JP2023147528A - Method for manufacturing conjugant - Google Patents

Abstract

To provide a manufacturing method capable of manufacturing a conjugant having sufficiently high joint strength that can restrain a joining material from protruding from end portions of joint target members when the joining material is interposed between the joint target members and the joining material is fired to form a conductive joint portion, thereby manufacturing the conjugant in which the members are joined to each other by the conductive joint portion.SOLUTION: A method for manufacturing a conjugant includes steps of: producing a first laminate 1011 including a first member 9, a film-shaped fired material 1, and a second member 8 which are laminated in this order; heating the film-shaped fired material 1 while applying a pressure of 0.1 MPa or more in the lamination direction to the first laminate 1011 so that a protrusion width L of the film-shaped fired material 1 from the second member 8 is equal to 220 μm or less, thereby forming a second laminate 1012; and firing the heated film-shaped fired material 1 while applying a pressure of 3 MPa or more in the lamination direction to the second laminate 1012 to form a metal sintered layer 10, thereby manufacturing a conjugant 101.SELECTED DRAWING: Figure 4

Description

The present invention relates to a method for manufacturing a joined body.

A method of joining components using a conductive joint (conductive joint) is to interpose a joining material containing metal particles and a binder between the members to be joined, and to connect these members with the joining material. A method is known in which a conductive joint is formed by heating while pressurizing and firing the joining material. According to this method, the binder is decomposed by firing the bonding material, the metal particles adhere to each other to form a conductive joint, and the members can be bonded together by bonding them together.

Such a method of joining members together can be used, for example, to manufacture power semiconductor elements (power devices). Power semiconductor devices are used under high voltage and high current conditions, and in recent years, as automobiles, air conditioners, computers, etc. have become increasingly high voltage and current, they are often installed in these devices. In such power semiconductor devices, heat generation from the semiconductor device tends to be a problem, but because the conductive joints have excellent heat dissipation properties, sufficient heat dissipation can be achieved without providing a heat sink around the semiconductor device. It becomes possible.

As a method for joining members together using a conductive joint, for example, the members to be joined are joined using a joining material containing silver nanoparticles, silver carbonate or silver oxide, and carboxylic acids containing crystals. A method has been disclosed in which members are joined together by sandwiching the joining material and applying pressure while heating the joining material so that the joining temperature reaches or exceeds the joining temperature (see Patent Document 1).

Japanese Patent Application Publication No. 2009-279649

On the other hand, when the joining materials are fired while pressurizing the members and the joining materials, there is a problem in that the softened joining materials may protrude from the ends of the members during the heating process during firing. Ta. If the softened bonding material protrudes in this way, the thickness of the final sintered part, that is, the conductive bond, may become thinner than the desired value, or the handling of the laminate with the bonding material protruding may become difficult. My sexuality gets worse. On the other hand, if the pressure during pressurization is reduced in order to reduce the amount of protrusion of the bonding material, there is a problem in that the bonding strength between the members decreases. The joining method disclosed in Patent Document 1 cannot solve these problems.

The present invention produces a joined body in which these members are joined by a conductive joint by interposing a joining material between the members to be joined, firing the joining material, and forming a conductive joint. An object of the present invention is to provide a manufacturing method capable of suppressing the protrusion of the joining material from the end portions of the members and manufacturing a joined body having sufficiently high joining strength.

In order to solve the above problems, the present invention employs the following configuration.
[1]. A method for manufacturing a joined body, the method comprising:
The joined body includes a first member, a sintered metal layer, and a second member, and the first member and the second member are joined by the sintered metal layer,
The manufacturing method includes the first member, the film-like sintered material for forming the metal sintered layer, and the second member, which are laminated in this order in the thickness direction. Step (I) of producing one laminate;
In the first laminate, the first member and the film are attached to the first laminate so that the protrusion width of the film-like fired material from the first member or the second member is 220 μm or less. A second laminate is produced by heating the film-like sintered material in the first laminate while applying a pressure of 0.1 MPa or more in the lamination direction of the sintered material and the second member. Step (II) of
After the step (II), the film-like sintered material in the second laminate is fired while applying a pressure of 3 MPa or more to the second laminate in the same direction as the lamination direction, and forming a metal sintered layer to produce the joined body (III);
A test sample consisting of a silicon chip with a thickness of 345.5 μm, a silver film with a thickness of 0.5 μm, and a test piece of the film-like fired material were laminated in this order in the thickness direction. A laminate, wherein the silicon chip has a rectangular planar shape and a size of 2 mm x 2 mm, and the silver film is provided on the surface of the silicon chip on the side of the film-like fired material by vapor deposition. the silver film covers the entire surface of the silicon chip on the side of the film-like fired material, the test piece of the film-like fired material has the same size as the silicon chip, and A test laminate in which the film-like fired material does not protrude from the outer periphery of the silicon chip is produced, and the entire exposed surface of the test piece in the test laminate is brought into contact with a copper plate, and the test laminate is Laminating the silicon chip, the silver film, and the test piece on the test laminate while placing it on the copper plate and heating the test laminate and the copper plate to 300°C. A method for manufacturing a bonded body, wherein when a pressure of 10 MPa is applied from the silicon chip side for 3 minutes in the direction, the maximum width of the protrusion of the test piece from the outer periphery of the silicon chip exceeds 220 μm.
[2]. A support sheet-attached film-like fired material comprising a support sheet and the film-like fired material provided on one surface of the support sheet is prepared, and an undivided member is prepared,
The support sheet includes a base film and an adhesive layer provided on one surface of the base film, and in the film-like fired material with a support sheet, the film-like fired material includes: provided on the surface of the adhesive layer opposite to the base film side,
The undivided member becomes the second member by the division,
By pasting the surface of the film-like fired material in the film-like fired material with a support sheet, the side opposite to the support sheet side, to the undivided member, the film-like fired material with a support sheet, The undivided member is laminated to produce an undivided laminate, the undivided member in the undivided laminate is divided to produce the second member, and the film-form baking is performed. By cutting the material, a film-like fired material is provided on the support sheet, the film-like fired material comprising the second member and the cut film-like fired material provided on one surface of the second member. After producing a second member and peeling off the second member with the film-like fired material from the support sheet, the part of the film-like fired material in the second member with the film-like fired material on the second member side The method for manufacturing a bonded body according to [1], wherein the step (I) is performed by attaching the opposite surface to the first member.
[3]. The adhesive layer is energy ray curable, and after the adhesive layer is cured by irradiation with energy rays, the second member with the film-like fired material is peeled from the cured product of the adhesive layer. 2], the method for manufacturing a joined body.

According to the present invention, a bonding material is interposed between the members to be bonded, the bonding material is fired, and a conductive bonding portion is formed, thereby forming a bonded body in which these members are bonded together by the conductive bonding portion. Provided is a manufacturing method that can suppress the protrusion of the bonding material from the ends of the members and produce a bonded body with sufficiently high bonding strength.

FIG. 1 is a cross-sectional view schematically showing an example of a bonded body obtained by a method for manufacturing a bonded body according to an embodiment of the present invention. FIG. 3 is a cross-sectional view schematically illustrating a method for measuring the shear strength of a bonded body obtained by a method for manufacturing a bonded body according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a film-like fired material with a support sheet used in a method for manufacturing a bonded body according to an embodiment of the present invention. 1 is a cross-sectional view schematically showing an example of a method for manufacturing a joined body according to an embodiment of the present invention. A sectional view for schematically illustrating an example of step (I) in a method for manufacturing a bonded body according to an embodiment of the present invention, in which a film-like fired material with a support sheet is used. It is.

◇Method for manufacturing a bonded body In the method for manufacturing a bonded body according to an embodiment of the present invention, the bonded body includes a first member, a sintered metal layer, and a second member, and the first member and The second member is configured to be joined by the metal sintered layer, and the manufacturing method includes the first member, a film-shaped sintered material for forming the metal sintered layer, and the first member. 2 members are laminated in this order in the thickness direction to produce a first laminate; In the lamination direction of the first member, the film-like fired material, and the second member, the first laminate is 0.0 μm or less so that the protrusion width of the film-like fired material is 220 μm or less. step (II) of producing a second laminate by heating the film-like fired material in the first laminate while applying a pressure of 1 MPa or more; The film-like sintered material in the second laminate is fired while applying a pressure of 3 MPa or more to the second laminate in the same direction as the lamination direction to form the metal sintered layer. step (III) of producing a bonded body, a silicon chip with a thickness of 345.5 μm, a silver film with a thickness of 0.5 μm, and a test piece of the film-shaped fired material in this order. , a test laminate configured by laminating these silicon chips in the thickness direction, wherein the silicon chip has a rectangular planar shape and a size of 2 mm x 2 mm, and the silver film is The silver film is provided on the surface of the film-like fired material side of the chip by vapor deposition, and the silver film covers the entire surface of the silicon chip on the film-like fired material side. Producing a test laminate in which the test piece has the same size as the silicon chip and in which the film-like fired material does not protrude from the outer periphery of the silicon chip, and exposing the test piece in the test laminate. The test laminate is placed on the copper plate with the entire surface in contact with the copper plate, and while the test laminate and the copper plate are heated to 300°C, the silicon is applied to the test laminate. When a pressure of 10 MPa is applied from the silicon chip side for 3 minutes in the stacking direction of the chip, the silver film, and the test piece, the maximum value of the protrusion width of the test piece from the outer periphery of the silicon chip. However, it exceeds 220 μm.

According to the method for manufacturing a joined body of the present embodiment, the film-like sintered material for forming a metal sintered layer is interposed between the first member and the second member to be joined, and the lamination of these materials is performed. The step (I) of producing a product, that is, the first laminate is performed, and the step (II) is performed using the first laminate. Thereby, in the step (II), it is possible to suppress the film-like fired material from protruding from the ends of the first member and the second member. As a result, by performing the step (III), it is possible to suppress the protrusion of the metal sintered layer from the ends of the first member and the second member in the step (III). Furthermore, in step (II), the adhesion between the film-like fired material and the first member is improved, and the adhesion between the film-like fired material and the second member is improved. As a result, by performing step (III), the bonding strength between the first member and the second member via the metal sintered layer becomes sufficiently high. That is, in the obtained joined body, protrusion of the metal sintered layer from the ends of the first member and the second member is suppressed, and the bonding strength between the first member and the second member is sufficient. becomes higher.

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

Hereinafter, the present invention will be described in detail with reference to the drawings. Note that the figures used in the following explanation may show important parts enlarged for convenience in order to make it easier to understand the features of the present invention, and the dimensional ratio of each component may be the same as the actual one. Not necessarily.

＜＜Zygote＞＞
First, the joined body obtained by the manufacturing method of this embodiment will be explained.
FIG. 1 is a cross-sectional view schematically showing an example of the joined body.
The joined 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. It is composed of

The first member 9 is not particularly limited as long as it can be joined by the metal sintered layer 10.
More specifically, the first member 9 may include, for example, a substrate.

The second member 8 is also not particularly limited as long as it can be joined by the metal sintered layer 10.
More specifically, the second member 8 may include, for example, various chips such as semiconductor chips.

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 bonding surface) in order to increase the bonding strength with the metal sintered layer 10. That is, the second member 8 may have a multi-layer structure in which the metal film is provided on one surface, and such a second member 8 may have a metal sintered structure in the metal film therein. It may contact layer 10 and be joined to first member 9 .

The metal sintered layer 10 is composed of a sintered body formed by melting and bonding sinterable metal particles.
The metal sintered layer 10 can be formed, for example, by firing a film-like firing 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 layers, When consisting 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.

In this specification, "the plurality of layers may be the same or different from each other" is not limited to the case of these (the first member 9, the second member 8, and the metal sintered layer 10). may be the same, all the layers may be different, or only some of the layers may be the same," and "the layers are different from each other" means " "At least one of the constituent materials and thicknesses of each layer is different from each other."

The thickness of the first member 9 can be arbitrarily set depending on the purpose and is not particularly limited.
The thickness of the first member 9 is, for example, preferably 100 to 2000 μm, more preferably 200 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 consisting of multiple layers refers to the thickness of the entire first member 9. means the total thickness of the layers.

In this specification, "thickness" is not limited to the case of the first member, and unless otherwise specified, "thickness" means the average value of the thickness measured at five randomly selected locations on the object. , can be obtained using a constant pressure thickness measuring device according to JIS K7130.

The thickness of the second member 8 can be arbitrarily set depending on the purpose and is not particularly limited.
The thickness of the second member 8 is, for example, preferably 100 to 1000 μm, more preferably 200 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 consisting of multiple layers refers to the thickness of the entire second member 8. means the total thickness of the layers. Therefore, when the second member 8 includes the metal film, the thickness of the second member 8 shown here is the total thickness including the metal film.

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

The thickness of the metal sintered layer 10 can be arbitrarily set depending on the purpose and is not particularly limited.
The thickness of the metal sintered layer 10 is, for example, preferably 5 to 100 μm, more preferably 14 to 38 μm. The metal sintered layer 10 having such a thickness suppresses protrusion from the ends of the first member 9 and the second member 8 (substantially the ends of the second member 8), and prevents the first member 9 and the second member 8 from protruding from each other. Both the sufficiently high bonding strength of the second member 8 (the sufficiently high bonding strength of the joined body 101) can be realized more stably. Further, the joined body 101 including the metal sintered layer 10 having such a thickness is particularly suitable for forming a power semiconductor element (power device), 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 consisting of multiple layers refers to the thickness of the metal sintered layer 10. means the total thickness of all the layers that make up the layer.

In the joined body 101, the protruding width of the metal sintered layer 10 from the end of the second member 8 is preferably 220 μm or less, more preferably 200 μm or less, for example, 180 μm or less, and 160 μm or less. It may be either. Particularly, when the thickness of the metal sintered layer 10 is within the above numerical range (for example, 12 to 40 μm), the joined body 101 in which the protrusion of the metal sintered layer 10 is suppressed in this way can be easily obtained. .
The lower limit of the protrusion width of the metal sintered layer 10 is 0 μm (the metal sintered layer 10 may not protrude).
Note that here, the protrusion width of the metal sintered layer 10 is calculated based on the end of the second member 8, but the reference when calculating the protrusion width of the metal sintered layer is based on the structure of the joined body. You can select as appropriate. For example, when the second member is larger than the first member, the protruding width of the sintered metal layer may be calculated based on the end of the first member.

In the joined body 101, when the protrusion of the metal sintered layer 10 is suppressed, the thickness of the metal sintered layer 10 can be prevented from becoming thinner than necessary. Furthermore, the laminate in which the film-like sintered material protrudes before forming the metal sintered layer 10 is easy to handle.

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

The shear strength of the joined body 101 can be measured, for example, by the following method.
That is, at room temperature, as shown in FIG. 2, a portion of the joined body 101 where the outer periphery (side surface) 10c of the metal sintered layer 10 and the outer periphery (side surface) 8c of the second member 8 are aligned. At the same time, at a speed of 200 μm/s in a direction parallel to one surface (the surface opposite to the first member 9 side) 8a of the second member 8 (in this case, the direction of arrow P). Add force. This direction is synonymous with, for example, "a direction parallel to the surface 9a of the first member 9 on the second member 8 side." When applying force to the part, for example, a plate-shaped pressing means 7 made of metal is used, and by applying force to the part through this pressing means 7, joining can be easily and with higher precision. Strength can be measured. The pressing means 7 is arranged so that its tip on the first member 9 side does not come into contact with 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 peels off from the first member 9 or the second member 8 is measured, and the measured value can be adopted as the shear strength of the joined body 101.

As used herein, "normal temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and includes, for example, a temperature of 15 to 25°C.

The shear strength of the joined body 101 is preferably 35 MPa or more, more preferably 45 MPa or more, even more preferably 60 MPa or more, and may be, for example, either 75 MPa or more and 85 MPa or more. .
The upper limit of the shear strength is not particularly limited. For example, the joined body 101 having the shear strength of 130 MPa or less can be manufactured more easily.
The shear strength of the bonded body 101 may be, for example, any one of 35 to 130 MPa, 45 to 130 MPa, 60 to 130 MPa, 75 to 130 MPa, and 85 to 130 MPa. However, these are examples of the shear strength.

The joined body obtained by the manufacturing method of the present embodiment is not limited to that shown in FIG. 1, but may be one in which a part of the structure of the one shown in FIG. 1 is changed or deleted within the range that does not impair the effects of the present invention. Alternatively, other configurations may be added to those described above.
For example, the joined body may include other elements that do not correspond to any of the first member, the sintered metal layer, and the second member.

<Film-shaped fired material>
The film-like sintered material is a forming material of the metal sintered layer.
Examples of the film-like sintered material include those containing sinterable metal particles and a binder component that is solid at 25°C.

[Sinterable metal particles]
By heating the film-like sintered material at a temperature equal to or higher than the melting point of the sinterable metal particles, the sinterable metal particles are melted and bonded to each other to form a metal sintered layer (sintered body). By forming the metal sintered layer, the metal sintered layer and the member fired in contact with the metal sintered layer are sintered and bonded. In this embodiment, the first member and the second member are joined by 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 the sinterable metal particles include particles of metals of these metal types, particles of oxides of one or more of the metals, particles of alloys of one or more of the metals, and the like. Examples of the oxides of two or more of the metals include barium titanate.
Among these, preferred sinterable metal particles include silver particles and silver oxide particles.

The film-shaped fired material may contain only one type of sinterable metal particles, or may contain two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. .

In this specification, "sinterable metal particles" specifically mean particles containing a metal element with a particle size 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, and may be, for example, either 50 nm or less or 30 nm or less. Sinterable metal particles having such a particle size have higher sinterability.

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

For sinterable metal particles, the number average of the particle diameters of metal particles observed with an electron microscope, determined for particles whose projected area circle equivalent diameter is 100 nm or less, is, for example, 0.1 to 95 nm. , 0.3 to 50 nm, and 0.5 to 30 nm. At this time, the metal particles to be measured are 100 or more randomly selected metal particles per sheet of the film-like fired material. For example, the metal particles to be measured may be 100 randomly selected metal particles per sheet of the film-like fired material.

The film-like sintered material of this embodiment includes metal particles with a particle size of 100 nm or less (i.e., sinterable metal particles) and metal particles with a particle size of more than 100 nm (hereinafter referred to as "non-sinterable metal particles"). (sometimes referred to as "sinterable metal particles").

In this specification, "non-sinterable metal particles" specifically mean particles containing a metal element with a particle diameter of more than 100 nm.

For non-sinterable metal particles, the number average of the particle size of metal particles observed with an electron microscope, determined for particles with a projected area circle equivalent diameter of more than 100 nm, is, for example, more than 150 nm and 50,000 nm or less. , 150 to 10,000 nm, and 180 to 5,000 nm. At this time, the metal particles to be measured are 100 or more randomly selected metal particles per sheet of the film-like fired material. For example, the metal particles to be measured may be 100 randomly selected metal particles per sheet of the film-like fired material.

Examples of the metal species of the non-sinterable metal particles include the same metal species as those exemplified as the metal species of the sinterable metal particles described above.
Preferred non-sinterable metal particles include silver particles, copper particles, silver oxide particles, and copper oxide particles.

The film-shaped fired material may contain only one type of non-sinterable metal particles, or may contain two or more types, and if there are two or more types, the combination and ratio thereof can be selected arbitrarily. can.

In the film-shaped fired material, the metal species of the sinterable metal particles and the metal species of the non-sinterable metal particles may be the same or different. 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. Further, for example, the film-shaped fired material may contain silver particles or silver oxide particles as sinterable metal particles, and may contain copper particles or copper oxide particles as non-sinterable metal particles.

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

In the film-shaped fired material, the surface of either or both of the sinterable metal particles and the non-sinterable metal particles may be coated with an organic substance. The sinterable metal particles and non-sinterable metal particles coated with an organic substance have improved compatibility with the binder component, can further suppress aggregation of particles, and can be dispersed more uniformly.
When the surface of the sinterable metal particles or non-sinterable metal particles is coated with an organic substance, a value including the organic substance is used as the mass of the sinterable metal particles or non-sinterable metal particles.

[Binder component]
The binder component is solid at 25° C., and by containing the binder component, the film-like fired material can maintain a film-like shape and has adhesive properties.
The binder component may be thermally decomposable, which thermally decomposes during firing (heat treatment) of the film-shaped fired material.

As used herein, "liquid" means a state in which the viscosity can be measured using a B-type viscometer under a temperature condition of 25°C. "Solid" means a state in which the viscosity cannot be measured using a B-type viscometer under a temperature condition of 25°C.

The binder component is not particularly limited as long as the effects of the present invention can be obtained.
Preferred binder components include, for example, resins.
Examples of the resin include acrylic resin, polycarbonate, polylactic acid, and polymers of cellulose derivatives, with acrylic resin being more preferred.
The acrylic resin includes, for example, a homopolymer of one (meth)acrylate compound; a copolymer of two or more (meth)acrylate compounds; one or more (meth)acrylate compounds; Examples include copolymers with one or more other copolymerizable monomers.

In this specification, "(meth)acrylate" is a concept that includes both "acrylate" and "methacrylate." The same applies to terms similar to (meth)acrylate; for example, "(meth)acrylic acid" is a concept that includes both "acrylic acid" and "methacrylic acid."

In the 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 to 100% by mass, and preferably 80 to 80% by mass. It is more preferably 100% by mass, and even more preferably 90 to 100% by mass.

Examples of (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, 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, dodecyl ( meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth)acrylate, n-octadecyl (meth)acrylate (stearyl (meth)acrylate), isooctadecyl (meth)acrylate (isostearyl (meth)acrylate), etc., where the alkyl group constituting the alkyl ester has 1 carbon number. ~18 chain structure, alkyl (meth)acrylate;
Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate Acrylate, hydroxyalkyl (meth)acrylate such as 4-hydroxybutyl (meth)acrylate;
Phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate;
Alkoxyalkyl (meth)acrylate such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-methoxybutyl (meth)acrylate, etc. ) acrylate;
Polyethylene glycol mono(meth)acrylate, ethoxydiethylene glycol(meth)acrylate, methoxypolyethylene glycol(meth)acrylate, phenoxypolyethylene glycol(meth)acrylate, nonylphenoxypolyethylene glycol(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxypolypropylene Polyalkylene glycol (meth)acrylates such as glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate;
Cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, bornyl (meth)acrylate, isobornyl ( cycloalkyl (meth)acrylates such as meth)acrylate, tricyclodecanyl (meth)acrylate;
Aralkyl (meth)acrylates such as benzyl (meth)acrylate;
Examples include tetrahydrofurfuryl (meth)acrylate.

The (meth)acrylate compound is preferably an alkyl (meth)acrylate or an alkoxyalkyl (meth)acrylate, such as butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, isodecyl (meth)acrylate. or 2-ethoxyethyl (meth)acrylate, more preferably 2-ethylhexyl (meth)acrylate, particularly preferably 2-ethylhexyl methacrylate.

Preferably, the acrylic resin has a structural unit derived from a methacrylate compound. A 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 unsaturated carboxylic acids (having an unsaturated bond) such as (meth)acrylic acid, vinylbenzoic acid (ethenylbenzoic acid), maleic acid, and vinyl phthalic acid (ethenyl phthalic acid). (carboxylic acid); Examples include vinyl group-containing radically polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methylstyrene, butadiene, and isoprene.

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 such a range, the film strength and flexibility of the film-shaped fired material become higher.

In this specification, the "weight average molecular weight" is a polystyrene equivalent value measured by gel permeation chromatography (GPC) unless otherwise specified.

The glass transition temperature (Tg) of the resin that is the binder component is preferably -60 to 50°C, more preferably -30 to 10°C, and even more preferably -20°C or more and less than 0°C. preferable. When the Tg of the resin is less than or equal to the upper limit value, the flexibility of the film-like fired material becomes higher, and the adhesive force of the film-like fired material to the adherend (first member, second member) becomes higher. It gets expensive. When the Tg of the resin is equal to or higher than the lower limit, it is easier to maintain the film shape of the fired film material, and it is easier to separate the fired film material from a support sheet, etc., which will be described later.

The glass transition temperature (Tg) of the resin that is the binder component can be calculated using the Fox equation. 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 binder component.
As the glass transition temperature (Tg) of the homopolymer of each monomer in the Fox formula, values described in the Polymer Data Handbook, Adhesive Handbook, etc. can be used.

The number of binder components contained in the film-shaped fired material may be one, or two or more, and when there are two or more, the combination and ratio thereof can be arbitrarily selected.

The fact that the binder component has been thermally decomposed during firing (heat treatment) of the film-shaped fired material can be confirmed, for example, by a decrease in the mass of the binder component during firing.
In the present embodiment, all of the binder component may be thermally decomposed, or a part of the binder component may not be thermally decomposed during firing of the film-like fired material.
In the present embodiment, the ratio of the amount (parts by mass) of the binder component (in other words, the metal sintered layer) after firing to the total amount (parts by mass) of the binder component before firing is, for example, 10% by mass or less, 5% by mass or less. It may be either 3% by mass or less, 3% by mass or less, or 0% by mass.

The film-shaped fired material does not contain other components that do not fall under any of sinterable metal particles, non-sinterable metal particles, or binder components, within a range that does not impair the effects of the present invention. Good too.

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

The liquid component has a boiling point of 300 to 450°C and is a liquid component at 25°C. By containing such a liquid component, the film-shaped fired material has a sufficiently high adhesive strength with the support sheet described later, and is excellent in dicing suitability.Furthermore, during firing, the first member and the second member are bonded to each other. The seepage of liquid components from between the parts is suppressed.

As used herein, "boiling point" means the boiling point under normal pressure (101325 Pa).

The solvent has a boiling point below 300°C and is a liquid component at 25°C.
Examples of the solvent include water, organic solvents, and the like.
The solvent is a preferable component in that it improves the handleability of the firing material composition described below.

The additives are not particularly limited. Examples of the additives include various additives known in the art, such as dispersants, tackifiers, storage stabilizers, antifoaming agents, thermal decomposition promoters, and antioxidants.

The film-shaped fired material may contain only one kind of other components, or two or more kinds thereof, and when they are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

In the film-shaped fired material, the content ratio of the other components to the total mass of the film-shaped fired material is preferably 2% by mass or less, more preferably 1% by mass or less.

A film-like fired material with a support sheet, which will be described later, includes a film-like fired material and a support sheet provided on at least one surface of the film-like fired material.
In the film-shaped fired material with a support sheet, the adhesive strength (a2) of the film-shaped fired material to the support sheet is smaller than the adhesive strength (a1) of the film-shaped fired material to the silicon wafer, and the adhesive strength It is preferable that (a1) is 0.1 N/25 mm or more, and the adhesive force (a2) is 0.1 to 2 N/25 mm or 0.1 to 0.5 N/25 mm.

The adhesive force (a1) can be measured by the following method.
That is, prepare a silicon wafer (for example, a silicon wafer manufactured by Science and Technology Research Institute, 150 mm in diameter and 500 μm in thickness) that has been chemically mechanically polished until the arithmetic mean roughness (Ra) of the surface becomes 0.02 μm. The film-like fired material in the film-like fired material with support sheet is set at a temperature of 50° C. and is attached to the treated surface of the silicon wafer. Next, the support sheet is peeled off from the film-like fired material, and a polyethylene terephthalate film (PET film, thickness 12 μm) is attached to the exposed surface of the film-like fired material to firmly adhere (back) it. Next, this laminate of the PET film and the film-like fired material is cut into pieces with a width of 25 mm and a length of 100 mm or more to obtain a laminate in which the laminate consisting of the film-like fired material and the PET film is attached to a silicon wafer. get. Next, the obtained laminate was left for 20 minutes in an atmosphere with a temperature of 23° C. and a relative humidity of 50%, and then tested using a universal tensile tester (for example, "5581 model tester" manufactured by Instron). A 180° peel test is performed in accordance with Z0237:2000. More specifically, a film-like fired material lined with a PET film is peeled off from a silicon wafer at a peeling speed of 300 mm/min along with the PET film. At this time, the film-like fired material lined with the PET film is peeled off in its length direction so that the surfaces of the silicon wafer and the film-like fired material that were in contact with each other form an angle of 180°. Then, the load (peel force) in this 180° peel test is measured, and the measured value is adopted as the adhesive force (a1) (N/25 mm).

The adhesive force (a2) can be measured by the following method.
That is, after leaving the film-shaped fired material with a supporting sheet in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 20 minutes, it was tested using a universal tensile tester (for example, "Type 5581 tester" manufactured by Instron). , a 180° peel test is conducted in accordance with JIS Z0237:2000. More specifically, a polyethylene terephthalate film (PET film, thickness 12 μm) was pasted on the exposed surface of the film-like fired material in the film-like fired material with a support sheet, and the PET film was pasted from the support sheet. The film-like fired material is peeled together with the PET film at a peeling speed of 300 mm/min. At this time, the film-like fired material is peeled off along with the PET film in its length direction so that the surfaces of the support sheet and the film-like fired material that were in contact with each other form an angle of 180°. Then, the load (peel force) in this 180° peel test is measured, and the measured value is employed as the adhesive force (a2) (N/25 mm).

A film-shaped fired material obtained by using either the first member or the second member in place of the chemical-mechanically polished silicon wafer, but otherwise using the same method as the above-mentioned method for measuring adhesive force (a1). The adhesive force to either the first member or the second member is preferably 0.1 N/25 mm or more, more preferably 0.5 N/25 mm or more, and 1.0 N/25 mm or more. It is even more preferable that there be. When the adhesive force (a1) is greater than or equal to the lower limit, the dicing suitability of the film-shaped fired material becomes higher. Further, when the first member and the second member are transported while being temporarily fixed with the film-like firing material before firing, it is possible to suppress the position of the first member or the second member from shifting.

The above adhesive force (a2) is preferably 0.1 to 0.5 N/25 mm, more preferably 0.2 to 0.5 N/25 mm, and 0.2 to 0.4 N/25 mm. It is even more preferable that there be. When the adhesive force (a2) is equal to or greater than the lower limit value, the dicing suitability of the film-shaped fired material becomes higher.
Since the adhesive force (a2) is smaller than the adhesive force (a1) and is less than or equal to the upper limit value, either one of the first member and the second member can be divided (for example, by dicing in the case of a wafer). A laminate of a divided product obtained by singulation (for example, a chip in the case of a wafer) and a cut product of the film-like fired material (for example, a chip with the film-like fired material in the case of a wafer), When peeled from the support sheet, the film-like fired material is easily peeled off from the support sheet, and the laminate can be peeled off more easily.

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

In the film-shaped fired material, the ratio of the content to the total content of all components other than those that are liquid at 25 ° C. (herein sometimes referred to as "solid content") is 15 to 15. It is preferably 98% by mass, more preferably 15-95% by mass, and even more preferably 20-90% by mass. When the ratio is equal to or less than the upper limit, a sufficient content of the binder component can be ensured in the film-shaped fired material, so that the film shape can be maintained more stably. When the ratio is equal to or higher than the lower limit value, the fusion between sinterable metal particles or between sinterable metal particles and non-sinterable metal particles progresses more during firing, and the bonding strength of the bonded body increases. It gets expensive.

When the film-like fired material contains non-sinterable metal particles, the ratio of the total content of the sinterable metal particles and the non-sinterable metal particles to the total solid content in the film-like fired material is: It is preferably 50 to 98% by weight, more preferably 70 to 97% by weight, and even more preferably 80 to 95% by weight.

In the film-shaped fired material, the content ratio of the binder component to the total solid content is preferably 2 to 50% by mass, more preferably 3 to 30% by mass, and 5 to 20% by mass. % is more preferable. When the ratio is equal to or less than the upper limit value, a sufficient content of sinterable metal particles can be ensured in the film-like fired material, so that the bonding adhesive strength between the film-like fired material and the first member or the second member is improved. will be further improved. When the ratio is equal to or higher than the lower limit, the film shape of the film-shaped fired material can be maintained more stably.

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

In the film-shaped sintered material, the content ratio of the solvent (including a relatively high-boiling point solvent) contained in the sintered material composition described below to the total mass of the film-shaped sintered material may be 1% by mass or less. preferable.

[Physical properties of film-shaped fired material]
The film-like fired material has a softness above a certain value.
More specifically, the test laminate is configured by laminating a silicon chip, a metal film, and a test piece of the film-like fired material in this order in the thickness direction, The chip has a rectangular planar shape, the metal film is provided by vapor deposition on the surface of the silicon chip on the film-like fired material side, and the metal film is provided on the film-like fired material side of the silicon chip. A test laminate that covers the entire surface of the film, the test piece of the film-like fired material is the same size as the silicon chip, and the film-like fired material does not protrude from the outer periphery of the silicon chip. was prepared, the entire exposed surface of the test piece in the test laminate was brought into contact with a copper plate, the test laminate was placed on the copper plate, and the test laminate and the copper plate were heated at 300°C. While heating, a pressure of 10 MPa was applied to the test laminate for 3 minutes from the silicon chip side in the stacking direction of the silicon chip, the metal film, and the test piece, The maximum width of the protrusion of the test piece from the outer periphery of the silicon chip is more than 220 μm.
By setting the maximum value of the protrusion width within such a range, the protrusion of the metal sintered layer from the ends of the first member and the second member is suppressed, and the bonding strength between the first member and the second member is improved. A well-balanced effect can be obtained in which the amount of energy is sufficiently increased.
Here, the fact that the test piece of the film-like fired material is the same size as the silicon chip means that the area of the silicon chip side of the test piece of the film-like fired material is the same as that of the silicon chip. This means that the area of one side of the test is equivalent to the area of the other side.
Furthermore, since the metal film is provided on the surface of the silicon chip on the side of the film-like fired material by vapor deposition, the metal film does not protrude from the outer periphery of the silicon chip at all, or even if it does, it does not protrude. The width is extremely small and can be ignored, and it can be considered that there is no substantial protrusion.

In the test laminate, for example, the thickness of the silicon chip may be 50 to 1000 μm, the planar shape of the silicon chip is square, and the size is 1 to 3 mm x 1 to 3 mm. You can. The metal film may be a silver film. The thickness of the metal film may be, for example, 0.2 to 2 μm. As a particularly preferable test laminate, for example, the thickness of the silicon chip is 345.5 μm, the planar shape of the silicon chip is square, and the size is 2 mm x 2 mm, and the metal film has a thickness of One example is a silver film with a diameter of 0.5 μm.
That is, in this embodiment, a silicon chip with a thickness of 345.5 μm, a silver film with a thickness of 0.5 μm, and a test piece of the film-shaped fired material are placed in this order in the thickness direction. A test laminate configured by stacking, wherein the silicon chip has a rectangular planar shape and a size of 2 mm x 2 mm, and the silver film is formed of the film-like fired material of the silicon chip. The silver film is provided on the side surface by vapor deposition, and the silver film covers the entire surface of the silicon chip on the side of the film-like fired material, and the test piece of the film-like fired material is attached to the silicon chip. A test laminate having the same size and in which the film-like fired material does not protrude from the outer periphery of the silicon chip is prepared, and the entire exposed surface of the test piece in the test laminate is brought into contact with a copper plate. Then, the test laminate is placed on the copper plate, and while the test laminate and the copper plate are heated to 300° C., the silicon chip and the silver film are placed on the test laminate. When a pressure of 10 MPa is applied for 3 minutes from the silicon chip side in the stacking direction of the test piece and the test piece, the maximum width of the protrusion of the test piece from the outer periphery of the silicon chip exceeds 220 μm. is particularly preferred.

The test laminate can be produced, for example, by the method shown below.
That is, first, one side of the film-shaped fired material is bonded to the exposed surface of the metal film of a silicon chip provided with a metal film (herein sometimes referred to as a "silicon chip with a metal film"). Laminate film-like fired materials. At this time, a film-like fired material is used in which the area of the one surface is larger than the area of the exposed surface of the metal film. Then, by bonding the one surface of the film-like fired material to the entire exposed surface of the metal film, an excess portion of the film-like fired material is generated over the entire outer periphery of the metal film. Next, this excess portion of the film-shaped fired material is cut and removed. In this embodiment, the film-like fired material after removing the surplus portion is treated as a test piece. In this way, when attaching the film-like fired material to the silicon chip with a metal film and when removing the excess portion of the film-like fired material, only the minimum necessary pressure is applied to the film-like fired material, It is preferable to adjust the shape and size of the film-like fired material so that they do not change. As a result, the outer periphery (side surface) of the test piece of the film-shaped fired material and the outer periphery (side surface) of the silicon chip with metal film are aligned, and the outer periphery (side surface) of one of them is aligned with the outer periphery (side surface) of the other. It is in a state where it does not protrude from the surface.
As described above, a silicon chip with a metal film and a test piece of film-like fired material of the same size are stacked, and the outer circumferences (side surfaces) of these are aligned. A test laminate is obtained in which the test piece of the film-like fired material does not protrude from the outer periphery.

More specifically, the protrusion width of the film-like fired material in the test laminate can be measured, for example, by the method shown below.
That is, first, of the test piece of the film-like fired material in the test laminate, the entire surface of the surface opposite to the silicon chip side with the metal film (i.e., the exposed surface) was brought into contact with one surface of the copper plate. , the test laminate is placed on a copper plate. At this time, a copper plate is used in which the area of the one surface thereof is larger than the area of the opposite surface of the test piece of the film-shaped fired material. By doing this, the copper plate protrudes from the entire area of the outer periphery (side surface) of the test laminate, that is, the outer periphery (side surface) of the film-shaped fired material test piece and the outer periphery (side surface) of the silicon chip. do. At this time, it is preferable to apply only the minimum necessary pressure to the test piece of the film-like fired material so that the shape and size of the test piece of the film-like fired material do not change.
Next, while heating the test laminate and the copper plate to 300° C., the metal film-covered silicon chip was applied to the test laminate in the direction in which the metal film-covered silicon chip and the test piece of the film-shaped fired material were laminated. A pressure of 10 MPa is applied from the chip side for 180 seconds. At this time, for example, the laminate of the test laminate and the copper plate may be sandwiched between a pair of heatable plates, and the test laminate and the copper plate may be heated together at 300°C with these plates; The test laminate and the copper plate may be heated together at 300°C by placing the laminate and the copper plate in an isolated environment whose temperature is controlled at 300°C. Then, while the laminate is supported on its copper plate side, a metal film-coated silicon chip in the laminate is exposed from the outside of the laminate in a direction from the silicon chip to the test piece of the film-like fired material. , a pressure of 10 MPa is applied for 180 seconds.
Next, after releasing both the above-described heating of the test laminate and the copper plate and the above-mentioned pressure applied to the test laminate, heating from the outer periphery of the metal film-coated silicon chip at room temperature, such as room temperature, is performed. The protrusion width of the test piece of the film-like fired material is measured over the entire outer periphery of the silicon chip with the metal film. Then, the maximum value among the measured values is determined, and this value is adopted as the maximum value of the protrusion width of the test piece of the film-shaped fired material from the outer periphery of the silicon chip with the metal film.
The thickness of the copper plate is preferably 1 to 5 mm, for example.

The maximum value of the protrusion width determined using the test laminate is more than 220 μm, and may be more than 235 μm, for example. On the other hand, the maximum value of the protrusion width is preferably less than 500 μm, and may be, for example, less than 400 μm. By setting the maximum value of the protrusion width within such a range, the protrusion of the metal sintered layer from the ends of the first member and the second member is suppressed, and the bonding of the first member and the second member is suppressed. The effect of sufficiently increasing the strength is increased in both cases.
The maximum value of the protrusion width may be, for example, more than 220 μm and less than 500 μm, more than 235 μm and less than 500 μm, more than 220 μm and less than 400 μm, and more than 235 μm and less than 400 μm.

The softness of the film-like fired material and the protrusion width of the film-like fired material from the outer periphery of the silicon chip described above can be adjusted by adjusting the components of the film-like fired material (components of the fired material composition described later). can. For example, by increasing the content of the binder component in the film-like fired material (fired material composition), the softness of the film-like fired material can be improved and the protrusion width of the above-mentioned film-like fired material can be increased.

Since the film-like fired material is film-like, it has excellent thickness stability.

The shape of the film-like fired material may be appropriately set according to the shape of the first member or the second member to be joined, and is not particularly limited. In this specification, the term "shape of the film-like fired material" means, unless otherwise specified, when the film-like fired material is viewed from above on the side to which it is attached to the first or second member. It means the shape at the time (i.e., the planar shape).
The shape of the film-like fired material is preferably circular or rectangular, for example. A circular shape is suitable, for example, when the second member is a semiconductor wafer. In this case, the film-like fired material and the second member (semiconductor wafer) have the same shape or approximately the same shape. A rectangle is a suitable shape, for example, when the second member is a chip. In this case, the film-like fired material and the second member (chip) have the same shape or approximately the same shape.

When the shape of the film-like fired material is circular, the area of the circle may be, for example, either 3.5 to 1600 cm ² or 85 to 1400 cm ² . When the shape of the film-like fired material is rectangular, the area of the rectangle may be, for example, either 0.01 to 25 cm ² or 0.25 to 9 cm ² .

The film-like fired material can be configured as a support sheet-attached film-like fired material in which a support sheet is provided on at least one surface of the film-like fired material.
The film-shaped fired material with support sheet will be explained in detail later.

<Method for manufacturing film-shaped fired material>
A film-like fired material can be formed using a fired material composition containing its constituent materials. The film-shaped fired material may contain a solvent.
For example, by coating or printing the firing material composition on the surface to be formed of the film-like fired material and evaporating the solvent as needed, the film-like fired material can be formed in the desired area.
The surface to be formed of the film-like fired material includes the release-treated surface of the release film.

When the firing material composition contains a solvent, the firing material composition may contain only one type of solvent, or two or more types, and when there are two or more types, a combination thereof. and the ratio can be selected arbitrarily.

When applying the firing material composition, the solvent preferably has a boiling point of less than 200°C. Examples of such solvents include n-hexane (boiling point 68°C), ethyl acetate (boiling point 77°C), 2-butanone (also known as methyl ethyl ketone, boiling point 80°C), n-heptane (boiling point 98°C), and methylcyclohexane. (boiling point: 101°C), toluene (boiling point: 111°C), acetylacetone (boiling point: 138°C), n-xylene (boiling point: 139°C), dimethylformamide (boiling point: 153°C), and the like.

The firing material composition may be applied by a known method. The fired material composition is, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a comma coater (registered trademark), a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, a Meyer bar coater. Coating can be performed using various coaters such as , kiss coater, etc.

When printing a fired material composition, the solvent may be any solvent as long as it can be volatilized and dried after printing, and preferably has a boiling point of 65 to 280°C. Such relatively high boiling point solvents include the aforementioned solvents with a boiling point of less than 200°C, as well as isophorone (boiling point 215°C), butyl carbitol (boiling point 230°C), and 1-decanol (boiling point 233°C). ), butyl carbitol acetate (boiling point 247°C), and the like.
When the boiling point of the solvent is 280° C. or less, the solvent easily evaporates during evaporation drying after printing, and it is easy to obtain a film-like fired material in the desired shape. Furthermore, the solvent is less likely to remain inside the film-like fired material during firing of the film-like fired material, and the bonding adhesiveness of the film-like fired material becomes higher. When the boiling point of the solvent is 65° C. or higher, volatilization of the solvent is suppressed during printing, and the uniformity of the thickness of the film-shaped fired material becomes higher. In particular, when the boiling point of the solvent is 200 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.

Printing of the fired material composition may be performed by a known method. The fired material composition can be applied, for example, to a letterpress printing method such as a flexo printing method; an intaglio printing method such as a gravure printing method; a lithography method such as an offset printing method; a screen printing method such as a silk screen printing method or a rotary screen printing method; It can be printed by a printing method using various printers such as an inkjet printer.
By printing the fired material composition, it is easier to form a film-like fired material in the desired shape than when coating it.

When the firing material composition contains a solvent, the content of the solvent is preferably 5 to 60% by mass with respect to the total mass of the firing material composition, for example, 5 to 30% by mass, and 5 to 30% by mass. It may be either 15% by mass. When the ratio is within such a range, the coating suitability or printing suitability of the fired material composition becomes higher.

The drying conditions for the fired material composition are not particularly limited, and when the fired material composition contains a solvent, it is preferable to dry it by heating. When drying the fired material composition by heating, it is preferable to dry it at, for example, 70 to 250°C or 80 to 180°C for 10 seconds to 15 minutes.

<Film-shaped fired material with support sheet>
The film-like fired material with a support sheet in this embodiment includes a support sheet and the film-like fired material provided on one surface of the support sheet.
Examples of the support sheet include those comprising a base film and an adhesive layer provided on one surface of the base film; and those comprising only the base film.
When the support sheet includes the base film and the adhesive layer, in the film-shaped fired material with the support sheet, the film-shaped fired material is opposite to the base film side of the adhesive layer. It is placed on the side surface.

The film-like fired material with a support sheet can be used, for example, to divide a member (herein sometimes referred to as an "undivided member") to form a second member by division. For example, when a wafer is used as the undivided member, it can be used as a dicing sheet for dividing the wafer into chips by dicing. At this time, the film-like fired material can also be cut together with the undivided members, and when the wafer is divided into chips by dicing, the wafer and the cut film-like fired material provided on the back surface of the wafer, A chip with a film-like fired material can be manufactured.
By using the film-like fired material with a support sheet, the first laminate can be produced in step (I) of the method for producing a bonded body, which will be described later.

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

The film-shaped fired material with a supporting sheet used in the manufacturing method of this embodiment is not limited to that shown in FIG. 3, and a part of the structure of that shown in FIG. The configuration may be deleted, or other configurations may be added to those described above.
For example, the film-like fired material with a support sheet may include other elements that do not correspond to any of the base film, the adhesive layer, and the film-like fired material. For example, in the film-like fired material with a support sheet shown in FIG. 3, the adhesive layer is provided in direct contact with one surface of the base film, and the film-like fired material is on the base film side of the adhesive layer. Although it is provided in direct contact with the opposite surface, the film-like fired material with a support sheet is provided between the base film and the adhesive layer, or between the adhesive layer and the film-like fired material, It may also include other layers (films).
In addition, in the film-shaped fired material with a support sheet shown in FIG. 3, an adhesive layer is provided on the entire surface of one surface of the base film, but on a part of the region of one surface of the base film. does not need to be provided with an adhesive layer.

[Base 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, polypropylene (PP), polybutene, polybutadiene, polymethylpentene, and ethylene-vinyl acetate copolymer. coalescence, ethylene-(meth)acrylic acid copolymer, ethylene-methyl(meth)acrylate copolymer, ethylene-ethyl(meth)acrylate copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Examples include polyurethane and ionomer.
Further, when higher heat resistance is required for the support sheet, examples of the resin include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefins such as polypropylene and polymethylpentene. .
Examples of the resin include those obtained by crosslinking the resins listed above (crosslinked resins), and modified resins obtained by irradiating or discharging the resins listed above.

The base film may be composed of one layer (single layer) or may be composed of two or more layers, and when it is composed of multiple layers, these multiple layers may be the same or different from each other. They may be different, 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 to 300 μm, and may be, for example, 50 to 200 μm. When the thickness of the base film is within such a range, even if the base film is cut by dicing, the base film is unlikely to be torn. Moreover, since the film-shaped fired material with a support sheet has sufficient flexibility, it exhibits 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 consisting of multiple layers is the total thickness of all the layers that make up the base film. means the thickness of

The surface of the base film may be subjected to release treatment using a release agent (or may have a release treatment surface). Examples of the release agent include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, or wax-based release agents.
Among these, particularly preferable release agents include alkyd-based, silicone-based, and fluorine-based release agents in terms of their heat resistance.

[Adhesive layer]
The adhesive layer may be, for example, weakly adhesive or energy ray curable.

As used herein, the term "energy ray" refers to electromagnetic waves or charged particle beams that have energy quanta, examples of which include ultraviolet rays, radiation, electron beams, and the like. The ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, fusion lamp, xenon lamp, black light, or LED lamp as an ultraviolet source. The electron beam can be generated by an electron beam accelerator or the like.
As used herein, "energy ray curability" means the property of being cured by irradiation with energy rays.

As the adhesive constituting the adhesive layer, various known adhesives (for example, general-purpose adhesives such as rubber-based, acrylic-based, silicone-based, urethane-based, vinyl ether-based, etc.; adhesives with uneven surfaces; energy ray-curable adhesives; adhesives containing thermal expansion components, etc.).

The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 2 to 80 μm, and even more preferably 3 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 consisting of multiple layers is the total thickness of all the layers that make up the adhesive layer. means the thickness of

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

<Method for manufacturing film-shaped fired material with support sheet>
The film-like fired material with a support sheet can be manufactured by sequentially laminating the above-mentioned layers in a corresponding positional relationship.
For example, when laminating an adhesive layer or a film-like fired material on one side of a base film, an adhesive composition containing components and a solvent for forming the adhesive layer is placed on the release film, Alternatively, a fired material composition containing components and a solvent for forming a film-like fired material is coated or printed, and if necessary, the solvent is evaporated by drying to form a film. An adhesive layer or a film-like sintered material is formed in advance on the wafer. Then, the exposed surface of the formed adhesive layer or film-shaped fired material on the side opposite to the release film side may be bonded to one surface of the base film. At this time, the pressure-sensitive adhesive composition or the firing material composition is preferably coated or printed on the release-treated surface of the release film. The release film may be removed as necessary after the laminated structure is formed.

For example, when laminating a film-like fired material on the side opposite to the base film side of the adhesive layer laminated on the base film, use the method described above to laminate the adhesive layer on the base film. Stack the agent layers. Separately, a firing material composition containing components and a solvent for forming the film-like fired material is coated or printed on the release film, and if necessary, the solvent is evaporated by drying to form a film-like fired material. By doing so, a film-like sintered material is formed on the release film in advance. Then, the exposed surface of the formed film-shaped fired material on the side opposite to the release film side may be bonded to the exposed surface of the adhesive layer laminated on the base film. At this time, the firing material composition is preferably coated or printed on the release-treated surface of the release film. The release film may be removed as necessary after the laminate structure is formed.

<<Method for manufacturing joined body>>
Next, a method for manufacturing the joined body of this embodiment will be explained.
FIG. 4 is a cross-sectional view schematically showing an example of the method for manufacturing the joined body of this embodiment. Here, the case of manufacturing the joined body 101 shown in FIG. 1 will be described as an example.

<<Step (I)>>
In the step (I), as shown in FIG. 4(a), the first member 9, the film-shaped sintered material 1 for forming the metal sintered layer 10, and the second member 8 are formed in this order. , a first laminate 1011 is manufactured by stacking these 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, those described above can be used.

In the first laminate 1011, it is preferable that the film-shaped fired material 1 does not protrude from the outer periphery of the smaller of the first member 9 and the second member 8, that is, the second member 8. By doing so, a second laminate 1012, which will be described later, can be obtained more easily.
In the first laminate 1011, the size of the film-like fired material 1 is equal to or smaller than the size of the second member 8 (the area of the contact surface of the film-like fired material 1 with the second member 8 is , is preferably equal to or smaller than the area of the contact surface of the second member 8 with the film-like fired material 1. For example, the area of the contact surface of the film-like fired material 1 with the second member 8 is preferably It may be either 80 to 100% or 90 to 100% of the area of the contact surface of the second member 8 with the film-shaped fired material 1. In such a case, in the joined body described below, the protrusion of the metal sintered layer from the end of the second member 8 is further suppressed, and the bonding strength between the first member 9 and the second member 8 is further increased.
In this specification, "equivalent in size" means that the objects to be compared are exactly the same size, or even if they are not exactly the same size, the difference in size is negligible. It means minute.

Here, the case where the second member is smaller than the first member is shown, but if the first member is smaller than the second member, in the first laminate, the film-like firing starts from the outer periphery of the first member. It is preferable that the material does not protrude, and the size of the film-like fired material is equal to or smaller than the size of the first member (the area of the contact surface of the film-like fired material with the first member is For example, the area of the contact surface of the film-like fired material with the first member is preferably equal to or smaller than the area of the contact surface of the member with the film-like fired material. It may be either 80 to 100% or 90 to 100% of the area of the contact surface with the material. In such a case, the same effect as above can be obtained.

Step (I) can be performed, for example, in the same manner as in the case of producing the test laminate described above.
That is, one side of the film-like fired material 1 is attached to one side of the second member 8, and the film-like fired material 1 is laminated. At this time, as the film-shaped fired material 1, the one whose area of the one surface is larger than the area of the one surface of the second member 8 is used. Then, by bonding the one surface of the film-shaped sintered material 1 to the entire surface of the one surface of the second member 8, the excess portion of the film-shaped sintered material 1 is removed over the entire outer periphery of the second member 8. bring about Next, this surplus portion of the film-shaped fired material 1 is cut and removed. In this way, when attaching the film-like fired material 1 to the second member 8 and when removing the excess portion of the film-like fired material 1, only the minimum necessary pressure is applied to the film-like fired material 1. Therefore, it is preferable to adjust the shape and size of the film-like fired material 1 so that they do not change. As a result, the outer periphery (side surface) of the film-shaped fired material 1 and the outer periphery (side surface) of the second member 8 are aligned, and the outer periphery (side surface) of one of them protrudes from the outer periphery (side surface) of the other. There will be no.
Next, the entire surface of the film-shaped fired material 1 in the obtained laminate, the surface opposite to the second member 8 side (i.e., the exposed surface), is brought into contact with one surface of the first member 9, The laminate is placed on the first member 9. At this time, the first member 9 used is one in which the area of the one surface is larger than the area of the opposite surface of the film-shaped fired material 1. By doing so, the first member 9 stands out. Also at this time, it is preferable to apply only the minimum necessary pressure to the film-like fired material 1 so that the shape and size of the film-like fired material 1 do not change.
As a result of the above, a first laminate 1011 shown in FIG. 4(a) in which the size of the film-shaped fired material 1 is equivalent to the size of the second member 8 is obtained.

Step (I) can also be performed using the film-shaped fired material with a support sheet.
That is, in the present embodiment, a support sheet-attached film-like fired material including a support sheet and the film-like fired material provided on one surface of the support sheet is prepared, and further, an undivided member is prepared, and the undivided member becomes the second member by dividing, and the surface of the film-shaped fired material in the film-shaped fired material with support sheet, which is opposite to the support sheet side, By pasting it on the undivided member, an undivided laminate including the support sheet-attached film-shaped fired material and the undivided member are laminated, and the undivided laminate in the undivided laminate is attached to the undivided member. By dividing the dividing member to produce the second member and cutting the film-like fired material, the second member and one surface of the second member are provided on the support sheet. In addition, after producing a second member with a film-like fired material including the cut film-like fired material, and peeling the second member with the film-like fired material from the support sheet, The step (I) can be carried out by attaching the surface of the film-like fired material in the attached second member on the side opposite to the second member to the first member.

The support sheet includes a base film and an adhesive layer provided on one surface of the base film, and the support sheet-attached film-like fired material is the film-like fired material. However, in the case of using an adhesive layer provided on the surface opposite to the base film side, the second member with the film-like fired material is peeled off from the adhesive layer. .
Furthermore, when the adhesive layer is energy ray curable, the adhesive layer is cured by irradiation with energy rays, and then the second member with the film-like sintered material is attached to the cured product of the adhesive layer. Peel from.

FIG. 5 is a cross-sectional view schematically illustrating an example of step (I) when using a film-like fired material with a support sheet. Here, an example will be described in which a film-shaped fired material 301 with a support sheet shown in FIG. 3 is used.

In this case, in step (I), as shown in FIG. , by attaching it to the undivided member 20, to produce an undivided laminate 320 in which the support sheet-attached film-like fired material 301 and the undivided member 20 are laminated.

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

Next, the undivided member 20 in the undivided laminate 320 is divided to produce a plurality of second members 8, and the film-shaped fired material 1 is cut, as shown in FIG. 5(b). , on the support sheet 2, the second member 8 and the cut film-shaped fired material ( In this specification, a plurality of second members 81 with a film-like sintered material are prepared, each of which includes 1 (sometimes simply referred to as a "film-form sintered material"). In this specification, a structure in which a plurality of second members 81 with film-like fired materials are held on the support sheet 2 is referred to as a second member group with film-like fired materials, and is designated by the reference numeral 321 here. It shows. The second member 81 with film-like fired material is held in contact with the adhesive layer 22 in the support sheet 2 by the film-like fired material 1 therein.

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-shaped fired material 1 can be performed using a dicing blade.

Next, as shown in FIG. 5(c), in the second member group 321 with film-like fired material, the second member 81 with film-like fired material is attached to the support sheet 2, more specifically, the adhesive in the support sheet 2. It peels off from the agent layer 22.
Peeling of the second member 81 with the film-like fired material can be performed by a known method, for example, a method of picking up a semiconductor chip, etc. can be applied.
Here, a case is shown in which the second member 81 with the film-like fired material is peeled off in the direction of arrow U using the peeling means 6 such as a vacuum collet. Note that the cross-sectional representation of the peeling means 6 is omitted here.

When the adhesive layer 22 is energy ray-curable, the adhesive layer 22 is cured by irradiation with energy rays, and then the second member 81 with the film-like sintered material is peeled off from the cured product of the adhesive layer 22. do. In FIG. 5(c), the cured product of the adhesive layer 22 is designated by the reference numeral 22'. Since the adhesive force of the cured product 22' of the adhesive layer is smaller than the adhesive force of the adhesive layer 22, the second member 81 with the film-like fired material is peeled off after the adhesive layer 22 is cured in this way. Thereby, the second member 81 with the film-like fired material can be peeled off more easily.

Next, the surface 1 b of the film-like fired material 1 in the second member 81 with film-like fired material, which is opposite to the second member 8 side, is attached to the first member 9 .
Through the above steps, a first laminate 1011 shown in FIG. 4(a) is obtained.

<<Step (II)>>
In the step (II), as shown in FIG. 4(b), in the first laminate 1011, the first layer is heated so that the protruding width L of the film-like fired material 1 from the second member 8 is 220 μm or less. With respect to the laminate 1011, the lamination direction of the first member 9, the film-shaped fired material 1, and the second member 8 (the direction D ₁ from the first member 9 to the second member 8, or the direction D 1 from the first member 9 to the second member 8) In the direction D2) from 8 to the first member ₉ , the film-shaped fired material 1 in the first laminate 1011 is heated while applying a pressure of 0.1 MPa or more. As a result, as shown in FIG. 4(c), the first member 9, the heated film-shaped fired material 1', and the second member 8 are laminated in this order in the thickness direction. A second laminate 1012 is produced.

The film-like fired material 1' after heating in the second laminate 1012 may be the same as the film-like fired material 1 in the first laminate 1011, or may be different. Which one it is depends on the composition of the film-shaped fired material 1. In this specification, the "film-like fired material after heating" may be simply referred to as the "film-like fired material."

In step (II), the pressure applied to the first laminate 1011 is not particularly limited as long as it is 0.1 MPa or more and the protrusion width L of the film-like fired material 1 is 220 μm or less. The pressure may be, for example, either 0.3 MPa or more and 0.5 MPa or more, or less than 3 MPa, 2.9 MPa or less, 2.5 MPa or less, 2 MPa or less, and 1.5 MPa or less. There may be.
In one embodiment, the pressure is, for example, 0.1 MPa or more and less than 3 MPa, 0.1 to 2.9 MPa, 0.3 to 2.9 MPa, 0.5 to 2.5 MPa, 0.5 to 2 MPa, and It may be any one of .5 to 1.5 MPa. However, these are examples of the above-mentioned pressures.
In step (II), the pressure applied to the first laminate 1011 is equal to or higher than the lower limit, so that in the second laminate 1012, the adhesion between the first member 9 and the film-shaped fired material 1' is improved; , the adhesion between the second member 8 and the film-shaped fired material 1' is improved. As a result, a joined body with high bonding strength between the first member 9 and the second member 8 can be obtained through step (III) described below.
In step (II), the pressure applied to the first laminate 1011 is equal to or less than the upper limit value, so that the protrusion width L of the film-like fired material becomes smaller.

In step (II), in the first laminate 1011, the protrusion width L of the film-like fired material from the second member 8 is set to 220 μm or less over the entire outer periphery (side surface) 8c of the second member 8.

In step (II), the protrusion width L of the film-like fired material 1 and the protrusion width of the film-like fired material 1' are both 220 μm or less, for example, any of 200 μm or less, 180 μm or less, and 160 μm or less. It may be. The smaller the protrusion width L of the film-like fired material 1 and the protrusion width of the film-like fired material 1', the smaller the protrusion width of the metal sintered layer 10 from the end of the second member 8 in the joined body 101, which will be described later. .
The lower limit of the protrusion width L of the film-shaped fired material 1 and the protrusion width of the film-shaped fired material 1' is 0 μm (the film-shaped fired material 1 and the film-shaped fired material 1' may not protrude), Usually, it is more than 0 μm, and may be, for example, 40 μm or more, or 80 μm or more.
In one embodiment, the protrusion width L of the film-like fired material 1 and the protrusion width of the film-like fired material 1' may be, for example, any one of more than 0 μm and 200 μm or less, 40 to 180 μm, and 80 to 160 μm. . However, these are examples of the protruding width L of the film-like fired material 1 and the protruding width of the film-like fired material 1'.

In step (II), for example, the first member 9 side only supports (receives pressure) the first laminate 1011, and no pressure is applied to the first laminate 1011 from the first member 9 side. Instead, pressure can be applied from the second member 8 side (pressure can be applied to the second member 8 in the direction _D2 ). Further, the second member 8 side only supports (receives pressure) the first laminate 1011, and no pressure is applied to the first laminate 1011 from the second member 8 side, and the first member 9 Pressure can be applied from the side (pressure applied to the first member 9 in direction _D1 ). Further, pressure is applied to the first laminate 1011 from both the first member 9 side and the second member 8 side (pressure is applied to the second member 8 in the direction _D2 , and the _first (pressure can be applied to member 9).

In step (II), for example, on the pressure applying surface of either or both of the first member 9 and the second member 8 (herein sometimes referred to as "pressure surface"), Pressure can be applied by bringing a pressure applying means into contact.
At this time, either surface of the pressurizing means may be brought into surface contact with the pressurizing surfaces of one or both of the first member 9 and the second member 8, and the first member 9 and the second member Either surface of the pressurizing means may be brought into surface contact with the entire surface of one or both of the pressurizing surfaces. By doing so, the pressure can be applied more uniformly to the first member 9 and the second member 8.

In step (II), for example, no pressure is applied to the first laminate 1011 until the temperature of the film-shaped sintered material 1 in the first laminate 1011 reaches a constant value. After the temperature reaches a certain value (in this specification, this temperature may be referred to as "pressurization start temperature"), a pressure of 0.1 MPa or more may be applied to the first laminate 1011. . By doing this, in the joined body described later, protrusion 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 further suppressed. , the bonding strength between the first member 9 and the second member 8 becomes higher.

In step (II), for example, heating of the first laminate 1011 can be started by placing the first laminate 1011 in an unheated state, such as at room temperature, in a heating environment. The temperature of the heating environment (heating temperature) in this case may be, for example, either 50° C. or higher or 55° C. or higher. When the temperature of the heating environment is equal to or higher than the lower limit, step (II) can be performed more efficiently.
The temperature of the heating environment may be, for example, 190°C or lower, 150°C or lower, or 110°C or lower. Since the temperature of the heating environment is below the upper limit, the film-shaped fired material 1 is prevented from protruding from the ends of the first member 9 and the second member 8 (substantially the ends of the second member 8). More restrained. As a result, also in the joined body described below, protrusion 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 further suppressed.
The temperature of the heating environment may be, for example, any of 50 to 190°C, 50 to 150°C, and 50 to 110°C, or any of 55 to 190°C, 55 to 150°C, and 55 to 110°C. It may be However, these are examples of the temperature of the heating environment.

In step (II), the pressure start temperature is preferably a temperature at which the film-like fired material 1 and the film-like fired material 1' are not fired rapidly.
The pressure start temperature may be, for example, either 260°C or higher or 280°C or higher. When the pressure start temperature is equal to or higher than the lower limit, the adhesion between the film-shaped fired material and the first member is further improved. As a result, the joint strength of the joined body (the joint strength between the first member 9 and the second member 8), which will be described later, becomes higher.
The pressure start temperature may be, for example, either 330°C or lower or 310°C or lower. Since the pressure start temperature is below the upper limit, the film-like fired material 1 is prevented from protruding from the ends of the first member 9 and the second member 8 (substantially the ends of the second member 8). More restrained. As a result, in the joined body described below, the protrusion 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 further suppressed.
The pressure start temperature may be, for example, any one of 260 to 330°C, 260 to 310°C, 280 to 330°C, and 280 to 310°C. However, these are examples of pressurization start temperatures.

In step (II), the temperature at which the film-shaped fired material 1 in the first laminate 1011 is heated while applying a pressure of 0.1 MPa or more to the first laminate 1011 (heating temperature of the film-shaped fired material 1) Examples of the temperature include a temperature in the same range as the above-mentioned pressure start temperature. For example, the heating temperature of the film-shaped fired material 1 may be any one of 260 to 330°C, 260 to 310°C, 280 to 330°C, and 280 to 310°C. However, these are examples of heating temperatures for the film-shaped fired material 1.

In step (II), the heating temperature of the film-shaped fired material 1 may be constant or may vary. For example, the heating temperature of the film-shaped fired material 1 may be the same as the above-mentioned pressure start temperature.

In step (II), the time for applying a pressure of 0.1 MPa or more to the first laminate 1011 (pressing time of the film-like fired material 1) is such that the film-like fired material 1 and the film-like fired material 1' are Preferably, the time is such that the baking time is not completely baked.
The pressurizing time of the film-shaped fired material 1 is preferably 10 seconds or more, and may be, for example, 20 seconds or more or 40 seconds or more. By setting the pressurizing time to be equal to or greater than the lower limit value, the film-like fired material 1 is prevented from protruding from the ends of the first member 9 and the second member 8 (substantially the ends of the second member 8). suppressed. As a result, in the joined body described below, the protrusion 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 further suppressed.
The pressurizing time of the film-shaped fired material 1 is preferably 80 seconds or less, and may be, for example, any of 65 seconds or less, 50 seconds or less, and 35 seconds or less. When the pressurizing time is below the upper limit value, the film-like fired material 1 and the film-like fired material 1' are not fired at all, or are only partially fired, and are not completely fired. , the joint strength of the joined body (the joint strength between the first member 9 and the second member 8), which will be described later, becomes higher.
In one embodiment, the pressurizing time of the film-shaped fired material 1 may be, for example, any of 10 to 80 seconds, 20 to 80 seconds, and 40 to 80 seconds, or 10 to 65 seconds, 10 to The duration may be 50 seconds and 10 to 35 seconds, or may be 20 to 65 seconds and 40 to 50 seconds. However, these are examples of the pressurizing time of the film-shaped fired material 1.

In the second laminate 1012, the film-shaped fired material 1' is preferably not fired at all or partially fired, but not completely fired. By placing the second laminate 1012 in such a state, the bonding strength of the bonded body (the bonding strength between the first member 9 and the second member 8), which will be described later, becomes higher.
The degree of firing of the film-like fired material 1' can be determined, for example, by the mass of the film-like fired material 1 before heating (before performing step (II)) and the mass of the film-like fired material 1 after heating (after performing step (II)). This can be determined based on the magnitude of the difference between the mass of the fired material 1' and the mass of the fired material 1'. It can be determined that the larger the difference is, the more advanced the firing of the film-like fired material 1' is.

In step (II), when adjusting the temperature, including when heating the first laminate 1011 (film-shaped fired material 1) and adjusting the temperature, the temperature adjusting means is set to the first laminate 1011. The first laminate is placed in contact with the first laminate 1011, or is placed near the first laminate 1011 without contacting the first laminate 1011, and adjusts the temperature conditions of the temperature adjusting means. The temperature of the body 1011 can be adjusted.
For example, it is preferable to arrange a pair of temperature adjusting means to sandwich the first laminate 1011 to adjust the temperature of the first laminate 1011 (film-shaped fired material 1), and the first member 9 and the second member 8 The temperature of the first laminate 1011 (film-shaped fired material 1) may be adjusted by bringing a temperature adjusting means into contact with either or both of the first member 9 and the second member 8. The temperature of the first laminate 1011 (film-shaped fired material 1) may be adjusted without contacting the temperature adjusting means.

In step (II), pressure is applied to the first laminate 1011 and the temperature of the first laminate 1011 is adjusted using a pressurizing temperature adjusting means having a configuration in which the pressure applying means and the temperature adjusting means are integrated. You may perform either or both of the following. For example, any surface of the pressurizing temperature adjusting means is preferably brought into surface contact with the pressurizing surfaces of one or both of the first member 9 and the second member 8, and more preferably, the first member 9 and the second member 8 are in contact with each other. Either surface of the pressurizing temperature adjusting means is brought into surface contact with the entire surface of the pressurizing surface of one or both of the second members 8 to apply pressure to the first laminate 1011 and to control the temperature of the first laminate 1011. By performing the adjustment together, step (II) can be performed more efficiently.

In step (II), the rate of temperature increase when heating the first laminate 1011 until its temperature reaches the pressure start temperature is not particularly limited, but is preferably 25 to 100 °C/sec, and 35 More preferably, the temperature is 65° C./sec. When the temperature increase rate is within this range, a bonded body with sufficiently high bonding strength can be efficiently obtained.

In step (II), the temperature increase rate may be constant or may vary.

Step (II) is performed, for example, under an atmosphere of air; nitrogen gas; rare gas such as helium gas or argon gas; reducing gas (gas having reducing power) such as hydrogen gas or carbon monoxide gas; It can be carried out.
Among these, step (II) is preferably carried out in an atmospheric atmosphere because the binder component is thermally decomposed at a lower temperature.

<<Step (III)>>
In the step (III), the lamination direction (the lamination direction of the first member 9, the film-shaped fired material 1, and the second member 8 in the first laminated body 1011) is applied to the second laminated body 1012. ), the film-like sintered material 1' in the second laminate 1012 is sintered while applying a pressure of 3 MPa or more to form the metal sintered layer 10, as shown in FIG. 4(d). , a joined body 101 is produced. By performing step (III), the desired joined body 101 is obtained.
Here, the direction in which a pressure of 3 MPa or more is applied to the second laminate 1012 is, in other words, the direction in which the pressure of 3 MPa or more is applied to the first member 9, the film-shaped fired material 1', and the second member 8 in the second laminate 1012. , is the stacking direction.

In step (III), the pressure applied to the second laminate 1012 is 3 MPa or more, and may be, for example, either 8 MPa or more or 13 MPa or more. When the pressure applied to the second laminate 1012 is equal to or greater than the lower limit, the bonding strength of the joined body 101 (the bonding strength between the first member 9 and the second member 8) becomes high.
The upper limit of the pressure applied to the second laminate 1012 is not particularly limited. For example, in terms of suppressing excessive pressure, the pressure applied to the second laminate 1012 is preferably 25 MPa or less.
In one embodiment, the pressure applied to the second laminate 1012 may be, for example, any one of 3 to 25 MPa, 8 to 25 MPa, and 13 to 25 MPa. However, these are examples of the above-mentioned pressures.

In step (III), the temperature at which the film-like sintered material 1' in the second laminate 1012 is fired while applying a pressure of 3 MPa or more to the second laminate 1012 (firing temperature of the film-form sintered material 1') Examples of the temperature range include the pressure start temperature and the heating temperature of the film-shaped fired material 1 in step (II) above. For example, the firing temperature of the film-shaped fired material 1' may be any one of 260 to 330°C, 260 to 310°C, 280 to 330°C, and 280 to 310°C. However, these are examples of the firing temperature of the film-like fired material 1'.

In step (III), the firing temperature of the film-like fired material 1' may be constant or may vary. The firing temperature of the film-like fired material 1' may be the same as, for example, the pressure start temperature or the heating temperature of the film-like fired material 1 other than the pressurization start temperature in step (II). Then, the pressure start temperature in step (II), the heating temperature of the film-shaped fired material 1 other than the pressure start temperature in step (II) (in other words, after the start of pressure), and the film in step (III). The firing temperatures of the shaped firing materials 1' may be all the same, all different, or only some of them may be the same.

In step (III), the time during which a pressure of 3 MPa or more is applied to the second laminate 1012 (pressing time of the film-like fired material 1') is the time during which the film-like fired material 1' is sufficiently fired. If so, there are no particular limitations.
The pressurizing time of the film-like fired material 1' is preferably 120 seconds or more, and may be, for example, any of 180 seconds or more, 240 seconds or more, and 300 seconds or more. When the pressurization time is equal to or greater than the lower limit value, the bonding strength of the bonded body 101 (the bonding strength between the first member 9 and the second member 8) becomes higher.
The upper limit of the pressurizing time of the film-like fired material 1' is not particularly limited. For example, in order to prevent the time from becoming excessively long, the pressurizing time of the film-shaped fired material 1' is preferably 720 seconds or less.
In one embodiment, the pressing time of the film-like fired material 1' may be, for example, any one of 120 to 720 seconds, 180 to 720 seconds, 240 to 720 seconds, and 300 to 720 seconds. However, these are examples of the pressurizing time of the film-shaped fired material 1'.

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

Step (III) is performed, for example, in an atmosphere of air; nitrogen gas; rare gas such as helium gas or argon gas; or reducing gas (gas having reducing power) such as hydrogen gas or carbon monoxide gas; It can be carried out.
Among these, step (III) is preferably carried out in the air atmosphere because the binder component is thermally decomposed at a lower temperature.

<<Other processes>>
The method for manufacturing the joined body of the present embodiment includes other steps that do not fall under any of step (I), step (II), and step (III) within a range that does not impair the effects of the present invention. may have.
The type of the other steps, the number of the other steps, and the timing of performing the other steps can be arbitrarily selected depending on the purpose and are not particularly limited.
However, the manufacturing method of this embodiment does not include the other steps between step (I) and step (II) and between step (II) and step (III) (in other words, , step (I), steps (II) and (III) are preferably performed consecutively).

<An example of a method for manufacturing a joined body>
As an example of a preferred method for manufacturing a bonded body according to the present embodiment, in step (II), a pressure of 0.1 MPa or more is applied to the first laminate, and a time period for applying the pressure of 0.1 MPa or more (film-form baking The pressure of 3 MPa or more applied to the second laminate and the time of applying the pressure of 3 MPa or more to the second laminate (film Examples include a manufacturing method in which the pressurizing time of the shaped fired material falls within any of the numerical ranges described above.
More specifically, as an example of a preferred method for manufacturing a joined body,
(ii-1) In step (II), the pressure of 0.1 MPa or more applied to the first laminate is any of 0.1 MPa or more, 0.3 MPa or more, and 0.5 MPa or more, and less than 3 MPa, 2.9 MPa or less, 2.5 MPa or less, 2 MPa or less, and 1.5 MPa or less,
(ii-2) In step (II), the time for applying a pressure of 0.1 MPa or more (pressurizing time of the film-shaped fired material) is any of 10 seconds or more, 20 seconds or more, and 40 seconds or more, and is any of 80 seconds or less, 65 seconds or less, 50 seconds or less, or 35 seconds or less,
(iii-1) In step (III), the pressure of 3 MPa or more applied to the second laminate is any of 3 MPa or more, 8 MPa or more, and 13 MPa or more,
(iii-2) In step (III), the time for applying a pressure of 3 MPa or more (pressurizing time of the film-shaped fired material) is any of 120 seconds or more, 180 seconds or more, 240 seconds or more, and 300 seconds or more. be,
Examples include manufacturing methods. However, the preferred method for manufacturing the joined body is not limited to this.

Hereinafter, the present invention will be explained in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.

<<Raw materials for producing fired material composition>>
The raw materials for producing the firing material compositions used in Examples and Comparative Examples are shown below.
[Sinterable metal particle-containing paste]
・Silver nanopaste (1) (“Arconano Silver Paste ANP-1” manufactured by Applied Nanoparticle Research Institute, silver nanoparticles coated with alcohol derivatives, silver particles with metal content of 70% by mass or more and average particle size of 100nm or less) (Sinterable metal particles) 60% by mass or more)
[Binder component]
・Acrylic polymer (1) (2-ethylhexyl methacrylate polymer, weight average molecular weight 280,000, Tg: -10°C)
The acrylic polymer (1) was used as a dispersion ("L-0818" manufactured by Mitsubishi Chemical Corporation) using methyl ethyl ketone as a dispersion medium (solvent) and having a concentration of 54.5% by mass.

[Example 1]
<<Manufacture of fired material composition>>
A fired material composition was obtained by mixing silver nanopaste (1) (87.7 parts by mass) and acrylic polymer (1) (12.3 parts by mass). The blending amount (12.3 parts by mass) of the acrylic polymer (1) shown here is the amount (solid content) of the acrylic polymer (1) itself excluding the solvent component.

<<Manufacture of film-shaped fired material>>
The fired material composition obtained above was printed on one side (release-treated side) of a release film with a width of 230 mm ("SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) to form a printed layer. At this time, the planar shape of the printing layer was made into a rectangular shape with a size of 10 mm x 10 mm. Then, the printed layer was dried at 150° C. for 10 minutes to obtain a film-like fired material with a thickness of 60 μm.

<<Evaluation of film-shaped fired materials>>
A silver film with a size of 2 mm x 2 mm, a thickness of 345.5 μm, a square planar shape, and one surface coated with a silver film (thickness of 0.5 μm), with a total thickness of 350 μm. A silicon chip with a film (hereinafter referred to as a "silicon chip with a silver film") was prepared. The silver film in this silicon chip with silver film was provided by vapor deposition.
One side of the film-like fired material obtained above was attached to the exposed surface of the silver film in the silicon chip with a silver film, and the film-like fired material was laminated. At this time, an excess portion of the film-like fired material was generated over the entire outer periphery of the silver film. Then, by cutting and removing this surplus portion of the film-like fired material, a silicon chip with a silver film of the same size (2 mm x 2 mm) and a test piece of the film-like fired material are laminated. A test laminate was obtained (in other words, the test piece of the film-like fired material did not protrude from the outer periphery of the silicon chip with the silver film).
Furthermore, among the test pieces of the film-like fired material in this test laminate, the entire surface of the surface opposite to the silicon chip side with the silver film (i.e., the exposed surface) was placed on one side of a copper plate (thickness 1.5 mm). The test laminate was placed on the copper plate in contact with the surface of the copper plate. That is, at this time, the copper plate was made to protrude from the entire outer periphery of the test laminate.

Up to this point, from bonding the film-shaped fired material to the silicon chip with a silver film to placing the test laminate on the copper plate, the minimum necessary amount for the film-shaped fired material and its test piece was carried out. The pressure was applied only to the pressure of 100 mL, so that the shape and size of the film-shaped fired material and its test piece did not change.

Next, while heating the test laminate and the copper plate to 300°C, the silver film-covered silicon chip was applied to the test laminate in the stacking direction of the silver film-covered silicon chip and the test piece of the film-like fired material. A pressure of 10 MPa was applied from the chip side for 180 seconds.
Next, after the above-mentioned heating of the test laminate and the copper plate and the above-mentioned pressure on the test laminate are released, a test piece of the film-shaped fired material is removed from the outer periphery of the silver-coated silicon chip at room temperature. The maximum value of the protrusion width was determined. As a result, the maximum value of the protrusion width was 240 μm.

<<Manufacture of joined body>>
<Manufacture of first laminate>
As the first member, a copper plate with a size of 30 mm x 30 mm, a thickness of 1.5 mm, and a rectangular planar shape was prepared. Moreover, the silicon chip with a silver film was prepared as a second member.
One side of the film-like fired material obtained above was bonded to the exposed surface of the silver film in the silicon chip with a silver film, and the film-like fired material was laminated. At this time, an excess portion of the film-like fired material was generated over the entire outer periphery of the silver film. Then, by cutting and removing this surplus portion of the film-like fired material, a laminate in which the silver-coated silicon chip and the film-like fired material of the same size (2 mm x 2 mm) were laminated was obtained. Furthermore, the surface of the film-like fired material in this laminate opposite to the silver-film-coated silicon chip side was bonded to one surface of the copper plate, and the copper plates were laminated. At this time, the copper plate was made to protrude from the entire outer periphery of the laminate (step (I)).
Up to this point (in step (I)), only the minimum necessary pressure was applied to the film-like fired material so that the shape and size of the film-like fired material did not change.
As described above, a first laminate was produced in which the copper plate, the film-shaped fired material, and the silicon chip with a silver film were laminated in this order in the thickness direction thereof.

<Manufacture of second laminate>
In the first laminate obtained above, aluminum foil (aluminum sheet, 40 μm thick) was placed on the entire surface of the silicon chip with silver film on the side opposite to the film-like fired material side (i.e., the exposed surface). Laminated. This is to prevent contamination of the sintering apparatus, which will be described later, in the steps after step (II), which will be described later.
In the obtained first laminate with aluminum foil, the entire exposed surface of the copper plate (the surface opposite to the film-shaped sintered material side) was placed in a sintering device ("HTM-3000" manufactured by Hakutosha). The first laminate with aluminum foil was placed on one of the two plates so as to be in contact with the surface thereof. At this time, the temperature of the one plate was previously set at 60°C. As a result, the one plate in the sintering device receives the first laminate with aluminum foil, heats the first laminate with aluminum foil from the copper plate side, and heats the first laminate with aluminum foil to the same level as the one plate. Heating was then started. Furthermore, the surface of the other of the two plates in the sintering device is applied to the entire exposed surface of the aluminum foil (the surface opposite to the silicon chip side with the silver film) in the first laminate with aluminum foil. were brought into light contact with each other, and the other plate was thereby placed in a position where no pressure was intentionally applied to the first laminate with aluminum foil. At this time, the temperature of the other plate was also previously set at 60°C. As a result, the first laminate with aluminum foil can be attached to the first laminate with aluminum foil by the other plate in the sintering device without intentionally applying pressure to the first laminate with aluminum foil (substantially applying pressure to 0 MPa). was heated from the aluminum foil side to the same temperature as the other plate, and heating was started.
As described above, the first laminate (first laminate with aluminum foil) is not subjected to pressure (applying Heating of the first laminate was started by setting the pressure to 0 MPa) and the temperature at which the first laminate was heated (temperature of the heating environment) to 60°C.

Next, without applying any pressure ( With an applied pressure of 0 MPa), the first laminate was heated by the two plates in the sintering device until its temperature reached 60°C.
Next, while no pressure was applied to the first laminate, the first laminate was heated by the two plates in the sintering apparatus until its temperature ranged from 60°C to 300°C. The temperature increase rate at this time was 50° C./sec.
Next, from the time when the temperature of the first laminate reaches 300° C., the copper plate, the film-shaped fired material, and the silicon chip with silver film in the first laminate are immediately added to the first laminate. The temperature of the first laminate was maintained at 300° C. for 60 seconds while applying a pressure of 1 MPa in the stacking direction (step (II)). That is, the pressure start temperature and the subsequent heating temperature of the film-shaped fired material were both 300°C. At this time, pressure was applied to the first laminate from the other plate (the plate on the aluminum foil side) in the sintering apparatus. Further, the temperature of the two plates in the sintering apparatus was raised before the temperature of the first laminate reached 60°C.
Through the above steps, a second laminate was produced (step (II)).

<Manufacture of joined body>
Next, after producing the second laminate (in other words, when the time for maintaining the temperature of the first laminate at 300° C. reaches 60 seconds), immediately apply the first laminate to the second laminate. The pressure applied in the same direction as the lamination direction of the copper plate, the film-shaped fired material, and the silicon chip with silver film in the body was 10 MPa, and while maintaining this pressure, the temperature of the second laminate was raised to 300 MPa for 600 seconds. It was maintained at ℃. At this time, pressure was applied to the second laminate from the other plate (the plate on the aluminum foil side) in the sintering apparatus. Thereby, the film-like sintered material was sintered to form a metal sintered layer (thickness: 20 μm) (step (III)). That is, the firing temperature of the film-shaped fired material was set to 300°C.
Through the above steps, a bonded body including the copper plate, a sintered metal layer, and a silicon chip with a silver film, and in which the copper plate and the silicon chip with a silver film are joined by the sintered metal layer is produced. did.

Note that step (I), step (II), and step (III) up to this point were all performed in an air atmosphere.

Four more zygotes were produced using the same method as above, making a total of 5 zygotes.

<<Evaluation of conjugate>>
<Evaluation of joint strength of joined body>
In an environment of 23 ° C., of the bonded body obtained above, the outer periphery (side surface) of the metal sintered layer and the outer periphery (side surface) of the silicon chip with silver film were aligned, At the same time, a force was applied at a speed of 200 μm/s in a direction parallel to the surface of the silicon chip with the silver film (the surface of the silicon chip on the side without the silver film in the silicon chip with the silver film). At this time, the pressing means for applying force is a stainless steel plate, and the tip of this pressing means is placed on the surface of the copper plate in the bonded body (the surface on the metal sintered layer side). ) to prevent the pressing means from coming into contact with the copper plate. Then, the maximum value of the force applied until the metal sintered layer was destroyed or the metal sintered layer peeled off from the copper plate was measured, and the measured value was adopted as the shear strength of the joined body.
Such shear strength was measured for all five bonded bodies, and the average value thereof was finally adopted as the shear strength of the bonded body. Then, the bonding strength of the bonded body was evaluated according to the following criteria. The results are shown in Table 1.
(Evaluation criteria)
A: The shear strength is 60 MPa or more, and the bonding strength is particularly high.
B: The shear strength is 35 MPa or more and less than 60 MPa, which is inferior to A, but the bonding strength is high.
C: Shear strength is less than 35 MPa, and bonding strength is low.

<Evaluation of the effect of suppressing the protrusion of the metal sintered layer in the joined body>
The maximum width of the protruding metal sintered layer from the outer periphery (side surface) of the silver-coated silicon chip when the above-obtained bonded body is viewed from above on the silver-coated silicon chip side. I asked for it. At this time, the above image in plan view was observed using a digital microscope ("VHX-5000" manufactured by Keyence Corporation), and the maximum value of the protruding width of the metal sintered layer was determined. Then, this maximum value was adopted as the protrusion width of the metal sintered layer.
Such protrusion widths were determined for all five joined bodies, and the average value thereof was finally adopted as the protrusion width of the metal sintered layer. Then, the effect of suppressing the protrusion of the metal sintered layer in the joined body was evaluated according to the following criteria. The results are shown in Table 1.
(Evaluation criteria)
A: The protrusion width is 200 μm or less, and the effect of suppressing protrusion is high.
B: The protrusion width is more than 200 μm and less than 220 μm, which is inferior to A, but the effect of suppressing protrusion is observed.
C: The protrusion width is more than 220 μm, and the effect of suppressing the protrusion is low.

<<Manufacture of film-shaped fired materials, and manufacture and evaluation of bonded bodies>>
[Example 2]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, in step (II), while applying a pressure of 1 MPa to the first laminate, the time for maintaining the temperature of the first laminate at 300°C (pressing time of the film-shaped fired material) is set to 60 seconds. A bonded body was produced and evaluated in the same manner as in Example 1, except that the duration was changed to 30 seconds. The results are shown in Table 1.

[Example 3]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, in step (II), while applying a pressure of 1 MPa to the first laminate, the time for maintaining the temperature of the first laminate at 300°C (pressing time of the film-shaped fired material) is set to 60 seconds. A bonded body was produced and evaluated in the same manner as in Example 1, except that the duration was changed to 10 seconds. The results are shown in Table 1.

[Example 4]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, in step (III), when maintaining the temperature of the second laminate at 300° C. for 600 seconds, the pressure applied to the second laminate was changed to 5 MPa instead of 10 MPa, as in Example 1. The zygote was manufactured and evaluated in the same manner as in the case of . The results are shown in Table 1.

[Example 5]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, in step (III), when the temperature of the second laminate was maintained at 300° C. for 600 seconds, the pressure applied to the second laminate was changed to 20 MPa instead of 10 MPa, as in Example 1. The zygote was manufactured and evaluated in the same manner as in the case of . The results are shown in Table 1.

[Example 6]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, in step (III), the time for maintaining the temperature of the second laminate at 300 ° C. while applying the pressure to the second laminate at 10 MPa (pressing time of the film-shaped fired material) was changed to 600 seconds. A bonded body was manufactured and evaluated in the same manner as in Example 1, except that the heating time was 300 seconds. The results are shown in Table 1.

[Example 7]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, in step (III), the time for maintaining the temperature of the second laminate at 300 ° C. while applying the pressure to the second laminate at 10 MPa (pressing time of the film-shaped fired material) was changed to 600 seconds. A bonded body was manufactured and evaluated in the same manner as in Example 1, except that the heating time was 180 seconds. The results are shown in Table 1.

<<Manufacture of film-shaped fired material, and manufacture and evaluation of comparative bonded body>>
[Comparative example 1]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, a first laminate was produced in the same manner as in Example 1 (Step (I)).
Hereinafter, while applying a pressure of 1 MPa to the first laminate, the time for maintaining the temperature of the first laminate at 300 ° C. (pressing time of the film-shaped fired material) was changed to 300 seconds instead of 60 seconds. Except for this point, the same method as in step (II) of Example 1 was adopted to produce a laminate.
This laminate was used as a comparative bonded body, and the comparative bonded body was evaluated in the same manner as the bonded body in Example 1. The results are shown in Table 2.

[Comparative example 2]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, a first laminate was produced in the same manner as in Example 1 (Step (I)).
Thereafter, instead of maintaining the temperature of the first laminate at 300 ° C. for 60 seconds while applying a pressure of 1 MPa to the first laminate, while applying a pressure of 2 MPa to the first laminate, A laminate was produced using the same method as in step (II) of Example 1, except that the temperature of the first laminate was maintained at 300° C. for 300 seconds.
This laminate was used as a comparative bonded body, and the comparative bonded body was evaluated in the same manner as the bonded body in Example 1. The results are shown in Table 2.

[Comparative example 3]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, a first laminate was produced in the same manner as in Example 1 (Step (I)).
Thereafter, instead of maintaining the temperature of the first laminate at 300 ° C. for 60 seconds while applying a pressure of 1 MPa to the first laminate, while applying a pressure of 3 MPa to the first laminate, A laminate was produced using the same method as in step (II) of Example 1, except that the temperature of the first laminate was maintained at 300° C. for 300 seconds.
This laminate was used as a comparative bonded body, and the comparative bonded body was evaluated in the same manner as the bonded body in Example 1. The results are shown in Table 2.

[Comparative example 4]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, a first laminate was produced in the same manner as in Example 1 (step (I)).
Thereafter, instead of maintaining the temperature of the first laminate at 300 ° C. for 60 seconds while applying a pressure of 1 MPa to the first laminate, while applying a pressure of 5 MPa to the first laminate, A laminate was produced using the same method as in step (II) of Example 1, except that the temperature of the first laminate was maintained at 300° C. for 300 seconds.
This laminate was used as a comparative bonded body, and the comparative bonded body was evaluated in the same manner as the bonded body in Example 1. The results are shown in Table 2.

[Comparative example 5]
Using the fired material composition obtained in Example 1, a film-like fired material was produced in the same manner as in Example 1.
Next, a first laminate was produced in the same manner as in Example 1 (Step (I)).
Thereafter, instead of maintaining the temperature of the first laminate at 300 ° C. for 60 seconds while applying a pressure of 1 MPa to the first laminate, while applying a pressure of 10 MPa to the first laminate, A laminate was produced using the same method as in step (II) of Example 1, except that the temperature of the first laminate was maintained at 300° C. for 300 seconds.
This laminate was used as a comparative bonded body, and the comparative bonded body was evaluated in the same manner as the bonded body in Example 1. The results are shown in Table 2.

As is clear from the above results, in Examples 1 to 7, the shear strength of the bonded bodies was 38 MPa or more (38 to 103 MPa), and the bonding strength of the bonded bodies was high. Further, in Examples 1 to 7, the protrusion width of the metal sintered layer was 214 μm or less (124 to 214 μm), and the protrusion of the metal sintered layer was suppressed.
In Examples 1 to 7, the pressure applied to the first laminate in step (II) was 1 MPa, and the time for applying pressure (pressurization time) was 10 seconds or more (10 to 60 seconds). Then, in step (III), the pressure applied to the second laminate was 5 MPa or more (5 to 20 MPa), and the time for applying pressure (pressurization time) was 180 seconds or more (180 to 600 seconds).

In particular, in Examples 1 to 3 and 5, the shear strength of the bonded bodies was 81 MPa or more (81 to 103 MPa), and the bonding strength of the bonded bodies was particularly high.
In Examples 1 to 3 and 5, the pressure applied to the second laminate in step (III) was 10 MPa or more (10 to 20 MPa), and the time for applying pressure (pressurization time) was 600 seconds. .

In particular, in Examples 1, 2, and 4 to 7, the protrusion width of the metal sintered layer was 188 μm or less (124 to 188 μm), and the effect of suppressing the protrusion of the metal sintered layer was particularly high.
In Examples 1, 2, 4 to 7, the time for applying pressure to the first laminate in step (II) (pressurization time) was 30 seconds or more (30 to 60 seconds).

In Examples 1, 2, and 5, the bonding strength of the joined bodies was particularly high, and the effect of suppressing the protrusion of the metal sintered layer was particularly high.
In Examples 1, 2, and 5, the time for applying pressure to the first laminate in step (II) (pressurization time) was 30 seconds or more (30 to 60 seconds), and the The pressure applied to the two laminates was 10 MPa or more (10 to 20 MPa), and the time for applying pressure (pressurization time) was 600 seconds.

As mentioned above, in Examples 1 to 7, the protrusion width of the metal sintered layer was 214 μm or less, the pressure applied to the first laminate in step (II) was 1 MPa, and the pressure application time (application time) was 1 MPa. pressure time) was 10 seconds or more. On the other hand, in Comparative Example 3, the pressure applied to the first laminate in the step after step (I) was 3 MPa, and the time for applying pressure (pressurization time) was 300 seconds. In both cases, the film-like sintered material was more strongly pressed than in step (II) of Examples 1 to 7, and the protruding width of the metal sintered layer in this case was 213 μm. From these results, it was determined that in step (II) of Examples 1 to 7, the protrusion width of the film-like fired material was 220 μm or less.

On the other hand, in Comparative Examples 1 to 3, the shear strength of the bonded bodies was 31 MPa or less (13 to 31 MPa), and the bonding strength of the bonded bodies was low.
In Comparative Examples 4 and 5, the protrusion width of the metal sintered layer was 236 μm or more (236 to 237 μm), and the protrusion of the metal sintered layer was not suppressed.

In Comparative Examples 1 to 3, neither step (II) nor step (III) was performed, and in the step after step (I), the pressure applied to the first laminate was 3 MPa or less (1 to 3 MPa). 3 MPa).
In Comparative Examples 4 and 5, neither step (II) nor step (III) was performed, and in the step after step (I), the pressure applied to the first laminate was 5 MPa or more (5 to 5 MPa). 10 MPa).

INDUSTRIAL APPLICATION This invention can be utilized for the manufacture of the joined body in general comprised by joining members by the metal sintered layer, and can be utilized suitably for the manufacture of the semiconductor element for electric power especially.

1,1'...Film-shaped 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 DESCRIPTION OF SYMBOLS 10... Metal sintered layer 101... Joined body 1011... First laminate 1012... Second laminate 2... Support sheet, 2a... One side of support sheet 20... - Undivided member 21...Base film, 21a...One surface of the base film 22...Adhesive layer, 22a...The surface of the adhesive layer opposite to the base film side 22 '... Cured product of adhesive layer 301... Film-shaped fired material with support sheet 320... Undivided laminate 8... Second member, 8b... One surface of second member 81. ...Second member with film-like fired material 9...First member L...Protrusion width of film-like fired material _D1 ...Direction from the first member to the second member (first member and film lamination direction of the shaped fired material and the second member)
_D2 ...Direction from the second member to the first member (direction in which the first member, the film-shaped fired material, and the second member are laminated)

Claims (3)

A method for manufacturing a joined body, the method comprising:
The joined body includes a first member, a sintered metal layer, and a second member, and the first member and the second member are joined by the sintered metal layer,
The manufacturing method includes the first member, the film-like sintered material for forming the metal sintered layer, and the second member, which are laminated in this order in the thickness direction. Step (I) of producing one laminate;
In the first laminate, the first member and the film are attached to the first laminate so that the protrusion width of the film-like fired material from the first member or the second member is 220 μm or less. A second laminate is produced by heating the film-like sintered material in the first laminate while applying a pressure of 0.1 MPa or more in the lamination direction of the sintered material and the second member. Step (II) of
After the step (II), the film-like sintered material in the second laminate is fired while applying a pressure of 3 MPa or more to the second laminate in the same direction as the lamination direction, and forming a metal sintered layer to produce the joined body (III);
A test sample consisting of a silicon chip with a thickness of 345.5 μm, a silver film with a thickness of 0.5 μm, and a test piece of the film-like fired material were laminated in this order in the thickness direction. A laminate, wherein the silicon chip has a rectangular planar shape and a size of 2 mm x 2 mm, and the silver film is provided on the surface of the silicon chip on the side of the film-like fired material by vapor deposition. the silver film covers the entire surface of the silicon chip on the side of the film-like fired material, the test piece of the film-like fired material has the same size as the silicon chip, and A test laminate in which the film-like fired material does not protrude from the outer periphery of the silicon chip is produced, and the entire exposed surface of the test piece in the test laminate is brought into contact with a copper plate, and the test laminate is Laminating the silicon chip, the silver film, and the test piece on the test laminate while placing it on the copper plate and heating the test laminate and the copper plate to 300°C. A method for manufacturing a bonded body, wherein when a pressure of 10 MPa is applied from the silicon chip side for 3 minutes in the direction, the maximum width of the protrusion of the test piece from the outer periphery of the silicon chip exceeds 220 μm. A support sheet-attached film-like fired material comprising a support sheet and the film-like fired material provided on one surface of the support sheet is prepared, and an undivided member is prepared,
The support sheet includes a base film and an adhesive layer provided on one surface of the base film, and in the film-like fired material with a support sheet, the film-like fired material includes: provided on the surface of the adhesive layer opposite to the base film side,
The undivided member becomes the second member by the division,
By pasting the surface of the film-like fired material in the support sheet-attached film-like fired material on the side opposite to the support sheet side to the undivided member, The undivided member is laminated to produce an undivided laminate, the undivided member in the undivided laminate is divided to produce the second member, and the film-form baking is performed. By cutting the material, on the support sheet, the second member and the cut film-like fired material provided on one surface of the second member are attached. After producing a second member and peeling off the second member with the film-like fired material from the support sheet, the part of the film-like fired material in the second member with the film-like fired material on the second member side The method for manufacturing a bonded body according to claim 1, wherein the step (I) is performed by attaching the opposite surface to the first member. The adhesive layer is energy ray curable, and after the adhesive layer is cured by irradiation with energy rays, the second member with the film-like fired material is peeled off from the cured product of the adhesive layer. Item 2. A method for producing a joined body according to item 2.

Images