Stacked film for monolithic body formation and method for manufacturing semiconductor device

Abstract

A laminated film for monolithic body formation is provided. The laminated film for monolithic body formation comprises, in order, a base film, a pressure-sensitive adhesive layer, and a film for monolithic body formation. The film for monolithic body formation comprises, in order from the pressure-sensitive adhesive layer, a first thermosetting resin layer, a rigid material layer, and a second thermosetting resin layer. The second thermosetting resin layer contains an epoxy resin, a curing agent, an elastomer, and silica particles having an average primary particle diameter of 30 to 400 nm.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a multilayer film for monolithic body formation and a semiconductor device, and more particularly to a semiconductor device having a support tomb structure, the support tomb structure including a substrate, a first chip disposed on the substrate, a plurality of support sheets disposed on the substrate and surrounding the first chip, and a second chip disposed in such a manner as to be supported by the plurality of support sheets and covering the first chip. Background Technology

[0002] In recent years, the field of semiconductor devices has demanded high integration, miniaturization, and high speed. As a type of semiconductor device, the structure of stacking semiconductor chips on a controller chip disposed on a substrate has attracted attention. For example, Patent Document 1 discloses a semiconductor die assembly including a controller die and a memory die supported on the controller die by a support member. It can be said that Patent Document 1… Figure 1 The semiconductor component 100 shown in A has a support tomb structure. The semiconductor component 100 includes a packaging substrate 102, a controller die 103 disposed on its surface, memory dies 106a and 106b disposed above the controller die 103, and support members 130a and 130b supporting the memory die 106a.

[0003] Patent Document 1 discloses that semiconductor materials such as silicon can be used as support components (support sheets), and more specifically, fragments of semiconductor materials obtained by dicing semiconductor wafers can be used. Furthermore, Patent Documents 2 and 3 disclose that a single sheet of resin film can be used instead of semiconductor materials such as silicon as support components (support sheets), and the resin film has a multilayer structure with resin material as the main component.

[0004] Previous technical documents Patent documents Patent Document 1: Japanese Patent Publication No. 2017-515306 Patent Document 2: International Publication No. 2020 / 217404 Patent Document 3: Japanese Patent Application Publication No. 2022-082247 Summary of the Invention

[0005] The technical problem to be solved by the invention The support component (support sheet) with resin material as the main component is formed as follows: after preparing a laminated film obtained by sequentially stacking a substrate film, a pressure-sensitive adhesive layer, and a resin film having the above-described multilayer structure, the resin film is cut to form a single sheet. According to the research of the inventors, it has been found that when a resin film having a conventional multilayer structure is cut to form a single sheet, interfacial delamination sometimes occurs between the layers of the resin film. This interfacial delamination tends to occur significantly between layers located at the points where it separates from the pressure-sensitive adhesive layer, requiring an increase in the adhesive strength between these layers.

[0006] The main objective of this invention is to provide a laminated film for forming monolithic bodies, which is a film for forming monolithic bodies that can be monolithically divided into multiple monolithic bodies by cutting, wherein interfacial delamination between the layers of the film can be suppressed when the monolithic body forming film is monolithically cut.

[0007] means for solving technical problems One aspect of the present invention relates to a laminated film for monolithic body formation, comprising multiple monolithic body formation films that are monolithically formed by cutting. The laminated film for monolithic body formation sequentially comprises a substrate film, a pressure-sensitive adhesive layer, and a monolithic body formation film. The monolithic body formation film, from the pressure-sensitive adhesive layer, sequentially comprises a first thermosetting resin layer, a rigid material layer, and a second thermosetting resin layer. The second thermosetting resin layer contains epoxy resin, a curing agent, an elastomer, and silica particles with an average primary particle size of 30-400 nm. The rigid material layer is a layer having higher rigidity than the first thermosetting resin layer and the second thermosetting resin layer, for example, a polyimide layer.

[0008] According to the research of the inventors, it has been found that by having a second thermosetting resin layer containing silica particles with an average primary particle size of 30 to 400 nm, the interlayer adhesion strength at the position separated from the pressure-sensitive adhesive layer, i.e., the adhesion strength between the second thermosetting resin layer and the rigid material layer, is improved.

[0009] The first thermosetting resin layer may contain the same epoxy resin, curing agent, elastomer, and silica particles with an average primary particle size of 30–400 nm as the second thermosetting resin layer. The composition of the first thermosetting resin layer may be the same as or different from that of the second thermosetting resin layer.

[0010] The monolithic body forming laminate can be a film used in the manufacturing process of a semiconductor device. The monolithic body formed by the monolithic body forming laminate can be used as a support sheet, for example, in a semiconductor device having a support structure including a substrate, a first chip disposed on the substrate, a plurality of support sheets disposed on the substrate and surrounding the first chip, and a second chip arranged such that it is supported and covered by the plurality of support sheets. That is, the monolithic body forming laminate can be used as a support sheet forming laminate, and the monolithic body forming film can be used as a support sheet forming film. Furthermore, in addition to being a support sheet, the monolithic body formed by the monolithic body forming laminate can also be used as a reinforcing sheet (reinforcing material) for a semiconductor chip, for example, by attaching it to a semiconductor chip.

[0011] Another aspect of the present invention relates to a method for manufacturing a semiconductor device. The semiconductor device has a support structure including a substrate, a first chip disposed on the substrate, a plurality of support sheets disposed on the substrate and surrounding the first chip, and a second chip disposed such that it is supported by the plurality of support sheets and covers the first chip. The semiconductor device includes an adhesive sheet disposed on one surface of the second chip and held between the second chip and the plurality of support sheets. In one embodiment, the first chip may be in contact with the adhesive sheet. In this case, the second chip may be disposed such that it is supported by the plurality of support sheets and the first chip. In another embodiment, the first chip may be detachable from the adhesive sheet.

[0012] The manufacturing method of this semiconductor device includes the following steps.

[0013] (A) A process for preparing a laminated film for forming a support sheet, wherein the laminated film for forming the support sheet sequentially comprises a substrate film, a pressure-sensitive adhesive layer, and a support sheet forming film, and the monolithic body forming film sequentially comprises a first thermosetting resin layer, a rigid material layer, and a second thermosetting resin layer from the pressure-sensitive adhesive layer, wherein the second thermosetting resin layer contains epoxy resin, a curing agent, an elastomer, and silica particles with an average primary particle size of 30-400 nm. (B) A process of forming multiple support sheets on the surface of a pressure-sensitive adhesive layer by cutting a film for forming support sheets. (C) Process of picking up the support sheet from the pressure-sensitive adhesive layer (D) The process of mounting the first chip on the substrate (E) The process of arranging a plurality of support sheets on a substrate and around the first chip or around the area where the first chip is to be arranged. (F) The process of preparing a chip with an adhesive sheet attached, comprising a second chip and an adhesive sheet disposed on one side of the second chip. (G) The process of constructing a stone-supported tomb structure by arranging chips with adhesive sheets attached on the surfaces of multiple support sheets. The manufacturing method of a semiconductor device may include a process of forming a support sheet into a film or heating the support sheet before the (G) process.

[0014] The present invention provides a method for manufacturing a multilayer film for forming a monolithic body as described in [1] to [3] and a semiconductor device as described in [4] to [7].

[0015] [1] A laminated film for forming monoliths, comprising a substrate film, a pressure-sensitive adhesive layer and a monolithic film in sequence, wherein the monolithic film comprises, from the pressure-sensitive adhesive layer, a first thermosetting resin layer, a rigid material layer and a second thermosetting resin layer, wherein the second thermosetting resin layer contains epoxy resin, a curing agent, an elastomer and silica particles with an average primary particle size of 30 to 400 nm.

[0016] [2] As described in [1], a laminated film for forming a monolithic body, wherein, The rigid material layer is a polyimide layer.

[0017] [3] A laminated film for forming a monolithic body as described in [1] or [2], wherein, The first thermosetting resin layer contains epoxy resin, curing agent, elastomer and silica particles with an average primary particle size of 30-400 nm.

[0018] [4] A method for manufacturing a semiconductor device, the semiconductor device having a support tomb structure, the support tomb structure including a substrate, a first chip disposed on the substrate, a plurality of support sheets disposed on the substrate and surrounding the first chip, and a second chip disposed such that it is supported by the plurality of support sheets and covers the first chip, the method for manufacturing the semiconductor device including: (A) a step of preparing a laminated film for forming support sheets, the laminated film for forming support sheets sequentially comprising a substrate film, a pressure-sensitive adhesive layer and a film for forming support sheets, the film for forming support sheets sequentially comprising a first thermosetting resin layer, a rigid material layer and a second thermosetting resin layer from the pressure-sensitive adhesive layer, the second thermosetting resin layer comprising epoxy resin, a curing agent, an elastomer and (A) A process of forming a plurality of support sheets on the surface of a pressure-sensitive adhesive layer by cutting the support sheet forming film; (C) A process of picking up the support sheets from the pressure-sensitive adhesive layer; (D) A process of placing a first chip on a substrate; (E) A process of placing a plurality of the support sheets on the substrate and around the first chip or around the area where the first chip is to be placed; (F) A process of preparing a chip with an adhesive sheet attached, the chip with the adhesive sheet attached having a second chip and an adhesive sheet disposed on one side of the second chip; and (G) A process of constructing a support structure by placing the chip with the adhesive sheet attached on the surface of the plurality of support sheets.

[0019] [5] The method for manufacturing a semiconductor device as described in [4], wherein, Prior to step (G), there is a step of forming the support sheet into a film or heating the support sheet.

[0020] [6] A method for manufacturing a semiconductor device as described in [4] or [5], wherein, The rigid material layer is a polyimide layer.

[0021] [7] A method for manufacturing a semiconductor device as described in any one of [4] to [6], wherein, The first thermosetting resin layer contains epoxy resin, curing agent, elastomer and silica particles with an average primary particle size of 30-400 nm.

[0022] Invention Effects According to the present invention, a stacked film for forming monolithic bodies is provided, comprising multiple monolithic bodies formed by dicing, wherein, during the monolithic body forming process of dicing the monolithic body forming film, interlayer delamination of the film can be suppressed. Furthermore, according to the present invention, a method for manufacturing a semiconductor device using such a stacked film for forming monolithic bodies (a stacked film for forming a support sheet) is provided. Attached Figure Description

[0023] Figure 1 (a) is a top view schematically illustrating one embodiment of a laminated film for forming a monolithic body. Figure 1 (b) is Figure 1 (a) Sectional view along line bb.

[0024] Figure 2 This is a schematic cross-sectional view illustrating the process of bonding a pressure-sensitive adhesive layer to a support sheet to form a film.

[0025] Figure 3 This is a schematic cross-sectional view illustrating a first embodiment of the semiconductor device of the present invention.

[0026] Figure 4 (a) and Figure 4 (b) is a top view that schematically shows an example of the positional relationship between the first chip and a plurality of support sheets.

[0027] Figure 5 (a) Figure 5 (b) Figure 5 (c) and Figure 5 (d) is a cross-sectional view schematically showing the manufacturing process of the support sheet.

[0028] Figure 6It is a schematic cross-sectional view showing the state of multiple support sheets arranged on a substrate and around the first chip.

[0029] Figure 7 This is a cross-sectional view schematically illustrating an example of a chip with an adhesive sheet attached.

[0030] Figure 8 It is a schematic cross-sectional view showing the supporting stone tomb structure formed on the substrate.

[0031] Figure 9 This is a cross-sectional view schematically illustrating a second embodiment of the semiconductor device of the present invention. Detailed Implementation

[0032] Hereinafter, embodiments of the present invention will be described with appropriate reference to the accompanying drawings. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including steps, etc.) are not essential, unless specifically indicated otherwise. The sizes of the constituent elements in the figures are conceptual, and the relative sizes of the constituent elements are not limited to those shown in the figures.

[0033] The numerical values ​​and their ranges in this invention are the same and do not limit the invention. In this specification, the numerical range indicated by "~" represents the range encompassed by the values ​​before and after "~" as the minimum and maximum values, respectively. Within the numerical ranges described in stages in this specification, the upper or lower limit value described in one numerical range can be replaced by the upper or lower limit value of other numerical ranges described in stages. Furthermore, within the numerical ranges described in this specification, the upper or lower limit value of the numerical range can be replaced by the values ​​shown in the embodiments.

[0034] In this specification, the term "layer," when viewed from above, includes not only the structure of a shape that forms the entire surface, but also the structure of a shape that forms a portion of it. Furthermore, in this specification, the term "process" includes not only individual processes, but also processes that, even if they cannot be clearly distinguished from other processes, are included as long as the desired effect of the process is achieved.

[0035] In this specification, (meth)acrylate refers to acrylate or its corresponding methacrylate. The same applies to other similar terms such as (meth)acryloyl, (meth)acrylic copolymers, etc.

[0036] Unless otherwise specified, each ingredient and material listed in this instruction manual may be used alone or in combination with two or more.

[0037] [Laminated film for monolayer formation] Figure 1(a) is a top view schematically illustrating one embodiment of a laminated film for forming a monolithic body. Figure 1 (b) is Figure 1 (a) is a cross-sectional view along line bb. The laminated film 20 for forming monolithic bodies (hereinafter, sometimes simply referred to as "laminated film 20") sequentially comprises a substrate film 1, a pressure-sensitive adhesive layer 2, and a monolithic body forming film D (hereinafter, sometimes simply referred to as "film D") that is cut into multiple pieces. The pressure-sensitive adhesive layer 2 is formed into a circular shape by punching or the like (see reference). Figure 1 (a) The membrane D is formed into a circle by punching or the like, and has a smaller diameter than the pressure-sensitive adhesive layer 2 (see reference). Figure 1 (a)).

[0038] Examples of substrate films 1 include polyester (polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, etc.), polyolefins (polyethylene, polypropylene, etc.), polycarbonate, polyamide, polyimide, polyamide-imide, polyether-imide, polyether sulfide, polyethersulfone, polyetherketone, polyphenylene ether, polyphenylene sulfide, ionomers, etc. These films can be single-layer films or multilayer films composed of two or more films. The thickness of substrate film 1 can be, for example, 1–200 μm, 20–150 μm, or 30–130 μm.

[0039] Pressure-sensitive adhesive layer 2 is a layer formed of pressure-sensitive adhesive. The pressure-sensitive adhesive can be any type commonly used in this field, and can be either a UV-curable pressure-sensitive adhesive or a non-UV-curable pressure-sensitive adhesive. That is, pressure-sensitive adhesive layer 2 can be either a UV-curable pressure-sensitive adhesive layer or a non-UV-curable pressure-sensitive adhesive layer. UV-curable pressure-sensitive adhesives are pressure-sensitive adhesives that have reduced adhesion upon exposure to ultraviolet light, and conventionally known pressure-sensitive adhesives can be used. Examples of UV-curable pressure-sensitive adhesives include, for example, photoreactive resins with carbon-carbon double bonds. More specifically, examples include acrylic resin-based pressure-sensitive adhesives. Examples of non-UV-curable pressure-sensitive adhesives include, for example, natural rubber-based, synthetic rubber-based, acrylic resin-based, polyvinyl ether resin-based, urethane resin-based, and silicone resin-based pressure-sensitive adhesives. The thickness of the pressure-sensitive adhesive layer 2 can be, for example, 1 to 100 μm.

[0040] Membrane D comprises, sequentially from pressure-sensitive adhesive layer 2, a first thermosetting resin layer 5, a rigid material layer 6, and a second thermosetting resin layer 7. The second thermosetting resin layer 7 contains epoxy resin, a curing agent, an elastomer, and silica particles with an average primary particle size of 30-400 nm. The presence of silica particles with an average primary particle size of 30-400 nm in the second thermosetting resin layer 7 tends to improve the adhesive strength between the second thermosetting resin layer 7 and the rigid material layer 6. Furthermore, the first thermosetting resin layer 5 may, for example, contain epoxy resin, a curing agent, an elastomer, and silica particles. The first thermosetting resin layer 5 may contain the same epoxy resin, curing agent, elastomer, and silica particles with an average primary particle size of 30-400 nm as the second thermosetting resin layer 7. The presence of silica particles with an average primary particle size of 30-400 nm in the first thermosetting resin layer 5 also tends to improve the adhesive strength between the first thermosetting resin layer 5 and the rigid material layer 6. The composition of the first thermosetting resin layer 5 and the composition of the second thermosetting resin layer 7 can be the same or different. In terms of the manufacturing efficiency of each layer, the composition of the first thermosetting resin layer 5 and the composition of the second thermosetting resin layer 7 can be the same.

[0041] The second thermosetting resin layer 7 (and consequently, the first thermosetting resin layer 5) can be obtained by molding a thermosetting resin composition containing epoxy resin, curing agent, elastomer, and silica particles with an average primary particle size of 30-400 nm. The thermosetting resin composition can be in a semi-cured (stage B) state followed by heat treatment to become a cured product (stage C). The thermosetting resin composition may further contain coupling agents, curing accelerators, etc., as needed. The first thermosetting resin layer 5 and the second thermosetting resin layer 7 can be in a semi-cured (stage B) state, or they can become cured products (stage C) after heat treatment.

[0042] Stage B refers to the intermediate stage in the reaction of a certain thermosetting resin, where the material swells when in contact with a certain liquid and softens when heated, but does not completely dissolve or melt. Stage C refers to the final stage in the reaction of a certain thermosetting resin, where the material is essentially insoluble and infusible.

[0043] (Epoxy resin) Epoxy resin is a component that cures by forming three-dimensional bonds between molecules through heating or other means, and exhibits adhesive properties after curing. Epoxy resins can be used without particular restrictions as long as they contain epoxy groups within their molecules. Epoxy resins can have two or more epoxy groups within their molecules.

[0044] Examples of epoxy resins include bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; and phenolic varnish-type epoxy resins such as phenolic varnish-type epoxy resin and cresolic varnish-type epoxy resin. Furthermore, commonly known epoxy resins can be used, including stilbene-type epoxy resins, epoxy resins containing a triazine backbone, epoxy resins containing a fluorene backbone, tricresylmethane-type epoxy resins, biphenyl-type epoxy resins, xylene-type epoxy resins, biphenyl aralkyl-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, polyfunctional phenols, and diglycidyl ether compounds of polycyclic aromatic hydrocarbons such as anthracene.

[0045] Based on the total amount of the thermosetting resin composition (first thermosetting resin layer 5 or second thermosetting resin layer 7), the epoxy resin content can be 1 to 40% by mass. Based on the total amount of the thermosetting resin composition (first thermosetting resin layer 5 or second thermosetting resin layer 7), the epoxy resin content can be 2% or more by mass, 3% or more by mass, or 5% or more by mass, or it can be less than 35% by mass, less than 30% by mass, or less than 25% by mass.

[0046] (Curing agent) Examples of curing agents include phenolic resins, ester compounds, aromatic amines, aliphatic amines, and acid anhydrides. Among these, phenolic resins are particularly suitable as curing agents for achieving high adhesive strength. Phenolic resins can be used without particular restrictions as long as they contain phenolic hydroxyl groups within their molecules. Examples of phenolic resins include phenolic varnish-type phenolic resins obtained by condensing or co-condensing phenolic compounds such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc., and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthol, etc., with formaldehyde and other aldehyde-containing compounds under an acidic catalyst; phenolic aralkyl resins synthesized from allylated bisphenol A, allylated bisphenol F, allylated naphthalene glycol, phenolic varnish, phenol, and other phenolic compounds and / or naphthols with dimethoxy-p-xylene or bis(methoxymethyl)biphenyl; naphthol aralkyl resins; biphenyl aralkyl type phenolic resins; and phenyl aralkyl type phenolic resins.

[0047] Based on the total amount of the thermosetting resin composition (first thermosetting resin layer 5 or second thermosetting resin layer 7), the content of the curing agent can be 1 to 40% by mass. Based on the total amount of the thermosetting resin composition (first thermosetting resin layer 5 or second thermosetting resin layer 7), the content of the curing agent can be 2% or more by mass, 3% or more by mass, or 5% or more by mass, or it can be less than 30% by mass, less than 25% by mass, or less than 20% by mass.

[0048] (Elastomer) Examples of elastomers include acrylic resins, polyester resins, polyamide resins, polyimide resins, silicone resins, polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxyl-modified acrylonitrile.

[0049] Regarding achieving high adhesive strength, the elastomer can be an acrylic resin. The acrylic resin can be an epoxy-containing (meth)acrylate copolymer or other acrylic resin obtained by polymerizing functional monomers such as glycidyl acrylate or glycidyl methacrylate, which have epoxy or glycidyl groups as crosslinking functional groups. Among these, the acrylic resin can be an epoxy-containing (meth)acrylate copolymer and an epoxy-containing acrylate rubber, preferably an epoxy-containing acrylate rubber. Epoxy-containing acrylate rubber is an epoxy-containing rubber, mainly composed of acrylates and copolymers of butyl acrylate, acrylonitrile, etc., or copolymers of ethyl acrylate, acrylonitrile, etc. In addition to epoxy groups, the acrylic resin may also have crosslinking functional groups such as alcoholic or phenolic hydroxyl groups and carboxyl groups.

[0050] Commercially available elastomers include, for example, SG-P3, SG-70L, SG-708-6, WS-023 EK30, and SG-280 EK23 (all manufactured by Nagase ChemteX Corporation).

[0051] In terms of achieving high adhesive strength, the glass transition temperature (Tg) of the elastomer can be -50 to 50°C or -30 to 20°C. The Tg of the elastomer refers to the value measured using DSC (Differential Scanning Calorimetry) (e.g., Rigaku Corporation, product name: Thermo Plus 2). In terms of achieving high adhesive strength, the weight-average molecular weight (Mw) of the elastomer can be 50,000 to 1.6 million, 100,000 to 1.4 million, or 300,000 to 1.2 million. The Mw of the elastomer refers to the value measured by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

[0052] Based on the total amount of the thermosetting resin composition (first thermosetting resin layer 5 or second thermosetting resin layer 7), the elastomer content can be 30 to 90% by mass. Based on the total amount of the thermosetting resin composition (first thermosetting resin layer 5 or second thermosetting resin layer 7), the elastomer content can be 35% or more by mass, 40% or more by mass, or 45% or more by mass, or it can be less than 85% by mass, less than 80% by mass, or less than 78% by mass.

[0053] (Silicon dioxide particles) Silica particles can include primary particles (particles that do not constitute secondary particles) that are integrally formed as a single particle based on their apparent geometry, and secondary particles formed by the aggregation of multiple primary particles.

[0054] Regarding the suppression of delamination between layers of the monolayer-forming film (especially between the second thermosetting resin layer 7 and the rigid material layer 6), the average primary particle size (average particle size of primary particles) of the silica particles is 30-400 nm, and can be 35 nm or more, 40 nm or more, 45 nm or more, or 50 nm or more, or 380 nm or less, 350 nm or less, 320 nm or less, or 300 nm or less. The average primary particle size of the silica particles can be measured by the following method. First, a thermosetting resin layer (film-like molded article) formed from a thermosetting resin composition is prepared. Next, the thermosetting resin layer (film-like molded article) is cut, and the cut surface (film cross-section) is observed using a scanning electron microscope, and an image of the cut surface (film cross-section) is taken. Then, the major diameter of 50 primary particles of silica is measured from the taken image, and the average value is taken as the average primary particle size.

[0055] The surface of silica particles can be chemically modified. Examples of materials for chemically modifying the surface of silica particles include silane coupling agents. Examples of functional groups that can be used in silane coupling agents include vinyl, acryloyl, epoxy, mercapto, amino, diamino, alkoxy, and ethoxy groups.

[0056] Chemically modified silica particles can be manufactured using known methods or commercially available products can be used directly.

[0057] Based on the total amount of the thermosetting resin composition (first thermosetting resin layer 5 or second thermosetting resin layer 7), the content of silica particles can be 1 to 50% by mass. Based on the total amount of the thermosetting resin composition (first thermosetting resin layer 5 or second thermosetting resin layer 7), the content of silica particles can be 3% or more by mass, 5% or more by mass, or 8% or more by mass, or it can be less than 45% by mass, less than 40% by mass, or less than 35% by mass.

[0058] (Coupled agent) The coupling agent can be a silane coupling agent. Examples of silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane. Regarding adhesive strength, the coupling agent may contain 3-phenylaminopropyltrimethoxysilane.

[0059] (Curing accelerator) Examples of curing accelerators include imidazoles and their derivatives, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. Among these, imidazoles and their derivatives are the most reactive curing accelerators.

[0060] Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole.

[0061] Thermosetting resin compositions may further contain other components. Examples of such other components include pigments, ion scavengers, antioxidants, etc.

[0062] Based on the total amount of the thermosetting resin composition (first thermosetting resin layer 5 or second thermosetting resin layer 7), the total content of coupling agent, curing accelerator and other components can be 0.005 to 10 by mass.

[0063] The thickness of the first thermosetting resin layer 5 can be, for example, 3–150 μm or 10–100 μm. The thickness of the second thermosetting resin layer 7 can be, for example, 3–150 μm or 10–100 μm. Furthermore, the thicknesses of the first thermosetting resin layer 5 and the second thermosetting resin layer 7 can be the same or different, but they can also be the same.

[0064] The rigid material layer 6 can be, for example, a resin layer or a metal layer having higher rigidity than the first thermosetting resin layer 5 and the second thermosetting resin layer 7. Here, rigidity can be based on various mechanical properties, such as the tensile modulus of elasticity. The tensile modulus of elasticity can be measured, for example, according to K7161-1:2014.

[0065] The resin layer 6, serving as the rigid material layer, is formed of a material different from the first thermosetting resin layer 5 and the second thermosetting resin layer 7, such as a polyimide layer. If the rigid material layer 6 is a resin layer (polyimide layer), it tends to have excellent pick-up properties even without the thermosetting treatment of the first thermosetting resin layer 5 and the second thermosetting resin layer 7 after being cut into single sheets. The metal layer 6, serving as the rigid material layer 6, can be, for example, a copper layer or an aluminum layer. If the rigid material layer 6 is a metal layer, in addition to excellent pick-up properties, it tends to have excellent visibility during the pick-up process due to the optical contrast between the resin material and the metal material.

[0066] The thickness of the rigid material layer 6 can be, for example, 5–200 μm or 10–150 μm.

[0067] The thickness of membrane D (the thickness of all layers constituting membrane D) can be, for example, 5–250 μm or 10–200 μm.

[0068] The laminated film 20 can be a film used in the manufacturing process of a semiconductor device. The monolithic body formed by the laminated film 20 can be used as a support sheet, for example, in a semiconductor device having a support structure including a substrate, a first chip disposed on the substrate, a plurality of support sheets disposed on the substrate and surrounding the first chip, and a second chip arranged in such a way as to be supported by the plurality of support sheets and covering the first chip.

[0069] Furthermore, the monolithic body formed by the laminated film 20 can be used as a semiconductor chip reinforcement sheet (reinforcing material) by attaching it to a semiconductor chip or the like. The monolithic body formed by the laminated film 20 can be manufactured by a method including steps (A) to (C) in the semiconductor device manufacturing method described later.

[0070] [Method for manufacturing laminated films for monolayer formation] The laminated film 20 can be manufactured, for example, by laminating a cut film having a substrate film 1 and a pressure-sensitive adhesive layer 2 on its surface to a laminated film having a cover film 3 and a film D on its surface (see reference). Figure 2 Cut films can be obtained, for example, by a method including the following steps: coating a pressure-sensitive adhesive on the surface of a substrate film 1 to form a pressure-sensitive adhesive layer 2, and processing the pressure-sensitive adhesive layer 2 into a predetermined shape (e.g., circular) by punching or the like. Laminated films can be obtained by a method including the following steps: coating a thermosetting resin composition on the surface of a cover film 3 (e.g., PET film or polyethylene film) to form a second thermosetting resin layer 7; forming a rigid material layer 6 (e.g., a polyimide layer) on the surface of the second thermosetting resin layer 7; coating a thermosetting resin composition on the surface of the rigid material layer 6 to form a first thermosetting resin layer 5; and processing the formed film D into a predetermined shape (e.g., circular) by punching or the like. Laminated films can also be obtained by: bonding one side of the rigid material layer 6 to the first thermosetting resin layer 5, and then bonding the other side of the rigid material layer 6 to the second thermosetting resin layer 7 disposed on the cover film 3. When using the laminated film 20, the cover film 3 is peeled off at the appropriate time.

[0071] In the formation of the second thermosetting resin layer 7, a varnish of the thermosetting resin composition (thermosetting resin varnish) can be used. When using a thermosetting resin varnish, the components of the thermosetting resin composition are mixed or kneaded in a solvent to prepare the thermosetting resin varnish, the obtained thermosetting resin varnish is applied, and the solvent is removed by heating and drying, thereby obtaining the second thermosetting resin layer 7.

[0072] Mixing or kneading can be carried out using common mixers, pounders, three-roll mills, ball mills, and other dispersers, which can be appropriately combined.

[0073] There are no restrictions on the solvent used to prepare thermosetting resin varnishes, as long as it can uniformly dissolve, mix, or disperse the components; conventionally known solvents can be used. Examples of such solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, as well as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, and xylene.

[0074] As a method for applying thermosetting resin varnish to a cover film or rigid material layer, known methods can be used, such as blade coating, roller coating, spraying, gravure coating, bar coating, and curtain coating. Heat drying is not particularly limited as long as the solvent used is sufficiently evaporated, and can be carried out in the range of 50–150°C for 1–30 minutes. Heat drying can be carried out gradually at different heating temperatures and for different heating times.

[0075] Regarding the first thermosetting resin layer 5, similarly to the second thermosetting resin layer 7, the components of the thermosetting resin composition are mixed or kneaded in a solvent to prepare a thermosetting resin varnish, the obtained thermosetting resin varnish is applied, and the solvent is removed by heating and drying, thereby obtaining the first thermosetting resin layer 5.

[0076] Semiconductor devices and manufacturing methods thereof <First Implementation> Figure 3 This is a schematic cross-sectional view illustrating a first embodiment of the semiconductor device of the present invention. Figure 3 The semiconductor device 100 shown includes: a substrate 10; a chip T1 (first chip) disposed on the surface of the substrate 10; a plurality of support sheets DXc disposed on the surface of the substrate 10 and around the chip T1; a chip T2 (second chip) disposed above the chip T1; an adhesive sheet Tc held by the chip T2 and the plurality of support sheets DXc; chips T3 and T4 stacked on the chip T2; a plurality of wires w electrically connecting electrodes (not shown) on the surface of the substrate 10 to the chips T1 to T4; and a sealing material 50 filling the gap between the chips T1 and T2, etc. The support sheets DXc can be cured materials of monolithic bodies formed by monolithizing the film D.

[0077] In this embodiment, a support structure is formed on the substrate 10 by multiple support sheets DXc, a chip T2, and an adhesive sheet Tc located between the support sheets DXc and the chip T2. The chip T1 is in contact with the adhesive sheet Tc. That is, the adhesive sheet Tc is in contact with the upper surface of the chip T1 and the upper surface of the support sheets DXc. For example, by appropriately setting the thickness of the film DX, the position of the upper surface of the chip T1 can be made to coincide with the position of the upper surface of the support sheet DXc. At this time, a portion of the wire w that electrically connects the electrode (not shown) on the surface of the substrate 10 to the chip T1 is embedded in the adhesive sheet Tc.

[0078] like Figure 3 As shown, an adhesive sheet Tc between chip T1 and chip T2 covers the region R in chip T2 opposite to chip T1, and extends continuously from region R to the periphery of chip T2. That is, one adhesive sheet Tc covers region R of chip T2 and is located between chip T2 and multiple support sheets, bonding them together. Furthermore, in Figure 3 The diagram illustrates an adhesive sheet Tc arranged to cover the entire lower surface of one side of chip T2. However, the adhesive sheet Tc may shrink during the manufacturing process of the semiconductor device 100, so it is sufficient to substantially cover the entire lower surface of one side of chip T2. For example, there may be areas on the periphery of chip T2 that are not covered by the adhesive sheet Tc. Figure 3 The lower surface of chip T2 corresponds to the back surface of the chip. In recent years, the back surface of chips has often been characterized by irregularities. By essentially covering the back surface of chip T2 with an adhesive sheet Tc, cracking or breakage on chip T2 can be suppressed.

[0079] The substrate 10 can be an organic substrate or a metal substrate such as a lead frame. Regarding the substrate 10, in terms of suppressing the warping of the semiconductor device 100, the thickness of the substrate 10 is, for example, 90 to 300 μm, or 90 to 210 μm.

[0080] Chip T1, for example, is a controller chip, bonded to substrate 10 by adhesive sheet T1c and electrically connected to substrate 10 via wire w. The shape of chip T1 when viewed from above is, for example, rectangular (square or elongated). The length of one side of chip T1 is, for example, less than 5 mm, but can also be 2–5 mm or 1–5 mm. The thickness of chip T1 is, for example, 10–150 μm, but can also be 20–100 μm.

[0081] Chip T2, for example, is a memory chip, bonded to the support sheet DXc and chip T1 by an adhesive sheet Tc. Viewed from above, chip T2 has a larger dimension than chip T1. The shape of chip T2, viewed from above, is, for example, rectangular (square or elongated). The length of one side of chip T2 is, for example, less than 20 mm, but can also be 4–20 mm or 4–12 mm. The thickness of chip T2 is, for example, 10–170 μm, but can also be 20–120 μm. Additionally, chips T3 and T4, also for example, are memory chips, bonded to chip T2 by an adhesive sheet Tc. The length of one side of chips T3 and T4 only needs to be the same as that of chip T2, and the thickness of chips T3 and T4 only needs to be the same as that of chip T2.

[0082] The support sheet DXc functions as a spacer forming a space around the chip T1. Starting from the substrate 10, the support sheet DXc sequentially comprises a first adhesive sheet 5c formed from a cured thermosetting resin composition constituting the first thermosetting resin layer 5, a rigid material sheet 6p, and a second adhesive sheet 7c (a layer formed by curing the second thermosetting resin layer 7) formed from a cured thermosetting resin composition constituting the second thermosetting resin layer 7. Additionally, as... Figure 4 As shown in (a), two support plates DXc (shape: rectangular) can be arranged at separate positions on both sides of chip T1, as follows: Figure 4 As shown in (b), a support sheet DXc (shape: square, 4 in total) can be arranged at a position corresponding to the corner of chip T1. The length of one side of the support sheet DXc when viewed from above is, for example, less than 20 mm, or 1 to 20 mm or 1 to 12 mm. The thickness (height) of the support sheet DXc is, for example, 10 to 180 μm, or 20 to 120 μm.

[0083] Next, the manufacturing method of the semiconductor device 100 will be described. The manufacturing method of this embodiment includes the following steps (A) to (G). The manufacturing method of this embodiment may further include the following step (H).

[0084] (A) A process for preparing a laminated film 20X (hereinafter sometimes simply referred to as "laminated film 20X") for forming a support sheet, wherein the laminated film 20X for forming a support sheet sequentially comprises a substrate film 1, a pressure-sensitive adhesive layer 2, and multiple support sheet forming films DX (hereinafter sometimes simply referred to as "film DX") that are monolithically formed by cutting. The film DX sequentially comprises a first thermosetting resin layer 5, a rigid material layer 6, and a second thermosetting resin layer 7 from the pressure-sensitive adhesive layer 2. The second thermosetting resin layer 7 contains epoxy resin, a curing agent, an elastomer, and silica particles with an average primary particle size of 30 to 400 nm.

[0085] (B) The process of forming multiple support sheets DXa on the surface of pressure-sensitive adhesive layer 2 by cutting the film DX (refer to) Figure 5 (b) (C) The process of picking up the support sheet DXa from the pressure-sensitive adhesive layer 2 (refer to) Figure 5 (d) (D) The process of arranging chip T1 on substrate 10 (E) A process of arranging a plurality of support sheets DXa on substrate 10 and around chip T1 or around the area where chip T1 is to be arranged (refer to) Figure 6 ) (F) The process of preparing a chip T2a with an adhesive sheet attached, wherein the chip T2a with the adhesive sheet attached includes a chip T2 and an adhesive sheet Ta disposed on one side of the chip T2 (see reference). Figure 7 ) (G) The process of constructing a stone-supported tomb structure by placing chips T2a with adhesive sheets attached on the surfaces of multiple support sheets DXc (refer to) Figure 8 ) (H) The process of sealing the gap between chip T1 and chip T2 with sealing material 50, etc. (refer to) Figure 3 ) (A) Process (A) is the process of preparing the laminated film 20X. The laminated film 20X can use the aforementioned laminated film 20. At this time, film D becomes film DX. When using the laminated film 20X, the cover film 3 is peeled off at the appropriate time.

[0086] (B) Process and (C) Process (B) is a process of forming multiple support sheets DXa on the surface of the pressure-sensitive adhesive layer 2 by cutting the film DX; (C) is a process of picking up the support sheets DXa from the pressure-sensitive adhesive layer 2. Figure 5 As shown in (a), a cutting ring DR is attached to the laminate from which the cover film 3 has been peeled off from the laminated film 20X. That is, the cutting ring DR is attached to the pressure-sensitive adhesive layer 2 of the laminated film 20X, such that the film DX is positioned inside the cutting ring DR. In this state, the film DX is monolithically cut (see reference). Figure 5 (b) Cutting can be, for example, blade-based cutting or laser-based cutting. Thus, multiple support sheets DXa can be obtained from the film DX. The support sheet DXa includes a first adhesive sheet 5p, a rigid material sheet 6p, and a second adhesive sheet 7p. Subsequently, when the pressure-sensitive adhesive layer 2 is an ultraviolet-cured pressure-sensitive adhesive layer, the adhesive force between the pressure-sensitive adhesive layer 2 and the support sheet DXa is reduced by irradiating the pressure-sensitive adhesive layer 2 with ultraviolet light. Figure 5 As shown in (c), the support sheets DXa are separated from each other by extending the pressure-sensitive adhesive layer 2. Figure 5As shown in (d), the support sheet DXa is peeled off from the pressure-sensitive adhesive layer 2 by pushing it upward with the upward jig 42, and then picked up by suction with the nozzle 44. Alternatively, the first thermosetting resin layer 5 and the second thermosetting resin layer 7 can be cured by heating the film DX before cutting or the support sheet DXa before picking up. During picking up, the support sheet DXa is properly cured, thus exhibiting excellent pick-up performance. The cut for monolithization is preferably formed to the outer edge of the film DX.

[0087] (D) Process (D) is the process of placing chip T1 on substrate 10. For example, firstly, chip T1 is placed at a predetermined position on substrate 10 via adhesive sheet T1c. Subsequently, chip T1 is electrically connected to substrate 10 via wire w. Process (D) can be performed before process (E) or after process (E), or it can be performed before process (A), between process (A) and process (B), between process (B) and process (C), or between process (C) and process (E).

[0088] (E) Process (E) The process is to arrange multiple support sheets DXa on the substrate 10 and around the chip T1 or around the area where the chip T1 should be arranged (see reference). Figure 6 After process (E), the product is manufactured. Figure 6 The structure 30 shown is a substrate 10, a chip T1 disposed on its surface, and a plurality of support sheets DXa. The support sheets DXa can be disposed by a pressing process. The pressing process can be performed, for example, at 80–180°C and 0.01–0.50 MPa for 0.5–3.0 seconds. Furthermore, the support sheets DXa can be fully cured to become support sheets DXc at the time of process (E), or they can be partially cured at that time. Preferably, the support sheets DXa are fully cured to become support sheets DXc before the start of process (G).

[0089] (F) Process (F) is the process of preparing a chip T2a with an adhesive sheet attached, which includes a chip T2 and an adhesive sheet Ta disposed on one side of the chip T2 (see reference). Figure 7 The chip T2a with adhesive sheet includes a chip T2 and an adhesive sheet Ta disposed on one surface of it. The chip T2a with adhesive sheet can be obtained, for example, using a semiconductor wafer and a die-cutting and mounting integrated film, through a dicing process and a pick-and-place process.

[0090] (G) process (G) The process involves placing a chip T2a with an adhesive sheet attached on the upper surface of multiple support sheets DXc and the upper surface of chip T1 in contact with the adhesive sheet Ta (see reference). Figure 8 Specifically, chip T2 is pressed onto the upper surface of support sheet DXc and the upper surface of chip T1 using adhesive sheet Ta. The pressing process can be performed for 0.5 to 3.0 seconds at 80–180°C and 0.01–0.50 MPa, for example. Next, adhesive sheet Ta is cured by heating. The curing process can be performed for 5 minutes or more at 60–175°C and 0.01–1.0 MPa, for example. Thus, adhesive sheet Ta is cured to become adhesive sheet Tc. Through this process, a support structure is constructed on substrate 10 (see reference). Figure 8 ).

[0091] After process (G) and before process (H), chip T3 is disposed on chip T2 via an adhesive sheet, and then chip T4 is disposed on chip T3 via an adhesive sheet. The adhesive sheet can be any thermosetting resin composition similar to the adhesive sheet Ta described above, and is cured by heat to become adhesive sheet Tc (see reference). Figure 3 On the other hand, chips T2, T3, and T4 are electrically connected to the substrate 10 by wires w, respectively. Furthermore, the number of chips stacked on top of chip T1 is not limited to three as in this embodiment, and can be appropriately set.

[0092] (H) process (H) is a process of sealing the gap between chip T1 and chip T2 with sealing material 50, etc. (refer to) Figure 3 After process (H), it is possible to obtain... Figure 3 The semiconductor device 100 shown.

[0093] <Second Implementation> Figure 9 This is a schematic cross-sectional view illustrating a second embodiment of the semiconductor device of the present invention. Unlike the semiconductor device 100 of the first embodiment, where the chip T1 is in contact with the adhesive sheet Tc, the semiconductor device 200 of this embodiment is in a configuration where the chip T1 is separated from the adhesive sheet Tc (see reference). Figure 9 For example, by appropriately setting the thickness of the support sheet DXc, space can be ensured for the wires w used to connect the upper surface of the chip T1 to the substrate 10. By separating the chip T1 from the adhesive sheet Tc, short circuits in the wires w caused by the upper part of the wires w connected to the chip T1 contacting the chip T2 can be prevented. Furthermore, since no wires need to be embedded in the adhesive sheet Tc that contacts the chip T2, it has the advantage of being able to make the adhesive sheet Tc thinner.

[0094] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments. For example, in the above embodiments, the case where the pressure-sensitive adhesive layer 2 is a UV-curable pressure-sensitive adhesive layer is illustrated, but the pressure-sensitive adhesive layer 2 can be a non-UV-curable pressure-sensitive adhesive layer.

[0095] Example The present invention will be described below through examples, but the present invention is not limited to these examples.

[0096] [Preparation of thermosetting resin varnishes] <Preparation of Varnish A> Varnish A, used to make the first and second thermosetting resin layers, was prepared using the following materials. Furthermore, the mass parts listed below refer to the mass parts of the solid components. The mass parts values ​​for varnishes B through G are the same.

[0097] (Epoxy resin) • N-500P-10 (Product name, manufactured by DIC Corporation, o-cresyl phenolic resin varnish type epoxy resin, epoxy equivalent: 204 g / eq, softening point: 75~85℃): 7.1 parts by weight (Curing agent) • MEH-7800M (product name, manufactured by MEIWA PLASTICS INDUSTRIES, LTD. (now UBE Corporation), phenylaralkyl phenolic resin, hydroxyl equivalent: 174 g / eq, softening point: 80℃): 3.2 parts by weight • GPH-103 (product name, manufactured by Nippon Kayaku Co., Ltd., biphenyl aryl phenolic resin, hydroxyl equivalent: 220~240g / eq, softening point: 99~106℃): 4.2 parts by weight (Elastomer) • Solvent-modified version of SG-P3 (SG-P3 is the product name (manufactured by Nagase ChemteX Corporation), and is an epoxy-containing acrylic resin (glass transfer temperature: 12°C): 75.6 parts by weight (Silicon dioxide particles) • YA050C-HHG (Product name, manufactured by ADMATECHS COMPANY LIMITED, vinyl silane surface-treated silica filler): 8.3 parts by weight (Coupled agent) • A-189 (Product name, manufactured by Momentive Performance Materials Japan LLC, γ-mercaptopropyltrimethoxysilane): 0.4 parts by weight • Y9669 (Product name, manufactured by Momentive Performance Materials Japan LLC, 3-phenylaminopropyltrimethoxysilane): 1.2 parts by weight (Curing accelerator) • 2PZ-CN (Product name, manufactured by SHIKOKU CHEMICALS CORPORATION, 1-cyanoethyl-2-phenylimidazolium): 0.01 parts by weight (solvent) Cyclohexanone <Preparation of Varnish B> Varnish B, used to make the first thermosetting resin layer and the second thermosetting resin layer, was prepared using the following materials.

[0098] (Epoxy resin) ·N-500P-10: 7.1 parts by weight (Curing agent) MEH-7800M: 3.2 parts by weight GPH-103: 4.2 parts by weight (Elastomer) • SG-P3 solvent-altered product: 67.8 parts by weight (Silicon dioxide particles) YA050C-HHG: 16.0 parts by weight (Coupled agent) • A-189: 0.4 parts by weight Y9669: 1.2 parts by weight (Curing accelerator) ·2PZ-CN: 0.01 parts by weight <Preparation of Varnish C> Varnish C, used to make the first thermosetting resin layer and the second thermosetting resin layer, was prepared using the following materials.

[0099] (Epoxy resin) ·N-500P-10: 7.1 parts by weight (Curing agent) MEH-7800M: 3.2 parts by weight GPH-103: 4.2 parts by weight (Elastomer) • SG-P3 solvent-altered product: 51.8 parts by weight (Silicon dioxide particles) YA050C-HHG: 32.1 parts by weight (Coupled agent) • A-189: 0.4 parts by weight Y9669: 1.2 parts by weight (Curing accelerator) ·2PZ-CN: 0.01 parts by weight (solvent) Cyclohexanone <Preparation of Varnish D> A varnish D for making a first thermosetting resin layer and a second thermosetting resin layer was prepared using the following materials.

[0100] (Epoxy resin) ·N-500P-10: 11.0 parts by weight • EXA-830CRP (Product name, manufactured by DIC Corporation, bisphenol F type liquid epoxy resin, epoxy equivalent: 155~163g / eq): 13.0 parts by weight (Curing agent) MEH-7800M: 18.7 parts by weight (Elastomer) • SG-P3 solvent-modified product: 48.8 parts by weight (Silicon dioxide particles) • K180SE-EH1 (Product name, manufactured by ADMATECHS COMPANY LIMITED): 8.3 parts by weight (Coupled agent) A-189: 0.1 parts by weight • A-1160 (Product name, manufactured by Momentive Performance Materials Japan LLC, γ-ureidopropyltriethoxysilane): 0.2 parts by weight (Curing accelerator) ·2PZ-CN: 0.06 parts by weight (solvent) Cyclohexanone <Preparation of Varnish E> Varnish E for making a first thermosetting resin layer and a second thermosetting resin layer was prepared using the following materials.

[0101] (Epoxy resin) ·N-500P-10: 11.0 parts by weight EXA-830CRP: 13.0 parts by weight (Curing agent) MEH-7800M: 18.7 parts by weight (Elastomer) • SG-P3 solvent-modified product: 48.8 parts by weight (Silicon dioxide particles) • 3SE-EH1 (Product name, manufactured by ADMATECHS COMPANY LIMITED): 8.3 parts by weight (Coupled agent) A-189: 0.1 parts by weight A-1160: 0.2 parts by weight (Curing accelerator) ·2PZ-CN: 0.06 parts by weight (solvent) Cyclohexanone <Preparation of Varnish F> A varnish F for making a first thermosetting resin layer and a second thermosetting resin layer was prepared using the following materials.

[0102] (Epoxy resin) ·N-500P-10: 9.7 parts by weight (Curing agent) MEH-7800M: 10.6 parts by weight (Elastomer) • SG-P3 solvent-modified product: 69.8 parts by weight (Silicon dioxide particles) • R972 (Product name, manufactured by ADMATECHS COMPANY LIMITED, dimethyl dichlorosilane surface-treated silica filler): 8.3 parts by weight (Coupled agent) • A-189: 0.4 parts by weight • A-1160: 1.3 parts by weight (Curing accelerator) ·2PZ-CN: 0.02 parts by weight (solvent) Cyclohexanone <Preparation of Varnish G> A varnish G for making a first thermosetting resin layer and a second thermosetting resin layer was prepared using the following materials.

[0103] (Epoxy resin) ·N-500P-10: 11.0 parts by weight EXA-830CRP: 13.0 parts by weight (Curing agent) MEH-7800M: 18.7 parts by weight (Elastomer) • SG-P3 solvent-modified product: 48.8 parts by weight (Silicon dioxide particles) • SC2050-HLG (Product name, manufactured by ADMATECHS COMPANY LIMITED): 8.3 parts by weight (Coupled agent) A-189: 0.1 parts by weight A-1160: 0.2 parts by weight (Curing accelerator) ·2PZ-CN: 0.06 parts by weight (solvent) Cyclohexanone (Example 1) Fabrication of laminated films for monolayer formation (laminated films for support sheet formation) (Fabrication of monolayer forming membrane (support sheet forming membrane)) As described above, cyclohexanone was used as a solvent to adjust the solid content of varnish A to 15% by mass. Varnish A was filtered through a 100-mesh filter and vacuum degassed. A polyethylene terephthalate (PET) film (38 μm thick) that had undergone a demolding treatment was prepared as the film (capping film) for coating varnish A. Vacuum-degassed varnish A was coated onto the surface of the PET film after the demolding treatment. The coated varnish A was heat-dried in two stages: heating and drying at 90°C for 5 minutes, followed by heating and drying at 140°C for 5 minutes. In this way, a thermosetting resin layer (first thermosetting resin layer and second thermosetting resin layer) in a stage B state (semi-cured state) was formed on the surface of the capping film, and a first laminate having a capping film and a thermosetting resin layer was obtained. Next, a thermosetting resin layer of the first laminate is attached to one surface of the polyimide film (thickness: 25 μm, tensile modulus: 46.4 MPa), which serves as a rigid material layer, on a hot plate at 60°C, thereby obtaining a second laminate comprising a cover film, a thermosetting resin layer (second thermosetting resin layer), and a polyimide film. Then, a thermosetting resin layer of the first laminate is attached to the opposite surface of the thermosetting resin layer (second thermosetting resin layer) of the polyimide film on a hot plate at 60°C, thereby fabricating a monolithic film with a three-layer structure (first thermosetting resin layer, polyimide film, and second thermosetting resin layer).

[0104] A laminated film (cut film) with a UV-curable pressure-sensitive adhesive layer was prepared according to the following sequence. First, a copolymer was obtained by solution free radical polymerization using 83 parts by mass of 2-ethylhexyl acrylate, 15 parts by mass of 2-hydroxyethyl acrylate, and 2 parts by mass of methacrylic acid as raw materials and ethyl acetate as solvent. Then, 12 parts by mass of 2-methacryloyloxyethyl isocyanate was reacted with this acrylic copolymer to synthesize a UV-curable acrylic copolymer with carbon-carbon double bonds. During the above reaction, 0.05 parts of hydroquinone monomethyl ether was used as a polymerization inhibitor. The weight-average molecular weight of the synthesized acrylic copolymer was determined by GPC to be 300,000 to 700,000. A UV-curable pressure-sensitive adhesive solution was prepared by mixing the thus obtained acrylic copolymer, 2.0 parts by solids of a polyisocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: CORONATE L) as a curing agent, and 0.5 parts by photopolymerization initiator of 1-hydroxycyclohexylphenyl ketone. A UV-irradiated pressure-sensitive adhesive solution was coated and dried on a polyethylene terephthalate (PET) release film (38 μm thick) to achieve a dried thickness of 10 μm. Subsequently, a polyolefin film (90 μm thick) treated with corona discharge on one side was laminated onto the pressure-sensitive adhesive layer. The resulting laminated film was cured in a constant temperature bath at 40°C for 72 hours to produce a cut film.

[0105] A three-layer monolithic body forming film is bonded to the pressure-sensitive adhesive layer of the aforementioned cutting film using a rubber roller on a hot plate at 60°C, such that the surface of the monolithic body forming film having the first thermosetting resin layer faces the pressure-sensitive adhesive layer. This yields the monolithic body forming laminated film of Example 1, which is a laminate of the monolithic body forming film and the cutting film. The thicknesses of the first thermosetting resin layer and the second thermosetting resin layer are both 25 μm.

[0106] [Determination of the average primary particle size of silica particles] Using the first laminate obtained above, the average primary particle size of the silica particles was determined. The thermosetting resin layer of the first laminate was cut, and the cut surface (film cross-section) was observed using a scanning electron microscope, and images of the cut surface (film cross-section) were captured. Based on the captured images, the major diameter of 50 silica particles was determined, and their average value was calculated. The average primary particle size of the silica particles contained in the thermosetting resin layer was 50 nm. The results are summarized in Table 1.

[0107] [Determination of peel strength of thermosetting resin layer relative to polyimide film] Using the second laminate obtained above, the 90° peel strength relative to the thermosetting resin layer (second thermosetting resin layer) of the polyimide film was measured. The 90° peel strength was measured using the following method: First, a 25mm wide × 100mm long section was cut from the second laminate and used as the test specimen. Next, the thermosetting resin layer (second thermosetting resin layer) was peeled off from a metal support plate with the polyimide film side fixed, under conditions of a test temperature of 25°C, a peel angle of 90°, and a peel speed of 50mm / min. The 90° peel strength was then measured, and the results showed that the 90° peel strength was sufficiently strong; no peeling was observed under the aforementioned test conditions. The results are summarized in Table 1.

[0108] (Example 2) Varnish A was replaced with varnish B, and otherwise, the monolayer film for forming Example 2 was obtained in the same manner as in Example 1. The average primary particle size of the silica particles contained in the thermosetting resin layer was measured in the same manner as in Example 1, and the result was that the average primary particle size of the silica particles was 50 nm. The peel strength of the thermosetting resin layer (second thermosetting resin layer) relative to the polyimide film was measured in the same manner as in Example 1, and the result was that the 90° peel strength was sufficiently strong, and no peeling was detected under the above test conditions. The results are summarized in Table 1.

[0109] (Example 3) Varnish A was replaced with varnish C, and otherwise, the monolayer film for forming Example 3 was obtained in the same manner as in Example 1. The average primary particle size of the silica particles contained in the thermosetting resin layer was measured in the same manner as in Example 1, and the result was that the average primary particle size of the silica particles was 50 nm. The peel strength of the thermosetting resin layer (second thermosetting resin layer) relative to the polyimide film was measured in the same manner as in Example 1, and the result was that the 90° peel strength was sufficiently strong, and no peeling was detected under the above test conditions. The results are summarized in Table 1.

[0110] (Comparative Example 1) Varnish A was replaced with varnish F, and otherwise, the monolayer film for forming Comparative Example 1 was obtained in the same manner as in Example 1. The average primary particle size of the silica particles contained in the thermosetting resin layer was measured in the same manner as in Example 1, and the result was that the average primary particle size of the silica particles was 16 nm. The peel strength of the thermosetting resin layer (second thermosetting resin layer) relative to the polyimide film was measured in the same manner as in Example 1, and the result was that the 90° peel strength was 1.5 N / 25 mm. The results are summarized in Table 1.

[0111] [Table 1]

[0112] (Example 4) Varnish A was replaced with varnish D, and otherwise, the monolayer film for forming Example 4 was obtained in the same manner as in Example 1. The average primary particle size of the silica particles contained in the thermosetting resin layer was measured in the same manner as in Example 1, and the result was that the average primary particle size of the silica particles was 180 nm. The peel strength of the thermosetting resin layer (second thermosetting resin layer) relative to the polyimide film was measured in the same manner as in Example 1, and the result was that the 90° peel strength was sufficiently strong, and no peeling was detected under the above test conditions. The results are summarized in Table 2.

[0113] (Example 5) Varnish A was replaced with varnish E, and otherwise, the monolayer film for forming Example 5 was obtained in the same manner as in Example 1. The average primary particle size of the silica particles contained in the thermosetting resin layer was measured in the same manner as in Example 1, and the result was that the average primary particle size of the silica particles was 300 nm. The peel strength of the thermosetting resin layer (second thermosetting resin layer) relative to the polyimide film was measured in the same manner as in Example 1, and the result was that the 90° peel strength was sufficiently strong, and no peeling was detected under the above test conditions. The results are summarized in Table 2.

[0114] (Comparative Example 2) Varnish A was replaced with varnish G, and otherwise, a monolayer film for forming a comparative example 2 was obtained in the same manner as in Example 1. The average primary particle size of the silica particles contained in the thermosetting resin layer was measured in the same manner as in Example 1, and the result was that the average primary particle size of the silica particles was 500 nm. The peel strength of the thermosetting resin layer (second thermosetting resin layer) relative to the polyimide film was measured in the same manner as in Example 1, and the result was that the 90° peel strength was 6.3 N / 25 mm. The results are summarized in Table 2.

[0115] [Table 2]

[0116] As shown in Tables 1 and 2, it was clarified that: a thermosetting resin layer containing silica particles with an average primary particle size of 30-400 nm has a greater 90° peel strength relative to the thermosetting resin layer (second thermosetting resin layer) of the polyimide film compared to a thermosetting resin layer containing silica particles with an average primary particle size outside the specified range. These results demonstrate that: for a monolithic body forming laminated film equipped with the monolithic body forming film of the present invention, the peel strength between the thermosetting resin layer and the rigid material layer is sufficiently strong, and interfacial peeling can be suppressed when the monolithic body forming film is cut into monoliths.

[0117] Symbol Explanation 1-Substrate film, 2-Pressure-sensitive adhesive layer, 3-Cover film, 5-First thermosetting resin layer, 5p-First adhesive sheet, 5c-First adhesive sheet (cured product), 6-Rigid material layer, 6p-Rigid material sheet, 7-Second thermosetting resin layer, 7p-Second adhesive sheet, 7c-Second adhesive sheet (cured product), 10-Substrate, 20-Laminated film for monolithic body formation, 20X-Laminated film for support sheet formation, 50-Sealing material, 100, 200-Semiconductor device, D-Mixed film for monolithic body formation, DX-Mixed film for support sheet formation, DXa-Support sheet, DXc-Support sheet (cured product), R-Region, T1, T2, T3, T4-Chip, T2a-Chip with adhesive sheet attached, Ta-Adhesive sheet, Tc-Adhesive sheet (cured product).

Claims

1. A laminated film for forming a monolayer, comprising, in sequence: Substrate film; Pressure-sensitive adhesive layer; and Membrane for monolayer formation The monolithic body forming film comprises, sequentially from the pressure-sensitive adhesive layer, a first thermosetting resin layer, a rigid material layer, and a second thermosetting resin layer. The second thermosetting resin layer contains epoxy resin, curing agent, elastomer and silica particles with an average primary particle size of 30-400 nm.

2. The laminated film for forming a monolithic body according to claim 1, wherein, The rigid material layer is a polyimide layer.

3. The laminated film for forming a monolithic body according to claim 1 or 2, wherein, The first thermosetting resin layer contains epoxy resin, curing agent, elastomer and silica particles with an average primary particle size of 30-400 nm.

4. A method for manufacturing a semiconductor device, the semiconductor device having a support tomb structure, the support tomb structure including a substrate, a first chip disposed on the substrate, a plurality of support sheets disposed on the substrate and surrounding the first chip, and a second chip disposed such that it is supported by the plurality of support sheets and covers the first chip, the method for manufacturing the semiconductor device comprising: (A) A process for preparing a laminated film for forming a support sheet, wherein the laminated film for forming a support sheet comprises a substrate film, a pressure-sensitive adhesive layer and a support sheet forming film in sequence, wherein the support sheet forming film comprises a first thermosetting resin layer, a rigid material layer and a second thermosetting resin layer in sequence from the pressure-sensitive adhesive layer, wherein the second thermosetting resin layer contains epoxy resin, curing agent, elastomer and silica particles with an average primary particle size of 30 to 400 nm; (B) A process of forming a plurality of support sheets on the surface of the pressure-sensitive adhesive layer by cutting the support sheet forming film; (C) The process of picking up the support sheet from the pressure-sensitive adhesive layer; (D) The process of mounting the first chip on the substrate; (E) The process of arranging a plurality of the support sheets on the substrate and around the first chip or around the area where the first chip should be arranged; (F) A process for preparing a chip with an adhesive sheet attached, the chip having an adhesive sheet attached comprising a second chip and an adhesive sheet disposed on one side of the second chip; and (G) The process of constructing a stone tomb structure by disposing the chip with the adhesive sheet on the surface of a plurality of the support sheets.

5. The method for manufacturing a semiconductor device according to claim 4, wherein, Prior to step (G), there is a step of forming the support sheet into a film or heating the support sheet.

6. The method of manufacturing a semiconductor device according to claim 4 or 5, wherein, The rigid material layer is a polyimide layer.

7. The method of manufacturing a semiconductor device according to claim 4 or 5, wherein, The first thermosetting resin layer contains epoxy resin, curing agent, elastomer and silica particles with an average primary particle size of 30-400 nm.

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