TW202335761A - Method of manufacturing joined assembly - Google Patents

Abstract

To provide a method of manufacturing a joined assembly wherein: by interposing a joining material between members to be joined and baking the joining material to form a conductive junction, the joining material can be inhibited from protruding from an end of the member upon making a joined assembly in which those members are joined together by the conductive junction. A method for making a joined assembly includes making a first laminate configured by layering a first member, a filmy baking material and a second member in this order, making a second laminate by heating the first laminate until the temperature thereof becomes a temperature (B) while keeping pressure applied in the layering direction on the first laminate at lower than 5 MPa, baking the filmy baking material by keeping the temperature of the second laminate at temperature (B)-5 DEG C or higher while maintaining pressure applied in the layering direction on the second laminate at 5 MPa or higher so as to form a metal sintered layer.

Description

Manufacturing method of joint body

The present invention relates to a method for manufacturing a joint body. This application claims priority based on Japanese Patent Application No. 2021-150994 filed in Japan on September 16, 2021, and the contents of this application are cited in this article.

As a method of joining members to each other via a conductive joining portion (conductive joining portion), a method is known in which a joining material containing metal particles and a binder is interposed between members to be joined, and These members and the bonding material are heated while being pressed, and the bonding material is fired, thereby forming a conductive bonding portion. According to this method, by firing the bonding material, the binder is decomposed, and the metal particles are in close contact with each other to form a conductive bonding portion, thereby bonding the components to each other, thereby joining the components to each other.

This method of joining members to each other can be used, for example, to manufacture electric semiconductor devices (power devices). Semiconductor elements for power are used under high voltage and high current. In recent years, as automobiles, air conditioners, computers, etc. have become higher voltage and higher current, there are many opportunities to be mounted on these devices. Regarding such a power semiconductor element, heat generation from the semiconductor element is likely to be a problem, but the conductive joint portion has excellent heat dissipation properties and can sufficiently dissipate heat without providing a heat sink around the semiconductor element.

As a method of joining members to each other through a conductive joint, for example, a method has been disclosed in which a joining material containing silver nanoparticles, silver carbonate or silver oxide, and carboxylic acid containing crystals is used, and the joining material is held on the member. The members are joined to each other by firing the joining material while pressing the members and the joining material (see Patent Document 1). In this method disclosed in Patent Document 1, in order to obtain necessary joint strength between members, the pressure during pressurization is set. Specifically, the pressure during pressurization is set to 20 MPa. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2009-279649.

[Problem to be solved by the invention]

On the other hand, there is a problem that when the joining material is fired while pressing the members and the joining material together, the softened joining material may come out of the ends of the components during the heating process during firing. Oozing. If the thus softened joint material bleeds out, the thickness of the finally formed sintered portion, that is, the thickness of the conductive joint portion will be thinner than the target value. As a result, the joint strength of the members will decrease. Furthermore, the bonding method disclosed in Patent Document 1 cannot solve this problem.

The object of the present invention is to provide a method for manufacturing a joined body, which interposes a joining material between components to be joined, and sinters the joining material to form a conductive joining portion, thereby manufacturing these components through conductive joining. When the components are joined together, the joining material can be prevented from seeping out from the ends of the components. [Means used to solve problems]

The present invention provides a method for manufacturing a joined body. The joining system includes a first member, a metal sintered layer, and a second member, and the first member and the second member are joined by the metal sintered layer. The aforementioned manufacturing method The method includes: step (I) of producing a first laminated body, the first laminated system, the first member, the film-like fired material used to form the metal sintered layer, and the second member in sequence according to the thickness of these layers. The step (II) is to set the pressure applied to the first laminated body in the lamination direction of the first member, the film-like fired material, and the second member to less than 5 MPa. , and simultaneously heating the first laminated body until the temperature of the first laminated body reaches temperature (B), thereby producing a second laminated body; and step (III) is to heat the aforementioned second laminated body in the aforementioned lamination direction. The pressure applied above is 5 MPa or more, and the temperature of the second laminated body is set to the temperature (B) - 5°C or more, whereby the film-shaped fired material is fired to form the metal sintered layer, Thus, the above-mentioned joined body is produced.

In the manufacturing method of the joint body of the present invention, it is also possible to prepare a film-like fired material with a support sheet made of the aforementioned film-shaped fired material provided on one side of the support sheet, and then prepare an undivided film-like fired material. Component; the aforementioned supporting sheet is provided with a base film and an adhesive layer provided on one side of the aforementioned base film; in the aforementioned film-shaped fired material with the supporting sheet, the aforementioned film-shaped fired material is provided on the aforementioned adhesive layer on the surface opposite to the base film side; the undivided member is divided into the second member; and the film-shaped fired material in the film-shaped fired material with the supporting sheet is The opposite side of the supporting sheet is attached to the undivided member, thereby producing an undivided laminated body composed of the film-like fired material having the supporting sheet and the undivided member laminated, and the undivided laminated body is The aforementioned undivided member is divided to produce the aforementioned second member, and the aforementioned film-like fired material is cut to produce the aforementioned second member on the aforementioned support sheet, and a cutout provided on one side of the aforementioned second member. The second member with the film-like fired material made of the cut film-shaped fired material is peeled off from the aforementioned support sheet, and then the aforementioned second member with the film-shaped fired material is peeled off. The surface of the film-shaped fired material in the second member that is opposite to the second member side is attached to the first member, whereby the aforementioned step (I) is performed. In the manufacturing method of the joint body of the present invention, the adhesive layer may be energy ray hardenable. After the adhesive layer is hardened by irradiating energy rays, the second member having the film-like fired material is removed from the The hardened material of the adhesive layer peels off. [Invention effect]

According to the present invention, a method for manufacturing a joined body is provided. A joining material is interposed between components to be joined, and the joining material is fired to form a conductive joining portion, whereby the components are manufactured through the conductive joining portion. When the joint body is formed by joining, the joint material can be prevented from seeping out from the ends of the components.

Manufacturing method of joint body In the manufacturing method of a joined body according to one embodiment of the present invention, the joining system includes a first member, a metal sintered layer, and a second member, and the first member and the second member are joined by the metal sintered layer. Composition; the aforementioned manufacturing method includes: step (I), which is to produce a first laminated body, the aforementioned first laminated system, the aforementioned first component, the film-like fired material used to form the aforementioned metal sintered layer, and the aforementioned second component in this order These layers are laminated in the thickness direction; step (II) involves applying pressure to the first laminated body in the lamination direction of the first member, the film-like fired material, and the second member. is less than 5 MPa, while heating the first laminated body until the temperature of the first laminated body reaches temperature (B), thereby producing a second laminated body; and step (III) is to heat the aforementioned second laminated body The pressure exerted on the body in the lamination direction is set to 5 MPa or more, and the temperature of the second laminated body is set to above temperature (B) - 5°C or more, whereby the film-shaped fired material is fired to form The aforementioned metal layer is sintered to produce the aforementioned joint body.

According to the manufacturing method of the joined body of this embodiment, by performing the aforementioned step (I) (interposing the aforementioned film-like fired material between the aforementioned first member and the aforementioned second member of the bonded object to form a metal sintered layer , prepare a laminate of these layers, that is, the aforementioned first laminate), and use the aforementioned first laminate to perform the aforementioned steps (II) and (III), thereby performing the aforementioned step (II) and step (III) , the film-like fired material can be suppressed from seeping out from the ends of the first member and the second member. As a result, in the obtained joint body, the metal sintered layer can be suppressed from exuding from the ends of the first member and the second member, so that the joint strength of the first member and the second member is sufficiently high.

In this specification, the "pressure" applied to the first laminated body or the second laminated body means "in the lamination direction of the first member, the film-shaped fired material, and the second member, unless otherwise specified." the pressure exerted."

Hereinafter, the present invention will be described in detail with reference to the drawings. In addition, in the drawings used in the following description, in order to make it easier to understand the characteristics of the present invention and for the sake of convenience, the main parts are sometimes enlarged and shown, and the dimensional ratio of each component is not necessarily the same as the actual one. .

[joint body] First, the joined body obtained by the manufacturing method of this embodiment is demonstrated. FIG. 1 is a cross-sectional view schematically showing an example of the aforementioned joint body. The joint body 101 shown here includes a first member 9 , a metal sintered layer 10 , and a second member 8 , and the first member 9 and the second member 8 are joined by the metal sintered layer 10 .

The first member 9 is not particularly limited as long as it is a joint object of the metal sintered layer 10 . More specifically, the first member 9 may include a substrate or the like, and may include a substrate or the like used in the field of semiconductor devices.

The second member 8 is not particularly limited as long as it is a bonding target of the metal sintered layer 10 . More specifically, examples of the second member 8 include various wafers such as semiconductor wafers.

In order to improve the bonding strength with the metal sintered layer 10, a metal film such as a silver film may be provided on the surface of the second member 8 on the metal sintered layer 10 side (that is, the joint surface). That is, the second member 8 may have a multilayer structure in which the metal film is provided on one side of the second member 8, and the metal film in the second member 8 may be in contact with the metal sintered layer 10, thereby being in contact with the metal sintered layer 10. 1 member 9 joins.

The metal sintered layer 10 is composed of a sintered body, and the sintered system is formed by melting and combining sinterable metal particles with each other. The metal sintered layer 10 can be formed, for example, by firing a film-like fired material containing sinterable metal particles and a binder component that is solid at 25°C.

The first member 9 , the second member 8 and the metal sintered layer 10 may each be composed of one layer (single layer) or may be composed of two or more multiple layers. When composed of multiple layers, these multiple layers may be the same as each other. However, the combination of these multiple layers is not particularly limited.

In this specification, it is not limited to the case of the first member 9, the second member 8, and the metal sintered layer 10. The so-called "multiple layers may be the same or different from each other" means "all the layers may be the same, or all the layers may be different. Only some of the layers may be the same." Furthermore, "multiple layers may be different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other."

The thickness of the first member 9 can be set arbitrarily according to the purpose and is not particularly limited. The thickness of the first member 9 is, for example, preferably 100 μm to 2000 μm, more preferably 200 μm to 1700 μm. Here, the "thickness of the first member 9" means the thickness of the entire first member 9. For example, the thickness of the first member 9 composed of multiple layers means the total of all the layers constituting the first member 9. thickness.

In this specification, the "thickness" is not limited to the case of the first member. Unless otherwise specified, it can be the average value of the thickness measured at 5 randomly selected parts of the object, using constant pressure in accordance with JIS K7130. Thickness measuring instrument.

The thickness of the second member 8 can be set arbitrarily according to the purpose and is not particularly limited. The thickness of the second member 8 is, for example, preferably 100 μm to 1000 μm, more preferably 200 μm to 600 μm. Here, the "thickness of the second member 8" means the thickness of the entire second member 8. For example, the thickness of the second member 8 composed of multiple layers means the total of all the layers constituting the second member 8. thickness. Therefore, when the second member 8 has the aforementioned metal film, the thickness of the second member 8 shown here is the total thickness including the metal film.

When the second member 8 is provided with the metal film, the thickness of the metal film is preferably 0.1 μm to 2 μm, more preferably 0.2 μm to 1 μm.

The thickness of the metal sintered layer 10 can be set arbitrarily according to the purpose and is not particularly limited. The thickness of the metal sintered layer 10 is, for example, preferably 12 μm to 40 μm, more preferably 14 μm to 38 μm. The metal sintered layer 10 with such a thickness can more stably suppress seepage from the ends of the first member 9 and the second member 8 (essentially the ends of the second member 8), and achieve a more stable function between the first member 9 and the second member 8. Both of the members 8 have sufficiently high joint strength. In addition, the joint body 101 having the metal sintered layer 10 having such a thickness is particularly suitable as a member constituting an electric semiconductor element (power element), for example. Here, the "thickness of the metal sintered layer 10" means the thickness of the entire metal sintered layer 10. For example, the thickness of the metal sintered layer 10 composed of multiple layers means the total of all the layers constituting the metal sintered layer 10. thickness.

In the joint body 101, the exudation amount of the metal sintered layer 10 from the end of the second member 8 is preferably 0.5 mm or less, for example, and may be either 0.4 mm or less or 0.2 mm or less. In particular, when the thickness of the metal sintered layer 10 is in the above numerical range (for example, 12 μm to 40 μm), the joint 101 in which the bleed-out of the metal sintered layer 10 is suppressed can be easily obtained. In addition, here, the bleeding amount of the metal sintered layer 10 is calculated based on the end of the second member 8. However, the standard for calculating the bleeding amount of the metal sintered layer can be appropriately selected according to the structure of the joint body, and the second member can also be used. 1 Calculated based on the end of the member.

In the joint body 101, if the bleeding of the metal sintered layer 10 is suppressed, the metal sintered layer 10 can be prevented from being thinner than necessary. As a result, the joint strength of the first member 9 and the second member 8 is sufficiently high. In particular, when the joint body 101 is subjected to a temperature cycle test (Temperature Cycling Test, sometimes referred to as "TCT" in this specification), that is, when the joint body 101 is forced to repeatedly cool and heat over time, the temperature after the TCT The joint strength of the first member 9 and the second member 8 is not significantly reduced compared to the joint strength of the first member 9 and the second member 8 without TCT, and is completely different from the previous joint in this respect.

The degree of bonding strength between the first member 9 and the second member 8 in the bonded body 101 can be judged using, for example, the shear strength of the bonded body 101 as an index.

The shear strength of the bonded body 101 that has not been subjected to TCT can be measured, for example, by the following method. That is, at normal temperature, as shown in FIG. 2 , at the position where the outer periphery (side surface) 10 c of the metal sintered layer 10 and the outer periphery (side surface) 8 c of the second member 8 are aligned with each other in the joint body 101 , at the same time, along the direction relative to the second member A force is applied at a speed of 200 μm/s in a direction parallel to the surface 8 (the surface opposite to the first member 9 side) 8a (here, the arrow P direction). This direction is synonymous with "a direction parallel to the surface 9 a of the first member 9 on the second member 8 side", for example. When a force is applied to the above-mentioned portion, for example, a metal plate-shaped pressing mechanism 7 is used, and the force is applied to the above-mentioned portion via the pressing mechanism 7, whereby the joint strength can be measured easily and with higher accuracy. The pressing mechanism 7 is arranged so that the front end of the pressing mechanism 7 on the first member 9 side does not contact the first member 9 . Then, the maximum value of the force applied until the metal sintered layer 10 is destroyed or the metal sintered layer 10 is peeled off from the first member 9 or the second member 8 is measured, and the measured value is used as the shear strength of the joint body 101 .

In this specification, "normal temperature" means a temperature that is not particularly cold or hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C.

The shear strength of the joint body 101 without TCT is preferably 40 MPa or more, more preferably 48 MPa or more, and may be any one of 56 MPa or more, 64 MPa or more, 72 MPa or more, and 80 MPa or more. The upper limit of the shear strength is not particularly limited. For example, in order to make the joint body 101 easier to manufacture, the shear strength is preferably 150 MPa or less, more preferably 95 MPa or less.

The shear strength of the bonded body 101 after TCT can also be measured by the same method as the shear strength of the bonded body 101 without TCT.

The shear strength of the joint body 101 after TCT is preferably 20 MPa or more, more preferably 40 MPa or more, for example, it can be any one of 50 MPa or more, 60 MPa or more, 70 MPa or more, and 80 MPa or more. The upper limit of the shear strength is not particularly limited. For example, in order to make the joint body 101 easier to manufacture, the shear strength is preferably 150 MPa or less, more preferably 95 MPa or less.

The joined body obtained by the manufacturing method of this embodiment is not limited to the joined body shown in FIG. 1 , and part of the structure of the joined body shown in FIG. 1 may be changed or deleted within the scope that does not impair the effects of the present invention. , or further add other structures to the joint described above. For example, the aforementioned joint body may include other elements that are not any of the first member, the metal sintered layer, and the second member.

[Film-like fired material] The film-like fired material is the material for forming the aforementioned metal sintered layer. Examples of the film-shaped fired material include materials containing sinterable metal particles and a binder component that is solid at 25°C.

[Sintered metal particles] By heat-treating the film-shaped fired material at a temperature higher than the melting point of the sintered metal particles, the sintered metal particles are melted and combined with each other to form a metal sintered layer (sintered body). By forming the metal sintered layer, the metal sintered layer is sintered and joined to the component that is fired in contact with the metal sintered layer. In this embodiment, the first member and the second member are joined via a metal sintered layer. Sinterable metal particles are easier to sinter than non-sinterable metal particles described below.

Examples of the metal species of the sinterable metal particles include silver, gold, copper, iron, nickel, aluminum, silicon, palladium, platinum, titanium, and barium. Examples of sinterable metal particles include particles of metals of these metal species, particles of oxides of one or more of the aforementioned metals, particles of alloys of one or more of the aforementioned metals, and the like. Examples of oxides of two or more of the aforementioned metals include barium titanate. Among these, preferred sinterable metal particles include silver particles and silver oxide particles.

The film-like fired material may contain only one type of sinterable metal particles or two or more types. In the case of two or more types, the combination and ratio of these sintered metal particles can be selected arbitrarily.

In this specification, "sinterable metal particles" specifically mean particles containing a metal element with a particle diameter of 100 nm or less. The particle diameter of the sinterable metal particles is not particularly limited as long as it is 100 nm or less and can exhibit the above-mentioned sinterability. For example, it may be either 50 nm or less and 30 nm or less. Sinterable metal particles with such a particle size have higher sinterability.

In this specification, the "particle diameter of metal particles" refers to the projected area circle equivalent diameter of the particle diameter of metal particles observed with an electron microscope. That is, when the shape of the observed image of the metal particles is a circle, the particle size of the metal particles refers to the diameter of the circle. When the shape of the observed image of the metal particles is other than a circle, the particle diameter of the metal particles refers to the diameter of a circle with the same area as the area of the image.

Among the sinterable metal particles, the number average of the particle diameter calculated for particles whose particle diameter is observed by an electron microscope and whose projected area circle equivalent diameter is 100 nm or less can be, for example, 0.1 nm to 95 nm, 0.3 Any of nm to 50nm and 0.5nm to 30nm. At this time, the metal particles to be measured are 100 or more metal particles randomly selected from each piece of the film-shaped fired material. For example, the metal particles to be measured may be 100 metal particles randomly selected from each piece of the film-shaped fired material.

The film-shaped fired material of this embodiment may also contain metal particles with a particle diameter of 100 nm or less (that is, sinterable metal particles), and metal particles with a particle diameter exceeding 100 nm that are not the aforementioned metal particles (in this specification, sometimes Called "non-sintered metal particles").

In this specification, "non-sintered metal particles" specifically mean particles containing a metal element with a particle diameter exceeding 100 nm.

Among non-sintered metal particles, the number average particle diameter calculated for particles whose particle diameter is observed by an electron microscope and whose projected area circle equivalent diameter exceeds 100 nm may be, for example, from more than 150 nm to less than 50,000 nm. Any of 150nm to 10000nm and 180nm to 5000nm. At this time, the metal particles to be measured are 100 or more metal particles randomly selected from each piece of the film-shaped fired material. For example, the metal particles to be measured may be 100 metal particles randomly selected from each piece of the film-shaped fired material.

Examples of the metal species of the non-sintered metal particles include the same metal species as those exemplified as the metal species of the sintered metal particles. Preferable non-sintered metal particles include silver particles, copper particles, silver oxide particles, and copper oxide particles.

The film-like fired material may contain only one type of non-sintered metal particles or two or more types. In the case of two or more types, the combination and ratio of these non-sintered metal particles can be selected arbitrarily.

In the film-shaped fired material, the metal species of the sinterable metal particles and the metal species of the non-sintered metal particles may be the same or different from each other. For example, the film-like fired material may contain silver particles as sinterable metal particles, and silver particles or silver oxide particles as non-sinterable metal particles. In addition, for example, the film-shaped fired material may contain silver particles or silver oxide particles as sinterable metal particles, and copper particles or copper oxide particles as non-sinterable metal particles.

The ratio of the content of the sinterable metal particles in the film-shaped fired material to the total content of the metal particles (in other words, the total content of the sintered metal particles and the non-sintered metal particles) may be, for example, 10% by mass to 100% by mass, and any one from 20 mass% to 95 mass%.

In the film-shaped fired material, either or both of the sintered metal particles and the non-sintered metal particles may be coated with an organic substance on the surface of the particles. The mutual solubility between the sintered metal particles and non-sintered metal particles coated with organic matter and the binder component is improved, and the aggregation of the particles is further suppressed, allowing for more uniform dispersion. When the surface of the sintered metal particles or non-sintered metal particles is coated with an organic substance, the mass of the sintered metal particles or non-sintered metal particles is a value including the organic substance.

[Binder ingredient] The aforementioned binder component is solid at 25° C., and the film-shaped fired material contains the binder component, thereby maintaining the film-like shape and thereby having adhesiveness. The binder component may be a thermally decomposable component that thermally decomposes when the film-shaped fired material is fired (during heat treatment).

In this specification, the so-called "liquid" means a state in which the viscosity can be measured using a B-type viscometer at a temperature of 25°C. The so-called "solid" means a state in which the viscosity cannot be measured using a B-type viscometer at a temperature of 25°C.

The binder components are not particularly limited as long as the effects of the present invention can be obtained. Preferred binder components include, for example, resin. Examples of the resin include acrylic resin, polycarbonate, polylactic acid, polymers of cellulose derivatives, and the like, and acrylic resin is more preferred. Examples of the acrylic resin include: homopolymers of one (meth)acrylate compound; copolymers of two or more (meth)acrylate compounds; one or more (meth)acrylate compounds; ) Copolymers of acrylate compounds and one or more other copolymerizable monomers other than the aforementioned compounds, etc.

In this specification, the concept of "(meth)acrylate" includes both "acrylate" and "methacrylate". The same applies to terms similar to (meth)acrylate. For example, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid".

In the aforementioned acrylic resin, the ratio of the amount (parts by mass) of the structural units derived from the (meth)acrylate compound to the total amount (parts by mass) of the structural units is preferably 50% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass. Preferably, it is 80 mass % to 100 mass %, and further more preferably, it is 90 mass % to 100 mass %.

Examples of the (meth)acrylate compound include: (methyl)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate (Basic) n-butyl acrylate, (meth)isobutyl acrylate, (meth)acrylic acid second butyl ester, (meth)acrylic acid third butyl ester, (meth)acrylic acid n-pentyl ester, (meth)acrylic acid Isoamyl ester, hexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, (meth)acrylate ) Lauryl acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, myristyl (meth)acrylate (myristyl acrylate), ( Pentadecyl methacrylate, cetyl (meth)acrylate (palm ester (meth)acrylate), heptadecyl (meth)acrylate, n-octadecyl (meth)acrylate The alkyl group constituting the alkyl ester (stearyl (meth)acrylate), isostearyl (meth)acrylate (isostearyl (meth)acrylate), etc. has a carbon number of 1 to 18 The chain structure of alkyl (meth)acrylate; hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid (Meth)hydroxyalkyl acrylates such as 3-hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; ( Phenoxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate and other phenoxyalkyl acrylates; 2-methoxyethyl (meth)acrylate Ester, 2-ethoxyethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-methoxy(meth)acrylate Alkoxyalkyl (meth)acrylates such as butyl ester; polyethylene glycol mono(meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxy poly Polyalkylene glycol (meth)acrylate such as propylene glycol (meth)acrylate, ethoxy polypropylene glycol (meth)acrylate, nonylphenoxy polypropylene glycol (meth)acrylate; (meth)acrylate ) Cyclohexyl acrylate, 4-butylcyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentadienyl (meth)acrylate (Meth)acrylic acid cycloalkyl esters such as alkenyl ester, (meth)bornyl acrylate, (meth)isobornyl acrylate, (meth)acrylic acid tricyclodecyl ester, etc.; (meth)acrylic acid benzyl ester, etc. ( Aralkyl methacrylate; tetrahydrofuran (meth)acrylate, etc.

The (meth)acrylate compound is preferably alkyl (meth)acrylate or alkoxyalkyl (meth)acrylate, more preferably butyl (meth)acrylate or 2-ethyl (meth)acrylate. ylhexyl ester, dodecyl (meth)acrylate, isodecyl (meth)acrylate or 2-ethoxyethyl (meth)acrylate, and more preferably 2-ethyl (meth)acrylate Hexyl ester, particularly 2-ethylhexyl methacrylate.

The acrylic resin preferably has a structural unit derived from a methacrylate compound. The film-shaped fired material containing such an acrylic resin as a binder component can be fired at a relatively low temperature, and a metal sintered layer having sufficient bonding strength can be easily obtained.

The other copolymerizable monomer is not particularly limited as long as it is a compound copolymerizable with the (meth)acrylate compound. Examples of the other copolymerizable monomers include: (meth)acrylic acid, vinyl benzoic acid (ethylidene benzoic acid), maleic acid, and vinyl phthalic acid (ethylidene phthalic acid). Formic acid) and other unsaturated carboxylic acids (carboxylic acids with unsaturated bonds); vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methylstyrene, butadiene, isoprene and other vinyl-containing free radical polymerizable compounds.

The weight average molecular weight (Mw) of the resin as a binder component is preferably 10,000 to 1,000,000, more preferably 10,000 to 800,000. When the weight average molecular weight of the resin is within this range, the film strength and flexibility of the film-shaped fired material become higher.

In this specification, the "weight average molecular weight" refers to the polystyrene-converted value measured by gel permeation chromatography (GPC; Gel Permeation Chromatography) unless otherwise specified.

The glass transition temperature (Tg) of the resin as a binder component is preferably -60°C to 50°C, more preferably -30°C to 10°C, and further preferably -20°C to less than 0°C. When the Tg of the resin is below the upper limit, the flexibility of the film-shaped fired material becomes higher, and the adhesive force of the film-shaped fired material to the adherend (the first member, the second member) becomes higher. Got higher. When the Tg of the resin is equal to or higher than the lower limit, the film shape of the film-shaped fired material can be more easily maintained, and the film-shaped fired material can be more easily separated from a support sheet or the like described below.

The glass transition temperature (Tg) of the resin mentioned above as a binder component can be calculated using the Fox formula. The Tg of the resin described in this specification is a value calculated using the Fox formula unless otherwise specified, regardless of whether the resin is the aforementioned binder component. For the glass transition temperature (Tg) of the homopolymer of each monomer in the Fox formula mentioned above, the value described in polymer materials, manuals, adhesive manuals, etc. can be used.

The film-like fired material may contain only one type of binder component, or may contain two or more types. In the case of two or more types, the combination and ratio of these binder components can be selected arbitrarily.

The fact that the binder component is thermally decomposed during the firing (during heat treatment) of the film-shaped fired material can be confirmed, for example, by the mass decrease of the binder component during firing. In this embodiment, when the film-shaped fired material is fired, all the binder components may be thermally decomposed, or part of the binder components may not be thermally decomposed. In this embodiment, the ratio of the amount (parts by mass) of the binder component after firing to the total amount (parts by mass) of the binder component before firing may be, for example, 10% by mass or less, 5% by mass or less, and Any content below 3% by mass may be 0% by mass.

The film-form fired material may contain other components that are not any of the sintered metal particles, non-sintered metal particles, and binder components within the range that does not impair the effects of the present invention.

Examples of the other components include liquid components, solvents, additives, and the like.

The aforementioned liquid component has a boiling point of 300°C to 450°C and is a liquid at 25°C. By making the film-shaped fired material contain such a liquid component, the adhesion force between the film-shaped fired material and the support sheet described below is sufficiently high, and the cutting property is excellent, and the liquid component is separated from the first member and the second member during firing. The leakage between them is inhibited.

In this specification, the so-called "boiling point" means the boiling point under normal pressure (101325 Pa).

The aforementioned solvent is a component whose boiling point does not reach 300°C and is liquid at 25°C. Examples of the solvent include water, organic solvents, and the like. The aforementioned solvent is a preferred component in terms of improving the workability of the fired material composition described later.

The aforementioned additives are not particularly limited. Examples of the additives include various additives known in the field such as dispersants, tackifiers, storage stabilizers, defoaming agents, thermal decomposition accelerators, and antioxidants.

The film-form fired material may contain only one type of other components mentioned above, or may contain two or more types. In the case of two or more types, the combination and ratio of these other components can be selected arbitrarily.

The content of the aforementioned other components in the film-shaped fired material is preferably 2 mass % or less, more preferably 1 mass % or less relative to the total mass of the film-shaped fired material.

The film-shaped fired material with a support sheet described later includes a film-shaped fired material and a support sheet provided on at least one side of the film-shaped fired material. In the aforementioned film-shaped fired material with a support sheet, it is preferable that the adhesion force (a2) of the aforementioned film-shaped fired material to the support sheet is less than the adhesion force (a1) of the aforementioned film-shaped fired material to the silicon wafer, and The aforementioned adhesive force (a1) is 0.1N/25mm or more, and the aforementioned adhesive force (a2) is 0.1N/25mm to 2N/25mm or 0.1N/25mm to 0.5N/25mm.

The aforementioned adhesive force (a1) can be measured by the following method. That is, a silicon wafer (for example, a silicon wafer with a diameter of 150 mm and a thickness of 500 μm manufactured by the Institute of Science and Technology Co., Ltd.) that is prepared to undergo chemical mechanical polishing until the arithmetic mean roughness (Ra) of the surface becomes 0.02 μm will have support The temperature of the film-shaped fired material among the film-shaped fired materials of the sheet was set to 50° C., and the film-shaped fired material was attached to the aforementioned processed surface of the aforementioned silicon wafer. Next, the support sheet was peeled off from the film-shaped fired material, and a polyethylene terephthalate film (PET film, thickness 12 μm) was attached to the exposed surface of the film-shaped fired material and firmly adhered (substrate ). Then, the laminate of the PET film and the film-shaped fired material is cut into a size of 25 mm in width and 100 mm in length to obtain a laminate composed of the film-shaped fired material and the PET film and attached to the silicon wafer. The layered body. Then, the obtained laminate is left for 20 minutes in an atmosphere with a temperature of 23°C and a relative humidity of 50%, and then a universal tensile testing machine (for example, "5581 type testing machine" manufactured by Instron) is used. According to JIS Z0237: In 2000, a 180° peel test was conducted. More specifically, the film-shaped fired material with the PET film substrate was peeled off from the silicon wafer together with the PET film at a peeling speed of 300 mm/min. At this time, the film-shaped fired material on the PET film substrate is peeled off along the length direction of the film-shaped fired material so that the contact surfaces of the silicon wafer and the film-shaped fired material are at an angle of 180° to each other. . Then, the load (peel force) in the 180° peel test was measured, and the measured value was used as the adhesive force (a1) (N/25mm).

The aforementioned adhesive force (a2) can be measured by the following method. That is, after leaving the film-shaped fired material with the supporting sheet in an atmosphere of 23°C and 50% relative humidity for 20 minutes, a universal tensile testing machine (for example, "5581 type testing machine" manufactured by Instron) is used. , according to JIS Z0237:2000, conduct 180° peel test. More specifically, a polyethylene terephthalate film (PET film, thickness 12 μm) is attached to the exposed surface of the film-like fired material with a supporting sheet, and the self-supporting sheet is attached The film-shaped fired material with the PET film is peeled off together with the PET film at a peeling speed of 300mm/min. At this time, the film-shaped fired material together with the PET film is peeled off along the longitudinal direction of the film-shaped fired material so that the contact surfaces of the support sheet and the film-shaped fired material are at an angle of 180°. Then, the load (peel force) in the 180° peel test was measured, and the measured value was used as the adhesive force (a2) (N/25mm).

Except that either the first member or the second member is used instead of the silicon wafer subjected to chemical mechanical polishing, the film-like fired material obtained by the same method as the measurement method of the above-mentioned adhesive force (a1) is used for the third member. The adhesive force of either the first member or the second member is preferably 0.1N/25mm or more, more preferably 0.5N/25mm or more, and further preferably 1.0N/25mm or more. By setting the adhesive force to be equal to or higher than the lower limit value, the film-like fired material has higher cutting suitability. In addition, when the first member and the second member are transported in a state where they are temporarily fixed by the film-shaped fired material before firing, positional deviation of the first member or the second member can be suppressed.

The above-mentioned adhesive force (a2) is preferably 0.1N/25mm to 0.5N/25mm, more preferably 0.2N/25mm to 0.5N/25mm, further preferably 0.2N/25mm to 0.4N/25mm. When the adhesive force (a2) is equal to or higher than the aforementioned lower limit, the film-shaped fired material has higher cutting suitability. When the adhesion force (a2) is less than the adhesion force (a1) and is less than the aforementioned upper limit, either the first member or the second member is divided (for example, in the case of a wafer, dicing). A laminate of a divided product obtained by singulation (for example, in the case of a wafer, a wafer) and a cut product of a film-like fired material (for example, in the case of a wafer, a film-shaped fired material) When the wafer) is peeled off from the supporting sheet, the film-like fired material is easily peeled off from the supporting sheet, and the laminate can be peeled off more easily.

[Composition of film-shaped fired material] The film-like fired material may be composed of sintered metal particles, a binder component, and the other components mentioned above, and the total content of these components may be 100% by mass. When the film-shaped fired material contains non-sintered metal particles, the film-shaped fired material may be composed of sintered metal particles, non-sintered metal particles, a binder component, and the other components mentioned above, and the total content of these components may be is 100% by mass.

In the film-like fired material, the ratio of the content of the sinterable metal particles to the total content of all components except components that are liquid at 25°C (sometimes referred to as "solid components" in this specification) is preferably 15 Mass% to 98 mass%, More preferably, it is 15 mass% to 95 mass%, More preferably, it is 20 mass% to 90 mass%. When the ratio is equal to or less than the upper limit, the content of the binder component in the film-shaped fired material can be sufficiently ensured, and therefore the film shape can be maintained more stably. When the ratio is equal to or higher than the lower limit, the fusion of the sintered metal particles or the sintered metal particles and the non-sintered metal particles further proceeds during firing, and the bonding strength of the bonded body becomes higher.

When the film-shaped fired material contains non-sintered metal particles, the ratio of the total content of the sintered metal particles and the non-sintered metal particles in the film-shaped fired material to the total content of the solid content is preferably 50 mass. % to 98 mass%, more preferably 70 mass% to 97 mass%, further preferably 80 mass% to 95 mass%.

The content of the binder component in the film-shaped fired material is preferably 2 to 50 mass%, more preferably 3 to 30 mass%, and still more preferably 5 mass% relative to the total solid content. to 20% by mass. When the ratio is below the upper limit, the content of the sinterable metal particles in the film-shaped fired material can be sufficiently ensured, and therefore the bonding strength between the film-shaped fired material and the first member or the second member is further improved. When the ratio is equal to or higher than the lower limit, the film shape of the film-like fired material can be maintained more stably.

In the film-shaped fired material, the ratio of [content of sinterable metal particles (parts by mass)]: [content of binder component (parts by mass)]) is preferably 50:1 to 1:1, more preferably 35 :1 to 2.5:1, more preferably 20:1 to 4:1. When the film-like fired material contains non-sintered metal particles, the ratio of [total content of sintered metal particles and non-sintered metal particles (parts by mass)]: [content of binder component (parts by mass)] is relatively Preferably it is 50:1 to 1:10, more preferably 35:1 to 1:4, and still more preferably 20:1 to 1:2.5.

In the film-shaped fired material, the content of the solvent (including a solvent with a relatively high boiling point) contained in the fired material composition described below is preferably 1 mass % or less relative to the total mass of the film-shaped fired material. .

The film-shaped fired material is film-shaped and therefore has excellent thickness stability.

The shape of the film-like fired material is not particularly limited as long as it is appropriately set according to the shape of the first member or the second member to be joined. In this specification, the "shape of the film-shaped fired material" means, unless otherwise specified, the film is viewed from above the side of the film-shaped fired material adhering to the first member or the second member. The shape of the material when it is fired (that is, the planar shape). The shape of the film-like fired material is preferably circular or rectangular, for example. The circular shape is a shape suitable for a case where the second member is a semiconductor wafer, for example. In this case, the film-shaped fired material and the second member (semiconductor wafer) have the same shape or substantially the same shape. For example, the rectangular shape is suitable for the case where the second member is a wafer. In this case, the film-shaped fired material and the second member (wafer) have the same shape or substantially the same shape.

When the shape of the film-like fired material is a circle, the area of the circle may be, for example, any one of 3.5 cm ² to 1600 cm ² and 85 cm ² to 1400 cm ² . When the shape of the film-like fired material is a rectangle, the area of the rectangle may be, for example, any one of 0.01 cm ² to 25 cm ² and 0.25 cm ² to 9 cm ² .

The film-shaped fired material may be a film-shaped fired material with a supporting sheet provided with a supporting sheet on at least one side of the film-shaped fired material. The film-shaped fired material with the support sheet will be described in detail later.

[Production method of film-shaped fired material] The film-shaped fired material can be formed using a fired material composition containing the constituent materials of the film-shaped fired material. The film-shaped fired material preferably contains a solvent. For example, by coating or printing the aforementioned fired material composition on the surface to be formed of the film-shaped fired material, and volatilizing the solvent if necessary, the film-shaped fired material can be formed at the target site. An example of the surface to be formed of the film-shaped fired material is the release-treated surface of the release film.

When the fired material composition contains a solvent, the fired material composition may contain only one type of solvent or two or more types. In the case of two or more types, the combination and ratio of these solvents may be Take your pick.

When applying the fired material composition, the solvent is preferably a solvent with a boiling point of less than 200°C. Examples of such a solvent include: n-hexane (boiling point 68°C), ethyl acetate (boiling point 77°C), 2-butanone (boiling point 80°C), n-heptane (boiling point 98°C), methylcyclohexane Alkane (boiling point 101°C), toluene (boiling point 111°C), acetyl acetone (boiling point 138°C), n-xylene (boiling point 139°C), dimethylformamide (boiling point 153°C), etc.

The firing material composition may be applied using a known method. The fired material composition can be coated, for example, by using the following various coaters: air knife coater, blade coater, rod coater, gravure coater, notched wheel coater (comma) coater) (registered trademark), roller coater, roller knife coater, curtain coater, die coater, knife coater, screen coater, Mayer rod coater, Light touch coater, etc.

When printing and firing the material composition, the aforementioned solvent only needs to be a solvent that can evaporate and dry after printing, preferably a solvent with a boiling point of 65°C to 280°C. Examples of such solvents with relatively high boiling points include the above-exemplified solvents with boiling points below 200°C, and further examples include isophorone (boiling point 215°C) and butyl carbitol (boiling point 230°C). ), 1-decanol (boiling point 233°C), butyl carbitol acetate (boiling point 247°C), etc. Since the boiling point of the solvent is 280°C or lower, the solvent is easily volatilized during volatilization and drying after printing, and it is easy to obtain the film-shaped fired material in the target shape. In addition, when the film-shaped fired material is fired, the solvent is less likely to remain inside the film-shaped fired material, and the joint adhesiveness of the film-shaped fired material becomes higher. Since the boiling point of the solvent is 65° C. or higher, volatilization of the solvent during printing is suppressed, and the thickness uniformity of the film-shaped fired material becomes higher. Among them, when the boiling point of the solvent is 200°C to 280°C, the increase in viscosity of the fired material composition due to volatilization of the solvent during printing is further suppressed, and the printability becomes higher.

The fired material composition may be printed using a known method. The fired material composition can be printed by, for example, relief printing methods such as flexographic printing; gravure printing methods such as gravure printing; flat printing methods such as offset printing; screen printing methods, rotary screen printing methods, etc. Screen printing method; printing method using various printers such as inkjet printers, etc. By printing the fired material composition, it is easier to form a film-shaped fired material of a target shape than by coating.

When the fired material composition contains a solvent, the proportion of the solvent content relative to the total mass of the fired material composition is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, and further Preferably, it is 15 mass % to 40 mass %. When the aforementioned ratio is in such a range, the coating suitability or printability of the fired material composition becomes higher.

The drying conditions of the fired material composition are not particularly limited. When the fired material composition contains a solvent, it is preferable to perform heating and drying. When the fired material composition is heated and dried, it is preferably dried at 70°C to 250°C or 80°C to 180°C for 10 seconds to 10 minutes, for example.

[Film-shaped fired material with supporting sheet] The film-shaped fired material with a support sheet in this embodiment includes a support sheet, and the film-shaped fired material provided on one side of the support sheet. Examples of the support sheet include a support sheet including a base film and an adhesive layer provided on one side of the base film; a support sheet consisting only of the base film; and the like. When the support sheet is a support sheet having the aforementioned base material film and an adhesive layer, in the aforementioned film-like fired material having the support sheet, the aforementioned film-like fired material is provided in the aforementioned adhesive layer and is in contact with the aforementioned base. The film side is the opposite side.

The film-like fired material with the support sheet can be used, for example, to divide the member used to form the second member (sometimes referred to as "undivided member" in this specification) by dividing, for example, using a wafer as the undivided member. In the case of components, a dicing blade can be used to divide the wafer into wafers by dicing. At this time, the film-like fired material may be cut together with the undivided members. When the wafer is divided into wafers by dicing, it is possible to manufacture a wafer having a wafer and a post-cut material provided on the inner surface of the wafer. A wafer with a film-shaped fired material made of film-shaped fired material. By using the film-shaped fired material with the support sheet, the first laminated body can be produced by step (I) in the method of manufacturing a bonded body described later.

FIG. 3 is a cross-sectional view schematically showing a film-shaped fired material with a supporting sheet. The film-shaped fired material 301 with a supporting sheet shown here includes a supporting sheet 2 and a film-shaped fired material 1 provided on one side 2 a of the supporting sheet 2 . The support sheet 2 includes a base film 21 and an adhesive layer 22 provided on one side 21 a of the base film 21 . In the film-shaped fired material 301 with a support sheet, the film-shaped fired material 1 is provided on the surface 22 a of the adhesive layer 22 opposite to the base film 21 side. The surface 22 a of the adhesive layer 22 opposite to the base film 21 side is the same as the surface 2 a of the support sheet 2 .

The film-shaped fired material with the support sheet used in the manufacturing method of this embodiment is not limited to the film-shaped fired material shown in Figure 3. The film-shaped fired material shown in Figure 3 can also be changed within the range that does not impair the effect of the present invention. A part of the composition of the film-shaped fired material shown is changed or deleted, or other compositions are added to the film-shaped fired material described above. For example, the film-shaped fired material with the support sheet may have other elements that are not any of the base film, the adhesive layer, and the film-shaped fired material. In addition, in the film-shaped fired material with a support sheet shown in FIG. 3, the adhesive layer is provided on the entire surface of one side of the base film, but it may not be provided on a part of one side of the base film. Adhesive layer.

[Substrate film] Examples of the constituent material of the base film include resin. Examples of the resin include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-propylene copolymer, and polypropylene (PP). , polybutene, polybutadiene, polymethylpentene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)methyl acrylate copolymer, ethylene-(meth)acrylate copolymer base) ethyl acrylate copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyurethane, ionomer, etc. When higher heat resistance is required for the support sheet, examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. ester; polypropylene, polymethylpentene and other polyolefins, etc. Examples of the resin include resins obtained by cross-linking the resins listed above (cross-linked resins), and modified resins obtained by irradiating the resins listed above by irradiation with radiation or electric discharge.

The base film may be composed of one layer (single layer), or may be composed of two or more multiple layers. When it is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

The thickness of the base film is not particularly limited, but is preferably 30 μm to 300 μm, more preferably 50 μm to 200 μm. When the thickness of the base film is within this range, even if the base film is cut due to cutting, the base film is not easily broken. In addition, since the film-shaped fired material having the support sheet has sufficient flexibility, it shows good adhesion to the first member or the second member. Here, the "thickness of the base film" means the thickness of the entire base film. For example, the thickness of a base film composed of multiple layers means the total thickness of all the layers constituting the base film.

The surface of the base film may be peeled off using a release agent (it may also have a peeling surface). Examples of the release agent include alkyd-based, polysilicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based or wax-based release agents. Among these, examples of the release agent that are particularly preferred in terms of having heat resistance include alkyd-based, polysilicone-based, or fluorine-based release agents.

[Adhesive layer] The adhesive layer may have weak adhesiveness or energy ray hardening properties, for example.

In this specification, "energy rays" mean electromagnetic waves or charged particle beams having energy quanta. Examples of the energy rays include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like. In this specification, "energy ray curability" means the property of being hardened by irradiation with energy rays.

Examples of the adhesive constituting the adhesive layer include various well-known adhesives (for example, general-purpose adhesives such as rubber-based, acrylic-based, polysiloxane-based, urethane-based, and vinyl ether-based adhesives; adhesives with uneven surfaces). Adhesives; energy ray-hardening adhesives; adhesives containing thermal expansion components, etc.).

The thickness of the adhesive layer is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 2 μm to 80 μm, and further preferably 3 μm to 50 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of an adhesive layer composed of multiple layers means the total thickness of all the layers constituting the adhesive layer.

The thickness of the film-shaped fired material with the supporting sheet is preferably 1 μm to 500 μm, more preferably 5 μm to 300 μm, and further preferably 10 μm to 150 μm.

[Method for manufacturing film-shaped fired material with supporting sheet] The film-shaped fired material with the support sheet can be produced by sequentially stacking the above-mentioned layers so as to have a corresponding positional relationship. For example, when an adhesive layer or film-like fired material is laminated on one side of a base film, an adhesive composition containing components and solvents for forming the adhesive layer is applied or printed on the release film, or an adhesive composition containing The calcined material composition is composed of components constituting the film-shaped calcined material and a solvent. If necessary, the solvent is volatilized by drying to form a film, thereby forming an adhesive layer or a film-shaped calcined material on the release film in advance. Then, the exposed surface of the formed adhesive layer or film-shaped fired material that is opposite to the peeling film side is bonded to one side of the base film. At this time, the adhesive composition or the fired material composition is preferably coated or printed on the release treatment surface of the release film. After the laminated structure is formed, the release film can be removed if necessary.

For example, when a film-like fired material is laminated on the side opposite to the base film side of the adhesive layer laminated on the base film, the adhesive layer is laminated on the base film using the above method. Then, a calcined material composition containing components and a solvent for constituting the film-shaped calcined material is separately coated or printed on the release film, and if necessary, the solvent is evaporated by drying to form a film, thereby pre-printing the film on the release film. A film-like fired material is formed. Then, the exposed surface of the formed film-shaped fired material opposite to the side of the release film is bonded to the exposed surface of the adhesive layer laminated on the base film. At this time, the fired material composition is preferably applied or printed on the release-treated surface of the release film. After the laminated structure is formed, the release film can be removed if necessary.

[Method for manufacturing joint body] Next, the manufacturing method of the joined body of this embodiment is demonstrated. 4A to 4C are cross-sectional views schematically showing an example of the manufacturing method of the joined body according to this embodiment. Here, a case of manufacturing the joint body 101 shown in FIG. 1 will be described as an example.

[Step (I)] In the aforementioned step (I), as shown in FIG. 4A , the first laminated body 1011 is produced. The first laminated body 1011 is the first member 9 , the film-like fired material 1 used to form the metal sintered layer 10 , and the first laminated body 1011 . 2. The member 8 is constructed by laminating these layers in order in the thickness direction. For this purpose, the first member 9, the film-shaped fired material 1, and the second member 8 may be laminated in this order. As the film-shaped fired material 1, the film-shaped fired material described above can be used.

Step (I) can also be performed using the aforementioned film-shaped fired material with a supporting sheet. That is, in this embodiment, it is possible to prepare an undivided member including a support sheet and a film-like fired material with a support sheet made of the film-shaped fired material provided on one side of the support sheet; The undivided member is divided into the second member; and the surface of the film-shaped fired material with the support sheet that is opposite to the support sheet side is attached to the undivided member, Thereby, an undivided laminated body composed of the film-like fired material with a supporting sheet and the undivided member laminated is produced, and the undivided member in the undivided laminated body is divided to produce the second member, and The film-shaped fired material is cut to produce a film-shaped fired material having the second member and the cut film-shaped fired material provided on one side of the second member on the support sheet. The second member of the material is to peel the second member with the film-like fired material from the supporting sheet, and then combine the film-shaped fired material in the second member with the film-shaped fired material with the aforementioned second member. The aforementioned step (I) is performed by attaching the surface opposite to the member side to the first member.

Furthermore, the support sheet is provided with a base film and an adhesive layer provided on one side of the base film, and the film is provided on a side of the adhesive layer opposite to the side of the base film. In the case where the film-shaped fired material with a supporting sheet is a film-shaped fired material with a supporting sheet made of a shaped fired material, the second member with the film-shaped fired material is peeled from the adhesive layer. Furthermore, when the adhesive layer has energy ray curability, after the adhesive layer is hardened by irradiating energy rays, the second member having the film-like fired material is peeled off from the hardened product of the adhesive layer. .

5A to 5C are cross-sectional views schematically illustrating an example of step (I) in the case of using a film-like fired material having a supporting sheet. Here, the case where the film-shaped fired material 301 with the support sheet shown in FIG. 3 is used is taken as an example and demonstrated.

In this case, in step (I), as shown in FIG. 5A , the surface 1 a of the film-shaped fired material 1 in the film-shaped fired material 301 with a support sheet that is opposite to the support sheet 2 side is attached. In the undivided member 20, an undivided laminated body 320 composed of the film-like fired material 301 having a supporting sheet and the undivided member 20 is laminated in this manner is produced.

At this time, the temperature (attachment temperature) of the film-like fired material 301 with the support sheet when attached to the undivided member 20 is preferably 23°C to 150°C, more preferably 23°C to 100°C. The speed (attachment speed) when the film-like fired material 301 with the support sheet is attached to the undivided member 20 is preferably 0.1 mm/sec to 100 mm/sec, more preferably 1 mm/sec to 20 mm/sec. When attaching the film-shaped fired material 301 with the support sheet to the undivided member 20, the pressure (adhesion pressure) applied to the film-shaped fired material 301 with the support sheet is preferably 0.1 MPa to 1 MPa.

Next, the undivided member 20 in the undivided laminated body 320 is divided to produce a plurality of second members 8, and the film-shaped fired material 1 is cut to produce it on the support sheet 2 as shown in FIG. 5B. It is provided with the second member 8 and a cut film-shaped fired material (hereinafter referred to as "film-shaped fired material" in this specification) provided on one side (opposite side to the aforementioned surface) 8 b of the second member 8 》)1, a plurality of second members 81 with film-like fired materials. In this specification, a structure in which a plurality of second members 81 having a film-like fired material is held on the support sheet 2 is called a second member group having a film-shaped fired material, and is denoted by a symbol 321 here. The second member 81 with the film-shaped fired material is held by the film-shaped fired material 1 in the second member 81 being in contact with the adhesive layer 22 in the support sheet 2 .

Both the division of the undivided member 20 and the cutting of the film-like fired material 1 can be performed by known methods. For example, when the undivided member 20 is a wafer, both the division of the undivided member 20 and the cutting of the film-like fired material 1 can be performed using a dicing blade.

Next, as shown in FIG. 5C , in the second member group 321 having the film-like fired material, the second member 81 having the film-shaped fired material is placed on the self-supporting sheet 2 , more specifically, the self-supporting sheet 2 The adhesive layer 22 is peeled off. The second member 81 having the film-shaped fired material can be peeled off by a known method, for example, a method of picking up a semiconductor wafer can be applied. Here, the second member 81 having the film-like fired material is peeled off in the direction of the arrow U using the peeling mechanism 6 such as a vacuum collet. Furthermore, the cross-sectional representation of the peeling mechanism 6 is omitted here.

When the adhesive layer 22 has energy ray curability, after the adhesive layer 22 is hardened by irradiating energy rays, the second member 81 having the film-like fired material is peeled off from the hardened product of the adhesive layer 22 . In Fig. 5C, the hardened material of the adhesive layer 22 is marked with a symbol 22'. Since the adhesive force of the hardened material 22' of the adhesive layer is smaller than the adhesive force of the adhesive layer 22, after the adhesive layer 22 is hardened in this way, the second member 81 with the film-like fired material can be peeled off more easily. The second member 81 having the film-like fired material is peeled off.

Next, the surface 1 b of the film-shaped fired material 1 opposite to the second member 8 side of the second member 81 having the film-shaped fired material is attached to the first member 9 . Through the above steps, the first laminated body 1011 shown in FIG. 4A is obtained.

[Step (II)] In the aforementioned step (II), the pressure (sometimes referred to as "pressure" in this specification) is applied to the first laminated body 1011 in the lamination direction of the first member 9, the film-shaped fired material 1, and the second member 8. "Pressure (a)") is set to less than 5 MPa, and the first laminated body 1011 is heated until the temperature of the first laminated body 1011 reaches the temperature (B), thereby obtaining the second laminated body as shown in FIG. 4B 1012.

The film-like fired material 1' in the second laminated body 1012 may be similar to or different from the film-shaped fired material 1 in the first laminated body 1011. Which case it is depends on the composition of the film-shaped fired material 1 .

In step (II), the aforementioned pressure (pressure (a)) applied to the first laminated body 1011 may be, for example, any one of 4.5 MPa or less, 2.5 MPa or less, and 0.5 MPa or less. The lower limit of the pressure in step (II) is 0 MPa (in step (II), the pressure does not need to be applied to the first laminated body 1011). The pressure in step (II) may be, for example, any one of from 0 MPa to less than 5 MPa, from 0 MPa to 4.5 MPa, from 0 MPa to 2.5 MPa, and from 0 MPa to 0.5 MPa.

In the step (II), when the aforementioned pressure (pressure (a)) is applied to the first laminated body 1011, for example, the first laminated body 1011 may be merely supported (withstanding the pressure) on the first member 9 side, and the first laminated body 1011 may be subjected to pressure. The first laminated body 1011 applies pressure from the second member 8 side but does not apply pressure from the first member 9 side. In addition, the first laminated body 1011 may be merely supported (under pressure) on the second member 8 side, and pressure may be applied to the first laminated body 1011 from the first member 9 side without applying pressure from the second member 8 side. In addition, pressure can be applied to the first laminated body 1011 from both sides of the first member 9 side and the second member 8 side.

In the step (II), when the aforementioned pressure (pressure (a)) is applied to the first laminated body 1011, for example, a pressurizing mechanism for applying pressure may be used to contact the first member 9 and the second member 8 Either or both of the pressure-applying surfaces (sometimes referred to as the "pressure surface" in this specification) exert pressure. At this time, any surface of the pressurizing mechanism may be brought into surface contact with the pressurizing surfaces of either or both of the first member 9 and the second member 8 , or any surface of the pressurizing mechanism may be brought into surface contact with the first member 9 The entire pressure surface of either or both of the second member 8 and the second member 8 is in surface contact. Thereby, the said pressure can be applied to the 1st member 9 and the 2nd member 8 more uniformly.

In step (II), in order to heat the first laminated body 1011 until the temperature of the first laminated body 1011 reaches the temperature (B), for example, by placing the first laminated body 1011 in an unheated state such as normal temperature. It is sufficient to start heating the first laminated body 1011 in a heating environment. In this specification, the heating temperature (temperature of the heating environment) when heating of the first laminated body 1011 is started is called "temperature (A)". In step (II), in order to set the temperature of the first laminated body 1011 to the temperature (B), it is preferable to change the heating temperature (the temperature of the heating environment) from the temperature (A) after starting the heating of the first laminated body 1011. ) rises further.

In step (II), the aforementioned temperature (A) is preferably a temperature at which the film-shaped fired material 1 and the film-shaped fired material 1' are not fired. The temperature (A) may be, for example, normal temperature or higher, or may be lower than 50°C, preferably 50°C or higher, for example, it may be 60°C or higher. When the temperature (A) is equal to or higher than the aforementioned lower limit, step (II) can be performed more efficiently. The temperature (A) may be, for example, any one of 190°C or lower, 150°C or lower, or 110°C or lower, and is preferably 80°C or lower. When the temperature (A) is below the aforementioned upper limit, the film-like fired material 1 in step (II) is heated from the ends of the first member 9 and the second member 8 (essentially the end of the second member 8) The infiltration is further inhibited. As a result, in the joint body described below, the infiltration of the metal sintered layer from the end portions of the first member 9 and the second member 8 (substantially the end portions of the second member 8) is also suppressed, and the first member 9 and the second member 8 are 2. The joint strength of the member 8 becomes higher. For example, the temperature (A) can be appropriately adjusted to be within a range set by any combination of any of the above-mentioned lower limit values and any of the upper limit values. For example, the temperature (A) can be any one of above normal temperature and less than 50°C, 50°C to 190°C, 50°C to 150°C, and 50°C to 110°C, preferably 50°C to 80°C. However, these temperatures are examples of temperature (A).

In step (II), the aforementioned temperature (B) is preferably 200°C or above, for example, it can be any one of 240°C or above, 280°C or above, and 320°C or above. When the temperature (B) is equal to or higher than the lower limit, the film-shaped fired material 1' can be more fully fired in the step (III) described below, and the metal sintered layer can be formed with higher purity. The temperature (B) is preferably 400°C or lower, and may be either 380°C or lower and 360°C or lower, for example. For example, the temperature (B) can be appropriately adjusted to be within a range set by any combination of any of the above-mentioned lower limit values and any of the upper limit values. For example, the temperature (B) is preferably 200°C to 400°C, and may be any one of 240°C to 400°C, 280°C to 400°C, and 320°C to 400°C. However, these temperatures are examples of temperature (B).

In step (II), the difference between the aforementioned temperature (B) and the aforementioned temperature (A) (the temperature difference between the aforementioned temperature (B) and the aforementioned temperature (A)) is not particularly limited. For example, it can be 160°C or above, preferably The temperature is 200°C or higher, more preferably 230°C or higher, further preferably 260°C or higher. Since the aforementioned difference (temperature difference) is equal to or greater than the aforementioned lower limit, the film-like fired material 1 in step (II) is separated from the ends of the first member 9 and the second member 8 (essentially, the end of the second member 8 The infiltration of parts) is further inhibited. As a result, in the joint body described below, the infiltration of the metal sintered layer from the ends of the first member 9 and the second member 8 (substantially the ends of the second member 8) is also suppressed, and the first member 9 and the second member 8 are 2. The joint strength of the member 8 becomes higher. The upper limit of the difference between temperature (B) and temperature (A) (the aforementioned temperature difference) is not particularly limited. In order to efficiently obtain a joint body with sufficiently high joint strength, the difference between temperature (B) and temperature (A) (the aforementioned temperature difference) is preferably 300° C. or less. The difference between temperature (B) and temperature (A) (the aforementioned temperature difference) may be, for example, any one of 160°C to 300°C, 200 to 300°C, 230°C to 300°C, and 260°C to 300°C. However, these temperatures are examples of the aforementioned temperature differences.

In step (II), when the temperature of the first laminated body 1011 is adjusted to the temperature (B), the temperature adjustment mechanism is placed in contact with the first laminated body 1011, or is disposed without being in contact with the first laminated body 1011. 1011 is arranged in contact with the first laminated body 1011 and adjusts the temperature condition of the temperature adjustment mechanism, thereby adjusting the temperature of the first laminated body 1011. For example, it is preferable to arrange a pair of temperature adjustment mechanisms sandwiching the first laminated body 1011 to adjust the temperature of the first laminated body 1011. The temperature adjustment mechanism may be in contact with either the first member 9 or the second member 8. One or both of them may be used to adjust the temperature of the first laminated body 1011 , or the temperature adjustment mechanism may not be in contact with both the first member 9 and the second member 8 to adjust the temperature of the first laminated body 1011 .

In step (II), a pressurizing and temperature adjusting mechanism having a structure in which the aforementioned pressurizing mechanism and the aforementioned temperature regulating mechanism are integrated can be used to pressurize the first laminated body 1011 and adjust the temperature of the first laminated body 1011. either or both. For example, it is preferable that any surface of the pressurizing temperature adjusting mechanism is in surface contact with the pressurizing surfaces of either or both of the first member 9 and the second member 8 , and more preferably, any surface of the pressurizing temperature adjusting mechanism is brought into surface contact. One side is in surface contact with the entire pressure surface of either or both of the first member 9 and the second member 8 to simultaneously pressurize the first laminated body 1011 and adjust the temperature of the first laminated body 1011 , whereby step (II) can be performed more efficiently.

In the step (II), the temperature rise rate when the first laminated body 1011 is heated to the temperature of the first laminated body 1011 becomes the temperature (B) is not particularly limited, but is preferably 5°C/sec to 15°C/sec. More preferably, it is 7°C/sec to 12°C/sec. By setting the temperature rise rate within this range, a joined body with sufficiently high joint strength can be efficiently obtained.

In step (II), the aforementioned heating rate may be fixed or variable.

[Step (III)] In the aforementioned step (III), the second laminated body 1012 is placed in the aforementioned laminating direction (the same as the laminating direction of the first member 9, the film-like fired material 1', and the second member 8 in the first laminated body 1011. The pressure (sometimes referred to as "pressure (b)" in this specification) applied in the direction) is 5 MPa or more, and the temperature of the second laminated body 1012 is set to the aforementioned temperature (B) - 5°C or more. Thereby, the film-shaped fired material 1' is fired to form the metal sintered layer 10, and as shown in Fig. 4C, a joint body 101 is produced. By performing step (III), the target joint body 101 can be obtained.

In step (III), the aforementioned pressure (pressure (b)) applied to the second laminated body 1012 may be, for example, any one of 8 MPa or more, 11 MPa or more, and 14 MPa or more. The upper limit of the pressure in step (II) is not particularly limited. For example, in order to avoid excessive pressure, the pressure in step (II) is preferably 50 MPa or less, for example, it can be any one of 40 MPa or less and 30 MPa or less. The pressure in step (III) can be appropriately adjusted, for example, within a range set by any combination of any of the above lower limit values and any of the upper limit values. For example, the aforementioned pressure is preferably any one of 5MPa to 50MPa, 8MPa to 50MPa, 11MPa to 50MPa, and 14MPa to 50MPa, and can be any one of 5MPa to 40MPa, 8MPa to 40MPa, 11MPa to 40MPa, and 14MPa to 40MPa, or It may be any one of 5MPa to 30MPa, 8MPa to 30MPa, 11MPa to 30MPa, and 14MPa to 30MPa. However, these pressures are examples of the aforementioned pressure (pressure (b)).

The method of applying pressure (pressure (b)) to the second laminated body 1012 in step (III) is the same as the method of applying pressure (pressure (a)) to the first laminated body 1011 in step (II).

In step (III), while applying the aforementioned pressure (pressure (b)) to the second laminated body 1012, the temperature of the second laminated body 1012 is set to the aforementioned temperature (B)-5°C or more for a period of time (in this specification) (sometimes referred to as "firing time") is not particularly limited as long as the film-shaped fired material can be fully fired. It is preferably 10 seconds or more, for example, it can be 60 seconds or more, 110 seconds or more, and 160 seconds. Anything above seconds. The upper limit of the aforementioned firing time is not particularly limited. In order to avoid excessively long firing time, the above-mentioned firing time is preferably 600 seconds or less. The aforementioned firing time is, for example, preferably 10 seconds to 600 seconds, and may be any one of 60 seconds to 600 seconds, 110 seconds to 600 seconds, and 160 seconds to 600 seconds.

In step (III), the temperature of the second laminated body 1012 when the aforementioned pressure (pressure (b)) is applied to the second laminated body 1012 may be equal to or higher than the temperature (B). In this case, the metal sintered layer 10 can be formed more efficiently. That is, in the step (III), the pressure (pressure (b)) may be set to 5 MPa or more, and the temperature of the second laminated body 1012 may be set to the temperature (B) or more.

In step (III), the upper limit of the temperature of the second laminated body 1012 when the aforementioned pressure (pressure (b)) is applied to the second laminated body 1012 is not particularly limited. For example, when the temperature is temperature (B) + 5° C. or less, overheating of the second laminated body 1012 is suppressed. That is, in the aforementioned step (III), the pressure (pressure (b)) may be set to 5 MPa or more, and the temperature of the second laminated body 1012 may be set to a temperature (B)-5°C or more and a temperature (B )+5℃ or below.

As an example of a preferred method for manufacturing a joined body in this embodiment, there can be cited a method for manufacturing a joined body in which the joining system includes a first member, a metal sintered layer, and a second member, and the first member and the above-mentioned The second member is joined by the aforementioned metal sintered layer to form the aforementioned joint body; the aforementioned manufacturing method includes: step (I), which is to prepare a first laminated body; the aforementioned first laminated system and the aforementioned first member are used to form the aforementioned metal sintered layer The film-shaped fired material and the aforementioned second member are sequentially laminated in the thickness direction of these layers; step (II) involves placing the aforementioned first laminated body on the aforementioned first member and the aforementioned film-shaped fired material. , and the pressure applied in the lamination direction of the second member is set to less than 5 MPa, and the first laminated body is heated until the temperature of the first laminated body reaches temperature (B), thereby producing the second laminated body. ; and step (III), which is to set the pressure applied to the second laminated body in the lamination direction to 5 MPa or more, and at the same time set the temperature of the second laminated body to the above temperature (B) - 5°C or more, Thereby, the film-shaped fired material is fired to form the metal sintered layer, thereby producing the bonded body; in the step (II), in order to set the temperature of the first laminated body to the temperature (B), When the heating temperature when starting the heating of the first laminated body is taken as temperature (A), the difference between the aforementioned temperature (B) and the aforementioned temperature (A) is set to 160° C. or more. In this method of manufacturing a joined body, the temperature (A) is preferably a temperature at which the film-like fired material is not fired.

Another example of a preferred method for manufacturing a joined body according to this embodiment is a method for manufacturing a joined body in which the joining system includes a first member, a metal sintered layer, and a second member, and the first member and The aforementioned second member is joined by the aforementioned metal sintered layer to form the aforementioned joint body; the aforementioned manufacturing method includes: step (I), which is to prepare a first laminated body, and the aforementioned first laminated system and the aforementioned first member are used to form the aforementioned metal sintered body A layer of film-like fired material and the aforementioned second member are sequentially laminated in the thickness direction of these layers; step (II) involves firing the aforementioned first laminated body on the aforementioned first member and the aforementioned film-like member. The pressure applied in the lamination direction of the material and the second member is set to less than 5 MPa, and the first laminate is heated until the temperature of the first laminate reaches temperature (B), thereby producing the second laminate. body; and step (III), the pressure exerted on the aforementioned second laminated body in the aforementioned lamination direction is set to 5 MPa or more, and at the same time, the temperature of the aforementioned second laminated body is set to the aforementioned temperature (B)-5°C or more , whereby the aforementioned film-like fired material is fired to form the aforementioned metal sintered layer, thereby producing the aforementioned joint body; in the aforementioned step (III), the aforementioned metal sintered layer is formed from the end of the aforementioned first member or the aforementioned first member. 2. The amount of bleeding at the end of the member is 0.5 mm or less, and the thickness of the metal sintered layer is 12 μm to 40 μm.

As another example of a preferred method of manufacturing a joined body according to this embodiment, there can be cited a method of manufacturing a joined body in which the joining system includes a first member, a metal sintered layer, and a second member, and the first member and The aforementioned second member is joined by the aforementioned metal sintered layer to form the aforementioned joint body; the aforementioned manufacturing method includes: step (I), which is to prepare a first laminated body, and the aforementioned first laminated system and the aforementioned first member are used to form the aforementioned metal sintered body A layer of film-like fired material and the aforementioned second member are sequentially laminated in the thickness direction of these layers; step (II) involves firing the aforementioned first laminated body on the aforementioned first member and the aforementioned film-like member. The pressure applied in the lamination direction of the material and the second member is set to less than 5 MPa, and the first laminate is heated until the temperature of the first laminate reaches temperature (B), thereby producing the second laminate. body; and step (III), the pressure exerted on the aforementioned second laminated body in the aforementioned lamination direction is set to 5 MPa or more, and at the same time, the temperature of the aforementioned second laminated body is set to the aforementioned temperature (B)-5°C or more , whereby the aforementioned film-shaped fired material is fired to form the aforementioned metal sintered layer, thereby producing the aforementioned joint body; the aforementioned film-shaped fired material contains sinterable metal particles and a binder component that is solid at 25°C, and Non-sintered metal particles may also be included; the content of other components in the film-shaped fired material that are not any of the aforementioned sintered metal particles, the aforementioned non-sintered metal particles, and the aforementioned binder components is relative to the aforementioned film-shaped material. The ratio of the total mass of the fired materials is 2 mass% or less. [Example]

Hereinafter, the present invention will be described in more detail through specific examples. However, the present invention is not limited to the Examples shown below at all.

[Raw materials for the production of fired material compositions] The raw materials for producing the calcined material compositions used in Examples and Comparative Examples are shown below. [Solder paste containing sinterable metal particles] ・Silver Nano Solder Paste (1) ("Alconano Silver Solder Paste ANP-4" manufactured by Applied Nanoparticle Research Institute Co., Ltd., silver nanoparticles coated with alcohol derivatives, metal content of 80% by mass or more, average particle size 100nm The following silver particles (sinterable metal particles) 25% by mass or more) [Binder ingredient] ・Acrylic polymer (1) (2-ethylhexyl methacrylate polymer, weight average molecular weight 250000, Tg: -10℃)

[Example 1] [Manufacture of fired material compositions] The fired material composition was obtained by mixing silver nano solder paste (1) (91 parts by mass) and acrylic polymer (1) (9 parts by mass). The acrylic polymer (1) is mixed in the state of a dispersion containing a solvent (dispersion medium), but the preparation amount (9 parts by mass) shown here is the amount of the acrylic polymer (1) itself excluding the solvent component (solid amount of ingredients).

[Production of film-shaped fired material (1)] The fired material composition obtained above was printed on one side (release-treated side) of a release film ("SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) with a width of 230 mm to form a printed layer. At this time, the planar shape of the printed layer was a square shape with a size of 10 mm×10 mm. Then, the printed layer was dried at 150° C. for 10 minutes, thereby obtaining a film-like fired material (1) with a thickness of 60 μm.

[Production of film-shaped fired material (2)] Except that the planar shape of the printed layer is a quadrilateral shape of 4 mm × 4 mm instead of the quadrilateral shape of 10 mm × 10 mm, the same method as in the case of the film-shaped fired material (1) is used to obtain a thickness of 60μm film-like fired material (2).

[Manufacture of joint body] [Production of the first laminated body (1)] As the first member, a silicon wafer having a size of 20 mm×20 mm, a thickness of 350 μm, and a quadrangular planar shape (hereinafter referred to as “silicon wafer”) is prepared. In addition, as the second member, a silicon wafer with a silver film (hereinafter, a thickness of 350 μm) having a size of 8 mm × 8 mm, a thickness of 345.5 μm, a quadrangular planar shape, one side covered with a silver film (thickness: 0.5 μm), and a total thickness of 350 μm was prepared. It is called "Silicon wafer with silver film (1)"). The film-shaped fired material (1) obtained above is bonded to the exposed surface of the silver film in the silicon wafer (1) with the silver film, and the film-shaped fired material (1) is laminated. At this time, the remainder of the film-like fired material (1) is formed on the entire outer periphery of the silver film. Then, the remaining portion of the film-shaped fired material (1) is cut and removed, thereby obtaining a silicon wafer (1) with a silver film of the same size (8 mm × 8 mm) and a laminate of the film-shaped fired material (1). Made up of layers. Furthermore, the surface of the film-shaped fired material (1) in the laminate that is opposite to the side of the silicon wafer (1) having the silver film is bonded to one side of the silicon wafer to stack the silicon wafer. At this time, the silicon wafer is made to protrude from the entire outer periphery of the laminate (step (I)). Through the above steps, a first laminated body (1) is produced. The first laminated body (1) is composed of the silicon wafer, the film-shaped fired material (1), and the silicon wafer (1) with a silver film in this order. The layers are stacked in the thickness direction.

[Production of the second laminated body (1)] The entire area of the surface opposite to the film-like fired material (1) side (that is, the exposed surface) of the silicon wafer (1) with the silver film in the first laminated body (1) obtained above layer of aluminum foil (aluminum sheet, thickness 40 μm). This is to prevent contamination of the sintering device (1) to be described later in the steps after step (II) to be described later. The entire exposed surface of the silicon wafer (the surface opposite to the film-like fired material (1) side) in the obtained first laminated body (1) with aluminum foil is brought into contact with the sintering device (1) ( The aforementioned first laminated body (1) with aluminum foil is placed on the surface of one of the two plates ("HTM-3000" manufactured by Hakton Co., Ltd.). At this time, the temperature of one of the aforementioned plates is preset to 70°C. Thereby, the first laminated body (1) with aluminum foil is received by one of the plates in the sintering device (1), and the first laminated body (1) with aluminum foil is removed from the side of the silicon wafer. Heating is performed, and the temperature is adjusted to be the same as that of one of the aforementioned plates, and heating is started. Furthermore, the surface of the other of the two plates in the sintering device (1) is lightly brought into contact with the exposed surface of the aluminum foil in the first laminated body (1) with the aluminum foil (with the silicon wafer with the silver film). (1) side is the entire surface of the opposite side), thereby arranging the other plate in a position where the first laminated body (1) with aluminum foil is not deliberately pressed. At this time, the temperature of the other plate is also preset to 70°C. Thereby, by using the other plate in the sintering device (1) without deliberately applying pressure to the first laminated body (1) with the aluminum foil (substantially, the applied pressure is set to 0 MPa), the said first laminated body (1) with the aluminum foil is made. The first laminated body (1) of aluminum foil is heated from the aluminum foil side in the middle, and is adjusted to be heated to the same temperature as the other plate, and heating is started. Through the above steps, the first laminated body (1) (the first laminated body (1) with aluminum foil) is not used on the aforementioned silicon wafer, film-shaped fired material (1), and silicon wafer (1) with silver film. Pressure was applied in the lamination direction (the applied pressure was set to 0 MPa), the temperature (A) was set to 70°C, and heating was started.

Then, in the aforementioned state, the first laminated body (1) (the first laminated body (1) with aluminum foil) is not placed on the silicon wafer, the film-shaped fired material (1), and the silicon wafer (1) with the silver film. 1) Apply pressure in the lamination direction (the applied pressure is set to 0 MPa), and heat the first laminated body (1) with the two plates in the sintering device (1) until the first laminated body (1) The temperature becomes 70℃. Then, without applying pressure to the first laminated body (1), the first laminated body (1) is heated by the two plates in the sintering device (1) until the first laminated body (1) The temperature changes from 70°C to 350°C (step (II)). The temperature rise rate at this time was set to 10°C/sec. The temperature of the two plates in the sintering device (1) is raised in advance before the temperature of the first laminated body (1) reaches 70°C. Through the above steps, the second laminated body (1) is produced.

[Production of joint body (1)] Next, immediately after the second laminated body (1) is produced (in other words, at the stage when the temperature of the first laminated body (1) reaches 350°C), the second laminated body (1) is placed in contact with the first laminated body. The pressure applied in the same direction as the stacking direction of the silicon wafer, the film-shaped fired material (1), and the silicon wafer with the silver film (1) in (1) is 20 MPa, and the second layer is placed for 180 seconds. The temperature of the laminated body (1) was maintained at 350°C. At this time, pressure is applied to the second laminated body (1) from the other plate (the plate on the aluminum foil side) in the self-sintering device (1). Thereby, the film-shaped fired material (1) is fired to form a metal sintered layer (step (III)). Through the above steps, a bonded body (1) is produced. The bonded body (1) is provided with the silicon wafer, the metal sintered layer, and the silicon wafer with a silver film (1), and the silicon wafer and the silicon wafer with the silver film are (1) The bonded body (1) is formed by bonding the aforementioned metal sintered layers.

[Manufacture of joint body] [Production of the first laminated body (2)] As the first member, prepare a copper plate with a size of 30 mm × 30 mm, a thickness of 1.5 mm, and a quadrangular planar shape. In addition, as the second member, prepare a silicon wafer with a silver film (hereinafter, a thickness of 2 mm × 2 mm, a thickness of 345.5 μm, a quadrangular planar shape, one side covered with a silver film (thickness: 0.5 μm), and a total thickness of 350 μm). It is called "Silicon wafer with silver film (2)"). The film-shaped fired material (2) obtained above is bonded to the exposed surface of the silver film in the silicon wafer (2) with the silver film, and the film-shaped fired material (2) is laminated. At this time, the remainder of the film-like fired material (2) is formed on the entire outer periphery of the silver film. Then, the remaining portion of the film-shaped fired material (2) is cut and removed, thereby obtaining a silicon wafer (2) with a silver film of the same size (2 mm × 2 mm) and a laminate of the film-shaped fired material (2). Made up of layers. Furthermore, the surface of the film-shaped fired material (2) in the laminate that is opposite to the side of the silicon wafer (2) having the silver film is bonded to one side of the copper plate, and the copper plate is laminated. At this time, the copper plate is made to protrude from the entire outer periphery of the laminated product (step (I)). Through the above steps, a first laminated body (2) is produced. The first laminated body (2) is composed of the copper plate, the film-shaped fired material (2), and the silicon wafer (2) with a silver film in this order. It is composed of layers stacked in the thickness direction.

Thereafter, the first laminated body (2) provided with the film-shaped fired material (2) is used instead of the first laminated body (1) provided with the film-shaped fired material (1). In addition to this aspect, the bonded body is used. In the same manner as in (1), a bonded body (2) is produced from the second laminated body (2). In step (II), in the same manner as in the case of the above-mentioned joint body (1), the exposed surface (and the side of the film-shaped fired material (2)) of the copper plate in the first laminated body (2) with aluminum foil is made to be The entire surface of the opposite side) is in contact with the surface of one of the two plates in the sintering device (1). Through the above steps, a joint body (2) is produced. The joint body (2) includes the copper plate, the metal sintered layer, and the silicon wafer (2) with a silver film, and the copper plate and the silicon wafer (2) with the silver film. ) constitutes a joint body (2) by joining the aforementioned metal sintered layers.

[Evaluation of the joint] [Measurement of the bleeding amount of the metal sintered layer in the joint body (1)] Determine the value of the metal sintered layer from the silicon wafer (1) with the silver film when looking down from above the silicon wafer (1) with the silver film of the bonded body (1) obtained above. The maximum value of the bleeding amount on the outer periphery (side surface) is used as the bleeding amount of the metal sintered layer. The results are shown in Table 1.

[Measurement of the thickness of the metal sintered layer in the joint body (1)] In the bonded body (1) obtained above, a cross section in the lamination direction of each layer was made, and the cross section was polished. The thickness of the metal sintered layer was measured at five arbitrary locations in the polished cross section, and the average value of the thicknesses was used as the thickness of the metal sintered layer. The results are shown in Table 1.

[Measurement of shear strength of joint body (2)] The joint body (2) obtained above was placed inside a TCT testing machine ("TSE-11A" manufactured by ESPEC Corporation), left to stand in an environment of -40°C for 15 minutes, and then immediately left to stand in an environment of 200°C. 15 minutes, and then immediately return to the environment of -40°C, exposing the joint body (2) to the temperature cycle of cooling at -40°C for 15 minutes and heating at 200°C for 15 minutes for a total of 1,000 times. to conduct TCT. Then, in an environment of 23° C., in the joint body (2) after TCT, the outer periphery (side surface) of the metal sintered layer and the outer periphery (side surface) of the silicon wafer (2) with the silver film are aligned with each other. Apply at a speed of 200 μm/s in a direction parallel to the surface of the silicon wafer with silver film (2) (the surface of the silicon wafer without the silver film in the silicon wafer with silver film (2)) force. At this time, as a pressing mechanism for applying force, a plate-shaped pressing mechanism made of stainless steel is used, and the position of the front end of the pressing mechanism is set at a distance from the surface of the copper plate (the metal sintered layer side) in the joint body (2). surface) to a height of 20μm to prevent the pressing mechanism from contacting the copper plate. Then, the maximum value of the force applied until the metal sintered layer is destroyed or the metal sintered layer is peeled off from the copper plate is measured, and the measured value is used as the shear strength of the joint body (2). The measurement results are shown in the "After TCT" column in the "Shear Strength (MPa)" column in Table 1. Furthermore, the shear strength of the joint body (2) obtained above was measured by the same method as above without performing the above-mentioned TCT. The measurement results are shown in the "TCT not performed" column in the "Shear Strength (MPa)" column in Table 1.

[Example 2] [Production of fired material composition, production of film-shaped fired material (1), production of film-shaped fired material (2)] Using the same method as in Example 1, a fired material composition, a film-shaped fired material (1), and a film-shaped fired material (2) were produced.

[Manufacture of joint body] [Production of the first laminated body (1)] The first laminated body (1) was produced in the same manner as in Example 1.

[Production of the second laminated body (1)] The entire area of the surface opposite to the film-like fired material (1) side (that is, the exposed surface) of the silicon wafer (1) with the silver film in the first laminated body (1) obtained above A layer of aluminum foil (aluminum sheet, thickness 40 μm). This purpose is the same as the case of Embodiment 1. The entire exposed surface of the silicon wafer (the surface opposite to the film-like fired material (1) side) in the obtained first laminated body (1) with aluminum foil is brought into contact with the sintering device (2) ( On the surface of one of the two plates "HTB-MM" manufactured by ALPHA DESIGN Co., Ltd.), the first laminated body (1) with the aluminum foil was placed on the one plate. At this time, the temperature of one of the aforementioned plates is preset to 70°C. Thereby, the first laminated body (1) with aluminum foil is received by one of the plates in the sintering device (2), and the first laminated body (1) with aluminum foil is removed from the side of the silicon wafer. Heating is performed, and the temperature is adjusted to be the same as that of one of the aforementioned plates, and heating is started. Furthermore, the surface of the other of the two plates in the sintering device (2) is lightly brought into contact with the exposed surface of the aluminum foil in the first laminated body (1) with the aluminum foil (with the silicon wafer with the silver film). (1) side is the entire surface of the opposite side), thereby arranging the other plate in a position where the first laminated body (1) with aluminum foil is not deliberately pressed. At this time, the temperature of the other plate is also preset to 70°C. Thereby, by using the other plate in the sintering device (2), the first laminated body (1) with the aluminum foil does not deliberately apply pressure (substantially the applied pressure is set to 0 MPa), and the aforementioned The first laminated body (1) with aluminum foil is heated from the aluminum foil side in the middle, and is adjusted to be heated to the same temperature as the other plate, and heating is started. Through the above steps, the first laminated body (1) (the first laminated body (1) with aluminum foil) is not used on the aforementioned silicon wafer, film-shaped fired material (1), and silicon wafer (1) with silver film. Pressure was applied in the lamination direction (the applied pressure was set to 0 MPa), the temperature (A) was set to 70°C, and heating was started.

Then, in the aforementioned state, the first laminated body (1) (the first laminated body (1) with aluminum foil) is not placed on the silicon wafer, the film-shaped fired material (1), and the silicon wafer (1) with the silver film. 1) Apply pressure in the lamination direction (the applied pressure is set to 0 MPa), and heat the first laminated body (1) through the two plates in the sintering device (2) until the first laminated body (1) ) temperature becomes 70°C. Next, the pressure applied to the first laminated body (1) in the lamination direction was immediately set to 1 MPa. At this time, pressure is applied to the first laminated body (1) from the other plate (the plate on the aluminum foil side) in the self-sintering device (2). Then, while applying a pressure of 1 MPa to the first laminated body (1), the first laminated body (1) is heated by the two plates in the sintering device (2) until the first laminated body (1) The temperature changes from 70°C to 350°C (step (II)). The temperature rise rate at this time was set to 10°C/sec. Before the temperature of the first laminated body (1) reaches 70°C, the temperatures of the two plates in the sintering device (2) are raised in advance. Through the above steps, the second laminated body (1) is produced.

[Production of joint body (1)] Next, immediately after the second laminated body (1) is produced (in other words, at the stage when the temperature of the first laminated body (1) reaches 350°C), the second laminated body (1) is placed in contact with the first laminated body. The pressure applied in the same direction as the stacking direction of the silicon wafer, the film-shaped fired material (3), and the silicon wafer with the silver film (1) in (1) was set to 20 MPa, and the second layer was placed for 180 seconds. The temperature of the laminated body (1) was maintained at 350°C. At this time, pressure is also applied to the second laminated body (1) from the other plate (the plate on the aluminum foil side) in the sintering device (2). Thereby, the film-shaped fired material (1) is fired to form a metal sintered layer (step (III)). Through the above steps, a bonded body (1) is produced. The bonded body (1) is provided with the silicon wafer, the metal sintered layer, and the silicon wafer with a silver film (1), and the silicon wafer and the silicon wafer with the silver film are (1) The bonded body (1) is formed by bonding the metal sintered layers.

[Manufacture of joint body] The first laminated body (2) was produced in the same manner as in Example 1.

Thereafter, the first laminated body (2) provided with the film-shaped fired material (2) is used instead of the first laminated body (1) provided with the film-shaped fired material (1). In addition to this aspect, the bonded body is used. In the same manner as in (1), a bonded body (2) is produced from the second laminated body (2). In step (II), in the same manner as in the case of the above-mentioned joint body (1), the exposed surface of the copper plate in the first laminated body (2) with aluminum foil (and the side of the film-shaped fired material (2) is opposite to The entire side surface) is in contact with the surface of one of the two plates in the sintering device (2). Through the above steps, a joint body (2) is produced. The joint body (2) includes the copper plate, the metal sintered layer, and the silicon wafer (2) with a silver film, and the copper plate and the silicon wafer (2) with the silver film. ) constitutes a joint body (2) by joining the aforementioned metal sintered layers.

[Evaluation of the joint] The bonded body (1) and the bonded body (2) obtained above were evaluated by the same method as in Example 1. The results are shown in Table 1.

[Manufacture and evaluation of joints] [Example 3] In the aforementioned step (II), except that the pressure applied to the first laminated body (1) was 4 MPa instead of 1 MPa, the bonded body (1) and Joined bodies (2), and evaluated these joined bodies. The results are shown in Table 1.

[Example 4] In the aforementioned step (II), the temperature at which heating of the first laminated body (1) is started (temperature (A)) is set to 180°C instead of 70°C. The same method as in Example 2 is used except for this point. , the bonded body (1) and the bonded body (2) were produced, and these bonded bodies were evaluated. That is, in the step (II), no pressure is applied to the first laminated body (1) (the first laminated body (1) with the aluminum foil), and the first laminated body (1) is sintered by the two plates in the sintering device (2). The laminated body (1) is heated until the temperature of the first laminated body (1) reaches 180°C, and then the pressure applied to the first laminated body (1) is immediately set to 1 MPa. With this pressure applied, The first laminated body (1) is heated by the two plates in the sintering device (2) until the temperature of the first laminated body (1) changes from 180°C to 350°C (step (II)). The temperature rise rate at this time was set to 10°C/sec. The results are shown in Table 1.

[Comparative example 1] In the aforementioned step (II), instead of producing the second laminated body (1) without applying pressure to the first laminated body (1), the other one of the aforementioned self-sintering devices (1) for the first laminated body (1) is The second laminated body (1) was produced with a pressure of 10 MPa applied to the plate. Except for this point, the bonded body (1) and the bonded body (2) were produced in the same manner as in Example 1, and these were evaluated. Joint body. The results are shown in Table 1.

[Comparative example 2] In the aforementioned step (II), except that the pressure applied to the first laminated body (1) was 20 MPa instead of 1 MPa, the bonded body (1) and Joined bodies (2), and evaluated these joined bodies. The results are shown in Table 1.

[Comparative example 3] In the aforementioned step (III), except that the pressure applied to the second laminated body (1) was 4 MPa instead of 20 MPa, the bonded body (1) and Joined bodies (2), and evaluated these joined bodies. The results are shown in Table 1.

[Table 1] Example Comparative example 1 2 3 4 1 2 3 manufacturing conditions Step (I) Separation of silicon wafers and cutting of film-shaped fired materials without without without without without without without Step (II) Pressure (a) (MPa) 0 1 4 1 10 20 1 Temperature (A) (℃) 70 70 70 180 70 70 70 Temperature (B) (℃) 350 350 350 350 350 350 350 Temperature(B)-Temperature(A) (℃) 280 280 280 170 280 280 280 Step (III) Pressure (b) (MPa) 20 20 20 20 20 20 4 Evaluation results Leakage amount of metal sintered layer (mm) 0.1 0.3 0.5 0.5 0.9 1 0.1 Thickness of metal sintered layer (μm) 32 35 twenty one 16 8 10 42 Shear strength (MPa) No TCT 50 89 75 58 45 103 36 After TCT 50 90 73 45 4 2.5 6

From the above results, it is clear that in Examples 1 to 4, the amount of bleeding of the metal sintered layer was 0.5 mm or less (0.1 mm to 0.5 mm), which was suppressed to a low level. This indicates that the bleeding of the film-like fired material (1) from the end portion of the silicon wafer (1) (second member) having the silver film is suppressed before the joint body (1) is produced. Reflecting this, the thickness of the metal sintered layer in the joint body (1) is 16 μm or more (16 μm to 35 μm), which is a sufficient thickness. Reflecting this, the shear strength of the joint body (2) is the same when TCT is performed as when TCT is not performed. The copper plate (first member) with a metal sintered layer and the silicon wafer (2) with a silver film are used. The joint strength of the (second member) is stable and high. The shear strength of the joint body (2) without TCT is 50 MPa or more (50 MPa to 89 MPa). In contrast, the shear strength of the joint body (2) with TCT is 45 MPa or more (45 MPa to 90 MPa). ).

In Examples 1 to 4, the pressure (a) in step (II) is 4 MPa or less (0 MPa to 4 MPa), and the pressure (b) in step (III) is 20 MPa. On the other hand, in Examples 1 to 4, the temperature (A) in step (II) is above 70°C (70°C to 180°C), and the temperature (B) in step (II) is 350°C, The difference between temperature (B) and temperature (A) is 170°C or more (170°C to 280°C).

According to the comparison between Example 2 and Example 4, in the example in which the temperature (A) in step (II) is relatively low and the difference between temperature (B) and temperature (A) is large, the amount of infiltration of the metal sintered layer is reduced, Reflecting this, the thickness of the metal sintered layer in the joint body (1) becomes thicker. As a result, the shear strength of the joint body (2) becomes higher both when TCT is performed and when TCT is not performed. tendency.

On the other hand, in Comparative Examples 1 to 2, the bleeding amount of the metal sintered layer was 0.9 mm or more (0.0 mm to 1 mm), which was a high level and was not suppressed. This indicates that the bleeding of the film-like fired material (1) from the end portion of the silicon wafer (1) (second member) having the silver film is not suppressed before the joint body (1) is produced. Furthermore, reflecting this, the thickness of the metal sintered layer in the joint body (1) is thin, being 10 μm or less (8 μm to 10 μm). As a result, the shear strength of the joint body (2) when TCT was performed was 4 MPa or less (2.5 MPa to 4 MPa), which was significantly lower than the value when TCT was not performed (45 MPa to 103 MPa). Utilizing the strength of the metal sintered layer The bonding strength between the copper plate (first member) and the silicon wafer (2) with silver film (second member) is significantly reduced. In Comparative Examples 1 to 2, the pressure (a) in step (II) is 10 MPa or more (10 MPa to 20 MPa).

On the other hand, in Comparative Example 3, the amount of bleeding of the metal sintered layer was suppressed to a low level, and the thickness of the metal sintered layer in the joint body (1) was also sufficient. However, the shear strength of the joint body (2) was low both when TCT was not performed and when TCT was performed. When TCT is performed, the shear strength is lower than when TCT is not performed. It is speculated that the reason is that the density of the metal sintered layer is low because the pressure (b) in step (III) is too low. [Industrial Availability]

The present invention can be used to manufacture an entire joint body composed of components joined by a metal sintered layer, and is particularly suitable for manufacturing power semiconductor elements.

1,1’: film-like fired material 1a: The surface of the film-shaped fired material opposite to the support sheet side 1b: The surface of the film-shaped fired material opposite to the second member side 2: Support piece 2a:Support side 6: Divestment organization 7:Pressing mechanism 8: 2nd component 8a: One side of the second member 8b: The other side of the second member 8c: Outer circumference (side) of second member 8 9: 1st component 9a: One side of the first member 10:Metal sintered layer 10c: outer periphery (side) of metal sintered layer 10 20: Undivided components 21:Substrate film 21a: One side of the base film 22: Adhesive layer 22a: The side of the adhesive layer opposite to the base film side 22’: Hardened material of adhesive layer 81: Second member with film-like fired material 101:joint body 301: Film-like fired material with supporting sheet 320: Undivided laminated body 321: 2nd component group 1011: 1st layered body 1012:Second layered body

[Fig. 1] is a cross-sectional view schematically showing an example of a joined body obtained by a method for manufacturing a joined body according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically illustrating a method for measuring the shear strength of a joined body obtained by a method for manufacturing a joined body according to one embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing a film-like fired material having a support sheet used in a method for manufacturing a joined body according to an embodiment of the present invention. [Fig. 4A] is a cross-sectional view schematically showing an example of a manufacturing method of a joined body according to an embodiment of the present invention. [Fig. 4B] is a cross-sectional view schematically showing an example of a manufacturing method of a joined body according to an embodiment of the present invention. [Fig. 4C] is a cross-sectional view schematically showing an example of a method of manufacturing a joined body according to an embodiment of the present invention. [Fig. 5A] is an example of step (I) for schematically illustrating a case where a film-like fired material having a support sheet is used in step (I) of the manufacturing method of a joined body according to one embodiment of the present invention. Cutaway view. [Fig. 5B] is an example of step (I) for schematically explaining a case where a film-like fired material having a support sheet is used in step (I) of the manufacturing method of a joined body according to one embodiment of the present invention. Cutaway view. [Fig. 5C] is an example of step (I) for schematically illustrating a case where a film-like fired material having a support sheet is used in step (I) of the manufacturing method of a joined body according to one embodiment of the present invention. Cutaway view.

8: 2nd component

9: 1st component

10:Metal sintered layer

101:joint body

Claims (3)

A method of manufacturing a joined body, the joining system includes a first member, a metal sintered layer, and a second member, and the first member and the second member are joined by the metal sintered layer to form the joined body; The aforementioned manufacturing methods include: Step (I) is to prepare a first laminated body. The first laminated system, the first member, the film-like fired material used to form the metal sintered layer, and the second member are sequentially arranged in the thickness direction of these layers. composed of layers; Step (II) is to set the pressure applied to the first laminated body in the lamination direction of the first member, the film-shaped fired material, and the second member to less than 5 MPa, and at the same time, The laminated body is heated until the temperature of the first laminated body reaches temperature (B), thereby producing a second laminated body; and In step (III), the pressure applied to the second laminated body in the lamination direction is set to 5 MPa or more, and the temperature of the second laminated body is set to the above temperature (B) - 5°C or more, thereby The film-shaped fired material is fired to form the metal sintered layer, thereby producing the bonded body. The manufacturing method of the joint body according to Claim 1 is to prepare a film-like fired material having a support sheet and a film-shaped fired material provided on one side of the aforementioned film-shaped fired material. Undivided components; The support sheet includes a base film and an adhesive layer provided on one side of the base film. In the film-shaped fired material with the support sheet, the film-shaped fired material is provided in the adhesive layer. The surface opposite to the side of the aforementioned base material film; The aforementioned undivided member is divided into the aforementioned second member; The surface of the film-shaped fired material with a support sheet that is opposite to the support sheet side is attached to the undivided member to produce a film-shaped fired material with a support sheet. An undivided laminated body composed of a material and the undivided member laminated by dividing the undivided member in the undivided laminated body to produce the second member, and cutting the film-like fired material, thereby A second member with a film-like fired material is produced on the said support sheet and is provided with the said second member and the cut said film-shaped fired material provided on one side of the said second member, and the said film-shaped fired material is After the second member is peeled off from the supporting sheet, the surface of the film-shaped fired material of the second member having the film-shaped fired material that is opposite to the side of the second member is attached to the first member. , thereby performing the aforementioned step (I). The manufacturing method of a joint body according to claim 2, wherein the adhesive layer is energy ray hardenable, and after the adhesive layer is hardened by irradiating energy rays, the second member having the film-like fired material is automatically The hardened material of the adhesive layer is peeled off.

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