Film-shaped sintered material, film-shaped sintered material with support sheet, and method for manufacturing semiconductor device

Abstract

To provide a film-shaped sintered material and a method for manufacturing a semiconductor device, which, even when a semiconductor wafer and the film-shaped sintered material are bonded together at room temperature, reduces chip flying when the semiconductor wafer is diced together with the film-shaped sintered material on a support sheet and has excellent pick-up suitability.SOLUTION: A film-shaped sintered material (1) contains sinterable metal particles (10) and a binder component (20), and the binder component (20) contains a copolymer of an alkyl methacrylate having 8 or less carbon atoms and an alkyl methacrylate having 9 to 13 carbon atoms.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a film-shaped sintered material, a film-shaped sintered material with a support sheet, and a method for manufacturing a semiconductor device. [Background technology]

[0002] In recent years, the demand for power semiconductor elements (power devices) mounted in automobiles, air conditioners, personal computers, etc. has increased in line with the trend toward higher voltages and currents. Because power semiconductor elements are used under high voltages and currents, heat generation from the semiconductor elements can easily become a problem. Conventionally, a heat sink is sometimes attached around a semiconductor element to dissipate the heat generated by the semiconductor element, but if the thermal conductivity at the joint between the heat sink and the semiconductor element is poor, efficient heat dissipation will be hindered.

[0003] As a bonding material with excellent thermal conductivity, for example, Patent Document 1 discloses a paste-like metal microparticle composition that is a mixture of specific heat-sinterable metal particles, a specific polymer dispersant, and a specific volatile dispersion medium. When this composition is sintered, it is said to become a solid metal with excellent thermal conductivity.

[0004] Patent Document 2 discloses a film-shaped sintered material containing sinterable metal particles and a binder component. By providing a support sheet on the film-shaped sintered material, the support sheet can be used as a dicing sheet to separate a semiconductor wafer into chips together with the film-shaped sintered material. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-111800 A [Patent Document 2] Japanese Patent Application Publication No. 2019-204850 Summary of the Invention [Problem to be solved by the invention]

[0006] Patent Document 2 explains that a film-like sintered material with a support sheet was heated to 50°C and attached to the processing surface of a silicon wafer, and subsequent dicing and pick-up suitability evaluations showed that chip skipping and wafer contamination during dicing could be suppressed, and stable dicing and pick-up were also achieved. However, when the film-like sintered material with a support sheet that received an excellent rating in Patent Document 2 was attached to the processing surface of a silicon wafer at room temperature and then evaluated for dicing and pick-up suitability, chip skipping occurred during dicing, and there was a risk of stable dicing being impossible or pick-up failure occurring.

[0007] The present invention has been made to solve the above-mentioned problems, and aims to provide a film-shaped sintered material, a film-shaped sintered material with a support sheet, and a method for manufacturing a semiconductor device that has little chip flying when the semiconductor wafer is singulated together with the film-shaped sintered material on the support sheet, even when the semiconductor wafer and the film-shaped sintered material are bonded together at room temperature, and that has excellent pick-up suitability. [Means for solving the problem]

[0008] That is, the present invention has the following aspects. [1] A film-shaped sintered material containing sinterable metal particles and a binder component, The film-shaped fired material, wherein the binder component contains a copolymer of an alkyl methacrylate having 8 or less carbon atoms and an alkyl methacrylate having 9 to 13 carbon atoms. [2] A film-shaped sintered material with a support sheet, comprising a support sheet having a base film and an adhesive layer provided on the base film, and the film-shaped sintered material described in [1] provided on the adhesive layer. [3] The film-shaped baking material with a support sheet according to [2], wherein the adhesive layer is energy ray curable. [4] A step of attaching a semiconductor wafer to the exposed surface of the film-shaped sintered material with a support sheet according to [2] or [3] to form a laminate in which the support sheet, the film-shaped sintered material, and the semiconductor wafer are stacked in this order; A step of dicing the semiconductor wafer and the film-shaped fired material of the laminate; a step of peeling off the diced film-shaped sintering material and the support sheet to pick up the semiconductor chip with the film-shaped sintering material; A step of attaching the semiconductor chip with the film-shaped sintered material to a surface of a substrate; A step of firing and pressurizing the film firing material of the semiconductor chip with film-shaped firing material to bond the semiconductor chip with film-shaped firing material to a substrate; A method for manufacturing a semiconductor device having the above structure. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a film-shaped sintered material, a film-shaped sintered material with a support sheet, and a method for manufacturing a semiconductor device, which have excellent pick-up suitability and little chip flying when the semiconductor wafer is singulated together with the film-shaped sintered material on the support sheet, even when the semiconductor wafer and the film-shaped sintered material are bonded together at room temperature. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a cross-sectional view schematically illustrating a state in which a film-shaped sintered material according to one embodiment of the present invention is attached to a release film. [Figure 2] 1 is a cross-sectional view showing a state in which a film-shaped sintered material with a support sheet is attached to a ring frame according to one embodiment of the present invention. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0011] <Film-shaped baking material> The film-shaped sintered material of this embodiment is a film-shaped sintered material containing sinterable metal particles and a binder component, and the binder component contains a copolymer of an alkyl methacrylate having 8 or less carbon atoms and an alkyl methacrylate having 9 to 13 carbon atoms.

[0012] Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings. In addition, the figures used in the following explanation may show enlarged essential parts for the sake of convenience in order to make the features of the present invention easier to understand, and the dimensional ratios of each component may not necessarily be the same as in reality.

[0013] FIG. 1 is a cross-sectional view schematically showing a state in which a film-shaped sintered material 1 of this embodiment is releasably attached to a release film 15. As shown in FIG. As shown in FIG. 1, the film-shaped sintered material 1 contains sinterable metal particles 10 and a binder component 20.

[0014] The film-shaped sintered material may consist of one layer (single layer), or may consist of two or more layers. When the film-shaped sintered material consists 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 as long as it does not impair the effects of the present invention. In this specification, not only in the case of film-shaped fired materials, "multiple layers may be the same or different" means "all layers may be the same, all layers may be different, or only some layers may be the same", and further "multiple layers are different" means "at least one of the constituent materials, the composition ratio of the constituent materials, and the thickness of each layer is different".

[0015] The thickness of the film-shaped fired material before firing is not particularly limited, but is preferably 30 to 200 μm, more preferably 40 to 150 μm, and even more preferably 50 to 90 μm. Here, "thickness of the film-shaped sintered material" means the thickness of the entire film-shaped sintered material; for example, the thickness of a film-shaped sintered material consisting of multiple layers means the total thickness of all layers that make up the film-shaped sintered material.

[0016] In this specification, the "thickness" is a value expressed as an average of thicknesses measured at any five points, and can be obtained using a constant pressure thickness measuring device in accordance with JIS K7130.

[0017] <Sinterable metal particles> Sinterable metal particles are metal particles that can be fused and bonded to form a sintered body by heat treatment at a temperature above the melting point of the metal particles when firing a film-shaped sintered material. By forming a sintered body, it is possible to sinter-bond the film-shaped sintered material with an article that is sintered in contact with it. Specifically, it is possible to sinter-bond a chip and a substrate via the film-shaped sintered material.

[0018] Examples of materials constituting the sinterable metal particles include elemental metals, barium titanate, and oxides and alloys of the elemental metals. Examples of the elemental metals include silver, gold, copper, iron, nickel, aluminum, silicon, palladium, platinum, and titanium. Preferred materials for the sinterable metal particles are silver and silver oxide. Only one type of sinterable metal particle may be blended, or two or more types may be blended in combination.

[0019] The sinterable metal particles are preferably silver nanoparticles, which are nano-sized silver particles.

[0020] The particle size of the sinterable metal particles contained in the film-shaped sintered material is not particularly limited as long as it can exhibit the above-mentioned sinterability, but it may be 100 nm or less, 50 nm or less, or 30 nm or less. Note that the particle size of the metal particles contained in the film-shaped sintered material is the diameter of the projected area circle equivalent of the particle size of the metal particles observed with an electron microscope. Metal particles within the above particle size range are preferred because they have excellent sinterability. The particle size of the sinterable metal particles contained in the film-shaped sintered material may be 0.1 to 95 nm, 0.3 to 50 nm, or 0.5 to 30 nm, as determined by observing the particle size of metal particles with a projected area circle equivalent diameter of 100 nm or less under an electron microscope. Note that the number of metal particles to be measured is 100 or more randomly selected per film-shaped sintered material.

[0021] In addition to metal particles (sinterable metal particles) having a particle diameter of 100 nm or less, the film-shaped sintered material may further contain non-sinterable metal particles having a particle diameter exceeding 100 nm that do not fall into this category. The particle diameter of the non-sinterable metal particles having a particle diameter exceeding 100 nm may be a number average particle diameter of more than 150 nm and not more than 50,000 nm, 150 to 10,000 nm, or 180 to 5,000 nm, as determined for metal particles having a projected area circle equivalent diameter exceeding 100 nm as observed with an electron microscope.

[0022] The content of metal particles having a particle diameter (diameter of a circle equivalent to a projected area) of more than 300 nm relative to the total mass (100% by mass) of all metal particles is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit of this content may be, for example, 90% by mass or less, 85% by mass or less, or 80% by mass or less. As an example of the range of the above numerical value, the content of metal particles having the above particle diameter (diameter equivalent to a circle having a projected area) of more than 300 nm relative to the total mass (100 mass%) of all metal particles may be 10 to 90 mass%, 15 to 85 mass%, or 20 to 80 mass%.

[0023] Examples of metal species for non-sinterable metal particles having a particle size of more than 100 nm include the same metal species as those exemplified above for the sinterable metal particles, with silver, copper, and oxides of these being preferred. The metal particles having a particle size of 100 nm or less and the non-sinterable metal particles having a particle size of more than 100 nm may be the same metal species or different metal species. For example, the metal particles having a particle size of 100 nm or less may be silver particles, and the non-sinterable metal particles having a particle size of more than 100 nm may be silver or silver oxide particles. For example, the metal particles having a particle size of 100 nm or less may be silver or silver oxide particles, and the non-sinterable metal particles having a particle size of more than 100 nm may be copper or copper oxide particles.

[0024] In the film-shaped sintered material, the content of sinterable metal particles relative to the total mass (100 mass%) of all metal particles may be 10 mass% or more, 10 to 90 mass%, or 20 to 85 mass%.

[0025] The surfaces of the sinterable metal particles and / or the non-sinterable metal particles may be coated with an organic material, which improves compatibility with the binder component, prevents aggregation of particles, and allows for uniform dispersion. When the surfaces of sinterable metal particles and / or non-sinterable metal particles are coated with an organic substance, the mass and particle diameter of the sinterable metal particles and non-sinterable metal particles are values ​​including the coating.

[0026] <Binder component> The addition of a binder component allows the fired material to be formed into a film and provides adhesiveness to the fired film material before firing. The resin constituting the binder component (hereinafter sometimes referred to as "binder resin") may be thermally decomposable, so that it is thermally decomposed by heat treatment during firing of the fired film material.

[0027] The binder resin contains a copolymer of an alkyl methacrylate having 8 or less carbon atoms and an alkyl methacrylate having 9 to 13 carbon atoms. A homopolymer of an alkyl methacrylate having 8 or less carbon atoms has a relatively high glass transition temperature (Tg) of approximately -10°C to 110°C. A homopolymer of an alkyl methacrylate having 9 to 13 carbon atoms has a relatively low glass transition temperature (Tg) of approximately -80°C to -10°C. By containing a copolymer of an alkyl methacrylate having 8 or less carbon atoms, the homopolymer glass transition temperature (Tg) of which is relatively high, and an alkyl methacrylate having 9 to 13 carbon atoms, the homopolymer glass transition temperature (Tg) of which is relatively low, the adhesive strength with the support sheet can be optimized. After the film-shaped sintered material with the support sheet is formed, even when the semiconductor wafer and the film-shaped sintered material are bonded together at room temperature, there is little chip flying when the semiconductor wafer is diced together with the film-shaped sintered material on the support sheet, and the dicing suitability can be improved. Furthermore, when the film-shaped sintered material is separated from the support sheet, the semiconductor chip with the film-shaped sintered material attached thereto can be made to have excellent pick-up suitability.

[0028] In this specification, "room temperature" means a temperature that is neither particularly cold nor hot, that is, an ordinary temperature, and examples thereof include temperatures of 15 to 25°C.

[0029] As the alkyl methacrylate having 8 or less carbon atoms, from the viewpoint of easily optimizing the adhesive strength between the support sheet and the film-shaped fired material when combined with an alkyl methacrylate having 9 to 13 carbon atoms, alkyl methacrylates having 2 to 8 carbon atoms are preferred, alkyl methacrylates having 3 to 8 carbon atoms are more preferred, alkyl methacrylates having 4 to 8 carbon atoms are even more preferred, and branched alkyl methacrylates having 6 to 8 carbon atoms are particularly preferred. As the alkyl methacrylate having 9 to 13 carbon atoms, from the viewpoint of easily optimizing the adhesive strength between the support sheet and the film-shaped fired material when combined with an alkyl methacrylate having 8 or less carbon atoms, alkyl methacrylates having 9 to 12 carbon atoms are preferred, alkyl methacrylates having 10 to 12 carbon atoms are more preferred.

[0030] Specific examples of alkyl methacrylates having 8 or less carbon atoms include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, pentyl methacrylate, isopentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, isooctyl methacrylate, and 2-ethylhexyl methacrylate. Specific examples of alkyl methacrylates having 9 to 13 carbon atoms include nonyl methacrylate, decyl methacrylate, isodecyl methacrylate, undecyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, and isostearyl methacrylate.

[0031] The binder resin may contain a polymer compound derived from a (meth)acrylate compound that does not fall under the copolymer of the alkyl methacrylate having 8 or less carbon atoms and the alkyl methacrylate having 9 to 13 carbon atoms. "Derived from" here means that the monomer has undergone the structural changes necessary for polymerization.

[0032] The copolymer may contain a structural unit derived from another copolymerizable monomer that does not fall under the category of alkyl methacrylate having 13 or less carbon atoms. The other copolymerizable monomer is not particularly limited as long as it is a compound that can be copolymerized with the (meth)acrylate compound, and examples thereof include unsaturated carboxylic acids such as alkyl methacrylates, alkyl acrylates, (meth)acrylic acid, vinyl benzoic acid, maleic acid, and vinyl phthalic acid having 14 or more carbon atoms; and vinyl group-containing radically polymerizable compounds such as vinylbenzyl methyl ether, vinyl glycidyl ether, styrene, α-methylstyrene, butadiene, and isoprene.

[0033] In this specification, the term "(meth)acrylate" is a concept that encompasses both "acrylate" and "methacrylate." The acrylic resin is preferably methacrylate. When the binder resin contains a structural unit derived from methacrylate, it can be fired at a relatively low temperature, and the conditions for obtaining sufficient adhesive strength after sintering can be easily met.

[0034] The glass transition temperature (Tg) of the copolymer of the binder resin can be calculated using the Fox equation shown below. It may be -80°C or higher and -15°C or lower, preferably -65 to -15°C, more preferably -60 to -20°C, and even more preferably -55 to -25°C. Having the Tg of the copolymer calculated using the Fox equation below the upper limit is preferable because the film-shaped sintered material with a support sheet can be formed and then attached to a semiconductor wafer at room temperature without heating. Furthermore, having the Tg of the copolymer below the upper limit reduces chip flying when the semiconductor wafer is diced together with the film-shaped sintered material on the support sheet at room temperature, resulting in excellent dicing suitability. On the other hand, having the Tg of the copolymer calculated using the Fox equation above the lower limit allows the shape of the film-shaped sintered material to be maintained, improving the pick-up suitability of the semiconductor chips with the film-shaped sintered material when the film-shaped sintered material is separated from the support sheet.

[0035] 1 / Tg=(W1 / Tg1)+(W2 / Tg2)+...+(Wm / Tgm) (where Tg is the glass transition temperature of the binder resin, Tg1, Tg2,...Tgm are the glass transition temperatures of the homopolymers of the monomers that are raw materials for the binder resin, and W1, W2,...Wm are the mass fractions of the monomers, where W1+W2+...+Wm=1.) The glass transition temperature of the homopolymer of each monomer in the Fox formula can be the value listed in the Polymer Data Handbook or the Adhesion Handbook.

[0036] For example, in the case of a binder resin, when the binder resin is a homopolymer of an alkyl (meth)acrylate compound, the longer the alkyl group of the alkyl (meth)acrylate, the lower the glass transition temperature (Tg). Furthermore, when the alkyl group length is the same, the glass transition temperature (Tg) of the homopolymer of the alkyl acrylate compound tends to be lower than the glass transition temperature (Tg) of the homopolymer of the alkyl methacrylate compound. The glass transition temperature (Tg) of a copolymer of two or more (meth)acrylate compounds can be appropriately adjusted by adjusting the respective content ratios of the structural units derived from the (meth)acrylate compounds in the copolymer.

[0037] The desired glass transition temperature (Tg) of the copolymer of the binder resin can be obtained by adjusting the copolymerization ratio of the alkyl methacrylate having 8 or less carbon atoms to the alkyl methacrylate having 9 or more and 13 or less carbon atoms. The copolymerization ratio (mass ratio of each monomer) of the alkyl methacrylate having 8 or less carbon atoms to the alkyl methacrylate having 9 or more and 13 carbon atoms is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, still more preferably 20 / 80 to 80 / 20, and particularly preferably 30 / 70 to 70 / 30.

[0038] The weight average molecular weight (Mw) of the binder resin is preferably 100,000 to 1,000,000, more preferably 150,000 to 800,000, and even more preferably 200,000 to 600,000. When the weight average molecular weight of the resin is within the above range, the film exhibits sufficient strength and is easily imparted with flexibility. In this specification, unless otherwise specified, the "mass average molecular weight" is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0039] In the binder resin, the content of the copolymer of alkyl methacrylate having 8 or less carbon atoms and alkyl methacrylate having 9 to 13 carbon atoms is preferably 50 to 100 mass%, more preferably 80 to 100 mass%, even more preferably 90 to 100 mass%, even more preferably 95 to 100 mass%, and may be 100 mass%, relative to the total mass (100 mass%) of the binder components.

[0040] The content of the structural units derived from alkyl methacrylates having 13 or less carbon atoms is preferably 90 to 100 mass%, more preferably 95 to 100 mass%, and even more preferably 98 to 100 mass%, relative to the total mass (100 mass%) of the structural units of the copolymer, and may be 100 mass%.

[0041] In the binder resin, the content of the (meth)acrylate-derived structural unit relative to the total mass (100 mass%) of the structural units of the binder resin is preferably 50 to 100 mass%, more preferably 80 to 100 mass%, even more preferably 90 to 100 mass%, even more preferably 95 to 100 mass%, and may be 100 mass%.

[0042] The binder component may be thermally decomposable, being thermally decomposed by heat treatment as the firing of the film-shaped fired material. The thermal decomposition of the binder component can be confirmed by the mass reduction of the binder component due to firing. Note that the components blended as the binder component may be almost thermally decomposed by firing, but the entire mass of the components blended as the binder component may not be thermally decomposed by firing. The binder component may be one whose mass after firing is 10% by mass or less, 5% by mass or less, or 3% by mass or less of the total mass (100% by mass) of the binder component before firing.

[0043] A copolymer or homopolymer containing a large amount of structural units derived from an alkyl methacrylate compound has better thermal decomposition properties when formed into a film-shaped fired material than a copolymer or homopolymer containing a large amount of structural units derived from an alkyl acrylate compound. Therefore, the content of structural units derived from an alkyl methacrylate compound is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and may be 100% by mass, relative to the total mass (100% by mass) of the structural units of the binder resin.

[0044] In addition to the above-mentioned sinterable metal particles, non-sinterable metal particles, and binder components, the film-shaped sintered material may also contain other additives that do not fall under the category of sinterable metal particles, non-sinterable metal particles, and binder components, within a range that does not impair the effects of the present invention.

[0045] Other additives that may be contained in the film-shaped sintered material include solvents, dispersants, plasticizers, tackifiers, storage stabilizers, antifoaming agents, thermal decomposition accelerators, and antioxidants. Only one type of additive may be contained, or two or more types may be contained. These additives are not particularly limited, and can be appropriately selected from those commonly used in this field.

[0046] It is preferable that the binder component be thermally decomposed by heat treatment when the film-shaped fired material is fired. Therefore, the content of thermosetting resin such as epoxy resin is preferably 10% by mass or less, more preferably 5% by mass or less, relative to 100% by mass of the binder component, and even more preferably, the material is substantially free of thermosetting resin. From the same viewpoint, the content of acrylate-derived structural units from "acrylate" and "methacrylate" relative to the total mass (100 mass%) of the structural units of the binder resin is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably is substantially free of acrylate-derived structural units.

[0047] <Composition> The film-shaped sintered material may be composed of sinterable metal particles, a binder component, and other additives, and the sum of their contents (mass%) may be 100 mass%. When the film-shaped sintered material contains non-sinterable metal particles, the film-shaped sintered material may be composed of sinterable metal particles, non-sinterable metal particles, a binder component, and other additives, and the sum of their contents (mass%) may be 100 mass%.

[0048] In the film-shaped sintered material, the content of sinterable metal particles relative to the total mass (100 mass%) of all components other than the solvent (hereinafter referred to as "solids") is preferably 15 to 88 mass%, more preferably 15 to 85 mass%, and even more preferably 20 to 80 mass%. When the content of sinterable metal particles is equal to or less than the above upper limit, the content of the binder component can be sufficiently ensured, making it easier to maintain the film shape. On the other hand, when the content of sinterable metal particles is equal to or greater than the above lower limit, sinterable metal particles or sinterable metal particles and non-sinterable metal particles fuse together during sintering, resulting in the effect of exhibiting high bonding strength (shear adhesive strength) after sintering.

[0049] When the film-shaped sintered material contains non-sinterable metal particles, the total content of sinterable metal particles and non-sinterable metal particles relative to the total mass (100 mass%) of the solid content in the film-shaped sintered material is preferably 50 to 98 mass%, more preferably 70 to 95 mass%, and even more preferably 80 to 95 mass%.

[0050] The content of the binder component relative to the total mass (100 mass%) of the solid content in the film-shaped sintered material is preferably 2 to 50 mass%, more preferably 5 to 30 mass%, and even more preferably 5 to 20 mass%. When the content of the binder component is equal to or less than the above upper limit, the content of the sinterable metal particles can be sufficiently ensured, thereby further improving the bonding and adhesive strength between the film-shaped sintered material and the adherend. On the other hand, when the content of the binder component is equal to or more than the above lower limit, it becomes easier to maintain the film shape.

[0051] In the film-shaped sintered material, the mass ratio of the sinterable metal particles to the binder component (sinterable metal particles:binder component) is preferably 50:1 to 1:5, more preferably 20:1 to 1:2, and even more preferably 10:1 to 1:1. When the film-shaped sintered material contains non-sinterable metal particles, the mass ratio of the sinterable metal particles and non-sinterable metal particles to the binder component ((sinterable metal particles + non-sinterable metal particles):binder component) is preferably 50:1 to 1:1, more preferably 20:1 to 2:1, and even more preferably 9:1 to 4:1.

[0052] (Release film) The film-shaped sintered material can be formed with a release film laminated thereon. When in use, the release film is peeled off and the film-shaped sintered material is placed on the object to be sinter-bonded. The release film also functions as a protective film to prevent damage to the film-shaped sintered material and adhesion of dirt. The release film needs to be provided on at least one side of the film-shaped sintered material, and may be provided on both sides of the film-shaped sintered material.

[0053] The thickness of the release film is usually about 10 to 500 μm, preferably about 15 to 300 μm, and particularly preferably about 20 to 250 μm.

[0054] [Manufacturing method for film-shaped fired material] The film-shaped fired material can be formed using a fired material composition containing the constituent materials. For example, a firing material composition containing the components and solvent for constituting the film-shaped fired material can be coated or printed onto the surface on which the film-shaped fired material is to be formed, and the solvent can be evaporated as necessary to form a film-shaped fired material in the desired location. The surface on which the film-shaped fired material is formed can be the surface of a release film.

[0055] When applying the fired material composition, the solvent preferably has a boiling point of less than 200°C, such as n-hexane (boiling point: 68°C), ethyl acetate (boiling point: 77°C), 2-butanone (boiling point: 80°C), n-heptane (boiling point: 98°C), methylcyclohexane (boiling point: 101°C), toluene (boiling point: 111°C), acetylacetone (boiling point: 138°C), n-xylene (boiling point: 139°C), and dimethylformamide (boiling point: 153°C). These may be used alone or in combination.

[0056] The baking material composition may be applied by a known method, such as a method using various coaters such as 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 Mayer bar coater, or a kiss coater.

[0057] When printing the sintered material composition, the solvent may be any solvent that can be evaporated and dried after printing, and preferably has a boiling point of 65 to 350° C. Examples of such solvents include the solvents with a boiling point of less than 200° C. listed above, as well as isophorone (boiling point: 215° C.), butyl carbitol (boiling point: 230° C.), 1-decanol (boiling point: 233° C.), butyl carbitol acetate (boiling point: 247° C.), and isobornyl cyclohexanol (boiling point: 318° C.). If the boiling point exceeds 350°C, the solvent will be difficult to volatilize during evaporative drying after printing, making it difficult to obtain the desired shape, and the solvent may remain in the film during baking, potentially degrading bonding and adhesion. If the boiling point is below 65°C, the solvent will volatilize during printing, potentially compromising thickness stability. Using a solvent with a boiling point of 200 to 350°C can suppress the increase in viscosity due to solvent volatilization during printing, ensuring printability.

[0058] The firing material composition can be printed by a known printing method, but is preferably printed by a screen printing method such as silk screen printing or rotary screen printing.

[0059] The shape of the film-shaped sintered material may be appropriately set to match the shape of the object to be sintered and bonded, and is preferably circular or rectangular. A circular shape corresponds to the shape of a semiconductor wafer. A rectangular shape corresponds to the shape of a chip. The corresponding shape may be the same as or approximately the same as the shape of the object to be sintered and bonded. When the film-shaped baking material is circular, the area of ​​the circle is 3.5 to 1,600 cm 2 may be 85 to 1,400 cm 2 When the film-shaped fired material is rectangular, the area of ​​the rectangle may be 0.01 to 25 cm 2 may be 0.25 to 9 cm 2 It may be. In particular, if the fired material composition is printed, it is easy to form a film-shaped fired material in a desired shape.

[0060] The drying conditions for the fired material composition are not particularly limited. However, when the fired material composition contains a solvent, it is preferable to heat-dry it. In this case, it is preferable to dry it at a temperature of, for example, 70 to 250°C, e.g., 80 to 180°C, for 10 seconds to 10 minutes.

[0061] <Film-shaped baking material with support sheet> The film-shaped sintered material with support sheet of this embodiment comprises a support sheet having a base film and an adhesive layer provided on the base film, and the film-shaped sintered material described in the above-mentioned embodiment provided on the adhesive layer.

[0062] FIG. 2 is a cross-sectional view schematically showing a state in which the film-shaped sintered material with a support sheet of this embodiment is attached to a ring frame. The film-like sintered material with support sheet 100 comprises a film-like sintered material 1 temporarily and releasably attached to a support sheet 2. The support sheet 2 comprises a base film 3 on which an adhesive layer 4 is provided, and the film-like sintered material 1 is provided on the adhesive layer 4. The film-like sintered material 1 is provided in direct contact with the adhesive layer 4.

[0063] The film-shaped sintered material with support sheet of this embodiment can be used as a dicing sheet used when singulating a semiconductor wafer into chips. Furthermore, by singulating it together with the semiconductor wafer using a blade or the like, it can be processed into a film-shaped sintered material of the same shape as the chip, and chips with the film-shaped sintered material can be manufactured. The film-shaped sintered material with support sheet 100 of this embodiment includes the film-shaped sintered material described in the above embodiment. Therefore, even when the semiconductor wafer and the film-shaped sintered material are bonded together at room temperature, there is little chip flying when the semiconductor wafer is singulated together with the film-shaped sintered material on the support sheet, and the pick-up suitability is excellent.

[0064] Examples of semiconductor wafers include silicon wafers, and examples of insulator wafers include, but are not limited to, glass wafers and sapphire wafers.

[0065] The support sheet 2 has an adhesive portion on the outer periphery. In a preferred embodiment, a film-shaped sintered material 1 having a smaller diameter than the support sheet 2 is concentrically laminated on the circular support sheet 2. The adhesive portion on the outer periphery is used to fix a ring frame 5 as shown in the figure. The support sheet-attached film-shaped sintered material 100 having the above-described configuration is attached to a ring frame 5 at the adhesive layer 4 exposed on the outer periphery of the support sheet 2 .

[0066] Furthermore, a separate annular double-sided tape or adhesive layer may be provided on the margin for gluing to the ring frame (the exposed adhesive layer at the outer periphery of the adhesive sheet). The double-sided tape has a structure of adhesive layer / core material / adhesive layer, and the adhesive layer in the double-sided tape is not particularly limited, and adhesives such as rubber-based resins, acrylic resins, silicone resins, and polyvinyl ethers are used. The adhesive layer is attached to the ring frame at its outer periphery when manufacturing the chip-attached substrate described below. Preferred examples of the core material for the double-sided tape include polyester film, polypropylene film, polycarbonate film, polyimide film, fluororesin film, and liquid crystal polymer film.

[0067] In the support sheet-attached film-shaped sintered material of this embodiment, after the semiconductor wafer and the support sheet-attached film-shaped sintered material are bonded at room temperature, the adhesive strength (a1) between the adhesive layer and the film-shaped sintered material may be 250 to 3500 mN / 10 mm, preferably 300 to 3300 mN / 10 mm, more preferably 350 to 3000 mN / 10 mm, even more preferably 280 to 3500 mN / 10 mm, even more preferably 450 to 2500 mN / 10 mm, and particularly preferably 1500 to 2500 mN / 10 mm. By having the adhesive strength (a1) between the adhesive layer and the film-shaped sintered material be equal to or greater than the above lower limit, after the support sheet-attached film-shaped sintered material is attached to the semiconductor wafer at room temperature, the semiconductor wafer on the support sheet When the film-shaped sintered material is diced into individual pieces, there is little chip flying, and the dicing suitability is excellent. On the other hand, when the adhesive strength (a1) between the adhesive layer and the film-shaped sintered material is below the upper limit value, the pick-up suitability of the semiconductor chip with the film-shaped sintered material is more likely to be improved when the film-shaped sintered material is pulled away from the support sheet.

[0068] The adhesive strength (a1) between the pressure-sensitive adhesive layer and the film-shaped fired material is determined in accordance with JIS Z0237:2000, and specifically, can be measured by the following method. When the pressure-sensitive adhesive layer is energy ray-curable, the adhesive strength (a1) is a value measured before irradiation with energy rays. First, the surface of the silicon wafer is subjected to chemical mechanical polishing until the arithmetic mean roughness (Ra) becomes 0.02 μm or less. Next, the film-shaped sintered material with support sheet is cut into strips with a width of 10 mm and a length of 150 mm or more, and attached to the treated surface of the silicon wafer at room temperature to form a laminate in which the base film, the adhesive layer, the film-shaped sintered material, and the silicon wafer are stacked in this order. The obtained laminate was left for 20 minutes in an atmosphere of 23°C and 50% relative humidity, and then, using a universal tensile tester in accordance with JIS Z0237:2000, the support sheet was peeled off from the silicon wafer at a peeling speed of 300 mm / min so that the surfaces of the support sheet and the film-like sintered material that had been in contact with each other formed an angle of 180°. The load (peel force) at this 180° peel was measured, and this measured value was taken as the adhesive strength (a1) [mN / 10 mm].

[0069] The thickness of the film-shaped fired material with a support sheet is preferably 1 to 500 μm, more preferably 5 to 300 μm, and even more preferably 10 to 200 μm.

[0070] (Base film) The base film 3 is not particularly limited, and examples thereof include films made of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene-propylene copolymer, polypropylene, polybutene, polybutadiene, polymethylpentene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-methyl (meth)acrylate copolymer, ethylene-ethyl (meth)acrylate copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyurethane film, ionomer, and the like. Furthermore, when higher heat resistance is required for the support sheet, examples of the substrate film 3 include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polymethylpentene. Crosslinked films of these films and films modified by radiation, discharge, etc. can also be used. The substrate film may be a laminate of the above films.

[0071] Two or more of these films can be laminated or used in combination. Furthermore, these films can be colored or printed. The film can be a sheet made by extrusion molding of a thermoplastic resin, or a stretched film, or a sheet made by thinning and curing a curable resin by a predetermined means can be used.

[0072] The thickness of the substrate film is not particularly limited, but is preferably 30 to 300 μm, more preferably 50 to 200 μm. By setting the thickness of the substrate film within the above range, the substrate film is less likely to tear even when cut by dicing. In addition, the film-shaped sintered material with support sheet is given sufficient flexibility, so it exhibits good adhesion to workpieces (e.g., semiconductor wafers, etc.).

[0073] The substrate film can also be obtained by applying a release agent to the surface to perform a release treatment. Examples of the release agent used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents, but alkyd-based, silicone-based, and fluorine-based release agents are particularly preferred because of their heat resistance.

[0074] In order to perform a release treatment on the surface of a substrate film using the above-mentioned release agent, the release agent may be applied as is without a solvent, or after diluting with a solvent or making it into an emulsion, using a gravure coater, a Mayer bar coater, an air knife coater, a roll coater, or the like, and the substrate film to which the release agent has been applied may be subjected to curing at room temperature or under heat, or may be cured with an electron beam, or a laminate may be formed by wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion processing, or the like.

[0075] (Adhesive layer) The pressure-sensitive adhesive layer 4 is in the form of a sheet or film, and can contain a pressure-sensitive adhesive. As shown in Fig. 2, the support sheet 2 may be a conventional adhesive sheet having an adhesive layer 4 on the entire upper surface of a substrate film 3, or may be configured such that the inner peripheral surface of the adhesive layer 4 is covered with a film-like sintered material, with the adhesive portion exposed on the outer peripheral portion. In this case, the outer peripheral portion of the adhesive layer 4 is used to fix the ring frame 5, and the film-like sintered material is releasably laminated on the inner peripheral portion. An energy ray-curable adhesive is preferably used as the adhesive layer 4, and specifically, an acrylic adhesive is preferred.

[0076] In this specification, the term "energy ray" refers to an electromagnetic wave or a charged particle beam that has an energy quantum, and examples thereof include ultraviolet rays, radioactive rays, and electron beams. Ultraviolet light can be irradiated using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, etc. Electron beams generated by an electron beam accelerator or the like can be irradiated. In this specification, "energy ray curable" means a property of being cured by irradiation with energy rays, and "non-energy ray curable" means a property of not being cured even when irradiated with energy rays.

[0077] 2, when an energy ray-curable adhesive layer is used, as the glass transition temperature (Tg) of the copolymer in the film-shaped sintered material increases, the adhesive strength (a1) between the adhesive layer and the film-shaped sintered material and the adhesive strength between the film-shaped sintered material and the semiconductor wafer before energy ray irradiation tend to decrease, making the material more susceptible to peeling from the support sheet after energy ray irradiation. On the other hand, when the glass transition temperature (Tg) of the copolymer in the film-shaped sintered material is lowered, the adhesive strength (a1) between the adhesive layer and the film-shaped sintered material and the adhesive strength between the film-shaped sintered material and the semiconductor wafer before energy ray irradiation tend to increase, but these adhesive strengths after energy ray irradiation are also high, making the material more difficult to peel from the support sheet. The film-shaped sintered material with support sheet of this embodiment includes the film-shaped sintered material described in the above embodiment, and the binder resin contains a copolymer of an alkyl methacrylate having 8 or less carbon atoms, which has a relatively high homopolymer glass transition temperature (Tg), and an alkyl methacrylate having 9 to 13 carbon atoms, which has a relatively low homopolymer glass transition temperature (Tg). Even when the semiconductor wafer and the film-shaped sintered material with support sheet are bonded together at room temperature, the adhesive strength (a1) between the adhesive layer and the film-shaped sintered material can be optimized. When the semiconductor wafer and the film-shaped sintered material are diced together on the support sheet before energy beam irradiation, chip flying is reduced, resulting in excellent dicing suitability. Furthermore, when the film-shaped sintered material is separated from the support sheet after energy beam irradiation, the pick-up suitability of the semiconductor chips with the film-shaped sintered material can be improved.

[0078] When the adhesive layer is energy ray curable, the adhesive layer and the film-like sintered material with a support sheet are bonded together at room temperature, and the adhesive layer is irradiated with energy rays to cure the adhesive layer. The adhesive strength (a2) between the adhesive layer and the film-like sintered material after the energy ray curing may be 60 to 1000 mN / 10 mm, preferably 80 to 800 mN / 10 mm, more preferably 100 to 600 mN / 10 mm, even more preferably 140 to 550 mN / 10 mm, even more preferably 160 to 520 mN / 10 mm, and particularly preferably 160 to 500 mN / 10 mm. When the adhesive strength (a2) between the adhesive layer and the film-like sintered material is above the lower limit, after the film-like sintered material with a support sheet is attached to the semiconductor wafer at room temperature, there is little chip flying when the semiconductor wafer is diced together with the film-like sintered material on the support sheet, and the dicing suitability is excellent. On the other hand, when the adhesive strength (a2) between the adhesive layer and the film-shaped sintered material is below the upper limit value, the pick-up suitability of the semiconductor chip with the film-shaped sintered material is more likely to be improved when the film-shaped sintered material is pulled away from the support sheet.

[0079] The adhesive strength (a2) between the adhesive layer and the film-shaped fired material after the adhesive layer is irradiated with energy rays to harden the adhesive layer is determined in accordance with JIS Z0237:2000, and specifically, can be measured by the following method. First, the surface of the silicon wafer is subjected to chemical mechanical polishing until the arithmetic mean roughness (Ra) becomes 0.02 μm or less. Next, the film-shaped sintered material with support sheet is cut into strips with a width of 10 mm and a length of 150 mm or more, and attached to the treated surface of the silicon wafer at room temperature to form a laminate in which the base film, the adhesive layer, the film-shaped sintered material, and the silicon wafer are stacked in this order. The resulting laminate was left for 20 minutes in an atmosphere of 23°C and 50% relative humidity, and then the laminate was irradiated with energy rays from the substrate film side to energy ray cure the adhesive layer. Then, using a universal tensile tester in accordance with JIS Z0237:2000, the support sheet was peeled off from the silicon wafer at a peeling speed of 300 mm / min so that the surfaces of the support sheet and the film-like sintered material that had been in contact with each other formed an angle of 180°. The load (peel force) at this 180° peel was measured, and this measured value was designated as the adhesive strength (a2) [mN / 10 mm].

[0080] The thickness of the pressure-sensitive adhesive layer 4 is not particularly limited, but is preferably 1 to 100 μm, more preferably 2 to 80 μm, and particularly preferably 3 to 50 μm.

[0081] The pressure-sensitive adhesive layer may consist of one layer (single layer) or two or more layers. When the pressure-sensitive adhesive layer consists 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 as long as it does not impair the effects of the present invention.

[0082] <Adhesive composition> The pressure-sensitive adhesive layer can be formed using a known pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive composition can be applied to the surface on which the pressure-sensitive adhesive layer is to be formed, and then dried as necessary to form the pressure-sensitive adhesive layer at the desired location. A more specific method for forming the pressure-sensitive adhesive layer will be described in detail later, along with methods for forming other layers. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer.

[0083] [Method for manufacturing a film-shaped fired material with a support sheet] The film-shaped sintered material with support sheet of the above-mentioned embodiment can be manufactured by a method comprising the steps of: coating or printing a sintered material composition containing sinterable metal particles, a binder component, and a solvent onto the release-treated surface of a release film to form a film-shaped sintered material; preparing a support sheet having a base film and an adhesive layer provided on the base film; and bonding the support sheet to the exposed surface of the film-shaped sintered material using the exposed surface of the adhesive layer.

[0084] The film-shaped sintered material with a support sheet may be stored with a release film attached to the outermost surface of the film-shaped sintered material on the side opposite the support sheet. The release film may be removed as needed after the film-shaped sintered material with a support sheet is formed.

[0085] <Method for manufacturing semiconductor device> The method for manufacturing a semiconductor device of this embodiment includes the steps of: attaching a semiconductor wafer to the exposed surface of the film-shaped sintered material with a support sheet described in the above embodiment, thereby forming a laminate in which the support sheet, the film-shaped sintered material, and the semiconductor wafer are stacked in this order; dicing the semiconductor wafer and film-shaped sintered material of the laminate; peeling off the diced film-shaped sintered material and support sheet and picking up the semiconductor chip with film-shaped sintered material; attaching the semiconductor chip with film-shaped sintered material to the surface of a substrate; and firing and pressurizing the film-shaped sintered material of the semiconductor chip with film-shaped sintered material, thereby joining the semiconductor chip with film-shaped sintered material to the substrate.

[0086] The method for manufacturing a semiconductor device of this embodiment includes the film-shaped sintered material with support sheet described in the above-mentioned embodiment, and therefore, even when the semiconductor wafer and the film-shaped sintered material with support sheet are bonded together at room temperature, there is little chip flying when the semiconductor wafer is singulated together with the film-shaped sintered material on the support sheet, and the method has excellent pick-up suitability. [Example]

[0087] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[0088] [Example 1] <Production of film-shaped fired material> <Production of fired material composition> The components used in the production of the sintered material composition are shown below. Here, metal particles with a particle size of 100 nm or less are referred to as "sinterable metal particles."

[0089] (Sinterable metal particle-containing paste material) Sinterable metal particle-containing paste material: Alconano silver paste ANP-4 (organically coated composite silver nanopaste, manufactured by Applied Nanoparticles Research Institute Co., Ltd.: alcohol derivative-coated silver particles, metal content 80 wt% or more, average particle size 100 nm or less, 25 wt% or more silver particles)

[0090] (binder resin) Acrylic copolymer 1 (2-ethylhexyl methacrylate (2EHMA) / lauryl methacrylate (LMA) copolymer, copolymerization mass ratio 5 / 95, mass average molecular weight 250,000, Tg: -63°C) The Tg of the acrylic polymer 1 is a calculated value using the Fox formula.

[0091] A sintered material composition was obtained by mixing 88.0 parts by weight of a sinterable metal particle-containing paste material and 12.0 parts by weight of a binder resin (acrylic polymer 1), adjusting the solids content to 80.0% using butyl carbitol acetate as a solvent. Because the sinterable metal particle-containing paste material is sold containing a high-boiling point solvent, which remains in the film-shaped sintered material after coating or drying, the components of the sinterable metal particle-containing paste material are listed including this. Considering that the solvent in the binder resin evaporates during drying, the solids content is expressed as parts by weight excluding the solvent component.

[0092] <Production of film-shaped fired material> The sintered material composition obtained above was printed in a circle with a diameter of 155 mm on one side of a release film (thickness 38 μm, SP-PET381031, manufactured by Lintec Corporation) and dried at 150°C for 5 minutes to obtain a film-like sintered material with a thickness of 75 μm on the release film.

[0093] <Production of film-shaped fired material with support sheet> <Support sheet> A dicing sheet (Adwill D-458J, manufactured by Lintec Corporation) was used as a support sheet having a UV-curable adhesive layer laminated on a substrate film.

[0094] <Production of film-shaped fired material with support sheet> The exposed surface of a film-like sintered material printed in a circle with a diameter of 155 mm was attached to the exposed surface of the adhesive layer of the support sheet using a laminator (MCK Corporation, MCL-650) at room temperature under conditions of a speed of 0.3 m / min and a pressure of 0.3 MPa. The support sheet was then concentrically cut from the base film side into circles with a diameter of 207 mm, yielding a film-like sintered material with a support sheet in which a circular film-like sintered material and a release film were laminated on top of a support sheet having an adhesive layer on a base film.

[0095] [Example 2] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Example 2 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was changed to the following acrylic polymer 2 as the binder resin.

[0096] (binder resin) Acrylic copolymer 2 (2-ethylhexyl methacrylate (2EHMA) / lauryl methacrylate (LMA) copolymer, copolymerization mass ratio 10 / 90, mass average molecular weight 250,000, Tg: -61°C)

[0097] <Production of film-shaped fired material with support sheet> A film-shaped sintered material with a support sheet of Example 2 was obtained in the same manner as in Example 1 above, except that the film-shaped sintered material of Example 2 was used.

[0098] [Example 3] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Example 3 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was changed to the following acrylic polymer 3 as the binder resin.

[0099] (binder resin) Acrylic copolymer 3 (2-ethylhexyl methacrylate (2EHMA) / lauryl methacrylate (LMA) copolymer, copolymerization mass ratio 20 / 80, mass average molecular weight 250,000, Tg: -56°C)

[0100] <Production of film-shaped fired material with support sheet> A film-shaped sintered material with a support sheet of Example 3 was obtained in the same manner as in Example 1 above, except that the film-shaped sintered material of Example 3 was used.

[0101] [Example 4] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Example 4 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was changed to the following acrylic polymer 4 as the binder resin.

[0102] (binder resin) Acrylic copolymer 4 (2-ethylhexyl methacrylate (2EHMA) / lauryl methacrylate (LMA) copolymer, copolymerization mass ratio 30 / 70, mass average molecular weight 250,000, Tg: -51°C)

[0103] <Production of film-shaped fired material with support sheet> A film-shaped sintered material with a support sheet of Example 4 was obtained in the same manner as in Example 1 above, except that the film-shaped sintered material of Example 4 was used.

[0104] [Example 5] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Example 5 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was replaced with the following acrylic polymer 5 as the binder resin.

[0105] (binder resin) Acrylic copolymer 5 (2-ethylhexyl methacrylate (2EHMA) / lauryl methacrylate (LMA) copolymer, copolymerization mass ratio 40 / 60, mass average molecular weight 270,000, Tg: -46°C)

[0106] <Production of film-shaped fired material with support sheet> A film-shaped sintered material with a support sheet of Example 5 was obtained in the same manner as in Example 1 above, except that the film-shaped sintered material of Example 5 was used.

[0107] [Example 6] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Example 6 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was replaced with the following acrylic polymer 6 as the binder resin.

[0108] (binder resin) Acrylic copolymer 6 (2-ethylhexyl methacrylate (2EHMA) / lauryl methacrylate (LMA) copolymer, copolymerization mass ratio 50 / 50, mass average molecular weight 230,000, Tg: -41°C)

[0109] <Production of film-shaped fired material with support sheet> A film-shaped sintered material with a support sheet of Example 6 was obtained in the same manner as in Example 1 above, except that the film-shaped sintered material of Example 6 was used.

[0110] [Example 7] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Example 7 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was replaced with the following acrylic polymer 7 as the binder resin.

[0111] (binder resin) Acrylic copolymer 7 (2-ethylhexyl methacrylate (2EHMA) / lauryl methacrylate (LMA) copolymer, copolymerization mass ratio 60 / 40, mass average molecular weight 260,000, Tg: -35°C)

[0112] <Production of film-shaped fired material with support sheet> A film-shaped sintered material with a support sheet of Example 7 was obtained in the same manner as in Example 1 above, except that the film-shaped sintered material of Example 7 was used.

[0113] [Example 8] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Example 8 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was replaced with the following acrylic polymer 8 as the binder resin.

[0114] (binder resin) Acrylic copolymer 8 (2-ethylhexyl methacrylate (2EHMA) / lauryl methacrylate (LMA) copolymer, copolymerization mass ratio 70 / 30, mass average molecular weight 250,000, Tg: -29°C)

[0115] <Production of film-shaped fired material with support sheet> A film-shaped sintered material with a support sheet of Example 8 was obtained in the same manner as in Example 1 above, except that the film-shaped sintered material of Example 8 was used.

[0116] [Example 9] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Example 9 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was changed to the following acrylic polymer 9 as the binder resin.

[0117] (binder resin) Acrylic copolymer 9 (2-ethylhexyl methacrylate (2EHMA) / lauryl methacrylate (LMA) copolymer, copolymerization mass ratio 80 / 20, mass average molecular weight 270,000, Tg: -23°C)

[0118] <Production of film-shaped fired material with support sheet> A film-shaped sintered material with a support sheet of Example 9 was obtained in the same manner as in Example 1 above, except that the film-shaped sintered material of Example 9 was used.

[0119] [Example 10] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Example 10 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was replaced with the following acrylic polymer 10 as the binder resin.

[0120] (binder resin) Acrylic copolymer 10 (2-ethylhexyl methacrylate (2EHMA) / lauryl methacrylate (LMA) copolymer, copolymerization mass ratio 90 / 10, mass average molecular weight 250,000, Tg: -17°C)

[0121] <Production of film-shaped fired material with support sheet> A film-shaped sintered material with a support sheet of Example 10 was obtained in the same manner as in Example 1 above, except that the film-shaped sintered material of Example 10 was used.

[0122] [Example 11] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Example 11 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was changed to the following acrylic polymer 11 as the binder resin.

[0123] (binder resin) Acrylic copolymer 11 (2-ethylhexyl methacrylate (2EHMA) / isodecyl methacrylate (IDMA) copolymer, copolymerization mass ratio 20 / 80, mass average molecular weight 240,000, Tg: -35°C)

[0124] <Production of film-shaped fired material with support sheet> A film-like sintered material with a support sheet of Example 11 was obtained in the same manner as in Example 1 above, except that the film-like sintered material of Example 11 was used.

[0125] [Comparative Example 1] <Production of film-shaped fired material> In producing the film-shaped sintered material, the film-shaped sintered material of Comparative Example 1 was obtained in the same manner as in Example 1 above, except that the acrylic polymer 1 in Example 1 was changed to the following acrylic polymer 12 as the binder resin.

[0126] (binder resin) Acrylic polymer 12 (2-ethylhexyl methacrylate polymer, mass average molecular weight 250,000, Tg: -10°C)

[0127] <Production of film-shaped fired material with support sheet> A film-shaped sintered material with a support sheet of Comparative Example 1 was obtained in the same manner as in Example 1 above, except that the film-shaped sintered material of Comparative Example 1 was used.

[0128] <Evaluation of film-shaped fired materials> The film-like sintered materials and film-like sintered materials with a support sheet obtained above in the Examples and Comparative Examples were evaluated for the following items.

[0129] (Measurement of adhesive strength (a1) before UV irradiation) A silicon wafer (manufactured by Science and Technology Research Institute, diameter: 150 mm, thickness: 500 μm) whose surface had been chemically and mechanically polished until the arithmetic mean roughness (Ra) was 0.02 μm or less was prepared as an adherend to be adhered. Next, the film-like fired material with the support sheet was cut into strips with a width of 10 mm and a length of 150 mm or more, and these were attached to the treated surface of a silicon wafer at room temperature.

[0130] The resulting laminate was left for 20 minutes in an atmosphere of 23°C and 50% relative humidity, and then the 180° peel adhesive strength between the support sheet and the film-like sintered material was measured using a universal tensile tester (Instron, Model 5581) in accordance with JIS Z0237:2000. Specifically, the support sheet was peeled from the silicon wafer at a peel rate of 300 mm / min. The support sheet was peeled in its length direction so that the surfaces of the support sheet and the film-like sintered material that had been in contact with each other formed a 180° angle. The load (peel force) at this 180° peel was then measured, and this measurement value was taken as the adhesive strength (a1) [mN / 10 mm].

[0131] (Measurement of adhesive strength (a2) after UV irradiation) A silicon wafer (manufactured by Science and Technology Research Institute, diameter: 150 mm, thickness: 500 μm) whose surface had been chemically and mechanically polished until the arithmetic mean roughness (Ra) was 0.02 μm or less was prepared as an adherend to be adhered. Next, the film-like fired material with the support sheet was cut into strips with a width of 10 mm and a length of 150 mm or more, and these were attached to the treated surface of a silicon wafer at room temperature.

[0132] The resulting laminate was left for 20 minutes in an atmosphere of 23°C and 50% relative humidity, and then exposed to UV light using a UV irradiation device (Adwill RAD2000m / 12) at a dominant wavelength of 365 nm and 200 mW / cm 2 , 200mJ / cm 2UV irradiation was performed from the support sheet side under the conditions of , and the adhesive layer was UV-cured. Then, using a universal tensile tester (Instron, Model 5581) in accordance with JIS Z0237:2000, the 180° peel adhesive strength between the support sheet and the film-like sintered material was measured. Specifically, the support sheet was peeled from the silicon wafer at a peeling rate of 300 mm / min. The support sheet was peeled in its length direction so that the surfaces of the support sheet and the film-like sintered material that had been in contact with each other formed a 180° angle. The load (peel force) at this 180° peel was then measured, and this measured value was designated as the adhesive strength (a2) [mN / 10 mm].

[0133] (Evaluation of dicing suitability) The release film was removed from the film-shaped sintered material with support sheet, and a silicon wafer (manufactured by Science and Technology Research Institute, diameter: 150 mm, thickness: 500 μm) whose surface had been chemically mechanically polished until the arithmetic mean roughness (Ra) was 0.02 μm or less was bonded to the exposed surface of the film-shaped sintered material of the film-shaped sintered material with support sheet at room temperature. The obtained laminate test piece was then mounted on a dicing SUS ring frame (manufactured by Disco Corporation) and diced using a dicing device (DFD6362, manufactured by Disco Corporation) under the following conditions to obtain 100 silicon chips with film-like sintered material, each measuring 2 mm x 2 mm.

[0134] <Dicing conditions> Dicing blade: NBC-ZH2050-SE27HECC, manufactured by Disco Blade thickness: 25μm width Blade rotation speed: 40,000 rpm ·Cutting speed: 40mm / s ·Cutting water amount: 1.5L / min ·Cutting water temperature: 24℃

[0135] After dicing, the number of chips that broke off was counted for 100 chips, and the dicing suitability was evaluated according to the following criteria.

[0136] ·Evaluation criteria for chip flying A: Less than 5 chips B: The number of chips is 5 or more but less than 10 C: 10 or more chips scattered

[0137] (Pickup aptitude evaluation) In the evaluation of chip flying, silicon chips with film-like sintered material on a support sheet obtained by normal dicing were used as the targets. The chips were placed on a substrate at a slider speed of 10 mm / s and picked up using a die bonder (BESTEM-D02, manufactured by Canon Machinery) under the following pickup conditions.

[0138] <Pickup conditions> Collet: Voidless type Collet size: 2mm x 2mm Pickup method: Slider type (needleless type) Slider width: 2mm Expanded: 3mm

[0139] At this time, any pickup failures, such as the device stopping because the chip was not picked up or the chip being damaged, were confirmed, and the ratio of the number of silicon chips with film-like sintered material that had pickup failures to the number of silicon chips with film-like sintered material on the support sheet that were obtained by dicing normally (pickup failure rate) was calculated, and the pick-up suitability was evaluated using the following evaluation criteria.

[0140] Pickup suitability evaluation criteria A: Pickup defect rate is less than 5% B: Pickup defect rate is between 5% and 10% C: Pickup defect rate is 10% or more

[0141] The evaluation results are shown in Tables 1 and 2 below.

[0142] [Table 1]

[0143] [Table 2]

[0144] The film-shaped sintered materials of Examples 1 to 11 are film-shaped sintered materials 1 containing sinterable metal particles 10 and binder components 20, and the binder components 20 contain a copolymer of alkyl methacrylate having 8 or less carbon atoms and alkyl methacrylate having 9 to 13 carbon atoms, thereby optimizing the adhesive strength with the support sheet before and after irradiation with energy rays, and when made into film-shaped sintered materials with a support sheet, they have excellent dicing suitability and pick-up suitability. In contrast to these, the film-shaped fired material of Comparative Example 1 was inferior in dicing suitability and pick-up suitability. [Explanation of symbols]

[0145] 1...film-shaped sintered material, 2...support sheet, 3...base film, 4...adhesive layer, 5...ring frame, 10...sinterable metal particles, 15...release film, 20...binder component, 100...film-shaped sintered material with support sheet

Claims

1. A film-shaped sintered material containing sinterable metal particles and a binder component, The film-shaped fired material, wherein the binder component contains a copolymer of an alkyl methacrylate having 8 or less carbon atoms and an alkyl methacrylate having 9 to 13 carbon atoms.

2. A film-like sintered material with a support sheet, comprising: a support sheet having a base film and an adhesive layer provided on the base film; and the film-like sintered material described in claim 1 provided on the adhesive layer.

3. The film-shaped sintered material with a support sheet according to claim 2 , wherein the adhesive layer is energy ray curable.

4. A bonding step of bonding a semiconductor wafer to the exposed surface of the film-shaped sintered material with a support sheet according to claim 2 or 3, to form a laminate in which the support sheet, the film-shaped sintered material, and the semiconductor wafer are laminated in this order; A step of dicing the semiconductor wafer and the film-shaped fired material of the laminate; a step of peeling off the diced film-shaped sintering material and the support sheet to pick up the semiconductor chip with the film-shaped sintering material; A step of attaching the semiconductor chip with the film-shaped sintered material to a surface of a substrate; A step of firing and pressurizing the film firing material of the semiconductor chip with film-shaped firing material to bond the semiconductor chip with film-shaped firing material to a substrate; A method for manufacturing a semiconductor device having the above structure.

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