically, the measurement target is an area of ​​45μm x 30μm at a magnification of 2000x. This measurement target area is divided into nine sections of 5μm x 30μm by dividing the 45μm side at 5μm intervals. In each of the nine divided sections, the thickness of the glass layer is measured at an arbitrary point. In this way, the glass layer thickness is measured at nine points from one measurement target. The above 45 μm×30 μm measurement object is selected from three arbitrary locations on the sealing base film formed in a frame shape so as not to measure locally. When the sealing base film is formed in a rectangular shape, for example, an arbitrary side is selected, and a total of three locations are selected, including both ends or their vicinity, and the center or its vicinity. In other words, there are three 45 μm×30 μm measurement objects, and the glass layer thickness is measured at nine points for each measurement object, so the glass layer thickness is measured at a total of 27 points, and the average thickness is taken as the average glass layer thickness. Although details will be described later, Fig. 10 shows an SEM image of the cross section of the cover member with the sealing base film obtained in Example 1. Here, the darkest part at the top of the image is the cover member, the layer in the middle measured to be 2.13 μm thick is the glass layer, and the layer below that where uneven shading can be seen is the metal matrix layer. In Fig. 10, the measurement target is an area of ​​approximately 30 μm × 20 μm at 3000x magnification, which is different from the measurement target used for the average thickness of the glass layer described above, but the distinction between the cover member, glass layer, and metal matrix layer is the same.

[0022] The metal matrix layer 22' includes a metal phase 22a' and a glass phase 22b' as shown in Fig. 3. The metal constituting the metal phase 22a' is at least one metal selected from the group consisting of gold (Au), tin (Sn), antimony (Sb), silver (Ag) and copper (Cu).

[0023] In aspect 2 of this embodiment, the cover member 1'' is made of an inorganic material and has an inverted concave cross section, as shown in FIG. 2(a), an upper wall portion 1a'', side walls 1b'', 1c'', 1d'', 1e'', and a lower opening 1f''. As shown in FIG. 2(b), a sealing base film 2'' is formed in a frame shape on the bottom surfaces of the side walls 1b'', 1c'', 1d'', and 1e'' of the cover member 1''. As shown in FIG. 2(a), the sealing base film 2'' includes, in order from the cover member 1'' side, a glass layer 21'' and a metal matrix layer 22''.

[0024] The glass layer 21'' and the metal matrix layer 22'' are similar to the glass layer 21' and the metal matrix layer 22' in the first embodiment, respectively. That is, the average thickness of the glass layer 21'' is greater than 0 μm and equal to or less than 10 μm, similar to the first embodiment. As shown in FIG. 3, the metal matrix layer 22'' includes a metal phase 22a'' and a glass phase 22b''. The metal constituting the metal phase 22a'' is at least one metal selected from the group consisting of gold (Au), tin (Sn), antimony (Sb), silver (Ag) and copper (Cu).

[0025] Although (a) and (b) of FIG. 1 show a case where the cover member 1' is in the shape of a rectangular flat plate, the shape may be any shape, such as a polygon, a circle, or an irregular shape.

[0026] In addition, although (a) and (b) of Figures 2 above show a case in which the upper wall portion of the cover member 1'' is a rectangular flat plate and has four side wall portions, the upper wall portion may be a polygon represented by an n-sided polygon and there may be n side wall portions, the upper wall portion may be a circular portion and the side wall portions may be cylindrical side walls that follow the outer edge of the upper wall portion, or the upper wall portion and the side wall portion may be integrated into a dome shape.

[0027] <Base film for sealing> As shown in FIG. 3, the sealing base film 2 in this embodiment includes a glass layer 21 and a metal matrix layer 22 in this order from the cover member 1 side.

[0028] Glass layer Since the sealing base film 2 in this embodiment has the glass layer 21, the adhesion of the metal matrix layer 22, which is a metallized layer in the sealing base film 2, to the cover member 1 can be improved. Therefore, even if a coating method that is low-cost and has excellent mass productivity is used instead of the conventional sputtering method, the presence of the glass layer 21 makes it possible to realize a sealing base film 2 having high airtight sealing properties.

[0029] The glass layer 21 is a layer that is formed by using a metal paste containing glass powder and employing a coating method such as a printing method. Specifically, the glass layer 21 is formed by coating a metal paste that will become the sealing base film 2 on the cover member 1 and firing it.

[0030] It is believed that heating the metal paste increases the fluidity of the glass powder contained in the metal paste or the glass components formed by melting the glass powder, and for some reason, such as affinity with the cover member, the glass components gather at the interface with the cover member, forming glass layer 21.

[0031] The average thickness of the glass layer 21 may be more than 0 μm and not more than 10 μm, preferably 0.01 to 8 μm, and more preferably 0.05 to 5 μm. From the viewpoint of hermetic sealing, the average thickness is preferably more than 0 μm, more preferably 0.01 μm or more, and even more preferably 0.05 μm or more. From the viewpoint of the amount of glass added, the average thickness is preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 5 μm or less. The average thickness of the glass layer means the average thickness measured at a total of 27 points in an area of ​​45 μm×30 μm at a magnification of 2000 times using a cross-sectional SEM image as described above.

[0032] The glass layer 21 in this embodiment is a layer derived from glass powder contained in the metal paste. Although the preferred physical properties of the glass layer 21 vary depending on the cover member 1, for example, when the cover member 1 is made of a glass material, the glass transition temperature (Tg1) of the glass in the glass layer 21 is preferably lower than the glass transition temperature (Tg2) of the glass material constituting the cover member 1. This is to suppress softening of the glass material constituting the cover member 1 when the metal paste is fired in forming the sealing base film 2 including the glass layer 21.

[0033] The glass transition temperature (Tg1) of the glass in the glass layer 21 is preferably lower than the glass transition temperature (Tg2) of the glass material constituting the cover member 1, and more preferably 200° C. or higher and lower than (Tg2). From the viewpoint of suppressing softening of the glass material constituting the cover member 1 in the manufacturing process, the glass transition temperature (Tg1) is preferably lower than the glass transition temperature (Tg2), more preferably (Tg2-10)° C. or lower, and even more preferably (Tg2-40)° C. or lower. From the viewpoint of shape retention, the glass transition temperature (Tg1) is preferably 250° C. or higher, more preferably 300° C. or higher, and even more preferably 350° C. or higher.

[0034] Although it varies depending on the glass transition temperature (Tg2) of the glass material constituting the cover member 1, the glass transition temperature (Tg1) of the glass in the glass layer 21 is, for example, preferably 500°C or less, more preferably 450°C or less, even more preferably 425°C or less, and even more preferably 415°C or less.

[0035] From the viewpoint of lowering the glass transition temperature, the glass of the glass layer 21 preferably contains at least one of bismuth oxide and boron oxide in its composition. In the case of bismuth oxide glass, the composition based on oxides is preferably Bi2O3: 50-90 mass%, more preferably 60-85 mass%, and even more preferably 70-80 mass%. From the viewpoint of lowering the glass transition temperature, the content of Bi2O3 is preferably 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more. From the viewpoint of vitrification, the content is preferably 90 mass% or less, more preferably 85 mass% or less, and even more preferably 80 mass% or less.

[0036] In the case of bismuth oxide glass, in addition to Bi2O3, it may contain B2O3, CeO2, SiO2, RO, R'2O, R''2O3, R'''O2, etc. The above R is at least one element selected from the group consisting of Zn, Ba, Sr, Mg, Ca, Fe, Mn, Cr, Sn and Cu, and Zn is preferred from the viewpoint of vitrification. The above R' is at least one selected from the group consisting of Li, Na, K, Cs, and Cu. The above R'' is at least one selected from the group consisting of Al, Fe, and La. The above R''' is at least one selected from the group consisting of Zr, Ti, and Sn.

[0037] More specifically, the bismuth oxide glass is preferably, for example, glass that satisfies Bi2O3: 70 to 90 mass% and B2O3: 2 to 12 mass%, and more preferably glass that satisfies Bi2O3: 70 to 90 mass%, ZnO: 1 to 20 mass%, and B2O3: 2 to 12 mass%.

[0038] The B2O3 content is preferably 2 to 12 mass%, more preferably 4 to 11 mass%, and even more preferably 5 to 10 mass%. From the viewpoint of vitrification, the B2O3 content is preferably 2 mass% or more, more preferably 4 mass% or more, and even more preferably 5 mass% or more. From the viewpoint of the glass softening point, the B2O3 content is preferably 12 mass% or less, more preferably 11 mass% or less, and even more preferably 10 mass% or less.

[0039] The ZnO content is preferably 1 to 20 mass%, more preferably 5 to 16 mass%, and even more preferably 7 to 12 mass%. From the viewpoint of vitrification, the ZnO content is preferably 1 mass% or more, more preferably 5 mass% or more, and even more preferably 7 mass% or more. From the viewpoint of stability during glass molding, the ZnO content is preferably 20 mass% or less, more preferably 16 mass% or less, and even more preferably 12 mass% or less.

[0040] The bismuth oxide glass preferably further satisfies CeO2: 0-10 mass%, SiO2: 0-20 mass%, RO other than ZnO: 0-10 mass%, R'2O: 0-10 mass%, R''2O3: 0-20 mass%, and R'''O2: 0-10 mass%.

[0041] The borosilicate glass may contain CeO2, RO, R'2O, R''2O3, R'''O2, etc., in addition to SiO2 and B2O3, and preferably contains ZnO, K2O, and Na2O.

[0042] More specifically, for example, glass satisfying the following composition is preferred: SiO2: 23 to 35 mass %, B2O3: 40 to 55 mass %, ZnO: 10 to 20 mass %, and the total of K2O and Na2O: 3 to 15 mass %.

[0043] Below, each component other than bismuth oxide (Bi2O3) and boron oxide (B2O3) is described. SiO2 is a component that constitutes glass. However, if added in excess, there is a risk that the glass transition temperature (Tg) will become too high. CeO2 is a component that stabilizes the color tone of the glass powder after the glass raw materials are melted and vitrified. When bismuth oxide is contained in the glass, it is preferable to contain both. On the other hand, if added in excess, it may be prone to crystallization and it may be difficult to obtain a stable glass powder. Components represented by RO, including CaO, are effective in stabilizing glass and suppressing crystallization. However, adding too much of them can raise the glass transition temperature (Tg) too much. Components expressed as R'2O, including K2O and Na2O, lower the glass transition temperature (Tg). The smaller the atomic number of the element, the greater the effect. However, the smaller the atomic number of the element, the lower the insulating properties of the glass and the greater the content, which may impair reliability. Components represented by R''2O3, including Al2O3, are effective in stabilizing glass, suppressing crystallization, and improving the chemical durability of glass. However, if added in excess, there is a risk of the glass transition temperature (Tg) becoming too high. The component represented by R'''O2 is a component that supplies oxygen during bonding. However, if added in excess, there is a risk of foaming during bonding.

[0044] In the present embodiment, the cover member 1 may be made of an inorganic material and is not limited to a glass material. Therefore, when the cover member 1 is made of a ceramic material or a glass material such as quartz having a glass transition temperature (Tg) exceeding 1000° C., the glass of the glass layer 21 is not limited to a glass having a low glass transition temperature (Tg), and any glass may be used according to desired characteristics.

[0045] Metal matrix layer The sealing base film 2 in this embodiment includes a metal matrix layer 22 as a metallized layer for adhesion to a sealing material. The metal matrix layer 22 includes a metal phase 22a that serves as a matrix and a glass phase 22b. The presence of the metal phase 22a and the glass phase 22b can be confirmed by using a scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX).

[0046] The glass in the glass phase 22b can be considered to be substantially the same as the glass constituting the glass layer 21. This is because the glass powder contained in the metal paste used to form the sealing base film 2 becomes both the glass layer 21 and the glass phase 22b during the manufacturing process. Therefore, the preferred embodiment of the glass in the glass phase 22b is the same as the preferred embodiment of the glass layer 21 described above.

[0047] The shape and size of each glass phase 22b in the metal matrix layer 22 vary. Therefore, it is difficult to specify the shape and size of the glass phase 22b, but for example, in an SEM image of a cross section of a cover member with a sealing base film, a glass phase is defined as one that has a brightness different from the most frequent brightness and is approximately elliptical. Here, the approximately elliptical shape includes a perfect circle and an elliptical shape, as well as a shape that includes a straight line portion on the periphery.

[0048] In the above case, the average area ratio of the glass phase 22b in the metal matrix layer 22 is preferably more than 0% and not more than 15%, more preferably 0.5% to 12%, and even more preferably 1% to 10%. From the viewpoint of the wettability of the sealing material, the average area ratio is preferably not more than 15%, more preferably not more than 12%, and even more preferably not more than 10%. Also, from the viewpoint of the sinterability of the metal phase, the average area ratio is more than 0%, preferably not less than 0.5%, and more preferably not less than 1%. Here, the above average area ratio is a value measured using a scanning electron microscope (SEM) image of a cross section of the metal matrix layer 22.

[0049] A specific method for determining the above average area ratio will be described below with reference to FIGS. (I) A 5 μm×30 μm range is measured as an SEM image of a cross section of the metal matrix layer 22. Assuming that the frame on which the sealing base film is formed has n sides, two points are selected for the central region of each of the n sides: one point close to the outer edge and one point near the middle between the outer edge and the inner edge. A 5 μm×30 μm cross-sectional SEM image is obtained for the selected (n×2) measurement points. If the frame on which the adhesion base film is formed does not have n sides, such as if it is only curved, then 27 arbitrary points are selected to avoid localized measurement.

[0050] (II) An example of the cross-sectional SEM image is shown in Figure 4(a). The cross-sectional SEM image in Figure 4(a) is converted from red, green, and blue (RGB) to hue, saturation, and value (HSV), and then smoothed to remove noise components, to obtain a first histogram with value (unitless) on the horizontal axis, as shown in Figure 5(a). In the first histogram, the area with a value equal to or greater than the mode value corresponds to the metal phase 22a, which is the main component of the metal matrix layer, and the area with a value less than the mode value corresponds to the glass phase 22b.

[0051] (III) In the first histogram shown in Fig. 5(a), the midpoint between the most frequent brightness and the brightness with the next highest frequency after the most frequent brightness is set as the threshold value. This means the midpoint between the lowest brightness among the frequencies indicating the metallic phase and the highest brightness among the frequencies indicating the glass phase. The cross-sectional SEM image of Fig. 4(a) obtained in (II) above is further subjected to binarization processing and then inversion processing using the above threshold value in the first histogram shown in Fig. 5(a), thereby obtaining a cross-sectional SEM image as shown in Fig. 4(b). When a histogram is obtained for this image in the same manner as in Fig. 5(a), a second histogram is obtained in which the horizontal axis is brightness (unitless), as shown in Fig. 5(b). In this second histogram as well, the most frequent brightness corresponds to the metal phase 22a.

[0052] (IV) In the cross-sectional SEM image obtained in (III) above and subjected to the binarization and inversion processing of Fig. 4(b), a region having a brightness different from the brightness of the most frequent value in the second histogram shown in Fig. 5(b) above and having a substantially elliptical shape is regarded as the glass phase 22b. The number of pixels in the region regarded as the glass phase 22b divided by the total number of pixels in the range of 5 µm × 30 µm is regarded as the area ratio occupied by the glass phase 22b. (V) The above operations (II) to (IV) are performed on the (n × 2) cross-sectional SEM images selected in (I) above, and the average value of these images is regarded as the average area ratio occupied by the glass phase in the metal matrix layer.

[0053] The metal phase 22a which is the base of the metal matrix layer is made of at least one metal selected from the group consisting of gold, tin, antimony, silver and copper. The metal phase 22a may be selected according to the metal used in the sealing material. For example, when a gold-based solder such as a solder containing gold (Au) and tin (Sn) is used as the sealing material, the metal constituting the metal phase 22a preferably contains gold. Similarly, in the case of a solder containing antimony (Sb) and tin, the metal constituting the metal phase 22a preferably contains antimony, and in the case of a solder containing at least one of silver (Ag) and copper (Cu) and tin, the metal constituting the metal phase 22a preferably contains at least one of silver and copper. In addition, in accordance with the tin (Sn) contained in the solder, the metal constituting the metal phase 22a preferably contains tin, and in this case, it is also preferable to contain tin together with other metal components of the solder, i.e., gold, antimony, silver, copper, etc.

[0054] In particular, from the viewpoint of responding to the need to use gold-tin solder with high sealing and bonding reliability as a sealing material, it is preferable that the metal phase 22a contains gold. In this case, the proportion of gold in the metal phase 22a is preferably 70 mass% or more, more preferably 80 mass% or more, and may be 100 mass%, i.e., composed only of gold. Furthermore, from the viewpoint of sinterability, the proportion of gold may be 95 mass% or less. When the metal phase 22a contains a metal other than gold, the other metal may be tin, silver, or other metals that are inevitably contained.

[0055] The average thickness of the metal matrix layer 22 is preferably 5 to 30 μm, more preferably 6 to 20 μm, and even more preferably 6.5 to 18 μm. From the viewpoint of stress relaxation, the average thickness is preferably 5 μm or more, more preferably 6 μm or more, and even more preferably 6.5 μm or more. From the viewpoint of mass productivity, the average thickness is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 18 μm or less. The average thickness of the metal matrix layer 22, like the average thickness of the glass layer 21, means the average thickness measured at a total of 27 points in an area of ​​45 μm × 30 μm at a magnification of 2000 times using an SEM image of a cross section of the metal matrix layer.

[0056] Other layers The sealing base film 2 in this embodiment may include any other layers in addition to the glass layer 21 and the metal matrix layer 22.

[0057] Position of the sealing base film In this embodiment, the sealing base film 2 is formed in a frame shape on one outer edge of the main surface of the flat cover member 1', and the rest is optional. The frame shape is not particularly limited as long as it is continuous from the start point to the end point along the outer edge of the main surface. The start point and the end point are the same. That is, it may be a shape formed only by curves such as a circle (also called a loop shape), a polygonal shape including straight lines such as a square, a shape including straight lines and curves such as a rounded square, or a wavy shape. In addition, the sealing base film 2 may be a double or more multiple frame shape along the outer edge.

[0058] Furthermore, in this embodiment, the sealing base film 2 is optional as long as it is formed in a frame shape on at least the outer edge of the bottom surface of the side wall of the cover member 1'' having an inverted concave cross section. For example, in (b) of FIG. 2, the sealing base film 2 is provided on the entire bottom surface of the side wall, but depending on the area of ​​the bottom surface of the side wall, the sealing base film 2 may be provided on the outer edge of the bottom surface and the sealing base film 2 may not be provided in the area close to the lower opening of the bottom surface.

[0059] The frame shape here is not particularly limited as long as it is continuous from the start point to the end point along the outer edge of the main surface, as in the above case. That is, it may be a shape formed only by curves such as a circle (also called a loop shape), a polygonal shape including straight lines such as a square, a shape including straight lines and curves such as a rounded square, or a wavy shape. In addition, the sealing base film 2 may be a double or more multiple frame shape along the outer edge.

[0060] The width of the sealing base film 2 is not particularly limited. The width of the sealing base film 2' formed on the flat cover member 1' is, for example, preferably 0.1 to 5 mm, more preferably 0.15 to 4 mm, and even more preferably 0.2 to 1 mm. From the viewpoint of film-forming properties and sealing properties, the width is preferably 0.1 mm or more, more preferably 0.15 mm or more, and even more preferably 0.2 mm or more. From the viewpoint of effective area and cost, the width is preferably 5 mm or less, more preferably 4 mm or less, and even more preferably 1 mm or less.

[0061] The width of the sealing base film 2'' formed on the cover member 1'' having an inverted concave cross section is, for example, preferably 0.1 to 5 mm, more preferably 0.5 to 3 mm, and even more preferably 0.8 to 2 mm. From the viewpoint of the perpendicularity of the walls and bondability, the width is preferably 0.1 mm or more, more preferably 0.5 mm or more, and even more preferably 0.8 mm or more. From the viewpoint of mass productivity, the width is preferably 5 mm or less, more preferably 3 mm or less, and even more preferably 2 mm or less. In addition, the sealing base film 2'' may be formed on the entire lower end surface of the side wall portion of the cover member 1'', which is the lower opening side, or the sealing base film 2'' may be formed on only a part of the lower end surface.

[0062] <Cover member> The cover member 1 in this embodiment is made of an inorganic material. As described above, the cover member 1 may be a flat cover member 1' having a pair of opposing main surfaces as shown in FIG. 1(a), or may be a cover member 1'' having an inverted concave cross-sectional shape having an upper wall portion 1a'', side walls 1b'', 1c'', 1d'', 1e'' and a lower opening 1f'' as shown in FIG. 2(a).

[0063] The inorganic material may be selected depending on the application of the cover member 10 with a sealing base film according to this embodiment. For example, in the case of mounting various light emitting elements such as laser diodes as electronic components and forming a hermetically sealed device, the inorganic material is a light-transmitting inorganic material. That is, when the cover member 1 has a flat plate shape as shown in FIG. 1(a), the flat plate-shaped cover member 1' is made of a light-transmitting inorganic material.

[0064] Furthermore, when the cover member 1 has an inverted concave cross-sectional shape as shown in Figure 2(a), depending on the aspect of the device, the upper wall portion 1a'' may be made of a light-transmitting inorganic material, and one or more of the side wall portions 1b'', 1c'', 1d'', and 1e'' may be made of a light-transmitting inorganic material, or all of the upper wall portion 1a'' and the side wall portions 1b'', 1c'', 1d'', and 1e'' may be made of a light-transmitting inorganic material.

[0065] When an all-solid-state battery is mounted on the device to form an airtight sealed device, the inorganic material is a non-light-transmitting inorganic material. That is, when the cover member 1 has a flat plate shape as shown in FIG. 1(a), the flat plate-shaped cover member 1' is made of a non-light-transmitting inorganic material. Furthermore, when the cover member 1 has an inverted concave cross section as shown in FIG. 2(a), the upper wall portion 1a'' and the side walls 1b'', 1c'', 1d'', and 1e'' are all made of a non-light-transmitting inorganic material.

[0066] Examples of the light-transmitting inorganic material include glass, silicon, sapphire, etc. Quartz may be used as the glass. Examples of non-transparent inorganic materials include ceramic materials, including glass ceramics.

[0067] When a glass material that is reliable as a glass for electronic components is used as the inorganic material, it is preferable to use a low-melting point glass such as a bismuth oxide glass as the glass constituting the glass layer 21 and the glass phase 22b. In this case, the glass material as the inorganic material is preferably a glass having a glass transition temperature (Tg) higher than the glass constituting the glass layer 21 and the glass phase 22b. In other words, the glass transition temperature of the glass in the glass layer 21 and the glass phase 22b is preferably lower than the glass transition temperature of the glass material that becomes the cover member 1.

[0068] For example, the glass transition temperature of the glass material constituting the cover member 1 is preferably 680°C or higher, more preferably 690 to 1500°C, even more preferably 695 to 1400°C, and even more preferably 700 to 1300°C. Here, the glass transition temperature is preferably 680° C. or higher in relation to the glass transition temperature (Tg) of the glass constituting the glass layer 21 and the glass phase 22b, more preferably 690° C. or higher, even more preferably 695° C. or higher, and even more preferably 700° C. or higher. From the viewpoint of glass manufacturability, the glass transition temperature is preferably 1500° C. or lower, more preferably 1400° C. or lower, and even more preferably 1300° C. or lower.

[0069] When the glass material is used in a hermetically sealed device that has a temperature higher than the glass transition temperature of the glass in the glass layer 21 and the glass phase 22b and is equipped with various light emitting elements such as laser diodes, it is preferable to use, for example, alkali-free glass, quartz glass, or the like.

[0070] More specifically, when the glass material is a glass material other than quartz glass, the composition based on oxides is preferably as follows: SiO2: 50-75%, Al2O3: 0-25%, B2O3: 0-20%, MgO: 0-20%, CaO: 0-20%, SrO: 0-20%, and MgO+CaO+SrO: 5-40%.

[0071] In the above composition, SiO2 is a component constituting glass, and is preferably 50 to 75%, more preferably 60 to 73%, and even more preferably 62 to 72%. From the viewpoint of glass transition temperature, the content of SiO2 is preferably 50% or more, more preferably 60% or more, and even more preferably 62% or more. From the viewpoint of processability, the content is preferably 75% or less, more preferably 73% or less, and even more preferably 72% or less.

[0072] Al2O3 is a component for stabilizing glass, and is preferably 0 to 25%, more preferably 5 to 20%, and even more preferably 7 to 14%. Here, Al2O3 does not have to be contained, but if it is contained, from the viewpoint of suppressing phase separation of glass, its content is more preferably 5% or more, and even more preferably 7% or more. Also, from the viewpoint of meltability of glass, the content is preferably 25% or less, more preferably 20% or less, and even more preferably 14% or less.

[0073] B2O3 is a component that lowers the glass transition temperature, and is preferably 0 to 20%, more preferably 0.5 to 15%, and even more preferably 1.5 to 10%. Here, B2O3 may not be contained, but if it is contained, from the viewpoint of the melting property of the glass, the content is preferably 0.5% or more, and even more preferably 1.5% or more. Also, from the viewpoint of the sintering temperature of the sealing base film, the content is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less.

[0074] MgO is a component that improves the solubility, and is preferably 0 to 20%, more preferably 1.5 to 10%, and even more preferably 2.0 to 8.0%. Here, MgO may not be contained, but if it is contained, from the viewpoint of the meltability of the glass, the content is preferably 1.5% or more, and even more preferably 2.0% or more. Also, from the viewpoint of suppressing phase separation of the glass, the content is preferably 20% or less, more preferably 10% or less, and even more preferably 8.0% or less.

[0075] CaO is a component for stabilizing glass and suppressing crystallization, and is preferably 0 to 20%, more preferably 1.5 to 10%, and even more preferably 2.0 to 8.0%. Here, CaO may not be contained, but if it is contained, from the viewpoint of the meltability of glass, the content is preferably 1.5% or more, and even more preferably 2.0% or more. Also, from the viewpoint of suppressing phase separation of glass, the content is preferably 20% or less, more preferably 10% or less, and even more preferably 8.0% or less.

[0076] SrO is a component that improves meltability, and is preferably 0 to 20%, more preferably 1.5 to 10%, and even more preferably 2.0 to 8.0%. Here, SrO may not be contained, but if it is contained, from the viewpoint of suppressing phase separation of glass, the content is more preferably 1.5% or more, and even more preferably 2.0% or more. Also, from the viewpoint of suppressing an increase in the thermal expansion coefficient, the content is preferably 20% or less, more preferably 10% or less, and even more preferably 8.0% or less.

[0077] The total content of MgO+CaO+SrO is preferably 5 to 40%, more preferably 8 to 20%, and even more preferably 12 to 18%. From the viewpoint of the meltability of the glass, the content is preferably 5% or more, more preferably 8% or more, and even more preferably 12% or more. From the viewpoint of suppressing an increase in the thermal expansion coefficient, the content is preferably 40% or less, more preferably 20% or less, and even more preferably 18% or less.

[0078] When the above-mentioned inorganic material is a glass material such as quartz having a glass transition temperature (Tg) exceeding 1000°C, the glass of the glass layer 21 is not limited to one having a low glass transition temperature (Tg), and any glass can be used according to the desired characteristics.

[0079] From the viewpoint of applicability regardless of the glass transition temperature (Tg) of the glass layer 21 and the glass phase 22b in the sealing base film 2, quartz is preferable as the inorganic material among glass materials, and silicon, sapphire, and ceramic materials are also preferable.

[0080] Quartz is preferred as a light-transmitting material from the viewpoint of high transmittance over a wide wavelength range from the ultraviolet region to the infrared region. When the inorganic material is quartz, conventionally known quartz can be used.

[0081] Silicon is preferable as a light-transmitting material from the viewpoints of infrared transmittance and heat resistance. When the inorganic material is silicon, conventionally known silicon can be used.

[0082] Sapphire is preferable as a light-transmitting material from the viewpoints of mechanical strength and heat resistance. When the inorganic material is sapphire, any conventionally known sapphire can be used.

[0083] When the inorganic material is a ceramic material, a conventionally known ceramic material can be used, specifically, alumina (aluminum oxide, Al2O3), aluminum nitride (AlN), LTCC (Low Temperature Co-fired Ceramics), zirconia (zirconium oxide, ZrO2), etc.

[0084] The ceramic material may be a glass ceramic, which is a material in which a filler component is dispersed in a glass matrix. The glass matrix may be any glass known as a glass matrix for conventional glass ceramics, such as glasses containing at least one of bismuth oxide and boron oxide, generally known as bismuth oxide-based glasses or borosilicate-based glasses.

[0085] The bismuth oxide glass may contain, for example, B2O3, CeO2, SiO2, RO, R'2O, R''2O3, R'''O2, etc. in addition to Bi2O3. Here, R is at least one selected from the group consisting of Zn, Ba, Sr, Mg, Ca, Fe, Mn, Cr, Sn, and Cu. R' is at least one selected from the group consisting of Li, Na, K, Cs, and Cu. R'' is at least one selected from the group consisting of Al, Fe, and La. R''' is at least one selected from the group consisting of Zr, Ti, and Sn.

[0086] The borosilicate glass may contain, for example, CeO2, RO, R'2O, R''2O3, R'''O2, etc., in addition to SiO2 and B2O3, and preferably contains ZnO, K2O, and Na2O. Here, R, R'', and R''' are the same as R, R'', and R''' in bismuth oxide-based glass, respectively.

[0087] The filler component in the glass ceramic can be any known filler for glass ceramics, such as inorganic materials known as low thermal expansion fillers or negative thermal expansion fillers.

[0088] Low thermal expansion filler has a thermal expansion coefficient of 0 / ℃ or more than 40×10 -7 / °C or less, and examples of the filler include aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide, silicon dioxide, and mixtures thereof. Examples of the mixtures include cordierite (2MgO·2Al2O3·5SiO2), which is a mixture of magnesium oxide, aluminum oxide, and silicon dioxide.

[0089] A negative thermal expansion filler is a filler whose thermal expansion coefficient is a negative value, i.e., less than 0 / °C. For example, a thermal expansion coefficient of -20×10 -7 / ℃, the thermal expansion coefficient of zirconium phosphate is -50×10 -7 / ℃, and β-eucryptite (Li2O·Al2O3·2SiO2) with a thermal expansion coefficient of -7×10 -7 / ℃, and zirconium tungstate (ZrW2O8).

[0090] The thickness of the cover member 1 is not particularly limited, and may be appropriately selected depending on the application. For example, when the cover member 10 with a sealing base film according to this embodiment is used in a device equipped with electronic components and the inorganic material constituting the cover member 1 is a light-transmitting material, the thickness is, for example, preferably 200 μm to 1.5 mm, more preferably 250 μm to 1.2 mm, and even more preferably 300 μm to 1.1 mm. From the viewpoint of durability, the thickness is preferably 200 μm or more, more preferably 250 μm or more, and even more preferably 300 μm or more. On the other hand, from the viewpoints of transparency and miniaturization, the thickness is preferably 1.5 mm or less, more preferably 1.2 mm or less, and even more preferably 1.1 mm or less.

[0091] Furthermore, when the cover member 10 with a sealing base film according to this embodiment is used in a device equipped with an all-solid-state battery, and the inorganic materials constituting the cover member 1 are all non-translucent materials, the thickness is, for example, preferably 150 μm to 2.0 mm, more preferably 200 μm to 1.5 mm, and even more preferably 250 μm to 1.0 mm. From the viewpoints of durability and operability, the thickness is preferably 150 μm or more, more preferably 200 μm or more, and even more preferably 250 μm or more. On the other hand, from the viewpoint of miniaturization, the thickness is preferably 2.0 mm or less, more preferably 1.5 mm or less, and even more preferably 1.0 mm or less.

[0092] When the inorganic material constituting the cover member 1 is a light-transmitting material, an anti-reflection film (not shown) may be formed on the surface thereof. When the cover member 1' is a flat plate-like cover member, an anti-reflection film may be formed on at least one of the pair of opposing main surfaces. When the cover member 1'' has an inverted concave cross section, an anti-reflection film may be formed on at least one of the surfaces on the lower opening side and the outside of at least one of the upper wall portion and the side wall portion, which are made of a light-transmitting material. The anti-reflection film may also be formed on the area of ​​the sealing base film 2 that contacts the glass layer 21 .

[0093] Any known antireflection film can be used as the antireflection film 5, as long as it can reduce the reflectance of light at least at the design wavelength. Among them, a film made of an inorganic material is preferred from the viewpoint of maintaining good antireflection performance even during heat treatment in manufacturing the cover member 10 with the sealing base film.

[0094] Examples of anti-reflection films made of inorganic materials include thin films with a single layer structure and dielectric multilayer films in which two or more dielectric layers with different refractive indices, such as SiO2 and Ta2O5, are laminated.

[0095] In addition to the anti-reflection film, the cover member 1 may have a further layer having some function formed thereon, as long as the effect of the present invention is not impaired. For example, when the inorganic material constituting the cover member is a light-transmitting material, examples of the further layer include a light diffusion layer, a specific wavelength transmission layer, etc. Furthermore, regardless of whether the inorganic material is a light-transmitting material or a non-light-transmitting material, examples of the further layer include a conductive layer, a magnetic layer, etc.

[0096] From the viewpoint of airtight sealing, these additional layers are preferably made of inorganic materials. The light diffusing layer may be directly formed on the cover member 1 by surface processing.

[0097] <Method for manufacturing cover member with sealing base film> The method for producing the cover member 10 with a sealing base film according to this embodiment is not particularly limited as long as the sealing base film 2 having the metal matrix layer 22 present thereon is formed on the cover member 1 via the glass layer 21 .

[0098] One aspect of the method for manufacturing a cover member 10 with a sealing base film according to this embodiment is a method for manufacturing a cover member with a sealing base film, in which a sealing base film 2 is formed in a partial area of ​​a cover member 1 and the cover member is hermetically sealed to a substrate 4 via a sealing material 3 containing a metal, and includes the following steps 1 and 2.

[0099] Step 1: preparing a cover member 1 made of an inorganic material having a flat plate shape with a pair of opposing main surfaces, or a cross-sectional inverted concave shape with an upper wall portion, a side wall portion, and a lower opening portion. Step 2: A step of applying a metal paste in a frame shape to the region of the inorganic material that is to be in contact with at least a sealing material 3 containing a metal, and baking the metal paste to form a sealing base film 2.

[0100] ·Process 1 The inorganic material in the above step 1 can be any of the inorganic materials described in the above <Cover member>, and the preferred embodiments are the same. The inorganic material may be manufactured or may be commercially available, and a conventionally known method may be used for manufacturing. In addition, a conventionally known processing may be appropriately performed before use.

[0101] For example, when the cover member 1 has an inverted concave cross section and at least the side wall portion is made of glass ceramic, the upper wall portion is obtained by molding and firing a glass ceramic precursor, which is, for example, a mixture of glass powder and a filler component that forms a glass matrix, and sintering it.

[0102] Specifically, the precursor is formed into a sheet called a green sheet, and any number of sheets are stacked on the upper wall portion. A plurality of holes of the desired size and shape are then punched using a punching machine, and the resulting product is sintered to obtain a multi-piece cover member having an inverted concave cross-section and an upper wall portion and a side wall portion.

[0103] In addition to the above, a cover member having an inverted concave cross section may be obtained by directly joining an upper wall portion and a side wall portion, or by directly joining side wall portions together. Examples of direct bonding include heat fusion, heat and pressure, ultrasonic bonding, bonding by laser heating, and optical contact.

[0104] ·Process 2 The metal paste in step 2 above preferably contains at least one metal selected from the group consisting of gold, tin, antimony, silver and copper, glass powder, and a vehicle.

[0105] The metal contained in the metal paste is the same as the metal constituting the metal phase 22a in the metal matrix layer 22 of the sealing underlayer 2. The preferred embodiment of the metal is also the same as the preferred embodiment of the metal constituting the metal phase 22a, and preferably contains, for example, gold.

[0106] The metal content in the metal paste relative to the total of the metal and glass powder is preferably 60 to 99 mass%, more preferably 70 to 98 mass%, and even more preferably 90 to 97.5 mass%. From the viewpoint of bondability with glass, the content is preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more. From the viewpoint of wettability with a bonding agent, the content is preferably 99 mass% or less, more preferably 98 mass% or less, and even more preferably 97.5 mass% or less.

[0107] The glass powder contained in the metal paste becomes the glass layer 21 and the glass phase 22b in the metal matrix layer 22 of the sealing base film 2. The preferred aspects of the glass powder are the same as the preferred aspects of the glass constituting the glass layer 21 and the glass phase 22b. For example, when the inorganic material is a glass material, the glass transition temperature of the glass powder is preferably 500° C. or lower, more preferably 450° C. or lower, even more preferably 425° C. or lower, and even more preferably 415° C. or lower, although it varies depending on the glass transition temperature.

[0108] The glass powder having a glass transition temperature of 500°C or less can be the same as the glass described in the "Glass Layer" in the above <Sealing Base Film>, and preferred embodiments are also the same. For example, the composition based on oxides preferably satisfies Bi2O3: 50 to 90 mass%, more preferably satisfies Bi2O3: 70 to 90 mass%, ZnO: 1 to 20 mass%, and B2O3: 2 to 12 mass%.

[0109] The content of the glass powder in the metal paste relative to the total of the metal and glass powder is preferably 1 to 40 mass%, more preferably 2 to 30 mass%, and even more preferably 2.5 to 10 mass%. From the viewpoint of sinterability, the content is preferably 1 mass% or more, more preferably 2 mass% or more, and even more preferably 2.5 mass% or more. From the viewpoint of wettability with the metal sealing layer, the content is preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 10 mass% or less.

[0110] The glass powder has an average particle size of preferably 0.1 to 15 μm, more preferably 0.3 to 12 μm, and even more preferably 0.4 to 10 μm. From the viewpoint of dispersibility, the average particle size is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.4 μm or more. From the viewpoint of reactivity, the average particle size is preferably 15 μm or less, more preferably 12 μm or less, and even more preferably 10 μm or less. In this specification, the average particle size is the median diameter (D50) value at which 50 volume % of the particles have a particle size of less than or equal to this value, measured using a laser diffraction / scattering type particle size distribution measuring device.

[0111] The metal paste is prepared by adding the above metal and glass powder to a vehicle to form a paste. The vehicle preferably contains a solvent or a dispersion medium, and if desired, further contains a binder.

[0112] Examples of the binder include organic resins such as cellulose-based resins and acrylic-based resins. Examples of the cellulose-based resin include methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, and nitrocellulose. Examples of the acrylic resin include resins obtained by polymerizing one or more acrylic monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate, and 2-hydroxyethyl acrylate.

[0113] The above-mentioned solvent or dispersion medium varies depending on the binder. For example, when a cellulose-based resin is used as the binder, terpineol, butyl diglycol acetate, ethyl diglycol acetate, propylene glycol diacetate, etc. are preferred. When an acrylic resin is used as the binder, the solvent or dispersion medium is preferably methyl ethyl ketone, terpineol, butyl diglycol acetate, ethyl diglycol acetate, propylene glycol diacetate, or the like.

[0114] The ratio of the binder to the solvent in the vehicle is not particularly limited, but may be selected so that the viscosity of the resulting metal paste falls within a desired range. Specifically, the mass ratio of the binder to the solvent is preferably about 3:97 to 15:85, and more preferably about 5:95 to 10:90.

[0115] The content of the vehicle in the metal paste is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass. From the viewpoint of suppressing an increase in the viscosity of the metal paste and facilitating the formation of the sealing base film, the content is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. From the viewpoint of obtaining a sufficient coating thickness of the sealing base film, the content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. The content of the vehicle is related to the solid content of the metal paste. That is, when the metal paste is composed of only the metal, the glass powder, and the vehicle, the total content of the metal and the glass powder, which is the content other than the vehicle, is the solid content.

[0116] The metal paste may contain other additives in addition to the metal, glass powder, and vehicle, such as dispersants, antifoaming agents, and viscosity modifiers.

[0117] The metal paste can be prepared by mixing the above-mentioned constituent materials in a rotary mixer equipped with stirring blades, a crusher, a roll mill, a ball mill, or the like, using a known method.

[0118] In the manufacturing method according to the present embodiment, the metal paste is applied in a frame shape to a region of an inorganic material that is in contact with a sealing material 3 containing at least a metal, and then fired. As a result, a sealing base film 2 containing a glass layer 21 and a metal matrix layer 22 is formed.

[0119] It is believed that heating the metal paste increases the fluidity of the glass powder contained in the metal paste, and for some reason, such as affinity with the cover member, the glass components gather at the interface with the cover member, forming a glass layer 21. As a result, the sealing base film 2 can be configured to have, in order from the cover member 1 side, a glass layer 21 and a metal matrix layer 22.

[0120] The method of applying the metal paste is not particularly limited, and examples thereof include a screen printing method, a dispensing method, etc. In any of these application methods, the thickness of the application can be easily adjusted by the viscosity of the metal paste, the number of applications, the application speed, etc., and they are less expensive and more suitable for mass production than the sputtering method. Among these, the screen printing method is preferred from the viewpoint of process time. If necessary, a mask may be applied before applying the metal paste.

[0121] The atmosphere in which the metal paste is applied is not particularly limited, and examples thereof include air, an inert atmosphere, a hydrogen atmosphere, etc. Among these, air is preferred from the viewpoint of ease.

[0122] After the metal paste is applied, it may be dried as necessary before firing, for example at 80 to 200° C. for 5 to 30 minutes.

[0123] The conditions for firing the applied metal paste may be appropriately set depending on the type of inorganic material of the cover member 1, the type and average particle size of the glass powder, and the like.

[0124] For example, the firing temperature is preferably (Tg1+150)°C or higher, more preferably (Tg1+150) to (Tg2-10)°C, more preferably (Tg1+200) to (Tg2-30)°C, and even more preferably (Tg1+230) to (Tg2-40)°C, relative to the glass transition temperature (Tg1) of the glass powder and the glass transition temperature (Tg2) of the glass material constituting the cover member 1. Here, from the viewpoint of sinterability, the above temperature is preferably (Tg1+150)°C or higher, more preferably (Tg1+200)°C or higher, and even more preferably (Tg1+230)°C or higher. In addition, from the viewpoint of shape retention, the above temperature is preferably (Tg2-10)°C or lower, more preferably (Tg2-30)°C or lower, and even more preferably (Tg2-40)°C or lower.

[0125] Furthermore, for example, when the glass powder has a glass transition temperature of 450° C. or lower and the cover member has a glass transition temperature of 750° C. or higher, the firing temperature is preferably 600 to 740° C., more preferably 630 to 720° C., and even more preferably 650 to 700° C. From the viewpoint of bondability and sinterability, the temperature is preferably 600° C. or higher, more preferably 630° C. or higher, and even more preferably 650° C. or higher. From the viewpoint of the glass transition temperature, the temperature is preferably 740° C. or lower, more preferably 720° C. or lower, and even more preferably 700° C. or lower.

[0126] The firing time is, for example, preferably 10 to 120 minutes, more preferably 20 to 90 minutes, and even more preferably 30 to 80 minutes. From the viewpoint of sinterability, the time is preferably 10 minutes or more, more preferably 20 minutes or more, and even more preferably 30 minutes or more. From the viewpoint of mass productivity, the time is preferably 120 minutes or less, more preferably 90 minutes or less, and even more preferably 80 minutes or less.

[0127] The atmosphere in which the metal paste is fired is not particularly limited, and examples thereof include air, an inert atmosphere, a hydrogen atmosphere, etc. Among these, firing in air is preferred from the viewpoint of ease.

[0128] <Cover component with sealing material> As shown in Figures 6 and 7, the cover member with sealing material 100 (100', 100'') of this embodiment has a metal-containing sealing material 3 (3', 3'') formed in a frame shape on a cover member with a sealing base film 10 (10', 10'').

[0129] The cover member 10 with a sealing base film is the same as that described above in the section "Cover member with a sealing base film", and the preferred embodiments are also the same. That is, on the surface of the sealing base film 2 in the cover member 10 with a sealing base film opposite to the side in contact with the cover member 1, a sealing material 3 containing a metal is formed in a frame shape.

[0130] The metal-containing sealing material 3 may be formed on the sealing base film 2, and the metal-containing sealing material 3 does not have to be formed so as to cover the entire surface of the sealing base film 2. Also, a part of the metal-containing sealing material 3 may be formed directly on the surface of the cover member 1 on which the sealing base film 2 is not formed, but from the viewpoint of adhesion, it is preferable that the entire area of ​​the metal-containing sealing material 3 is formed via the sealing base film 2.

[0131] The metal in the metal-containing sealing material 3 may be any known metal known as a sealing material, but it is preferable that the metal contains at least one metal selected from the group consisting of gold, tin, antimony, silver and copper. Specifically, it is preferable that the metal constituting the metal phase 22a of the metal matrix layer 22 in the sealing base film 2 and the metal contained in the metal-containing sealing material 3 are the same, and it is more preferable that the metal contains gold, for example.

[0132] Examples of the sealing material 3 containing metal include metal rings formed from gold (Au)-tin (Sn)-based metal solder, tin (Sn)-antimony (Sb)-based metal solder, tin (Sn)-silver (Ag)-copper (Cu)-based metal solder, tin (Sn)-silver (Ag)-based metal solder, etc. Among these, from the viewpoint of sealing properties, metal rings formed from gold (Au)-tin (Sn)-based metal solder are preferred.

[0133] <<Hermetically sealed package>> As shown in Figures 8 and 9, the hermetically sealed package 200 (200', 200'') of this embodiment includes a cover member 10 (10', 10'') with a sealing base film and a substrate 4 (4', 4'') that are integrated via a sealing material 3 (3', 3'') containing a metal.

[0134] The cover member 10 with a sealing base film is the same as that described above in the section "Cover member with a sealing base film", and the preferred embodiments are also the same. That is, on the surface of the sealing base film 2 in the cover member 10 with a sealing base film opposite to the side in contact with the cover member 1, a sealing material 3 containing a metal is formed in a frame shape.

[0135] The metal-containing sealing material 3 is the same as that described above in the "Cover member with sealing material" section, and the preferred embodiments are also the same.

[0136] A conventionally known material can be used depending on the application for the substrate 4. Examples include alumina (aluminum oxide, Al2O3), aluminum nitride (AlN), LTCC (Low Temperature Co-fired Ceramics), and zirconia (zirconium oxide, ZrO2).

[0137] The hermetically sealed package 200 according to this embodiment preferably has a metal film (not shown) between the sealing material 3 containing metal and the substrate 4.

[0138] The metal film may be a conventionally known one, and preferably has a metal coating layer containing one or more selected from the group consisting of Au, Ag, Cu and Au-Sn alloy, and more preferably has an Ag layer or Au layer, on the outermost surface on the side in contact with the metal-containing sealing material 3. The metal film may further have a coating of Ni, Ti, Pd, Pt, Cu or the like as a base for the metal coating layer.

[0139] The metal film may be formed by a conventionally known method, for example, by a coating method, a plating method, or the like, on the substrate 4. In this way, the surface of the substrate 4 that is to be bonded to the metal-containing sealing material 3 is metallized, and high sealing performance can be achieved.

[0140] "device" In the device according to this embodiment, electronic components or an all-solid-state battery are provided on a substrate in a hermetically sealed package. The hermetically sealed package is the same as that described above in the "Hermetically sealed package" and the preferred embodiments are also the same.

[0141] Examples of the electronic components include light-emitting diode elements, semiconductor laser elements, and photodiodes. Devices equipped with these electronic components are suitable for use as, for example, backlights for liquid crystal displays and the like, light-emitting portions in operation buttons of small information terminals, automotive or decorative lighting, deep ultraviolet LEDs for sterilization purposes, etc., laser portions of 3D distance measuring sensors, and other light sources.

[0142] In this case, it is preferable that at least one surface of the cover member in the hermetically sealed package is made of an inorganic material that is a light-transmitting material.

[0143] Depending on the application of the device, the device may be provided with a system capable of detecting cracks in the cover member. An example of such a system is a cover member having an inverted concave cross section, a conductive film on at least a partial area of ​​the upper wall portion, and a metal conductor penetrating the side wall portion, such that the conductive film and the metal conductor are electrically connected to each other.

[0144] In all-solid-state batteries, in the case of secondary batteries that use alkaline ions, such as lithium-ion secondary batteries, two types of electrolytes are mainly used: oxide solid electrolytes and sulfide solid electrolytes. When these are used for applications such as vehicle backup power sources, high water resistance is required, and a package that can be sealed airtight may be necessary. In addition, sulfide solid electrolytes react with moisture to produce toxic gases, so higher airtightness is required. EXAMPLES

[0145] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these. Examples 1, 2, and 7 are examples, and Examples 3 to 6 are comparative examples.

[0146] Test Example Example 1: As a cover member, a flat glass plate made of borosilicate glass (AN-100, manufactured by AGC Inc., glass transition temperature 710°C) having dimensions of 50 mm x 50 mm x 0.3 mmt was prepared. The glass transition temperature Tg of this glass is 710°C. Next, a coating composition for a sealing base film was prepared. Specifically, Au powder: bismuth-based low melting point glass powder (AGC Corporation, ASF-4001B, glass transition temperature 406°C) was mixed to be 95:5 (mass ratio), and dispersed in a vehicle (Nissin Chemical Industry Co., Ltd., EC-200 FTR) so that the solid content concentration was 70% in mass percentage, and then kneaded in a ceramic mortar for 1 hour, and further dispersed three times with a three-roll mill to mix. The solid content concentration of 70% in mass percentage means that the vehicle content was 30 parts by mass with respect to the total of 100 parts by mass of Au powder and bismuth-based low melting point glass powder. The coating composition was applied in a frame shape to the outer edge of one main surface of a glass plate serving as a cover member by screen printing (Microtech, MT-320TV), and the cover member with a sealing primer film was obtained by firing the cover member at 650° C. for 60 minutes in an air atmosphere. The frame formed by the sealing primer film was a rectangle with a width of 0.35 mm.

[0147] <Example 2, Example 5> A cover member with a sealing primer film was obtained in the same manner as in Example 1, except that the coating composition that would become the sealing primer film was baked at 600° C. (Example 2) or 500° C. (Example 5).

[0148] <Example 3, Example 4> A cover member with a sealing base film was obtained in the same manner as in Example 1, except that the coating composition for the sealing base film was made of Au powder and bismuth-based low-melting point glass powder (ASF-4001B, manufactured by AGC Corporation, glass transition temperature 406°C) in a mass ratio of 100:0 (Example 3) or 50:50 (Example 4), and the powder was dispersed in a vehicle (EC-200 FTR, manufactured by Nisshin Chemical Industry Co., Ltd.) so that the solid content concentration was 70% in mass percentage.

[0149] Example 6: A cover member with a sealing base film was obtained in the same manner as in Example 1, except that the coating composition for the sealing base film was Ag powder:borosilicate-based low-melting-point glass frit (manufactured by AGC, YFT-525G, glass transition temperature 585°C) = 95:5 (mass ratio), dispersed in a vehicle (manufactured by Nisshin Chemical Industry Co., Ltd., EC-200 FTR) so that the solid concentration was 70% in mass percentage, and that Ni / Pd / Au was plated onto the coating composition for the cover member as the plating layer.

[0150] Example 7: A cover member with a sealing base film was obtained in the same manner as in Example 1, except that a flat sapphire plate measuring 50 mm x 50 mm x 0.7 mmt was used as the cover member, and the coating composition that would become the sealing base film was fired at 800°C.

[0151] "evaluation" 〈Zygosity〉 For the cover members with sealing base films of Examples 1 to 7, cellophane tape was adhered to the surface of the sealing base film opposite the cover member side and then peeled off to evaluate the bonding strength between the sealing base film and the cover member. The results are shown in Table 1, where "◯" indicates that the sealing primer film remained bonded to the cover member even after the tape was peeled off, and that the bonding between the sealing primer film and the cover member was good, and "×" indicates that when the tape was peeled off, the sealing primer film peeled off from the cover member together with the tape, and that the bonding between the sealing primer film and the cover member was poor.

[0152] <Glass layer> The cover members with the sealing primer film of Examples 1 to 7 were cut to expose their cross sections, which were then observed with a scanning electron microscope (SEM) to observe the bonding surface between the sealing primer film and the cover member. Specifically, the sample was cut to expose the cross section, embedded in resin, and physically polished using various grit abrasive papers (Sankyo Rikagaku Co., Ltd., DCCD-RT) so that the cross section of the cover member with the sealing base film and the resin were on the same plane. The surface was then mirror-polished using a polishing buff (PRESI Co., Ltd., NT) and diamond paste (PRESI Co., Ltd., Diamond Stick and Lubricant Lub) and subjected to SEM observation.

[0153] 10 shows an SEM image of a cross section of the cover member with a sealing base film obtained in Example 1. It was confirmed that the sealing base film was formed in the order of a glass layer and a metal matrix layer from the cover member side, and that a glass phase and a metal phase existed in the metal matrix layer. The same structure was confirmed not only for Example 1, but also for Examples 2, 4, and 7. On the other hand, in the sealing primer film of Example 3, no glass layer was present, and no glass phase was present in the metal matrix layer. In the sealing primer film of Example 5, no glass layer was present, and only a metal matrix layer containing a glass phase and a metal phase was observed. In the sealing primer film of Example 6, the bismuth-based glass added as glass powder was dissolved by the Ni / Pd / Au plating, and the adhesion between the sealing primer film and the cover member was reduced.

[0154] Next, for the cover members with the sealing base film of Examples 1, 2, 4, 5, and 7, the thickness of the glass layer was measured using a cross-sectional SEM image at a magnification of 2000 times within a range of 45 μm×30 μm. Specifically, as described above, an arbitrary side of the sealing base film formed in a frame shape was selected, and a total of three points were selected, including both ends or their vicinity, and the center or their vicinity. That is, three measurement points of 45 μm×30 μm were selected, and the thickness of the glass layer was measured at nine points per measurement object, for a total of 27 points, and the average thickness was taken as the average thickness of the glass layer. The results are shown in Table 1. Note that measurements could not be made for Examples 3 and 6, and therefore they are indicated as "-" in Table 1.

[0155] In addition, the average area ratio of the glass phase 22b in the metal matrix layer 22 was determined using cross-sectional SEM images for the cover members with the sealing base film of Examples 1, 2, 5, and 7. Specifically, as described above, the measurement target was an area of ​​5 μm×30 μm. Since the frame on which the sealing base film is formed is rectangular, i.e., has four sides, the measurement target was a total of eight points, one point near the outer edge of the central region of each of the four sides, and one point near the middle between the outer edge and the inner edge. The cross-sectional SEM images of eight locations in the range of 5 μm×30 μm obtained by SEM observation were subjected to image processing by the method described above, and a first histogram was obtained with the horizontal axis being brightness (unitless). Then, the cross-sectional SEM images were further binarized and inverted using the threshold value obtained from the first histogram to obtain cross-sectional SEM images and a second histogram. The area within the outline of this approximately ellipse was calculated to obtain the area of ​​the glass phase by regarding the peak brightness different from the brightness of the most frequent value in the second histogram as the glass phase. The number of pixels obtained by such calculation was divided by the total number of pixels in the range of 5 μm×30 μm to obtain the area ratio occupied by the glass phase. The average of the area ratios of the above eight locations obtained in the same manner was used as the average area ratio occupied by the glass phase in the metal matrix layer. The results are shown in Table 1. Note that since Example 4 was not measured, and Example 3 could not be measured, they are indicated as "-" in Table 1.

[0156] Furthermore, the thickness of the metal matrix layer was determined by averaging the thicknesses of a total of 27 points in an area of ​​45 μm × 30 μm at a magnification of 2000 times using a cross-sectional SEM image in the same manner as for the thickness of the glass layer. The results are shown in Table 1.

[0157] <Sealability> As a substrate, an LTCC (GCHP (registered trademark) manufactured by AGC Corporation) with a cavity structure of 6 mm x 6 mm x 1.4 mmt was prepared. The substrate had a multi-stage cavity structure with an element mounting section and a cover member mounting section. An electrolytic NiAu plating process was applied to the outer edge of the cover member mounting section so as to form a frame shape with a width of 0.55 mm, forming a metal film made of nickel with a thickness of 5 to 25 μm and gold with a thickness of 0.2 μm or more. On the other hand, a gold-tin solder was applied in a frame shape as a sealing material onto the surface of the sealing base film of the cover members with sealing base film of Examples 1, 2, 4, 5, and 7. The melting point of the gold-tin solder is 278°C. The sealing material of the cover member with sealing material was then placed on the substrate so that the sealing material was in contact with the metal film formed on the substrate, and the substrate was heated in a nitrogen atmosphere at 300°C for 1 minute, and then heated in air at 270°C for 1 minute, and then naturally cooled to room temperature. This resulted in a hermetically sealed package in which the cover member with sealing base film and the substrate were integrated via the metal-containing sealing material.

[0158] The obtained hermetically sealed package was subjected to a helium (He) leak test by a bombing method in accordance with JIS Z 2331:2006. Specifically, helium was pressurized at 5 kN for 2 hours, and then the helium leak rate was determined using a leak detector (Varian, 959Turbo). The results are shown in Table 1. "○" means that the helium leak rate was 1.0×10 ―8 Pa·m 3 / sec or less, indicating good sealing performance, and "x" indicates a helium leak rate of 1.0×10 ―8 Pa·m 3 / sec, indicating poor sealing.

[0159] [Table 1]

[0160] From the above results, the cover member with sealing base film according to this embodiment, and the cover member with sealing material and hermetically sealed package using the same have high hermetic sealing properties. In addition, since the cover member can be metallized by forming a sealing base film on it using a coating method, it is low cost and has excellent mass productivity. The effects of the present invention are preferably achieved not only when the cover member is made of glass material as in Examples 1 and 2, but also when it is made of sapphire as in Example 7.

[0161] On the other hand, as shown in Examples 3 and 5, when the sealing base film does not have a glass layer, the bonding between the sealing base film and the cover member is poor. Among them, in Example 5, the firing temperature of the sealing base film is too low to form a glass layer, but a glass phase exists in the metal matrix layer in the sealing base film. However, it was found that good bonding cannot be achieved only by the presence of a glass phase in the metal matrix layer, and good bonding can be achieved by the presence of a glass layer. In addition, the low firing temperature results in insufficient bonding between particles of the metal phase, poor wettability of the sealing material, and good airtight sealing cannot be achieved.

[0162] Moreover, as shown in Example 4, if the glass layer is too thick, the wettability of the sealing material is poor, and good airtight sealing cannot be achieved. Furthermore, as shown in Example 6, when an acidic plating layer is present, the glass constituting the glass phase in the sealing underlayer must be resistant to chemicals, and therefore it was suggested that gold, which does not need to have a plating layer, is preferable as the metal. [Explanation of symbols]

[0163] 1 Cover member 2 Base film for sealing 21 Glass layer 22 Metal matrix layer 22a Metal phase 22b Glass phase 3. Sealing materials containing metal 4. Board 10 Cover member with sealing base film 100 Cover member with sealing material 200 Hermetically sealed package

Claims

1. A cover member with a sealing base film, in which a sealing base film is formed in a partial area of ​​the cover member, The cover member is made of an inorganic material, The cover member is a flat plate having a pair of opposing main surfaces, the sealing base film is formed in a frame shape on one outer edge portion of the main surface; the sealing base film includes, in order from the cover member side, a glass layer and a metal matrix layer, The average thickness of the glass layer is more than 0 μm and not more than 10 μm, the metal matrix layer includes a metal phase and a glass phase; A cover member with a sealing underlayer, wherein the metal constituting the metal phase is at least one metal selected from the group consisting of gold, tin, antimony, silver and copper.

2. A cover member with a sealing base film, in which a sealing base film is formed in a partial area of ​​the cover member, The cover member is made of an inorganic material, The cover member has an inverted concave cross section having an upper wall portion, a side wall portion, and a lower opening portion, the sealing base film is formed in a frame shape on at least an outer edge portion of the bottom surface of the side wall portion, the sealing base film includes, in order from the cover member side, a glass layer and a metal matrix layer, The average thickness of the glass layer is more than 0 μm and not more than 10 μm, the metal matrix layer includes a metal phase and a glass phase; A cover member with a sealing underlayer, wherein the metal constituting the metal phase is at least one metal selected from the group consisting of gold, tin, antimony, silver and copper.

3. 3. The cover member with a sealing underlayer film according to claim 1, wherein an average area ratio of the glass phase in the metal matrix layer is 15% or less.

4. the inorganic material is a glass material, 3. The cover member with a sealing underlayer according to claim 1, wherein the glass transition temperatures of the glass in the glass layer and the glass phase are lower than the glass transition temperature of the glass material.

5. 5. The cover member with a sealing underlayer according to claim 4, wherein the glass material has a glass transition temperature of 700[deg.] C. or higher.

6. The glass material has a composition based on oxides of SiO ２ :50~75%, Al ２ O ３ : 0-25%, B ２ O ３ 5. The cover member with a sealing underlayer film according to claim 4, which satisfies the following: CaO: 0-20%, MgO: 0-20%, CaO: 0-20%, SrO: 0-20%, and MgO+CaO+SrO: 5-40%.

7. 3. The cover member with a sealing underlayer film according to claim 1, wherein the glass layer and the glass of the glass phase have a glass transition temperature of 450° C. or lower.

8. 3. The cover member with a sealing underlayer according to claim 1, wherein the metal constituting the metal phase is gold.

9. The glass of the glass layer and the glass phase has a composition based on oxides of Bi. ２ O ３ 3. The cover member with a sealing base film according to claim 1 or 2, wherein the content of the sealing base film is 50 to 90% by mass.

10. The glass of the glass layer and the glass phase has a composition based on oxides of Bi. ２ O ３ :70 to 90% by mass, ZnO: 1 to 20% by mass, and B ２ O ３ 10. The cover member with a sealing base film according to claim 9, wherein the content of the sealing base film satisfies 2 to 12 mass %.

11. 3. The cover member with a sealing underlayer according to claim 1, wherein the inorganic material is a ceramic material, quartz, or sapphire.

12. 3. The cover member with a sealing underlayer according to claim 1, wherein the inorganic material is a light-transmitting inorganic material.

13. 3. The cover member with a sealing underlayer film according to claim 1, wherein the metal matrix layer has a thickness of 5 to 30 μm.

14. 3. A cover member with a sealing base film according to claim 1 or 2, wherein a sealing material containing a metal is formed in a frame shape on a surface of the sealing base film opposite to the side in contact with the cover member.

15. 3. A hermetically sealed package comprising the cover member with the sealing underlayer according to claim 1 or 2 and a substrate, the cover member being integrated with a sealing material containing a metal.

16. A device comprising an electronic component or an all-solid-state battery provided on the substrate in the hermetically sealed package according to claim 15 and hermetically sealed.

17. A method for manufacturing a cover member with a sealing base film, the cover member being hermetically sealed to a substrate via a sealing material containing a metal, comprising: As the cover member, a flat plate-shaped inorganic material having a pair of opposing main surfaces or an inverted concave cross-sectional shape having an upper wall portion, a side wall portion and a lower opening portion is prepared; and applying a metal paste in a frame shape to at least a region of the inorganic material that is in contact with the sealing material containing the metal, and firing the metal paste to form a sealing base film; The metal paste contains at least one metal selected from the group consisting of gold, tin, antimony, silver, and copper, glass powder, and a vehicle; In the metal paste, the content of the glass powder with respect to the total of the metal and the glass powder is 1 to 40 mass %, The method for producing a cover member with a sealing base film, wherein the firing is carried out at a temperature 150° C. or more higher than the glass transition temperature of the glass powder.

18. 18. The method for producing a cover member with a sealing underlayer according to claim 17, wherein the glass powder in the metal paste has a glass transition temperature of 450° C. or lower.

19. The glass powder in the metal paste has a composition based on oxides of Bi. ２ O ３ 19. The method for producing a cover member with a sealing underlayer film according to claim 17 or 18, wherein the content of the sealing underlayer film is 50 to 90% by mass.

20. The glass powder in the metal paste has a composition based on oxides of Bi. ２ O ３ :70 to 90% by mass, ZnO: 1 to 20% by mass, and B ２ O ３ 20. The method for producing a cover member with a sealing underlayer film according to claim 19, wherein the content of the sealing underlayer is 2 to 12% by mass.

21. The method for producing a cover member with a sealing underlayer according to claim 17 or 18, wherein the metal in the metal paste is gold.

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