WO2023048188A1 - Film adhesive, dicing and die-bonding two-in-one film, semiconductor device, and manufacturing method for same - Google Patents

Film adhesive, dicing and die-bonding two-in-one film, semiconductor device, and manufacturing method for same Download PDF

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Publication number
WO2023048188A1
WO2023048188A1 PCT/JP2022/035193 JP2022035193W WO2023048188A1 WO 2023048188 A1 WO2023048188 A1 WO 2023048188A1 JP 2022035193 W JP2022035193 W JP 2022035193W WO 2023048188 A1 WO2023048188 A1 WO 2023048188A1
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Prior art keywords
adhesive
film
semiconductor element
mass
semiconductor
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PCT/JP2022/035193
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French (fr)
Japanese (ja)
Inventor
和弘 山本
強 田澤
知世 金子
利泰 秋吉
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株式会社レゾナック
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Priority to CN202280062217.8A priority Critical patent/CN117999641A/en
Publication of WO2023048188A1 publication Critical patent/WO2023048188A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers

Definitions

  • the present disclosure relates to a film adhesive, a dicing/die bonding integrated film, a semiconductor device, and a method for manufacturing the same.
  • laminated MCPs Multi Chip Packages
  • semiconductor elements semiconductor elements (semiconductor chips) are stacked in multiple layers
  • speeding up, high-density, high-integration, etc. of semiconductor packages are being promoted.
  • semiconductor wafers are becoming thinner, and problems such as wafer cracking during processing are likely to occur, which may cause a problem of yield reduction. Therefore, as the thickness of semiconductor wafers becomes thinner (for example, 50 ⁇ m or less), there is a shift from conventional physical grinding methods to new processing methods.
  • cooling expansion expansion under cooling conditions
  • a conventional dicing/die-bonding integrated film is applied to cooling expansion
  • an adhesive layer made of a film-like adhesive die-bonding film
  • problems arise such as a decrease in yield and a decrease in production time efficiency for sorting uncut products.
  • the film adhesive die bonding film of the die bonding integrated film
  • the film adhesive must be thin (for example, thickness 20 ⁇ m or less). It has been demanded.
  • the thickness of the conventional film adhesive is reduced, the die shear strength may not be ensured, and there is still room for improvement.
  • the main object of the present disclosure is to provide a film-like adhesive that is excellent in splittability by cooling expansion and has sufficient die shear strength when thinned.
  • the film adhesive contains a thermosetting resin, a curing agent, an elastomer, and an inorganic filler having an average particle size of 400 nm or less.
  • the content of the inorganic filler is 18-40% by mass based on the total amount of the film adhesive.
  • the content of the inorganic filler is 18% by mass or more based on the total amount of the film adhesive, the splitting property of the film adhesive by cooling expansion tends to be excellent.
  • the content of the inorganic filler is 40% by mass or less based on the total amount of the film adhesive, the film adhesive tends to have sufficient die shear strength when thinned.
  • the total content of the thermosetting resin and curing agent is 25% by mass or less based on the total amount of the film adhesive.
  • the amount of the elastomer is sufficient, so that thin film coating tends to be excellent. be.
  • the content of the elastomer may be 40% by mass or more based on the total amount of the film adhesive.
  • the content of the inorganic filler may be 22 parts by mass or more with respect to 100 parts by mass of the total amount of the thermosetting resin, curing agent, and elastomer.
  • the content of the elastomer may be 200 parts by mass or more with respect to 100 parts by mass of the total amount of the thermosetting resin and curing agent.
  • the thickness of the film adhesive may be 20 ⁇ m or less.
  • the film-like adhesive may be used in the manufacturing process of a semiconductor device in which multiple semiconductor elements are laminated.
  • the semiconductor device may be a stacked MCP (Multi Chip Package) in which semiconductor elements (semiconductor chips) are stacked in multiple stages, or may be a three-dimensional NAND memory.
  • the dicing/die-bonding integrated film includes a substrate layer, an adhesive layer, and an adhesive layer made of the film-like adhesive in this order.
  • the semiconductor device includes a semiconductor element, a support member on which the semiconductor element is mounted, and an adhesive member provided between the semiconductor element and the support member to bond the semiconductor element and the support member.
  • the adhesive member is a cured product of the film adhesive described above.
  • the semiconductor device may further include another semiconductor element laminated on the surface of the semiconductor element.
  • Another aspect of the present disclosure relates to a method of manufacturing a semiconductor device.
  • the film-like adhesive is interposed between the semiconductor element and the supporting member or between the first semiconductor element and the second semiconductor element, and the semiconductor element and the A step of adhering the support member or the first semiconductor element and the second semiconductor element is provided.
  • Another aspect of the method for manufacturing the semiconductor device includes the steps of: attaching a semiconductor wafer to the adhesive layer of the dicing/die bonding integrated film; dicing the semiconductor wafer to which the adhesive layer is attached; forming a plurality of individualized semiconductor elements with adhesive pieces by expanding the material layer under cooling conditions; picking up the semiconductor elements with adhesive pieces from the adhesive layer; and removing the semiconductor elements with adhesive pieces. and gluing to the support member via adhesive strips.
  • the method of manufacturing a semiconductor device may further comprise a step of adhering, via an adhesive piece, another semiconductor element with an adhesive piece to the surface of the semiconductor element adhered to the support member.
  • the present disclosure includes the film adhesive according to [1] to [7], the dicing/die bonding integrated film according to [8], the semiconductor device according to [9] and [10], and [11].
  • a semiconductor device and a manufacturing method thereof according to to [13] are provided.
  • [1] Contains a thermosetting resin, a curing agent, an elastomer, and an inorganic filler having an average particle size of 400 nm or less, and the content of the inorganic filler is 18 based on the total amount of the film adhesive. 40% by mass, and the total content of the thermosetting resin and the curing agent is 25% by mass or less based on the total amount of the film adhesive.
  • [5] The film adhesive according to any one of [1] to [4], which has a thickness of 20 ⁇ m or less.
  • [6] The film adhesive according to any one of [1] to [5], which is used in the manufacturing process of a semiconductor device formed by laminating a plurality of semiconductor elements.
  • [8] A dicing/die bonding integrated film comprising a substrate layer, an adhesive layer, and an adhesive layer made of the film-like adhesive according to any one of [1] to [5] in this order.
  • a semiconductor element a support member for mounting the semiconductor element, and an adhesive member provided between the semiconductor element and the support member for bonding the semiconductor element and the support member, wherein the adhesive member is a cured product of the film adhesive according to any one of [1] to [5].
  • the semiconductor device according to [9] further comprising another semiconductor element laminated on the surface of the semiconductor element.
  • a method of manufacturing a semiconductor device comprising a step of adhering a semiconductor element with an adhesive piece to a support member via an adhesive piece.
  • the method of manufacturing a semiconductor device according to [12] further comprising the step of adhering, via an adhesive piece, another semiconductor element with an adhesive piece to the surface of the semiconductor element adhered to the support member.
  • a film-like adhesive that is excellent in splittability by cooling expansion and has sufficient die shear strength when thinned.
  • a dicing/die-bonding integrated film using such a film-like adhesive, a semiconductor device, and a method for manufacturing the same are provided. Further, according to the present disclosure, there is provided a method of manufacturing a semiconductor device using such a dicing/die bonding integrated film.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of a film adhesive.
  • FIG. 2 is a perspective view schematically showing a sample fixed to a jig in a breaking test.
  • FIG. 3 is a cross-sectional view schematically showing a state in which a load is applied to a sample by a pressing jig in a breaking test.
  • FIG. 4 is a graph schematically showing an example of the results of the breaking test.
  • FIG. 5 is a schematic cross-sectional view showing an embodiment of a dicing/die bonding integrated film.
  • FIG. 6 is a schematic cross-sectional view showing one embodiment of a semiconductor device.
  • FIG. 7 is a schematic cross-sectional view showing another embodiment of the semiconductor device.
  • FIG. 8 is a schematic cross-sectional view showing another embodiment of the semiconductor device.
  • the numerical range indicated using “to” indicates the range including the numerical values before and after “to” as the minimum and maximum values, respectively.
  • the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. good.
  • the upper and lower limits of the numerical ranges may be replaced with the values shown in the examples.
  • (meth)acrylate means acrylate or its corresponding methacrylate.
  • the film adhesive comprises a thermosetting resin (hereinafter sometimes referred to as "(A) component”), a curing agent (hereinafter sometimes referred to as “(B) component”), and an elastomer (hereinafter sometimes referred to as “(B) component”). and an inorganic filler having an average particle diameter of 400 nm or less (hereinafter sometimes referred to as "(D) component”).
  • the film adhesive contains a coupling agent (hereinafter sometimes referred to as "(E) component”), curing An accelerator (hereinafter sometimes referred to as “component (F)”) and other components may be further contained.
  • the film-like adhesive comprises (A) component, (B) component, (C) component, and (D) component, and other components added as necessary ((E) component, (F) component, other component, etc.) can be obtained by forming the adhesive composition into a film.
  • the film-like adhesive adheresive composition
  • the film-like adhesive may be in a semi-cured (B stage) state and then in a cured (C stage) state after a curing treatment.
  • Thermosetting resin Component (A) may contain an epoxy resin, or may consist of one or more epoxy resins, from the viewpoint of adhesiveness.
  • Epoxy resins can be used without any particular restrictions as long as they have an epoxy group in the molecule.
  • Examples of epoxy resins include bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; phenol novolak type epoxy resin; cresol novolak type epoxy resin; bisphenol A novolac type epoxy resin; ; stilbene type epoxy resin; triazine skeleton-containing epoxy resin; fluorene skeleton-containing epoxy resin; triphenolmethane type epoxy resin; biphenyl type epoxy resin; xylylene type epoxy resin; and polycyclic aromatic diglycidyl ether compounds such as anthracene. You may use these individually by 1 type or in combination of 2 or more types.
  • the epoxy resin may contain a cresol novolak type epoxy resin or a fluorene skeleton-containing epoxy resin from the viewpoint of film tackiness, flexibility, and the like.
  • the epoxy equivalent of the epoxy resin is not particularly limited, but may be 90-300 g/eq, 110-290 g/eq, or 130-280 g/eq. When the epoxy equivalent of the epoxy resin is in such a range, better reactivity and fluidity tend to be obtained.
  • the content of component (A) may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and may be 30% by mass or less, 20% by mass or less, or It may be 15% by mass or less.
  • the content of component (A) is in this range, the elastic modulus after curing tends to be more excellent.
  • the flexibility before curing tends to be more excellent.
  • component (B) Component: Curing Agent Any commonly used curing agent for component (A) can be used.
  • component (A) contains an epoxy resin (consisting of one or more epoxy resins)
  • component (B) includes, for example, phenolic resins, ester compounds, aromatic amines, aliphatic amines, acid anhydrides. etc.
  • the component (B) may contain a phenolic resin, or may consist of one or more phenolic resins.
  • Phenolic resins include phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and/or naphthols such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene, and aldehydes such as formaldehyde. It can be a polycondensation product with Polycondensation is usually carried out in the presence of a catalyst such as an acid or a base. A phenolic resin obtained when an acid catalyst is used is particularly called a novolak-type phenolic resin.
  • novolac-type phenolic resins examples include phenol/formaldehyde novolac resin, cresol/formaldehyde novolac resin, xylenol/formaldehyde novolac resin, resorcinol/formaldehyde novolac resin, phenol-naphthol/formaldehyde novolac resin, and the like.
  • Phenol resins include, for example, phenols and/or naphthols such as allylated bisphenol A, allylated bisphenol F, allylated naphthalenediol, phenol novolac, phenol, and dimethoxyparaxylene or bis(methoxymethyl)biphenyl. Synthesized phenol aralkyl resins, naphthol aralkyl resins, biphenyl aralkyl type phenol resins, phenyl aralkyl type phenol resins and the like are also included.
  • the hydroxyl equivalent of the phenolic resin may be 80-300 g/eq, 90-280 g/eq, or 100-250 g/eq.
  • the storage elastic modulus tends to be further improved, and when it is 300 g/eq or less, it becomes possible to prevent problems due to the generation of foaming, outgassing, and the like.
  • the softening point of the phenolic resin may be 50-140°C, 55-130°C, or 60-120°C.
  • the softening point means a value measured by the ring and ball method according to JIS K7234.
  • component (B) may be 1% by mass or more, 2% by mass or more, or 3% by mass or more, and may be 20% by mass or less, 15% by mass or less, or It may be 10% by mass or less.
  • the ratio of the epoxy equivalent of the epoxy resin to the hydroxyl equivalent of the phenolic resin is From the viewpoint of curability, 0.30/0.70 to 0.70/0.30, 0.35/0.65 to 0.65/0.35, 0.40/0.60 to 0.60/ 0.40, or 0.45/0.55 to 0.55/0.45.
  • the corresponding weight ratio is 0.30/0.70 or more (the epoxy equivalent of the epoxy resin is 0.30 or more)
  • more sufficient curability tends to be obtained.
  • the corresponding weight ratio is 0.70/0.30 or less (the epoxy equivalent of the epoxy resin is 0.70 or less) it is possible to prevent the viscosity from becoming too high and obtain more sufficient fluidity. can be done.
  • the total content of components (A) and (B) is 25% by mass or less based on the total amount of the film adhesive. When the total content of component (A) and component (B) is in this range, the amount of component (C) is sufficient, so that thin film coatability tends to be excellent.
  • the total content of components (A) and (B) is 22% by mass or less, 20% by mass or less, or 18% by mass or less based on the total amount of the film adhesive, from the viewpoint of handleability. good too.
  • the total content of components (A) and (B) may be 1% by mass or more, 5% by mass or more, 10% by mass or more, or 12% by mass or more based on the total amount of the film adhesive. . When the total content of component (A) and component (B) is in this range, the adhesiveness tends to be further improved.
  • component (C) Elastomer
  • component (C) include acrylic resins, polyester resins, polyamide resins, polyimide resins, silicone resins, and butadiene resins; modified products of these resins. You may use these individually by 1 type or in combination of 2 or more types.
  • the component (C) is derived from a (meth)acrylic ester because it has few ionic impurities and is excellent in heat resistance, it is easy to ensure the connection reliability of a semiconductor device, and it is excellent in fluidity. It may be an acrylic resin (acrylic rubber) having structural units as a main component.
  • the content of structural units derived from (meth)acrylic acid ester in component (C) may be, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more based on the total amount of structural units.
  • the acrylic resin (acrylic rubber) may contain structural units derived from a (meth)acrylic acid ester having a crosslinkable functional group such as an epoxy group, an alcoholic or phenolic hydroxyl group, or a carboxyl group.
  • the glass transition temperature (Tg) of component (C) may be -50 to 50°C or -30 to 30°C.
  • Tg of component (C) is -50°C or higher, it tends to be possible to prevent the flexibility of the adhesive composition from becoming too high. This makes it easier to cut the film-like adhesive during wafer dicing, making it possible to prevent the occurrence of burrs.
  • Tg of the component (C) is 50° C. or less, it tends to be possible to suppress a decrease in the flexibility of the film-like adhesive. This tends to make it easier to sufficiently fill voids when the film-like adhesive is attached to the semiconductor wafer. Also, it is possible to prevent chipping during dicing due to deterioration of adhesion of the semiconductor wafer.
  • the glass transition temperature (Tg) means a value measured using a DSC (differential scanning calorimeter) (for example, "Thermo Plus 2" manufactured by Rigaku Corporation).
  • the Tg of the component (C) is the type and content of structural units that constitute the component (C) (structural units derived from (meth)acrylic acid esters when the component (C) is an acrylic resin (acrylic rubber)). can be adjusted to a desired range by adjusting .
  • the weight average molecular weight (Mw) of component (C) may be 100,000 to 3,000,000 or 200,000 to 1,000,000.
  • Mw means a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
  • component (C) Commercially available products of component (C) include SG-70L, SG-708-6, WS-023 EK30, SG-P3, SG-280 EK23, SG-80H, HTR-860P, HTR-860P-3, HTR- 860P-3CSP, HTR-860P-3CSP-3DB, HTR-860P-30B (all manufactured by Nagase ChemteX Corporation) and the like.
  • the content of component (C) may be 40% by mass or more, 45% by mass or more, or 50% by mass or more based on the total amount of the film adhesive. When the content of the component (C) is in such a range, it tends to be more excellent in thin film coatability.
  • the content of component (C) may be 80% by mass or less, 75% by mass or less, or 70% by mass or less based on the total amount of the film adhesive. When the content of component (C) is in this range, the content of components (A) and (B) can be sufficiently ensured, and other properties tend to be compatible.
  • the content of component (C) may be 200 parts by mass or more with respect to 100 parts by mass of the total amount of components (A) and (B). When the content of the component (C) is in such a range, it tends to be more excellent in thin film coatability.
  • the content of component (C) may be 250 parts by mass or more, 300 parts by mass or more, or 350 parts by mass or more with respect to 100 parts by mass of the total amount of components (A) and (B).
  • the content of component (C) may be 600 parts by mass or less, 550 parts by mass or less, or 500 parts by mass or less with respect to 100 parts by mass of the total amount of components (A) and (B). When the content of component (C) is in this range, the content of components (A) and (B) can be sufficiently ensured, and other properties tend to be compatible.
  • inorganic filler having an average particle size of 400 nm or less
  • inorganic fillers as component (D) include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, Calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, boron nitride, silica and the like. These may be used singly or in combination of two or more as long as the average particle diameter is 400 nm or less.
  • the inorganic filler may be silica from the viewpoint of adjusting the melt viscosity.
  • the shape of the inorganic filler is not particularly limited, but may be spherical.
  • the average particle diameter of component (D) is 400 nm or less, and may be 350 nm or less, or 300 nm or less, from the viewpoint of thin film coatability and adhesiveness.
  • the average particle size of the inorganic filler as component (D) may be, for example, 10 nm or more, 30 nm or more, 100 nm or more, or 150 nm or more.
  • the average particle size means the average particle size determined by the dynamic light scattering method.
  • the average particle size of component (D) can also be obtained by using a film-like adhesive containing component (D). In this case, the residue obtained by heating the film adhesive to decompose the resin component is dispersed in a solvent to prepare a dispersion liquid.
  • the average particle size of component (D) can be determined.
  • Component (D) may be composed of, for example, one or more inorganic fillers having an average particle size of 400 nm or less, and one or more inorganic fillers having an average particle size of 10 to 400 nm and an average particle size of 400 nm or less.
  • the content of component (D) is 18 to 40% by mass based on the total amount of the film adhesive.
  • the content of component (D) is 18% by mass or more, and may be 20% by mass or more, 22% by mass or more, or 24% by mass or more based on the total amount of the film adhesive.
  • the content of component (D) is 40% by mass or less, and may be 38% by mass or less, 35% by mass or less, or 32% by mass or less based on the total amount of the film adhesive.
  • the film adhesive tends to have sufficient die shear strength when thinned.
  • the content of component (D) based on the total amount of the film-like adhesive can also be obtained by using a film-like adhesive containing component (D).
  • the mass of the film-like adhesive and the mass of the residue obtained by heating the film-like adhesive to decompose the resin component are determined, and the content of the component (D) can be determined from the relationship between these masses.
  • the mass of the residue obtained by heating the film adhesive to decompose the resin component may be the mass measured after the residue is washed with a solvent and dried.
  • the content of component (D) may be 22 parts by mass or more, 25 parts by mass or more, and 28 parts by mass with respect to the total amount of 100 parts by mass of components (A), (B), and (C). or more, or 30 parts by mass or more.
  • the film adhesive is divided by cooling expansion.
  • the content of component (D) is 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, or 55 parts by mass with respect to 100 parts by mass of the total amount of components (A), (B), and (C). parts or less, or 50 parts by mass or less.
  • the film adhesive is thinned. It tends to have sufficient die shear strength.
  • the film adhesive may contain an inorganic filler with an average particle size of more than 400 nm in addition to the component (D).
  • an inorganic filler having an average particle size of more than 400 nm is preferred.
  • substantially does not contain means that the content of the inorganic filler having an average particle size of more than 400 nm is based on the total amount of the component (D) and the inorganic filler having an average particle size of more than 400 nm. , 5% by mass or less, 3% by mass or less, 1% by mass or less, or 0.1% by mass or less.
  • the (E) component may be a silane coupling agent.
  • Silane coupling agents include, for example, ⁇ -ureidopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, and the like. be done.
  • Component (F) Curing Accelerator
  • component (F) include imidazoles and their derivatives, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. You may use these individually by 1 type or in combination of 2 or more types. Among these, imidazoles and derivatives thereof may be used as the component (F) from the viewpoint of reactivity.
  • imidazoles examples include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole and the like. You may use these individually by 1 type or in combination of 2 or more types.
  • the film adhesive may further contain other components.
  • Other components include, for example, pigments, ion trapping agents, antioxidants, and the like.
  • the total content of component (E), component (F), and other components is 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass, based on the total amount of the film adhesive. % or more, and may be 20% by mass or less, 10% by mass or less, or 5% by mass or less.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of a film adhesive.
  • the film adhesive 1 shown in FIG. 1 can be a die bonding film used for bonding a semiconductor chip and a supporting member or bonding semiconductor chips to each other.
  • the film adhesive 1 is obtained by molding an adhesive composition into a film.
  • the film-like adhesive 1 is usually in a semi-cured (B stage) state, and can be in a cured (C stage) state after a curing treatment.
  • the film adhesive 1 can be formed by applying an adhesive composition to a support film.
  • a varnish of an adhesive composition may be used.
  • the components (A), (B), (C), and (D), and optionally added components are mixed or kneaded in a solvent to prepare the adhesive varnish.
  • the obtained adhesive varnish is applied to a support film, and the solvent is removed by heating and drying to obtain the film-like adhesive 1.
  • the support film is not particularly limited as long as it can withstand the heat drying described above. It's okay.
  • the support film may be a multi-layer film in which two or more types are combined, or the surface thereof may be treated with a release agent such as a silicone-based or silica-based release agent.
  • the thickness of the support film may be, for example, 10-200 ⁇ m or 20-170 ⁇ m.
  • Mixing or kneading can be carried out by using a dispersing machine such as a normal stirrer, squeegee machine, triple roll, ball mill, etc., and combining them appropriately.
  • a dispersing machine such as a normal stirrer, squeegee machine, triple roll, ball mill, etc., and combining them appropriately.
  • the solvent used for preparing the adhesive varnish is not limited as long as it can uniformly dissolve, knead, or disperse each component, and conventionally known solvents can be used.
  • solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene and xylene.
  • the solvent may be methyl ethyl ketone or cyclohexanone from a drying speed and cost point of view.
  • a known method can be used, for example, a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, a curtain coating method, or the like is used. be able to.
  • Heat drying is not particularly limited as long as the solvent used is sufficiently volatilized, but it can be carried out in the range of 50 to 150° C. for 1 to 30 minutes. Heat drying can be performed in stages at different heating temperatures and for different heating times.
  • the thickness of the film adhesive may be 20 ⁇ m or less, 18 ⁇ m or less, 15 ⁇ m or less, 12 ⁇ m or less, 10 ⁇ m or less, or 8 ⁇ m or less.
  • the lower limit of the thickness of the film adhesive is not particularly limited, it may be, for example, 1 ⁇ m or more.
  • the film-like adhesive produced on the support film may have a cover film on the side opposite to the support film of the film-like adhesive.
  • cover films include polyethylene films, polypropylene films, films treated with surface release agents, and the like.
  • the thickness of the cover film may be, for example, 15-200 ⁇ m or 30-170 ⁇ m.
  • a film-like adhesive can be made thinner, so it can be suitably used in the manufacturing process of a semiconductor device in which multiple semiconductor elements are laminated.
  • the semiconductor device may be a stacked MCP or a three-dimensional NAND memory.
  • the film-like adhesive 1 is a splitting property evaluation method using the results of a cleaving test performed under the following conditions (a film under low-temperature conditions (for example, a range of -15 ° C. to 0 ° C.) where cooling expansion is performed) method for evaluating splittability of adhesives), the adhesive may be a film adhesive having a breaking modulus m of 70 or less.
  • a breaking modulus m of 70 or less Width of sample: 5 mm Sample length: 23mm Relative speed between pushing jig and sample: 10 mm/min
  • the breaking test will be explained below.
  • the rupture test is classified as a bending strength test, and includes a step of pushing the central portion of the sample until the sample breaks while both ends of the sample are fixed.
  • the sample S is sandwiched and fixed between a pair of sample fixing jigs 20 and subjected to the breaking test.
  • the pair of sample fixing jigs 20 are made of, for example, cardboard having sufficient strength, and each have a rectangular opening 20a in the center.
  • a load is applied to the central portion of the fixed sample S using a pressing jig 21 (see FIG. 3).
  • the sample S may be obtained by cutting out the film-like adhesive to be evaluated, and the sample does not have to be prepared by laminating a plurality of adhesive pieces cut out from the film-like adhesive. That is, the thickness of the sample S may be the same as the thickness of the film adhesive.
  • the width of the sample S (Ws in FIG. 2) is, for example, 1 to 30 mm, and may be 3 to 8 mm. An appropriate width may be set according to the conditions of the measuring device.
  • the length of the sample S (Ls in FIG. 2) is, for example, 5-50 mm, and may be 10-30 mm or 6-9 mm. The length of the sample S depends on the size of the opening 20a of the jig 20 for fixing the sample. Note that the shape of the sample fixing jig 20 and the size of the sample S may be other than those described above as long as the fracture test can be performed.
  • the pressing jig 21 consists of a cylindrical member having a conical tip 21a.
  • the diameter (R in FIG. 3) of the pressing jig 21 is, for example, 3 to 15 mm, and may be 5 to 10 mm.
  • the angle of the tip portion 21a ( ⁇ in FIG. 3) is, for example, 40 to 120°, and may be 60 to 100°.
  • the breaking test is carried out in a constant temperature bath set at a predetermined temperature.
  • the constant temperature bath may be set at a constant temperature in the range of ⁇ 15° C. to 0° C. (expected cooling expansion temperature).
  • As the constant temperature bath for example, TLF-R3-FW-PL-S manufactured by ITEC Co., Ltd. can be used.
  • an autograph for example, AZT-CA01, load cell 50N, compression mode manufactured by A&D Co., Ltd.
  • the work at break W, the strength at break P, and the elongation at break L are obtained.
  • the relative speed between the pressing jig 21 and the sample S is, for example, 1 to 100 mm/min, and may be 5 to 20 mm/min. If this relative speed is too high, there is a tendency that sufficient data on the cleaving process cannot be obtained, and if it is too slow, the stress tends to relax, making it difficult to achieve cleaving.
  • the pushing distance of the pushing jig 21 is, for example, 1 to 50 mm, and may be 5 to 30 mm. If the pushing distance is too short, there is a tendency not to result in breakage. It is preferable to prepare a plurality of samples of the film-like adhesive to be evaluated, and to perform a cleaving test a plurality of times to confirm the stability of the test results.
  • FIG. 4 is a graph showing an example of the results of the breaking test.
  • the breaking work W is the area enclosed when a graph is created with the vertical axis representing the load and the horizontal axis representing the pressing amount until the sample S breaks.
  • the breaking strength P is the load when the sample S breaks.
  • the breaking elongation L is the elongation amount of the sample S when the sample S breaks.
  • the breaking elongation L may be calculated using a trigonometric function from the pushing distance when the sample S breaks and the width of the opening 20a of the jig 20 for fixing the sample.
  • the breaking modulus m may be 90 or less, 80 or less, 70 or less, 65 or less, or 60 or less.
  • the breaking modulus m is a parameter relating to stretchability of a film adhesive under low temperature conditions. When the breaking modulus m is 90 or less, the suitable stretchability of the film-like adhesive tends to result in sufficient breakability by cooling expansion. This tendency is more remarkable as the numerical value of the breaking modulus m becomes smaller.
  • the fracture modulus m (dimensionless) may be greater than 0 and may be 10 or more or 15 or more. When the breaking modulus m is 15 or more, the stress propagating property tends to be good.
  • a film adhesive having a breaking modulus m within such a range can be suitably used in a semiconductor device manufacturing process in which cooling expansion is performed.
  • the breaking resistance R may be more than 0 N/mm 2 and 45 N/mm 2 or less, may be 10 N/mm 2 or more or 20 N/mm 2 or more , and may be 40 N/mm 2 or less or 35 N/mm 2 or less.
  • the breaking resistance R is 45 N/mm 2 or less, the strength of the film-like adhesive does not become excessive and there is a tendency to obtain sufficient splittability.
  • the breaking resistance R is more than 0 N/mm 2 , good stress propagation occurs during cooling expansion, and there is a tendency to obtain better splitting properties. This tendency tends to become more pronounced when the breaking resistance R is 20 N/mm 2 or more.
  • FIG. 5 is a schematic cross-sectional view showing an embodiment of a dicing/die bonding integrated film.
  • a dicing/die-bonding integrated film 10 shown in FIG. 5 includes a substrate layer 2, an adhesive layer 3, and an adhesive layer 1A made of the adhesive composition in this order.
  • the adhesive layer 1A may be the film adhesive 1.
  • the base material layer 2 and the adhesive layer 3 may be a dicing tape 4 .
  • the dicing/die-bonding integrated film may be in the form of a film, a sheet, a tape, or the like.
  • the dicing tape 4 includes a base layer 2 and an adhesive layer 3 provided on the base layer 2 .
  • the base material layer 2 examples include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. These substrate layers 2 may be subjected to surface treatments such as primer coating, UV treatment, corona discharge treatment, polishing treatment, etching treatment, etc., as required.
  • the adhesive layer 3 is a layer made of an adhesive.
  • the adhesive is not particularly limited as long as it has sufficient adhesive strength to prevent the semiconductor elements from scattering during dicing and has low adhesive strength to the extent that the semiconductor elements are not damaged in the subsequent step of picking up the semiconductor elements. can be used.
  • the adhesive may be either non-radiation curable or radiation curable.
  • a non-radiation curable adhesive is an adhesive that exhibits a certain level of adhesiveness when pressed for a short period of time, and is an adhesive that does not lose its adhesiveness when exposed to radiation (for example, ultraviolet rays).
  • a radiation-curable pressure-sensitive adhesive is a pressure-sensitive adhesive that has the property of decreasing its adhesiveness when irradiated with radiation (for example, ultraviolet rays).
  • the radiation-curable adhesive may be, for example, an ultraviolet-curable adhesive.
  • the thickness of the dicing tape 4 may be 60 to 150 ⁇ m or 70 to 130 ⁇ m from the viewpoint of economy and film handling.
  • the dicing/die bonding integrated film 10 can be obtained, for example, by preparing a film adhesive 1 and a dicing tape 4 and bonding the film adhesive 1 and the adhesive layer 3 of the dicing tape 4 together. Further, the dicing/die-bonding integrated film 10 can be obtained, for example, by preparing the dicing tape 4 and applying an adhesive composition (adhesive varnish) to the dicing tape 4 in the same manner as in the method of forming the film adhesive 1 described above. It can also be obtained by coating on the pressure-sensitive adhesive layer 3 .
  • the dicing/die bonding integrated film 10 is applied under predetermined conditions (for example, room temperature (20° C.) or It can be formed by laminating the film adhesive 1 on the dicing tape 4 in a heated state).
  • predetermined conditions for example, room temperature (20° C.) or It can be formed by laminating the film adhesive 1 on the dicing tape 4 in a heated state.
  • the dicing/die-bonding integrated film 10 can be continuously produced and is highly efficient, so it may be formed using a roll laminator in a heated state.
  • the film-like adhesive and the dicing/die-bonding integrated film may be used in the manufacturing process of a semiconductor device, or may be used in the manufacturing process of a semiconductor device formed by laminating a plurality of semiconductor elements. good.
  • a film-like adhesive is also suitably used as an adhesive for adhering a semiconductor element and a supporting member on which the semiconductor element is mounted.
  • the film-like adhesive is also suitably used as an adhesive for bonding semiconductor elements in a laminated MCP (for example, a three-dimensional NAND memory), which is a semiconductor device formed by laminating a plurality of semiconductor elements. .
  • a laminated MCP for example, a three-dimensional NAND memory
  • the film adhesive is, for example, a protective sheet for protecting the back surface of the semiconductor element of the flip chip type semiconductor device, or a sealing sheet for sealing between the surface of the semiconductor element of the flip chip type semiconductor device and the adherend. etc. can also be used.
  • a semiconductor device manufactured using a film-like adhesive and a dicing/die-bonding integrated film will be specifically described below with reference to the drawings.
  • semiconductor devices with various structures have been proposed, and the application of the film-like adhesive and dicing/die bonding integrated film of the present embodiment is not limited to the semiconductor devices having the structures described below. do not have.
  • FIG. 6 is a schematic cross-sectional view showing one embodiment of a semiconductor device.
  • a semiconductor device 100 shown in FIG. 6 includes a semiconductor element 11 , a support member 12 on which the semiconductor element 11 is mounted, and an adhesive member 15 .
  • the adhesive member 15 is provided between the semiconductor element 11 and the support member 12 and bonds the semiconductor element 11 and the support member 12 together.
  • the adhesive member 15 is a cured product of an adhesive composition (cured film adhesive). Connection terminals (not shown) of the semiconductor element 11 are electrically connected to external connection terminals (not shown) via wires 13 and sealed with a sealing material 14 .
  • FIG. 7 is a schematic cross-sectional view showing another embodiment of the semiconductor device.
  • the first semiconductor element 11a is a support member 12 having terminals 16 formed by an adhesive member 15a (cured product of adhesive composition (cured product of film adhesive)).
  • the semiconductor element 11b in the second stage is further bonded onto the semiconductor element 11a in the first stage with an adhesive member 15b (cured product of adhesive composition (cured product of film-like adhesive)).
  • Connection terminals (not shown) of the first-stage semiconductor element 11 a and the second-stage semiconductor element 11 b are electrically connected to external connection terminals via wires 13 and sealed with a sealing material 14 .
  • the semiconductor device 110 shown in FIG. 7 further includes another semiconductor element (11b) laminated on the surface of the semiconductor element (11a) in the semiconductor device 100 shown in FIG.
  • FIG. 8 is a schematic cross-sectional view showing another embodiment of the semiconductor device.
  • a semiconductor device 120 shown in FIG. 8 includes a support member 12 and semiconductor elements 11 a, 11 b, 11 c, and 11 d stacked on the support member 12 .
  • the four semiconductor elements 11a, 11b, 11c, and 11d are offset from each other in the lateral direction (direction perpendicular to the stacking direction) for connection with connection terminals (not shown) formed on the surface of the support member 12. position (see FIG. 8).
  • the semiconductor element 11a is adhered to the support member 12 by an adhesive member 15a (cured product of adhesive composition (cured product of film adhesive)).
  • Adhesive members 15b, 15c, and 15d are interposed, respectively. It can be said that the semiconductor device 120 shown in FIG. 8 further includes other semiconductor elements (11b, 11c, 11d) laminated on the surface of the semiconductor element (11a) in the semiconductor device 100 shown in FIG. .
  • FIG. 8 illustrates a semiconductor device in which four semiconductor elements are stacked, but the number of stacked semiconductor elements is not limited to this.
  • FIG. 8 illustrates the semiconductor device in which the semiconductor elements are stacked at positions shifted in the lateral direction (direction orthogonal to the stacking direction), the semiconductor elements direction) may be stacked at positions that are not shifted from each other.
  • the semiconductor device (semiconductor package) shown in FIGS. 6, 7, and 8 is provided between the semiconductor element and the supporting member, or between the semiconductor element (first semiconductor element) and the semiconductor element (second semiconductor element). By interposing the film adhesive between and bonding the semiconductor element and the supporting member, or the semiconductor element (first semiconductor element) and the semiconductor element (second semiconductor element). be able to.
  • a method for interposing a film-like adhesive between the semiconductor element and the support member or between the semiconductor element (first semiconductor element) and the semiconductor element (second semiconductor element), as described later A method may be employed in which a semiconductor element with an adhesive piece is prepared in advance and then attached to a supporting member or a semiconductor element.
  • the method of manufacturing a semiconductor device using the dicing/die-bonding integrated film is not limited to the method of manufacturing a semiconductor device described below.
  • a semiconductor device includes, for example, a step of attaching a semiconductor wafer to the adhesive layer of the dicing/die bonding integrated film (laminating step), and a step of dicing the semiconductor wafer to which the adhesive layer is attached (dicing step). , a step of producing a plurality of individualized semiconductor elements with adhesive pieces by expanding the base material layer under cooling conditions (cooling expansion step), and a step of picking up the semiconductor elements with adhesive pieces from the adhesive layer ( picking up step) and a step of adhering the picked up semiconductor element with an adhesive piece to a support member via the adhesive piece (first adhesion step).
  • the method of manufacturing a semiconductor device may further include a step of bonding another semiconductor element with adhesive piece to the surface of the semiconductor element bonded to the support member via the adhesive piece (second bonding step). .
  • the lamination step is a step of pressing a semiconductor wafer onto the adhesive layer 1A of the dicing/die bonding integrated film 10, holding it by adhesion, and attaching it. This step may be performed while pressing with a pressing means such as a pressing roll.
  • a pressing means such as a pressing roll.
  • the semiconductor wafer the same semiconductor wafer as described above can be exemplified.
  • semiconductor wafers include monocrystalline silicon, polycrystalline silicon, various ceramics, and compound semiconductors such as gallium arsenide.
  • a dicing process is a process of dicing a semiconductor wafer. Dicing can be performed, for example, from the circuit surface side of the semiconductor wafer according to a conventional method.
  • a method called half-cut in which a semiconductor wafer is cut in half a method in which a modified region is formed and divided by laser (stealth dicing), or the like can be employed.
  • Stealth dicing is preferably adopted for the adhesive layer of the dicing/die-bonding integrated film as described above because it is excellent in splitting property by cooling expansion.
  • the dicing device used in this step is not particularly limited, and conventionally known devices can be used.
  • the cooling expansion step is a step of expanding the base material layer under cooling conditions. As a result, a plurality of individualized semiconductor devices with adhesive pieces can be obtained.
  • the expansion conditions under the cooling conditions can be arbitrarily set, but for example, the cooling temperature is ⁇ 30 to 5° C., the cooling time is 30 seconds to 5 minutes, the thrust amount is 5 to 20 mm, and the thrust speed is 50 to 300 mm/second. can do.
  • Examples of semiconductor elements include ICs (integrated circuits).
  • Examples of supporting members include lead frames such as 42 alloy lead frames and copper lead frames; plastic films such as polyimide resin and epoxy resin; glass non-woven fabrics and other substrates impregnated with plastics such as polyimide resin and epoxy resin and cured. modified plastic film; ceramics such as alumina;
  • the pick-up step is a step of picking up semiconductor elements with adhesive pieces while separating the semiconductor elements with adhesive pieces from each other in order to separate the semiconductor elements with adhesive pieces adhesively fixed to the dicing/die bonding integrated film.
  • the method of expanding for separating the semiconductor elements with adhesive strips is not particularly limited, and various conventionally known methods can be employed. As a method for separating the semiconductor elements with adhesive strips, for example, a method of expanding the base material layer can be mentioned. The expansion may optionally be expansion under chilled conditions.
  • the pickup method is not particularly limited, and conventionally known various methods can be employed. Examples of such a method include a method of pushing up individual semiconductor elements with adhesive pieces from the dicing/die bonding integrated film side with a needle and picking up the pushed-up semiconductor elements with adhesive pieces with a pickup device.
  • the pick-up step can be performed after irradiating the adhesive layer with radiation.
  • the adhesive strength of the pressure-sensitive adhesive layer to the adhesive piece is lowered, and the semiconductor element with the adhesive piece is easily peeled off.
  • the first bonding step is a step of bonding the picked-up semiconductor element with the adhesive piece to a supporting member for mounting the semiconductor element via the adhesive piece.
  • a step (second bonding step) of bonding another semiconductor element with an adhesive piece to the surface of the semiconductor element bonded to the support member via the adhesive piece may be provided. Any bonding can be performed by crimping.
  • the crimping conditions are not particularly limited, and can be appropriately set according to need.
  • the crimping conditions may be, for example, a temperature condition of 80 to 160° C., a load condition of 5 to 15 N, and a time condition of 1 to 10 seconds.
  • the support member can illustrate the same support member as the above.
  • the method of manufacturing a semiconductor device may include a step of thermally curing the adhesive piece, if necessary.
  • the adhesive pieces bonding the semiconductor element and the support member, or the semiconductor element (first semiconductor element) and the semiconductor element (second semiconductor element) are thermally cured, thereby making them more firmly.
  • Adhesive fixation is possible.
  • pressure may be applied at the same time for curing.
  • the heating temperature in this step can be appropriately changed depending on the composition of the adhesive piece.
  • the heating temperature may be, for example, 60-200.degree. Note that the temperature or pressure may be changed stepwise.
  • a method of manufacturing a semiconductor device includes, if necessary, a step (wire bonding step) of electrically connecting tips of terminal portions (inner leads) of a support member and electrode pads on a semiconductor element with bonding wires. good too.
  • the bonding wire for example, gold wire, aluminum wire, copper wire, or the like is used.
  • the temperature for wire bonding (providing bonding wires) may be in the range of 80 to 250°C or 80 to 220°C.
  • the heating time can be from a few seconds to several minutes.
  • the bonding wire may be performed in a heated state within the above-mentioned temperature range by using both vibrational energy of ultrasonic waves and crimping energy of applied pressure.
  • the method of manufacturing a semiconductor device may optionally include a step of sealing the semiconductor element with a sealing material (sealing step). This step is performed to protect the semiconductor element or bonding wires mounted on the support member. This step can be performed by molding resin for sealing (sealing resin) with a mold.
  • a sealing resin for example, an epoxy resin may be used.
  • the support member and residue are embedded by heat and pressure during sealing, and peeling due to air bubbles at the adhesion interface can be prevented.
  • the method of manufacturing a semiconductor device may include, if necessary, a process (post-curing process) for completely curing the sealing resin that is insufficiently cured in the sealing process. Even if the adhesive piece is not heat-cured in the sealing process, the adhesive piece can be heat-cured together with the curing of the sealing resin in the present process to enable adhesive fixation.
  • the heating temperature in this step can be appropriately set according to the type of sealing resin, and may be, for example, within the range of 165 to 185° C., and the heating time may be approximately 0.5 to 8 hours.
  • the method of manufacturing a semiconductor device may include, if necessary, a step of heating the semiconductor element with the adhesive piece adhered to the support member using a reflow furnace (heating and melting step).
  • a resin-sealed semiconductor device may be surface-mounted on the supporting member.
  • surface mounting methods include reflow soldering in which solder is preliminarily supplied onto a printed wiring board and then heated and melted by hot air or the like for soldering.
  • Examples of the heating method include hot air reflow and infrared reflow.
  • the heating method may be a method of heating the whole or a method of locally heating. The heating temperature may be within the range of 240-280° C., for example.
  • A Component: Epoxy resin (A-1) N-500P-10 (trade name, manufactured by DIC Corporation, o-cresol novolac type epoxy resin, epoxy equivalent: 203 g/eq) (A-2) PG-100 (trade name, manufactured by Osaka Gas Chemicals Co., Ltd., epoxy resin having a fluorene skeleton, epoxy equivalent: 260 g/eq)
  • C Component: Elastomer (C-1) HTR-860P (trade name, manufactured by Nagase ChemteX Corporation, acrylic rubber, weight average molecular weight: 800,000, Tg: -12°C) (C-2) HTR-860P-30B: manufactured by Nagase ChemteX Corporation, acrylic rubber, weight average molecular weight: 300,000, Tg: -12°C)
  • Component (E) Coupling agent (E-1) A-189 (trade name, ⁇ -mercaptopropyltrimethoxysilane manufactured by Nippon Unicar Co., Ltd.) (E-2) Y-9669 (trade name, manufactured by Momentive Performance Materials Japan, 3-phenylaminopropyltrimethoxysilane)
  • Curing accelerator (F-1) 2PZ-CN (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-cyanoethyl-2-phenylimidazole)
  • ⁇ Preparation of film adhesive> The prepared adhesive varnish was filtered through a 500 mesh filter and vacuum degassed.
  • a release-treated polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m was prepared as a support film, and an adhesive varnish after vacuum defoaming was applied onto the PET film.
  • the applied adhesive varnish is dried by heating in two stages: 90° C. for 5 minutes, followed by 140° C. for 5 minutes. Films of Examples 1 to 19 and Comparative Examples 1 to 3 in B stage. An adhesive (thickness: 7 ⁇ m) was obtained. In the film adhesive, the thickness of the film adhesive was adjusted to 7 ⁇ m by adjusting the coating amount of the adhesive varnish.
  • Adhesive pieces (width 5 mm ⁇ length 100 mm) were cut out from the film adhesives of Examples 1 to 19 and Comparative Examples 1 to 3, respectively. The adhesive pieces were fixed to a pair of jigs (cardboard), and portions of the adhesive pieces protruding from the jigs were removed. As a result, a sample (width 5 mm ⁇ length 23 mm) to be evaluated was obtained. A cleaving test was performed in a constant temperature bath (TLF-R3-FW-PL-S manufactured by ITEC Co., Ltd.) set at -15°C.
  • TEZ-R3-FW-PL-S manufactured by ITEC Co., Ltd.
  • breaking test was performed under the conditions of compression mode, speed of 10 mm/min, and pushing distance of 5 mm. Breaking work W, breaking strength P, and breaking elongation L were obtained. Further, the breaking modulus m and the breaking resistance R were calculated from the above formulas (1) and (2). Note that the breaking coefficient m and breaking resistance R are the average values obtained by carrying out breaking tests eight times or more for each example and each comparative example. As the value of the breaking modulus m becomes smaller, the splitting property by cooling expansion tends to be excellent.
  • the cutting was performed by a step cut method using two blades, and dicing blades ZH05-SD2000-N1-70-FF and ZH05-SD4000-N1-70-EE (both manufactured by DISCO Corporation) were used.
  • the cutting conditions were blade rotation speed: 4000 rpm, cutting speed: 50 mm/sec, and chip size: 3 mm ⁇ 3 mm.
  • the first stage of cutting was performed so that the semiconductor wafer remained about 200 ⁇ m, and the second stage of cutting was performed so that the dicing tape was cut to about 20 ⁇ m.
  • the adhesive layer made of the ultraviolet curable adhesive was irradiated with ultraviolet rays to cure the adhesive layer, and the semiconductor element with the adhesive piece was picked up.
  • the adhesive piece of the semiconductor element with the adhesive piece was pressure-bonded to an AUS410 substrate (organic substrate with solder resist) under conditions of a temperature of 120° C., a pressure of 0.1 MPa, and a time of 1.0 second to prepare a sample for evaluation. .
  • the die shear strength between the AUS410 substrate and the adhesive piece was measured at room temperature (25° C.).
  • a case where the die shear strength is 6 MPa or more is evaluated as being particularly excellent in thin film properties, "B" when the die shear strength is 4 MPa or more and less than 6 MPa, and "C” when the die shear strength is less than 4 MPa.
  • Tables 1, 2 and 3 also show values of die shear strength.
  • reflow resistance was produced by the following method. First, using a semiconductor element with an adhesive piece, a laminate laminated in four stages as shown in FIG. A package for evaluation was obtained by doing. The sealing conditions of the sealing material were 175° C./6.7 MPa/90 seconds, and the curing conditions were 175° C. and 5 hours. Twenty evaluation packages were prepared and exposed to the environment defined by JEDEC (level 3, 30° C., 60 RH %, 192 hours) to absorb moisture. Subsequently, the package for evaluation after moisture absorption was passed three times through an IR reflow oven (260° C., maximum temperature 265° C.).
  • the film adhesives of Examples 1 to 19 were excellent in terms of cooling splitting properties and thin film properties.
  • the film adhesives of Comparative Examples 1 to 3 were insufficient in at least one of thin film properties and cooling splitting properties. From these, it was confirmed that the film-like adhesive of the present disclosure has excellent splittability by cooling expansion and has sufficient die shear strength when thinned.

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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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Abstract

Disclosed is a film adhesive. The film adhesive contains a thermosetting resin, a curing agent, an elastomer, and an inorganic filler with an average particle diameter of 400 nm or less. The content of the inorganic filler is 18 to 40 % by mass based on the total amount of the film adhesive. The total content of the thermosetting resin and the curing agent is 25 % by mass or less based on the total amount of the film adhesive.

Description

フィルム状接着剤、ダイシング・ダイボンディング一体型フィルム、並びに半導体装置及びその製造方法Film adhesive, dicing/die bonding integrated film, semiconductor device and manufacturing method thereof
　本開示は、フィルム状接着剤、ダイシング・ダイボンディング一体型フィルム、並びに半導体装置及びその製造方法に関する。 The present disclosure relates to a film adhesive, a dicing/die bonding integrated film, a semiconductor device, and a method for manufacturing the same.
　近年、半導体素子（半導体チップ）を多段に積層した積層ＭＣＰ（Ｍｕｌｔｉ　Ｃｈｉｐ　Ｐａｃｋａｇｅ）が普及しており、携帯電話、携帯オーディオ機器用のメモリ半導体パッケージ等として搭載されている。また、携帯電話等の多機能化に伴い、半導体パッケージの高速化、高密度化、高集積化等も推し進められている。それに伴い、半導体ウェハの薄膜化も進行しており、加工時のウェハ割れ等の不具合が発生し易くなることで歩留まりの低下が問題になる場合がある。そのため、半導体ウェハの厚さが薄くなる（例えば、５０μｍ以下）につれて、従来の物理的な研削方法から新しい加工方法への移行が進んでいる。 In recent years, laminated MCPs (Multi Chip Packages), in which semiconductor elements (semiconductor chips) are stacked in multiple layers, have become popular, and are mounted as memory semiconductor packages for mobile phones and portable audio equipment. In addition, along with the multi-functionalization of mobile phones and the like, speeding up, high-density, high-integration, etc. of semiconductor packages are being promoted. Along with this, semiconductor wafers are becoming thinner, and problems such as wafer cracking during processing are likely to occur, which may cause a problem of yield reduction. Therefore, as the thickness of semiconductor wafers becomes thinner (for example, 50 μm or less), there is a shift from conventional physical grinding methods to new processing methods.
　新しい加工方法の１つとして、切断予定ライン上の半導体ウェハ内部にレーザー光を照射して改質領域を形成し、その後、外周部をエキスパンドによって半導体ウェハを切断する方法が近年提案されている（例えば、特許文献１、２）。この方法は、ステルスダイシングと呼ばれる。ステルスダイシング等の新しい加工方法の開発に伴い、これに適合可能な機能性フィルムの開発が進められている。このような機能性フィルムとして、例えば、ダイシングテープとダイボンディングフィルムとの性能を併せ持つダイシング・ダイボンディング一体型フィルムが報告されている（例えば、特許文献３、４）。 As one of the new processing methods, a method of irradiating laser light inside a semiconductor wafer on a line to cut to form a modified region and then cutting the semiconductor wafer by expanding the outer peripheral portion has been proposed in recent years ( For example, Patent Documents 1 and 2). This method is called stealth dicing. Accompanying the development of new processing methods such as stealth dicing, the development of functional films compatible with these methods is underway. As such a functional film, for example, a dicing/die-bonding integrated film having both the performance of a dicing tape and a die-bonding film has been reported (for example, Patent Documents 3 and 4).
特開２００２－１９２３７０号公報Japanese Patent Application Laid-Open No. 2002-192370 特開２００３－３３８４６７号公報JP-A-2003-338467 特開２０１５－２１１０８０号公報JP 2015-211080 A 特開２０１６－１１５７７５号公報JP 2016-115775 A
　ところで、半導体装置の製造プロセスにおいて、ステルスダイシングによって改質領域を形成して分断する場合、冷却条件下におけるエキスパンド（以下、「冷却エキスパンド」という場合がある。）を実施することがある。しかし、従来のダイシング・ダイボンディング一体型フィルムを冷却エキスパンドに適用すると、フィルム状接着剤（ダイボンディングフィルム）からなる接着剤層において未分断が発生する場合がある。接着剤層の未分断が発生すると、歩留まりの低下及び未分断品を選別するための生産時間効率の低下が問題になる。 By the way, in the manufacturing process of a semiconductor device, when a modified region is formed and divided by stealth dicing, expansion under cooling conditions (hereinafter sometimes referred to as "cooling expansion") may be performed. However, when a conventional dicing/die-bonding integrated film is applied to cooling expansion, an adhesive layer made of a film-like adhesive (die-bonding film) may not be cut. When the adhesive layer is not cut, problems arise such as a decrease in yield and a decrease in production time efficiency for sorting uncut products.
　また、積層ＭＣＰにおいては、半導体素子が多段に積層されることから、使用されるフィルム状接着剤（ダイボンディング一体型フィルムのダイボンディングフィルム）には、薄膜化（例えば、厚さ２０μｍ以下）が求められている。しかしながら、従来のフィルム状接着剤を薄膜化すると、ダイシェア強度が確保できない場合があり、未だ改善の余地がある。 In addition, in the laminated MCP, since the semiconductor elements are laminated in multiple stages, the film adhesive (die bonding film of the die bonding integrated film) used must be thin (for example, thickness 20 μm or less). It has been demanded. However, if the thickness of the conventional film adhesive is reduced, the die shear strength may not be ensured, and there is still room for improvement.
　そこで、本開示は、冷却エキスパンドによる分断性に優れるとともに、薄膜化したときに充分なダイシェア強度を有するフィルム状接着剤を提供することを主な目的とする。 Therefore, the main object of the present disclosure is to provide a film-like adhesive that is excellent in splittability by cooling expansion and has sufficient die shear strength when thinned.
　本開示の一側面は、フィルム状接着剤に関する。当該フィルム状接着剤は、熱硬化性樹脂と、硬化剤と、エラストマーと、平均粒径が４００ｎｍ以下である無機フィラーとを含有する。無機フィラーの含有量は、フィルム状接着剤の全量を基準として、１８～４０質量％である。無機フィラーの含有量が、フィルム状接着剤の全量を基準として、１８質量％以上であると、フィルム状接着剤の冷却エキスパンドによる分断性に優れる傾向にある。無機フィラーの含有量が、フィルム状接着剤の全量を基準として、４０質量％以下であると、フィルム状接着剤を薄膜化したときに充分なダイシェア強度を有する傾向にある。熱硬化性樹脂及び硬化剤の合計の含有量は、フィルム状接着剤の全量を基準として、２５質量％以下である。熱硬化性樹脂及び硬化剤の合計の含有量が、フィルム状接着剤の全量を基準として、２５質量％以下であると、エラストマーの量が充分となることから、薄膜塗工性に優れる傾向にある。 One aspect of the present disclosure relates to film adhesives. The film adhesive contains a thermosetting resin, a curing agent, an elastomer, and an inorganic filler having an average particle size of 400 nm or less. The content of the inorganic filler is 18-40% by mass based on the total amount of the film adhesive. When the content of the inorganic filler is 18% by mass or more based on the total amount of the film adhesive, the splitting property of the film adhesive by cooling expansion tends to be excellent. When the content of the inorganic filler is 40% by mass or less based on the total amount of the film adhesive, the film adhesive tends to have sufficient die shear strength when thinned. The total content of the thermosetting resin and curing agent is 25% by mass or less based on the total amount of the film adhesive. When the total content of the thermosetting resin and the curing agent is 25% by mass or less based on the total amount of the film-like adhesive, the amount of the elastomer is sufficient, so that thin film coating tends to be excellent. be.
　エラストマーの含有量は、フィルム状接着剤の全量を基準として、４０質量％以上であってよい。 The content of the elastomer may be 40% by mass or more based on the total amount of the film adhesive.
　無機フィラーの含有量は、熱硬化性樹脂、硬化剤、及びエラストマーの全量１００質量部に対して、２２質量部以上であってよい。 The content of the inorganic filler may be 22 parts by mass or more with respect to 100 parts by mass of the total amount of the thermosetting resin, curing agent, and elastomer.
　エラストマーの含有量は、熱硬化性樹脂及び硬化剤の全量１００質量部に対して、２００質量部以上であってよい。 The content of the elastomer may be 200 parts by mass or more with respect to 100 parts by mass of the total amount of the thermosetting resin and curing agent.
　フィルム状接着剤の厚さは、２０μｍ以下であってよい。 The thickness of the film adhesive may be 20 μm or less.
　フィルム状接着剤は、複数の半導体素子を積層してなる半導体装置の製造プロセスに用いられるものであってよい。この場合、半導体装置は、半導体素子（半導体チップ）を多段に積層した積層ＭＣＰ（Ｍｕｌｔｉ　Ｃｈｉｐ　Ｐａｃｋａｇｅ）であってよく、三次元ＮＡＮＤ型メモリであってもよい。 The film-like adhesive may be used in the manufacturing process of a semiconductor device in which multiple semiconductor elements are laminated. In this case, the semiconductor device may be a stacked MCP (Multi Chip Package) in which semiconductor elements (semiconductor chips) are stacked in multiple stages, or may be a three-dimensional NAND memory.
　本開示の他の一側面は、ダイシング・ダイボンディング一体型フィルムに関する。当該ダイシング・ダイボンディング一体型フィルムは、基材層と、粘着剤層と、上記のフィルム状接着剤からなる接着剤層とをこの順に備える。 Another aspect of the present disclosure relates to a dicing/die bonding integrated film. The dicing/die-bonding integrated film includes a substrate layer, an adhesive layer, and an adhesive layer made of the film-like adhesive in this order.
　本開示の他の一側面は、半導体装置に関する。当該半導体装置は、半導体素子と、半導体素子を搭載する支持部材と、半導体素子及び支持部材の間に設けられ、半導体素子と支持部材とを接着する接着部材とを備える。接着部材は、上記のフィルム状接着剤の硬化物である。半導体装置は、半導体素子の表面上に積層された他の半導体素子をさらに備えていてもよい。 Another aspect of the present disclosure relates to a semiconductor device. The semiconductor device includes a semiconductor element, a support member on which the semiconductor element is mounted, and an adhesive member provided between the semiconductor element and the support member to bond the semiconductor element and the support member. The adhesive member is a cured product of the film adhesive described above. The semiconductor device may further include another semiconductor element laminated on the surface of the semiconductor element.
　本開示の他の一側面は、半導体装置の製造方法に関する。当該半導体装置の製造方法の一態様は、半導体素子と支持部材との間、又は、第１の半導体素子と第２の半導体素子との間に上記のフィルム状接着剤を介在させ、半導体素子及び支持部材、又は、第１の半導体素子及び第２の半導体素子を接着する工程を備える。 Another aspect of the present disclosure relates to a method of manufacturing a semiconductor device. In one aspect of the method for manufacturing the semiconductor device, the film-like adhesive is interposed between the semiconductor element and the supporting member or between the first semiconductor element and the second semiconductor element, and the semiconductor element and the A step of adhering the support member or the first semiconductor element and the second semiconductor element is provided.
　当該半導体装置の製造方法の他の態様は、上記のダイシング・ダイボンディング一体型フィルムの接着剤層に半導体ウェハを貼り付ける工程と、接着剤層を貼り付けた半導体ウェハをダイシングする工程と、基材層を冷却条件下エキスパンドすることによって、複数の個片化された接着剤片付き半導体素子を作製する工程と、接着剤片付き半導体素子を粘着剤層からピックアップする工程と、接着剤片付き半導体素子を支持部材に接着剤片を介して接着する工程とを備える。半導体装置の製造方法は、他の接着剤片付き半導体素子を、支持部材に接着された半導体素子の表面に接着剤片を介して接着する工程をさらに備えていてもよい。 Another aspect of the method for manufacturing the semiconductor device includes the steps of: attaching a semiconductor wafer to the adhesive layer of the dicing/die bonding integrated film; dicing the semiconductor wafer to which the adhesive layer is attached; forming a plurality of individualized semiconductor elements with adhesive pieces by expanding the material layer under cooling conditions; picking up the semiconductor elements with adhesive pieces from the adhesive layer; and removing the semiconductor elements with adhesive pieces. and gluing to the support member via adhesive strips. The method of manufacturing a semiconductor device may further comprise a step of adhering, via an adhesive piece, another semiconductor element with an adhesive piece to the surface of the semiconductor element adhered to the support member.
　本開示は、［１］～［７］に記載のフィルム状接着剤、［８］に記載のダイシング・ダイボンディング一体型フィルム、［９］、［１０］に記載の半導体装置、及び［１１］～［１３］に記載の半導体装置及の製造方法を提供する。
［１］熱硬化性樹脂と、硬化剤と、エラストマーと、平均粒径が４００ｎｍ以下である無機フィラーとを含有し、前記無機フィラーの含有量が、フィルム状接着剤の全量を基準として、１８～４０質量％であり、前記熱硬化性樹脂及び前記硬化剤の合計の含有量が、フィルム状接着剤の全量を基準として、２５質量％以下である、フィルム状接着剤。
［２］前記エラストマーの含有量が、フィルム状接着剤の全量を基準として、４０質量％以上である、［１］に記載のフィルム状接着剤。
［３］前記無機フィラーの含有量が、前記熱硬化性樹脂、前記硬化剤、及び前記エラストマーの全量１００質量部に対して、２２質量部以上である、［１］又は［２］に記載のフィルム状接着剤。
［４］前記エラストマーの含有量が、前記熱硬化性樹脂及び前記硬化剤の全量１００質量部に対して、２００質量部以上である、［１］～［３］のいずれかに記載のフィルム状接着剤。
［５］厚さが２０μｍ以下である、［１］～［４］のいずれかに記載のフィルム状接着剤。
［６］複数の半導体素子を積層してなる半導体装置の製造プロセスに用いられる、［１］～［５］のいずれかに記載のフィルム状接着剤。
［７］前記半導体装置が三次元ＮＡＮＤ型メモリである、［６］に記載のフィルム状接着剤。
［８］基材層と、粘着剤層と、［１］～［５］のいずれかに記載のフィルム状接着剤からなる接着剤層とをこの順に備える、ダイシング・ダイボンディング一体型フィルム。
［９］半導体素子と、前記半導体素子を搭載する支持部材と、前記半導体素子及び前記支持部材の間に設けられ、前記半導体素子と前記支持部材とを接着する接着部材とを備え、前記接着部材が、［１］～［５］のいずれかに記載のフィルム状接着剤の硬化物である、半導体装置。
［１０］前記半導体素子の表面上に積層された他の半導体素子をさらに備える、［９］に記載の半導体装置。
［１１］半導体素子と支持部材との間、又は、第１の半導体素子と第２の半導体素子との間に［１］～［５］のいずれかに記載のフィルム状接着剤を介在させ、前記半導体素子及び前記支持部材、又は、前記第１の半導体素子及び前記第２の半導体素子を接着させる工程を備える、半導体装置の製造方法。
［１２］［８］に記載のダイシング・ダイボンディング一体型フィルムの前記接着剤層を半導体ウェハに貼り付ける工程と、前記接着剤層を貼り付けた前記半導体ウェハをダイシングする工程と、前記基材層を冷却条件下エキスパンドすることによって、複数の個片化された接着剤片付き半導体素子を作製する工程と、前記接着剤片付き半導体素子を前記粘着剤層からピックアップする工程と、ピックアップされた前記接着剤片付き半導体素子を支持部材に接着剤片を介して接着する工程とを備える、半導体装置の製造方法。
［１３］他の前記接着剤片付き半導体素子を、前記支持部材に接着された前記半導体素子の表面に接着剤片を介して接着する工程をさらに備える、［１２］に記載の半導体装置の製造方法。 The present disclosure includes the film adhesive according to [1] to [7], the dicing/die bonding integrated film according to [8], the semiconductor device according to [9] and [10], and [11]. A semiconductor device and a manufacturing method thereof according to to [13] are provided.
[1] Contains a thermosetting resin, a curing agent, an elastomer, and an inorganic filler having an average particle size of 400 nm or less, and the content of the inorganic filler is 18 based on the total amount of the film adhesive. 40% by mass, and the total content of the thermosetting resin and the curing agent is 25% by mass or less based on the total amount of the film adhesive.
[2] The film adhesive according to [1], wherein the content of the elastomer is 40% by mass or more based on the total amount of the film adhesive.
[3] The content of the inorganic filler according to [1] or [2], wherein the content of the inorganic filler is 22 parts by mass or more with respect to the total amount of 100 parts by mass of the thermosetting resin, the curing agent, and the elastomer. Film adhesive.
[4] The film-like material according to any one of [1] to [3], wherein the content of the elastomer is 200 parts by mass or more with respect to 100 parts by mass of the total amount of the thermosetting resin and the curing agent. glue.
[5] The film adhesive according to any one of [1] to [4], which has a thickness of 20 μm or less.
[6] The film adhesive according to any one of [1] to [5], which is used in the manufacturing process of a semiconductor device formed by laminating a plurality of semiconductor elements.
[7] The film adhesive according to [6], wherein the semiconductor device is a three-dimensional NAND memory.
[8] A dicing/die bonding integrated film comprising a substrate layer, an adhesive layer, and an adhesive layer made of the film-like adhesive according to any one of [1] to [5] in this order.
[9] A semiconductor element, a support member for mounting the semiconductor element, and an adhesive member provided between the semiconductor element and the support member for bonding the semiconductor element and the support member, wherein the adhesive member is a cured product of the film adhesive according to any one of [1] to [5].
[10] The semiconductor device according to [9], further comprising another semiconductor element laminated on the surface of the semiconductor element.
[11] Interposing the film-like adhesive according to any one of [1] to [5] between the semiconductor element and the supporting member or between the first semiconductor element and the second semiconductor element, A method of manufacturing a semiconductor device, comprising a step of bonding the semiconductor element and the supporting member, or the first semiconductor element and the second semiconductor element.
[12] A step of attaching the adhesive layer of the dicing and die bonding integrated film according to [8] to a semiconductor wafer, a step of dicing the semiconductor wafer with the adhesive layer attached, and the base material forming a plurality of singulated semiconductor elements with adhesive strips by expanding the layer under cooling conditions; picking up said semiconductor elements with adhesive strips from said adhesive layer; A method of manufacturing a semiconductor device, comprising a step of adhering a semiconductor element with an adhesive piece to a support member via an adhesive piece.
[13] The method of manufacturing a semiconductor device according to [12], further comprising the step of adhering, via an adhesive piece, another semiconductor element with an adhesive piece to the surface of the semiconductor element adhered to the support member. .
　本開示によれば、冷却エキスパンドによる分断性に優れるとともに、薄膜化したときに充分なダイシェア強度を有するフィルム状接着剤が提供される。また、本開示によれば、このようなフィルム状接着剤を用いたダイシング・ダイボンディング一体型フィルム、並びに半導体装置及びその製造方法が提供される。さらに、本開示によれば、このようなダイシング・ダイボンディング一体型フィルムを用いた半導体装置の製造方法が提供される。 According to the present disclosure, there is provided a film-like adhesive that is excellent in splittability by cooling expansion and has sufficient die shear strength when thinned. Further, according to the present disclosure, a dicing/die-bonding integrated film using such a film-like adhesive, a semiconductor device, and a method for manufacturing the same are provided. Further, according to the present disclosure, there is provided a method of manufacturing a semiconductor device using such a dicing/die bonding integrated film.
図１は、フィルム状接着剤の一実施形態を示す模式断面図である。FIG. 1 is a schematic cross-sectional view showing one embodiment of a film adhesive. 図２は、割断試験における冶具に固定された状態の試料を模式的に示す斜視図である。FIG. 2 is a perspective view schematically showing a sample fixed to a jig in a breaking test. 図３は、割断試験における押し込み冶具によって試料に荷重を加えている状態を模式的に示す断面図である。FIG. 3 is a cross-sectional view schematically showing a state in which a load is applied to a sample by a pressing jig in a breaking test. 図４は、割断試験の結果の一例を模式的に示すグラフである。FIG. 4 is a graph schematically showing an example of the results of the breaking test. 図５は、ダイシング・ダイボンディング一体型フィルムの一実施形態を示す模式断面図である。FIG. 5 is a schematic cross-sectional view showing an embodiment of a dicing/die bonding integrated film. 図６は、半導体装置の一実施形態を示す模式断面図である。FIG. 6 is a schematic cross-sectional view showing one embodiment of a semiconductor device. 図７は、半導体装置の他の実施形態を示す模式断面図である。FIG. 7 is a schematic cross-sectional view showing another embodiment of the semiconductor device. 図８は、半導体装置の他の実施形態を示す模式断面図である。FIG. 8 is a schematic cross-sectional view showing another embodiment of the semiconductor device.
　以下、図面を適宜参照しながら、本開示の実施形態について説明する。ただし、本開示は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（ステップ等も含む）は、特に明示した場合を除き、必須ではない。各図における構成要素の大きさは概念的なものであり、構成要素間の大きさの相対的な関係は各図に示されたものに限定されない。 Hereinafter, embodiments of the present disclosure will be described with reference to the drawings as appropriate. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including steps and the like) are not essential unless otherwise specified. The sizes of the components in each figure are conceptual, and the relative sizes of the components are not limited to those shown in each figure.
　本開示における数値及びその範囲についても同様であり、本開示を制限するものではない。本明細書において「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。 The same applies to the numerical values and their ranges in this disclosure, and they do not limit this disclosure. In this specification, the numerical range indicated using "to" indicates the range including the numerical values before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this specification, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. good. Moreover, in the numerical ranges described in this specification, the upper and lower limits of the numerical ranges may be replaced with the values shown in the examples.
　本明細書において、（メタ）アクリレートは、アクリレート又はそれに対応するメタクリレートを意味する。（メタ）アクリロイル基、（メタ）アクリル共重合体等の他の類似表現についても同様である。 In this specification, (meth)acrylate means acrylate or its corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl group and (meth)acrylic copolymer.
　本明細書に例示する各成分及び材料は、特に断らない限り、１種を単独で使用してもよく、２種以上を併用して使用してもよい。 Each component and material exemplified in this specification may be used singly or in combination of two or more unless otherwise specified.
［フィルム状接着剤］
　フィルム状接着剤は、熱硬化性樹脂（以下、「（Ａ）成分」という場合がある。）と、硬化剤（以下、「（Ｂ）成分」という場合がある。）と、エラストマー（以下、「（Ｃ）成分」という場合がある。）と、平均粒径が４００ｎｍ以下である無機フィラー（以下、「（Ｄ）成分」という場合がある。）とを含有する。フィルム状接着剤は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分に加えて、カップリング剤（以下、「（Ｅ）成分」という場合がある。）、硬化促進剤（以下、「（Ｆ）成分」という場合がある。）、その他の成分等をさらに含有していてもよい。 [Film adhesive]
The film adhesive comprises a thermosetting resin (hereinafter sometimes referred to as "(A) component"), a curing agent (hereinafter sometimes referred to as "(B) component"), and an elastomer (hereinafter sometimes referred to as "(B) component"). and an inorganic filler having an average particle diameter of 400 nm or less (hereinafter sometimes referred to as "(D) component"). In addition to the (A) component, (B) component, (C) component, and (D) component, the film adhesive contains a coupling agent (hereinafter sometimes referred to as "(E) component"), curing An accelerator (hereinafter sometimes referred to as "component (F)") and other components may be further contained.
　フィルム状接着剤は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分、並びに必要に応じて添加される他の成分（（Ｅ）成分、（Ｆ）成分、その他の成分等）を含有する接着剤組成物を、フィルム状に成形することによって得ることができる。フィルム状接着剤（接着剤組成物）は、半硬化（Ｂステージ）状態を経て、硬化処理後に硬化（Ｃステージ）状態となり得るものであってよい。 The film-like adhesive comprises (A) component, (B) component, (C) component, and (D) component, and other components added as necessary ((E) component, (F) component, other component, etc.) can be obtained by forming the adhesive composition into a film. The film-like adhesive (adhesive composition) may be in a semi-cured (B stage) state and then in a cured (C stage) state after a curing treatment.
（Ａ）成分：熱硬化性樹脂
　（Ａ）成分は、接着性の観点から、エポキシ樹脂を含んでいてもよく、１種又は２種以上のエポキシ樹脂からなるものであってもよい。 Component (A): Thermosetting resin Component (A) may contain an epoxy resin, or may consist of one or more epoxy resins, from the viewpoint of adhesiveness.
　エポキシ樹脂は、分子内にエポキシ基を有するものであれば、特に制限なく用いることができる。エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；ビスフェノールＳ型エポキシ樹脂；フェノールノボラック型エポキシ樹脂；クレゾールノボラック型エポキシ樹脂；ビスフェノールＡノボラック型エポキシ樹脂；ビスフェノールＦノボラック型エポキシ樹脂；スチルベン型エポキシ樹脂；トリアジン骨格含有エポキシ樹脂；フルオレン骨格含有エポキシ樹脂；トリフェノールメタン型エポキシ樹脂；ビフェニル型エポキシ樹脂；キシリレン型エポキシ樹脂；ビフェニルアラルキル型エポキシ樹脂；ナフタレン型エポキシ樹脂；多官能フェノール類、アントラセン等の多環芳香族類のジグリシジルエーテル化合物などが挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。これらの中でも、エポキシ樹脂は、フィルムのタック性、柔軟性等の観点から、クレゾールノボラック型エポキシ樹脂又はフルオレン骨格含有エポキシ樹脂を含んでいてもよい。 Epoxy resins can be used without any particular restrictions as long as they have an epoxy group in the molecule. Examples of epoxy resins include bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; phenol novolak type epoxy resin; cresol novolak type epoxy resin; bisphenol A novolac type epoxy resin; ; stilbene type epoxy resin; triazine skeleton-containing epoxy resin; fluorene skeleton-containing epoxy resin; triphenolmethane type epoxy resin; biphenyl type epoxy resin; xylylene type epoxy resin; and polycyclic aromatic diglycidyl ether compounds such as anthracene. You may use these individually by 1 type or in combination of 2 or more types. Among these, the epoxy resin may contain a cresol novolak type epoxy resin or a fluorene skeleton-containing epoxy resin from the viewpoint of film tackiness, flexibility, and the like.
　エポキシ樹脂のエポキシ当量は、特に制限されないが、９０～３００ｇ／ｅｑ、１１０～２９０ｇ／ｅｑ、又は１３０～２８０ｇ／ｅｑであってよい。エポキシ樹脂のエポキシ当量がこのような範囲にあると、より良好な反応性及び流動性が得られる傾向にある。 The epoxy equivalent of the epoxy resin is not particularly limited, but may be 90-300 g/eq, 110-290 g/eq, or 130-280 g/eq. When the epoxy equivalent of the epoxy resin is in such a range, better reactivity and fluidity tend to be obtained.
　（Ａ）成分の含有量は、フィルム状接着剤の全量を基準として、１質量％以上、３質量％以上、又は５質量％以上であってよく、３０質量％以下、２０質量％以下、又は１５質量％以下であってよい。（Ａ）成分の含有量がこのような範囲にあると、硬化後の弾性率により優れる傾向にある。（Ａ）成分の含有量がこのような範囲にあると、硬化前の柔軟性により優れる傾向にある。 The content of component (A) may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and may be 30% by mass or less, 20% by mass or less, or It may be 15% by mass or less. When the content of component (A) is in this range, the elastic modulus after curing tends to be more excellent. When the content of component (A) is in this range, the flexibility before curing tends to be more excellent.
（Ｂ）成分：硬化剤
　（Ａ）成分の硬化剤として一般的に使用されているものを用いることができる。（Ａ）成分がエポキシ樹脂を含む（１種又は２種以上のエポキシ樹脂からなる）場合、（Ｂ）成分としては、例えば、フェノール樹脂、エステル化合物、芳香族アミン、脂肪族アミン、酸無水物等が挙げられる。これらの中でも、反応性及び経時安定性の観点から、（Ｂ）成分はフェノール樹脂を含んでいてもよく、１種又は２種以上のフェノール樹脂からなるものであってもよい。 (B) Component: Curing Agent Any commonly used curing agent for component (A) can be used. When component (A) contains an epoxy resin (consisting of one or more epoxy resins), component (B) includes, for example, phenolic resins, ester compounds, aromatic amines, aliphatic amines, acid anhydrides. etc. Among these, from the viewpoint of reactivity and stability over time, the component (B) may contain a phenolic resin, or may consist of one or more phenolic resins.
　フェノール樹脂は、フェノール、クレゾール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ、フェニルフェノール、アミノフェノール等のフェノール類及び／又はα－ナフトール、β－ナフトール、ジヒドロキシナフタレン等のナフトール類と、ホルムアルデヒド等のアルデヒド類との重縮合生成物であり得る。重縮合は、通常、酸、塩基等の触媒存在下で行われる。酸触媒を用いた場合に得られるフェノール樹脂は、特にノボラック型フェノール樹脂と呼ばれる。ノボラック型フェノール樹脂としては、例えば、フェノール／ホルムアルデヒドノボラック樹脂、クレゾール／ホルムアルデヒドノボラック樹脂、キシレノール／ホルムアルデヒドノボラック樹脂、レゾルシノール／ホルムアルデヒドノボラック樹脂、フェノール－ナフトール／ホルムアルデヒドノボラック樹脂等が挙げられる。また、フェノール樹脂としては、例えば、アリル化ビスフェノールＡ、アリル化ビスフェノールＦ、アリル化ナフタレンジオール、フェノールノボラック、フェノール等のフェノール類及び／又はナフトール類と、ジメトキシパラキシレン又はビス（メトキシメチル）ビフェニルから合成されるフェノールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニルアラルキル型フェノール樹脂、フェニルアラルキル型フェノール樹脂なども挙げられる。 Phenolic resins include phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and/or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehydes such as formaldehyde. It can be a polycondensation product with Polycondensation is usually carried out in the presence of a catalyst such as an acid or a base. A phenolic resin obtained when an acid catalyst is used is particularly called a novolak-type phenolic resin. Examples of novolac-type phenolic resins include phenol/formaldehyde novolac resin, cresol/formaldehyde novolac resin, xylenol/formaldehyde novolac resin, resorcinol/formaldehyde novolac resin, phenol-naphthol/formaldehyde novolac resin, and the like. Phenol resins include, for example, phenols and/or naphthols such as allylated bisphenol A, allylated bisphenol F, allylated naphthalenediol, phenol novolac, phenol, and dimethoxyparaxylene or bis(methoxymethyl)biphenyl. Synthesized phenol aralkyl resins, naphthol aralkyl resins, biphenyl aralkyl type phenol resins, phenyl aralkyl type phenol resins and the like are also included.
　フェノール樹脂の水酸基当量は、８０～３００ｇ／ｅｑ、９０～２８０ｇ／ｅｑ、又は１００～２５０ｇ／ｅｑであってよい。フェノール樹脂の水酸基当量が８０ｇ／ｅｑ以上であると、貯蔵弾性率がより向上する傾向にあり、３００ｇ／ｅｑ以下であると、発泡、アウトガス等の発生による不具合を防ぐことが可能となる。 The hydroxyl equivalent of the phenolic resin may be 80-300 g/eq, 90-280 g/eq, or 100-250 g/eq. When the hydroxyl equivalent of the phenolic resin is 80 g/eq or more, the storage elastic modulus tends to be further improved, and when it is 300 g/eq or less, it becomes possible to prevent problems due to the generation of foaming, outgassing, and the like.
　フェノール樹脂の軟化点は、５０～１４０℃、５５～１３０℃、又は６０～１２０℃であってよい。なお、軟化点とは、ＪＩＳ　Ｋ７２３４に準拠し、環球法によって測定される値を意味する。 The softening point of the phenolic resin may be 50-140°C, 55-130°C, or 60-120°C. The softening point means a value measured by the ring and ball method according to JIS K7234.
　（Ｂ）成分の含有量は、フィルム状接着剤の全量を基準として、１質量％以上、２質量％以上、又は３質量％以上であってよく、２０質量％以下、１５質量％以下、又は１０質量％以下であってよい。 The content of component (B) may be 1% by mass or more, 2% by mass or more, or 3% by mass or more, and may be 20% by mass or less, 15% by mass or less, or It may be 10% by mass or less.
　（Ａ）成分がエポキシ樹脂であり、（Ｂ）成分がフェノール樹脂である場合、エポキシ樹脂のエポキシ当量とフェノール樹脂の水酸基当量との比（エポキシ樹脂のエポキシ当量／フェノール樹脂の水酸基当量）は、硬化性の観点から、０．３０／０．７０～０．７０／０．３０、０．３５／０．６５～０．６５／０．３５、０．４０／０．６０～０．６０／０．４０、又は０．４５／０．５５～０．５５／０．４５であってよい。当該当量比が０．３０／０．７０以上である（エポキシ樹脂のエポキシ当量が０．３０以上である）と、より充分な硬化性が得られる傾向にある。当該当量比が０．７０／０．３０以下である（エポキシ樹脂のエポキシ当量が０．７０以下である）と、粘度が高くなり過ぎることを防ぐことができ、より充分な流動性を得ることができる。 When the component (A) is an epoxy resin and the component (B) is a phenolic resin, the ratio of the epoxy equivalent of the epoxy resin to the hydroxyl equivalent of the phenolic resin (epoxy equivalent of epoxy resin/hydroxyl equivalent of phenolic resin) is From the viewpoint of curability, 0.30/0.70 to 0.70/0.30, 0.35/0.65 to 0.65/0.35, 0.40/0.60 to 0.60/ 0.40, or 0.45/0.55 to 0.55/0.45. When the corresponding weight ratio is 0.30/0.70 or more (the epoxy equivalent of the epoxy resin is 0.30 or more), more sufficient curability tends to be obtained. When the corresponding weight ratio is 0.70/0.30 or less (the epoxy equivalent of the epoxy resin is 0.70 or less), it is possible to prevent the viscosity from becoming too high and obtain more sufficient fluidity. can be done.
　（Ａ）成分及び（Ｂ）成分の合計の含有量は、フィルム状接着剤の全量を基準として、２５質量％以下である。（Ａ）成分及び（Ｂ）成分の合計の含有量がこのような範囲にあると、（Ｃ）成分の量が充分となることから、薄膜塗工性に優れる傾向にある。（Ａ）成分及び（Ｂ）成分の合計の含有量は、取扱い性の観点から、フィルム状接着剤の全量を基準として、２２質量％以下、２０質量％以下、又は１８質量％以下であってもよい。（Ａ）成分及び（Ｂ）成分の合計の含有量は、フィルム状接着剤の全量を基準として、１質量％以上、５質量％以上、１０質量％以上、又は１２質量％以上であってよい。（Ａ）成分及び（Ｂ）成分の合計の含有量がこのような範囲にあると、接着性がより向上する傾向にある。 The total content of components (A) and (B) is 25% by mass or less based on the total amount of the film adhesive. When the total content of component (A) and component (B) is in this range, the amount of component (C) is sufficient, so that thin film coatability tends to be excellent. The total content of components (A) and (B) is 22% by mass or less, 20% by mass or less, or 18% by mass or less based on the total amount of the film adhesive, from the viewpoint of handleability. good too. The total content of components (A) and (B) may be 1% by mass or more, 5% by mass or more, 10% by mass or more, or 12% by mass or more based on the total amount of the film adhesive. . When the total content of component (A) and component (B) is in this range, the adhesiveness tends to be further improved.
（Ｃ）成分：エラストマー
　（Ｃ）成分としては、例えば、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、シリコーン樹脂、ブタジエン樹脂；これら樹脂の変性体等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。これらの中でも、（Ｃ）成分は、イオン性不純物が少なく耐熱性により優れること、半導体装置の接続信頼性をより確保し易いこと、流動性により優れることから、（メタ）アクリル酸エステルに由来する構成単位を主成分として有するアクリル樹脂（アクリルゴム）であってよい。（Ｃ）成分における（メタ）アクリル酸エステルに由来する構成単位の含有量は、構成単位全量を基準として、例えば、７０質量％以上、８０質量％以上、又は９０質量％以上であってよい。アクリル樹脂（アクリルゴム）は、エポキシ基、アルコール性又はフェノール性水酸基、カルボキシル基等の架橋性官能基を有する（メタ）アクリル酸エステルに由来する構成単位を含むものであってよい。 Component (C): Elastomer Examples of component (C) include acrylic resins, polyester resins, polyamide resins, polyimide resins, silicone resins, and butadiene resins; modified products of these resins. You may use these individually by 1 type or in combination of 2 or more types. Among these, the component (C) is derived from a (meth)acrylic ester because it has few ionic impurities and is excellent in heat resistance, it is easy to ensure the connection reliability of a semiconductor device, and it is excellent in fluidity. It may be an acrylic resin (acrylic rubber) having structural units as a main component. The content of structural units derived from (meth)acrylic acid ester in component (C) may be, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more based on the total amount of structural units. The acrylic resin (acrylic rubber) may contain structural units derived from a (meth)acrylic acid ester having a crosslinkable functional group such as an epoxy group, an alcoholic or phenolic hydroxyl group, or a carboxyl group.
　（Ｃ）成分のガラス転移温度（Ｔｇ）は、－５０～５０℃又は－３０～３０℃であってよい。（Ｃ）成分のＴｇが－５０℃以上であると、接着剤組成物の柔軟性が高くなり過ぎることを防ぐことができる傾向にある。これによって、ウェハダイシング時にフィルム状接着剤を切断し易くなり、バリの発生を防ぐことが可能となる。（Ｃ）成分のＴｇが５０℃以下であると、フィルム状接着剤の柔軟性の低下を抑えることができる傾向にある。これにより、フィルム状接着剤を半導体ウェハに貼り付ける際に、ボイドを充分に埋め込み易くなる傾向にある。また、半導体ウェハの密着性の低下によるダイシング時のチッピングを防ぐことが可能となる。ここで、ガラス転移温度（Ｔｇ）は、ＤＳＣ（熱示差走査熱量計）（例えば、株式会社リガク製「Ｔｈｅｒｍｏ　Ｐｌｕｓ　２」）を用いて測定した値を意味する。（Ｃ）成分のＴｇは、（Ｃ）成分を構成する構成単位（（Ｃ）成分がアクリル樹脂（アクリルゴム）である場合、（メタ）アクリル酸エステルに由来する構成単位）の種類及び含有量を調整することによって、所望の範囲に調整することができる。 The glass transition temperature (Tg) of component (C) may be -50 to 50°C or -30 to 30°C. When the Tg of component (C) is -50°C or higher, it tends to be possible to prevent the flexibility of the adhesive composition from becoming too high. This makes it easier to cut the film-like adhesive during wafer dicing, making it possible to prevent the occurrence of burrs. When the Tg of the component (C) is 50° C. or less, it tends to be possible to suppress a decrease in the flexibility of the film-like adhesive. This tends to make it easier to sufficiently fill voids when the film-like adhesive is attached to the semiconductor wafer. Also, it is possible to prevent chipping during dicing due to deterioration of adhesion of the semiconductor wafer. Here, the glass transition temperature (Tg) means a value measured using a DSC (differential scanning calorimeter) (for example, "Thermo Plus 2" manufactured by Rigaku Corporation). The Tg of the component (C) is the type and content of structural units that constitute the component (C) (structural units derived from (meth)acrylic acid esters when the component (C) is an acrylic resin (acrylic rubber)). can be adjusted to a desired range by adjusting .
　（Ｃ）成分の重量平均分子量（Ｍｗ）は、１０万～３００万又は２０万～１００万であってよい。（Ｃ）成分のＭｗがこのような範囲にあると、フィルム形成性、フィルム強度、可撓性、タック性等を適切に制御することができるとともに、リフロー性に優れ、埋め込み性を向上することができる。ここで、Ｍｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定し、標準ポリスチレンによる検量線を用いて換算した値を意味する。 The weight average molecular weight (Mw) of component (C) may be 100,000 to 3,000,000 or 200,000 to 1,000,000. When the Mw of the component (C) is in such a range, the film formability, film strength, flexibility, tackiness, etc. can be appropriately controlled, and the reflow property is excellent and the embedding property is improved. can be done. Here, Mw means a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
　（Ｃ）成分の市販品としては、ＳＧ－７０Ｌ、ＳＧ－７０８－６、ＷＳ－０２３　ＥＫ３０、ＳＧ－Ｐ３、ＳＧ－２８０　ＥＫ２３、ＳＧ－８０Ｈ、ＨＴＲ－８６０Ｐ、ＨＴＲ－８６０Ｐ－３、ＨＴＲ－８６０Ｐ－３ＣＳＰ、ＨＴＲ－８６０Ｐ－３ＣＳＰ－３ＤＢ、ＨＴＲ－８６０Ｐ－３０Ｂ（いずれもナガセケムテックス株式会社製）等が挙げられる。 Commercially available products of component (C) include SG-70L, SG-708-6, WS-023 EK30, SG-P3, SG-280 EK23, SG-80H, HTR-860P, HTR-860P-3, HTR- 860P-3CSP, HTR-860P-3CSP-3DB, HTR-860P-30B (all manufactured by Nagase ChemteX Corporation) and the like.
　（Ｃ）成分の含有量は、フィルム状接着剤の全量を基準として、４０質量％以上、４５質量％以上、又は５０質量％以上であってよい。（Ｃ）成分の含有量がこのような範囲にあると、薄膜塗工性により優れる傾向にある。（Ｃ）成分の含有量は、フィルム状接着剤の全量を基準として、８０質量％以下、７５質量％以下、又は７０質量％以下であってよい。（Ｃ）成分の含有量がこのような範囲にあると、（Ａ）成分及び（Ｂ）成分の含有量を充分に確保することができ、他の特性との両立できる傾向にある。 The content of component (C) may be 40% by mass or more, 45% by mass or more, or 50% by mass or more based on the total amount of the film adhesive. When the content of the component (C) is in such a range, it tends to be more excellent in thin film coatability. The content of component (C) may be 80% by mass or less, 75% by mass or less, or 70% by mass or less based on the total amount of the film adhesive. When the content of component (C) is in this range, the content of components (A) and (B) can be sufficiently ensured, and other properties tend to be compatible.
　（Ｃ）成分の含有量は、（Ａ）成分及び（Ｂ）成分の全量１００質量部に対して、２００質量部以上であってよい。（Ｃ）成分の含有量がこのような範囲にあると、薄膜塗工性により優れる傾向にある。（Ｃ）成分の含有量は、（Ａ）成分及び（Ｂ）成分の全量１００質量部に対して、２５０質量部以上、３００質量部以上、又は３５０質量部以上であってもよい。（Ｃ）成分の含有量は、（Ａ）成分及び（Ｂ）成分の全量１００質量部に対して、６００質量部以下、５５０質量部以下、又は５００質量部以下であってよい。（Ｃ）成分の含有量がこのような範囲にあると、（Ａ）成分及び（Ｂ）成分の含有量を充分に確保することができ、他の特性との両立できる傾向にある。 The content of component (C) may be 200 parts by mass or more with respect to 100 parts by mass of the total amount of components (A) and (B). When the content of the component (C) is in such a range, it tends to be more excellent in thin film coatability. The content of component (C) may be 250 parts by mass or more, 300 parts by mass or more, or 350 parts by mass or more with respect to 100 parts by mass of the total amount of components (A) and (B). The content of component (C) may be 600 parts by mass or less, 550 parts by mass or less, or 500 parts by mass or less with respect to 100 parts by mass of the total amount of components (A) and (B). When the content of component (C) is in this range, the content of components (A) and (B) can be sufficiently ensured, and other properties tend to be compatible.
（Ｄ）成分：平均粒径が４００ｎｍ以下である無機フィラー
　（Ｄ）成分としての無機フィラーとしては、例えば、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、酸化アルミニウム、窒化アルミニウム、ホウ酸アルミウィスカ、窒化ホウ素、シリカ等が挙げられる。これらは、平均粒径が４００ｎｍ以下であれば、１種を単独で又は２種以上を組み合わせて用いてもよい。これらの中でも、無機フィラーは、溶融粘度の調整の観点から、シリカであってもよい。無機フィラーの形状は、特に制限されないが、球状であってよい。 (D) component: inorganic filler having an average particle size of 400 nm or less Examples of inorganic fillers as component (D) include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, Calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, boron nitride, silica and the like. These may be used singly or in combination of two or more as long as the average particle diameter is 400 nm or less. Among these, the inorganic filler may be silica from the viewpoint of adjusting the melt viscosity. The shape of the inorganic filler is not particularly limited, but may be spherical.
　（Ｄ）成分の平均粒径は、薄膜塗工性及び接着性の観点から、４００ｎｍ以下であり、３５０ｎｍ以下又は３００ｎｍ以下であってもよい。（Ｄ）成分としての無機フィラーの平均粒径は、例えば、１０ｎｍ以上、３０ｎｍ以上、１００ｎｍ以上、又は１５０ｎｍ以上であってよい。ここで、平均粒径は、動的光散乱法によって求められる平均粒径を意味する。なお、（Ｄ）成分の平均粒径は、（Ｄ）成分が含有されるフィルム状接着剤を用いることによっても求めることができる。この場合、フィルム状接着剤を加熱して樹脂成分を分解することによって得られる残渣を溶媒に分散して分散液を作製し、これに動的光散乱法を適用して得られる粒度分布から、（Ｄ）成分の平均粒径を求めることができる。 The average particle diameter of component (D) is 400 nm or less, and may be 350 nm or less, or 300 nm or less, from the viewpoint of thin film coatability and adhesiveness. The average particle size of the inorganic filler as component (D) may be, for example, 10 nm or more, 30 nm or more, 100 nm or more, or 150 nm or more. Here, the average particle size means the average particle size determined by the dynamic light scattering method. The average particle size of component (D) can also be obtained by using a film-like adhesive containing component (D). In this case, the residue obtained by heating the film adhesive to decompose the resin component is dispersed in a solvent to prepare a dispersion liquid. The average particle size of component (D) can be determined.
　（Ｄ）成分は、例えば、１種又は２種以上の平均粒径４００ｎｍ以下の無機フィラーから構成されるものであってよく、１種又は２種以上の、平均粒径１０～４００ｎｍ、平均粒径３０～４００ｎｍ、平均粒径１００～４００ｎｍ、平均粒径１５０～４００ｎｍ、平均粒径１０～３５０ｎｍ、平均粒径３０～３５０ｎｍ、平均粒径１００～３５０ｎｍ、平均粒径１５０～３５０ｎｍ、平均粒径１０～３００ｎｍ、平均粒径３０～３００ｎｍ、平均粒径１００～３００ｎｍ、又は平均粒径１５０～３００ｎｍの無機フィラーから構成されるものであってもよい。 Component (D) may be composed of, for example, one or more inorganic fillers having an average particle size of 400 nm or less, and one or more inorganic fillers having an average particle size of 10 to 400 nm and an average particle size of 400 nm or less. Diameter 30-400 nm Average particle size 100-400 nm Average particle size 150-400 nm Average particle size 10-350 nm Average particle size 30-350 nm Average particle size 100-350 nm Average particle size 150-350 nm Average particle size It may be composed of an inorganic filler having an average particle size of 10 to 300 nm, an average particle size of 30 to 300 nm, an average particle size of 100 to 300 nm, or an average particle size of 150 to 300 nm.
　（Ｄ）成分の含有量は、フィルム状接着剤の全量を基準として、１８～４０質量％である。（Ｄ）成分の含有量は、フィルム状接着剤の全量を基準として、１８質量％以上であり、２０質量％以上、２２質量％以上、又は２４質量％以上であってもよい。（Ｄ）成分の含有量が、フィルム状接着剤の全量を基準として、１８質量％以上であると、フィルム状接着剤の冷却エキスパンドによる分断性に優れる傾向にある。（Ｄ）成分の含有量は、フィルム状接着剤の全量を基準として、４０質量％以下であり、３８質量％以下、３５質量％以下、又は３２質量％以下であってもよい。（Ｄ）成分の含有量は、フィルム状接着剤の全量を基準として、４０質量％以下であると、フィルム状接着剤を薄膜化したときに充分なダイシェア強度を有する傾向にある。フィルム状接着剤の全量を基準とする（Ｄ）成分の含有量は、（Ｄ）成分が含有されるフィルム状接着剤を用いることによっても求めることができる。この場合、フィルム状接着剤の質量及びフィルム状接着剤を加熱して樹脂成分を分解することによって得られる残渣の質量を求め、これらの質量関係から（Ｄ）成分の含有量を求めることができる。フィルム状接着剤を加熱して樹脂成分を分解することによって得られる残渣の質量は、残渣を溶媒で洗浄し、乾燥した後に測定される質量であってもよい。 The content of component (D) is 18 to 40% by mass based on the total amount of the film adhesive. The content of component (D) is 18% by mass or more, and may be 20% by mass or more, 22% by mass or more, or 24% by mass or more based on the total amount of the film adhesive. When the content of the component (D) is 18% by mass or more based on the total amount of the film adhesive, the splitting property of the film adhesive by cooling expansion tends to be excellent. The content of component (D) is 40% by mass or less, and may be 38% by mass or less, 35% by mass or less, or 32% by mass or less based on the total amount of the film adhesive. When the content of component (D) is 40% by mass or less based on the total amount of the film adhesive, the film adhesive tends to have sufficient die shear strength when thinned. The content of component (D) based on the total amount of the film-like adhesive can also be obtained by using a film-like adhesive containing component (D). In this case, the mass of the film-like adhesive and the mass of the residue obtained by heating the film-like adhesive to decompose the resin component are determined, and the content of the component (D) can be determined from the relationship between these masses. . The mass of the residue obtained by heating the film adhesive to decompose the resin component may be the mass measured after the residue is washed with a solvent and dried.
　（Ｄ）成分の含有量は、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の全量１００質量部に対して、２２質量部以上であってよく、２５質量部以上、２８質量部以上、又は３０質量部以上であってもよい。（Ｄ）成分の含有量が、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の全量１００質量部に対して、２２質量部以上であると、フィルム状接着剤の冷却エキスパンドによる分断性により優れる傾向にある。（Ｄ）成分の含有量は、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の全量１００質量部に対して、７０質量部以下、６５質量部以下、６０質量部以下、５５質量部以下、又は５０質量部以下であってよい。（Ｄ）成分の含有量は、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の全量１００質量部に対して、７０質量部以下であると、フィルム状接着剤を薄膜化したときにより充分なダイシェア強度を有する傾向にある。 The content of component (D) may be 22 parts by mass or more, 25 parts by mass or more, and 28 parts by mass with respect to the total amount of 100 parts by mass of components (A), (B), and (C). or more, or 30 parts by mass or more. When the content of component (D) is 22 parts by mass or more with respect to the total amount of 100 parts by mass of components (A), (B), and (C), the film adhesive is divided by cooling expansion. tend to be superior in terms of The content of component (D) is 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, or 55 parts by mass with respect to 100 parts by mass of the total amount of components (A), (B), and (C). parts or less, or 50 parts by mass or less. When the content of component (D) is 70 parts by mass or less with respect to the total amount of 100 parts by mass of components (A), (B), and (C), the film adhesive is thinned. It tends to have sufficient die shear strength.
　フィルム状接着剤は、（Ｄ）成分に加えて、平均粒径が４００ｎｍ超である無機フィラーを含有していてもよい。他方、フィルム状接着剤は、本開示の効果がより顕著に奏される傾向にあることから、平均粒径が４００ｎｍ超である無機フィラーを実質的に含有していない（添加していない）ことが好ましい。ここで、「実質的に含有していない」とは、平均粒径が４００ｎｍ超である無機フィラーの含有量が、（Ｄ）成分及び平均粒径が４００ｎｍ超である無機フィラーの全量を基準として、５質量％以下、３質量％以下、１質量％以下、又は０．１質量％以下であることを意味する。 The film adhesive may contain an inorganic filler with an average particle size of more than 400 nm in addition to the component (D). On the other hand, since the film-like adhesive tends to exhibit the effects of the present disclosure more remarkably, it should not substantially contain (add) an inorganic filler having an average particle size of more than 400 nm. is preferred. Here, "substantially does not contain" means that the content of the inorganic filler having an average particle size of more than 400 nm is based on the total amount of the component (D) and the inorganic filler having an average particle size of more than 400 nm. , 5% by mass or less, 3% by mass or less, 1% by mass or less, or 0.1% by mass or less.
（Ｅ）成分：カップリング剤
　（Ｅ）成分は、シランカップリング剤であってよい。シランカップリング剤としては、例えば、γ－ウレイドプロピルトリエトキシシラン、γ－メルカプトプロピルトリメトキシシラン、３－フェニルアミノプロピルトリメトキシシラン、３－（２－アミノエチル）アミノプロピルトリメトキシシラン等が挙げられる。 (E) Component: Coupling Agent The (E) component may be a silane coupling agent. Silane coupling agents include, for example, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, and the like. be done.
（Ｆ）成分：硬化促進剤
　（Ｆ）成分としては、例えば、イミダゾール類及びその誘導体、有機リン系化合物、第二級アミン類、第三級アミン類、第四級アンモニウム塩等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。これらの中でも、反応性の観点から（Ｆ）成分はイミダゾール類及びその誘導体であってもよい。 Component (F): Curing Accelerator Examples of component (F) include imidazoles and their derivatives, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. You may use these individually by 1 type or in combination of 2 or more types. Among these, imidazoles and derivatives thereof may be used as the component (F) from the viewpoint of reactivity.
　イミダゾール類としては、例えば、２－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－メチルイミダゾール等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。 Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole and the like. You may use these individually by 1 type or in combination of 2 or more types.
　フィルム状接着剤は、その他の成分をさらに含有していてもよい。その他の成分としては、例えば、顔料、イオン補捉剤、酸化防止剤等が挙げられる。 The film adhesive may further contain other components. Other components include, for example, pigments, ion trapping agents, antioxidants, and the like.
　（Ｅ）成分、（Ｆ）成分、及びその他の成分の合計の含有量は、フィルム状接着剤の全量を基準として、０．１質量％以上、０．３質量％以上、又は０．５質量％以上であってよく、２０質量％以下、１０質量％以下、又は５質量％以下であってよい。 The total content of component (E), component (F), and other components is 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass, based on the total amount of the film adhesive. % or more, and may be 20% by mass or less, 10% by mass or less, or 5% by mass or less.
　図１は、フィルム状接着剤の一実施形態を示す模式断面図である。図１に示すフィルム状接着剤１は、半導体チップと支持部材との接着又は半導体チップ同士の接着に使用されるダイボンディングフィルムであり得る。フィルム状接着剤１は、接着剤組成物をフィルム状に成形してなるものである。フィルム状接着剤１は、通常、半硬化（Ｂステージ）状態で、硬化処理後に硬化（Ｃステージ）状態となるものであり得る。フィルム状接着剤１は、接着剤組成物を支持フィルムに塗布することによって形成することができる。フィルム状接着剤１の形成においては、接着剤組成物のワニス（接着剤ワニス）を用いてもよい。接着剤ワニスを用いる場合は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分、並びに必要に応じて添加される成分を溶剤中で混合又は混練して接着剤ワニスを調製し、得られた接着剤ワニスを支持フィルムに塗布し、溶剤を加熱乾燥して除去することによってフィルム状接着剤１を得ることができる。 FIG. 1 is a schematic cross-sectional view showing one embodiment of a film adhesive. The film adhesive 1 shown in FIG. 1 can be a die bonding film used for bonding a semiconductor chip and a supporting member or bonding semiconductor chips to each other. The film adhesive 1 is obtained by molding an adhesive composition into a film. The film-like adhesive 1 is usually in a semi-cured (B stage) state, and can be in a cured (C stage) state after a curing treatment. The film adhesive 1 can be formed by applying an adhesive composition to a support film. In forming the film adhesive 1, a varnish of an adhesive composition (adhesive varnish) may be used. When an adhesive varnish is used, the components (A), (B), (C), and (D), and optionally added components are mixed or kneaded in a solvent to prepare the adhesive varnish. is prepared, the obtained adhesive varnish is applied to a support film, and the solvent is removed by heating and drying to obtain the film-like adhesive 1.
　支持フィルムは、上記の加熱乾燥に耐えるものであれば特に限定されないが、例えば、ポリエステルフィルム、ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム、ポリイミドフィルム、ポリエーテルイミドフィルム、ポリエチレンナフタレートフィルム、ポリメチルペンテンフィルム等であってよい。支持フィルムは、２種以上を組み合わせた多層フィルムであってもよく、表面がシリコーン系、シリカ系等の離型剤などで処理されたものであってもよい。支持フィルムの厚さは、例えば、１０～２００μｍ又は２０～１７０μｍであってよい。 The support film is not particularly limited as long as it can withstand the heat drying described above. It's okay. The support film may be a multi-layer film in which two or more types are combined, or the surface thereof may be treated with a release agent such as a silicone-based or silica-based release agent. The thickness of the support film may be, for example, 10-200 μm or 20-170 μm.
　混合又は混練は、通常の撹拌機、らいかい機、三本ロール、ボールミル等の分散機を用い、これらを適宜組み合わせて行うことができる。 Mixing or kneading can be carried out by using a dispersing machine such as a normal stirrer, squeegee machine, triple roll, ball mill, etc., and combining them appropriately.
　接着剤ワニスの調製に用いられる溶剤は、各成分を均一に溶解、混練、又は分散できるものであれば制限はなく、従来公知のものを使用することができる。このような溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎメチルピロリドン、トルエン、キシレン等が挙げられる。溶剤は、乾燥速度及び価格の観点から、メチルエチルケトン又はシクロヘキサノンであってよい。 The solvent used for preparing the adhesive varnish is not limited as long as it can uniformly dissolve, knead, or disperse each component, and conventionally known solvents can be used. Examples of such solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene and xylene. The solvent may be methyl ethyl ketone or cyclohexanone from a drying speed and cost point of view.
　接着剤ワニスを支持フィルムに塗布する方法としては、公知の方法を用いることができ、例えば、ナイフコート法、ロールコート法、スプレーコート法、グラビアコート法、バーコート法、カーテンコート法等を用いることができる。加熱乾燥は、使用した溶剤が充分に揮散する条件であれば特に制限されないが、５０～１５０℃の範囲で、１～３０分の範囲で行うことができる。加熱乾燥は、異なる加熱温度で異なる加熱時間で段階的に行うことができる。 As a method for applying the adhesive varnish to the support film, a known method can be used, for example, a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, a curtain coating method, or the like is used. be able to. Heat drying is not particularly limited as long as the solvent used is sufficiently volatilized, but it can be carried out in the range of 50 to 150° C. for 1 to 30 minutes. Heat drying can be performed in stages at different heating temperatures and for different heating times.
　フィルム状接着剤の厚さは、２０μｍ以下であってよく、１８μｍ以下、１５μｍ以下、１２μｍ以下、１０μｍ以下、又は８μｍ以下であってもよい。フィルム状接着剤の厚さの下限は、特に制限されないが、例えば、１μｍ以上であってよい。 The thickness of the film adhesive may be 20 μm or less, 18 μm or less, 15 μm or less, 12 μm or less, 10 μm or less, or 8 μm or less. Although the lower limit of the thickness of the film adhesive is not particularly limited, it may be, for example, 1 μm or more.
　支持フィルム上に作製されたフィルム状接着剤は、損傷又は汚染を防ぐ観点から、フィルム状接着剤の支持フィルムとは反対側の面にカバーフィルムを備えていてもよい。カバーフィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、表面はく離剤処理フィルム等が挙げられる。カバーフィルムの厚さは、例えば、１５～２００μｍ又は３０～１７０μｍであってよい。 From the viewpoint of preventing damage or contamination, the film-like adhesive produced on the support film may have a cover film on the side opposite to the support film of the film-like adhesive. Examples of cover films include polyethylene films, polypropylene films, films treated with surface release agents, and the like. The thickness of the cover film may be, for example, 15-200 μm or 30-170 μm.
　フィルム状接着剤は、薄膜化が可能であることから、複数の半導体素子を積層してなる半導体装置の製造プロセスに好適に用いることができる。この場合、半導体装置は、積層ＭＣＰであってよく、三次元ＮＡＮＤ型メモリであってもよい。 A film-like adhesive can be made thinner, so it can be suitably used in the manufacturing process of a semiconductor device in which multiple semiconductor elements are laminated. In this case, the semiconductor device may be a stacked MCP or a three-dimensional NAND memory.
　フィルム状接着剤１は、以下の条件下で実施される割断試験の結果を利用した分断性評価方法（冷却エキスパンドが実施される低温条件（例えば、－１５℃～０℃の範囲）下におけるフィルム状接着剤の分断性評価方法）において、割断係数ｍが７０以下であるフィルム状接着剤であってよい。
＜条件＞
　試料の幅：５ｍｍ
　試料の長さ：２３ｍｍ
　押し込み冶具と試料との相対速度：１０ｍｍ／分 The film-like adhesive 1 is a splitting property evaluation method using the results of a cleaving test performed under the following conditions (a film under low-temperature conditions (for example, a range of -15 ° C. to 0 ° C.) where cooling expansion is performed) method for evaluating splittability of adhesives), the adhesive may be a film adhesive having a breaking modulus m of 70 or less.
<Condition>
Width of sample: 5 mm
Sample length: 23mm
Relative speed between pushing jig and sample: 10 mm/min
　以下、割断試験について説明する。割断試験は抗折強度試験に分類されるものであり、試料の両端を固定した状態で試料が破断するまで試料の中央部を押し込む工程を含む。図２に示すように、試料Ｓは一対の試料固定用冶具２０に挟まれて固定された状態で割断試験に供される。一対の試料固定用冶具２０は、例えば、充分な強度を有する厚紙からなり、中央に矩形の開口２０ａをそれぞれ有する。固定された状態の試料Ｓの中央部に、押し込み冶具２１を用いて荷重を加える（図３参照）。 The breaking test will be explained below. The rupture test is classified as a bending strength test, and includes a step of pushing the central portion of the sample until the sample breaks while both ends of the sample are fixed. As shown in FIG. 2, the sample S is sandwiched and fixed between a pair of sample fixing jigs 20 and subjected to the breaking test. The pair of sample fixing jigs 20 are made of, for example, cardboard having sufficient strength, and each have a rectangular opening 20a in the center. A load is applied to the central portion of the fixed sample S using a pressing jig 21 (see FIG. 3).
　試料Ｓは、評価対象のフィルム状接着剤を切り出したものであればよく、フィルム状接着剤から切り出した複数の接着剤片を積層して試料を作製しなくてもよい。すなわち、試料Ｓの厚さは、フィルム状接着剤の厚さと同じであってもよい。試料Ｓの幅（図２におけるＷｓ）は、例えば、１～３０ｍｍであり、３～８ｍｍであってもよい。測定装置の状況に応じて適当な幅に設定すればよい。試料Ｓの長さ（図２におけるＬｓ）は、例えば、５～５０ｍｍであり、１０～３０ｍｍ又は６～９ｍｍであってもよい。試料Ｓの長さは試料固定用冶具２０の開口２０ａのサイズに依存する。なお、試料固定用冶具２０の形状及び試料Ｓのサイズは、割断試験を実施できる限り、上記のもの以外であってもよい。 The sample S may be obtained by cutting out the film-like adhesive to be evaluated, and the sample does not have to be prepared by laminating a plurality of adhesive pieces cut out from the film-like adhesive. That is, the thickness of the sample S may be the same as the thickness of the film adhesive. The width of the sample S (Ws in FIG. 2) is, for example, 1 to 30 mm, and may be 3 to 8 mm. An appropriate width may be set according to the conditions of the measuring device. The length of the sample S (Ls in FIG. 2) is, for example, 5-50 mm, and may be 10-30 mm or 6-9 mm. The length of the sample S depends on the size of the opening 20a of the jig 20 for fixing the sample. Note that the shape of the sample fixing jig 20 and the size of the sample S may be other than those described above as long as the fracture test can be performed.
　押し込み冶具２１は、円錐状の先端部２１ａを有する円柱状部材からなる。押し込み冶具２１の直径（図３におけるＲ）は、例えば、３～１５ｍｍであり、５～１０ｍｍであってもよい。先端部２１ａの角度（図３におけるθ）は、例えば、４０～１２０°であり、６０～１００°であってもよい。 The pressing jig 21 consists of a cylindrical member having a conical tip 21a. The diameter (R in FIG. 3) of the pressing jig 21 is, for example, 3 to 15 mm, and may be 5 to 10 mm. The angle of the tip portion 21a (θ in FIG. 3) is, for example, 40 to 120°, and may be 60 to 100°.
　割断試験は、所定の温度に設定された恒温槽内で実施される。恒温槽は、－１５℃～０℃の範囲の一定の温度（想定される冷却エキスパンドの温度）に設定すればよい。恒温槽として、例えば、株式会社アイテック社製、ＴＬＦ－Ｒ３－Ｆ－Ｗ－ＰＬ－Ｓを使用できる。オートグラフ（例えば、株式会社エーアンドデイ製のＡＺＴ－ＣＡ０１、ロードセル５０Ｎ、圧縮モード）を使用し、割断仕事Ｗ、割断強度Ｐ、及び割断伸びＬを得る。 The breaking test is carried out in a constant temperature bath set at a predetermined temperature. The constant temperature bath may be set at a constant temperature in the range of −15° C. to 0° C. (expected cooling expansion temperature). As the constant temperature bath, for example, TLF-R3-FW-PL-S manufactured by ITEC Co., Ltd. can be used. Using an autograph (for example, AZT-CA01, load cell 50N, compression mode manufactured by A&D Co., Ltd.), the work at break W, the strength at break P, and the elongation at break L are obtained.
　押し込み冶具２１と試料Ｓとの相対速度は、例えば、１～１００ｍｍ／分であり、５～２０ｍｍ／分であってもよい。この相対速度が速すぎると割断過程のデータが充分に取得できない傾向にあり、遅すぎると応力が緩和して割断に至りにくい傾向にある。押し込み冶具２１の押し込み距離は、例えば、１～５０ｍｍであり、５～３０ｍｍであってもよい。押し込み距離が短すぎると割断に至らない傾向にある。評価対象のフィルム状接着剤について、複数の試料を準備し、割断試験を複数回行って試験結果の安定性を確認することが好ましい。 The relative speed between the pressing jig 21 and the sample S is, for example, 1 to 100 mm/min, and may be 5 to 20 mm/min. If this relative speed is too high, there is a tendency that sufficient data on the cleaving process cannot be obtained, and if it is too slow, the stress tends to relax, making it difficult to achieve cleaving. The pushing distance of the pushing jig 21 is, for example, 1 to 50 mm, and may be 5 to 30 mm. If the pushing distance is too short, there is a tendency not to result in breakage. It is preferable to prepare a plurality of samples of the film-like adhesive to be evaluated, and to perform a cleaving test a plurality of times to confirm the stability of the test results.
　図４は、割断試験の結果の一例を示すグラフである。図４に示すように、割断仕事Ｗは、縦軸を荷重とし、横軸を試料Ｓが破断するまでの押し込み量でグラフを作成したときに囲まれた面積である。割断強度Ｐは、試料Ｓが破断したときの荷重である。割断伸びＬは試料Ｓが破断したときの試料Ｓの伸び量である。割断伸びＬは、試料Ｓが破断したときの押し込み距離と試料固定用冶具２０の開口２０ａの幅から三角関数を用いて算出すればよい。 FIG. 4 is a graph showing an example of the results of the breaking test. As shown in FIG. 4, the breaking work W is the area enclosed when a graph is created with the vertical axis representing the load and the horizontal axis representing the pressing amount until the sample S breaks. The breaking strength P is the load when the sample S breaks. The breaking elongation L is the elongation amount of the sample S when the sample S breaks. The breaking elongation L may be calculated using a trigonometric function from the pushing distance when the sample S breaks and the width of the opening 20a of the jig 20 for fixing the sample.
　割断試験によって得られた割断仕事Ｗ（Ｎ・ｍｍ）、割断強度Ｐ（Ｎ）、及び割断伸びＬ（ｍｍ）の値から、式（１）及び式（２）より割断係数ｍ（無次元）及び割断抵抗Ｒ（Ｎ／ｍｍ２）を求める。
　ｍ＝Ｗ／［１０００×（Ｐ×Ｌ）］　（１）
　Ｒ＝Ｐ／Ａ　（２） From the values of the breaking work W (N mm), the breaking strength P (N), and the breaking elongation L (mm) obtained by the breaking test, the breaking coefficient m (dimensionless) is obtained from the formulas (1) and (2). And the breaking resistance R (N/mm 2 ) is obtained.
m=W/[1000×(P×L)] (1)
R=P/A (2)
　本発明者らの検討によると、以下の条件下で割断試験を実施したとき、割断係数ｍが９０以下であるフィルム状接着剤は、実際にステルスダイシングにおいて冷却エキスパンドによる分断性に優れる傾向にある。
＜条件＞
　試料の幅：５ｍｍ
　試料の長さ：２３ｍｍ
　押し込み冶具と試料との相対速度：１０ｍｍ／分 According to the studies of the present inventors, when a cleaving test was conducted under the following conditions, film adhesives with a cleaving modulus m of 90 or less actually tended to be excellent in cleavability by cooling expansion in stealth dicing. .
<Condition>
Width of sample: 5 mm
Sample length: 23mm
Relative speed between pushing jig and sample: 10 mm/min
　割断係数ｍ（無次元）は、９０以下であってよく、８０以下、７０以下、６５以下、又は６０以下であってもよい。割断係数ｍは低温条件下におけるフィルム状接着剤の延伸性に関するパラメータである。割断係数ｍが９０以下であると、フィルム状接着剤の適度な延伸性により、冷却エキスパンドによる分断性が充分となる傾向にある。この傾向は割断係数ｍの数値が小さくなるほど、より顕著である。割断係数ｍ（無次元）は、０超であってよく、１０以上又は１５以上であってもよい。割断係数ｍが１５以上であると、応力の伝播性が良好となる傾向にある。割断係数ｍがこのような範囲にあるフィルム状接着剤は、冷却エキスパンドが実施される半導体装置の製造プロセスに好適に用いることができる。 The breaking modulus m (dimensionless) may be 90 or less, 80 or less, 70 or less, 65 or less, or 60 or less. The breaking modulus m is a parameter relating to stretchability of a film adhesive under low temperature conditions. When the breaking modulus m is 90 or less, the suitable stretchability of the film-like adhesive tends to result in sufficient breakability by cooling expansion. This tendency is more remarkable as the numerical value of the breaking modulus m becomes smaller. The fracture modulus m (dimensionless) may be greater than 0 and may be 10 or more or 15 or more. When the breaking modulus m is 15 or more, the stress propagating property tends to be good. A film adhesive having a breaking modulus m within such a range can be suitably used in a semiconductor device manufacturing process in which cooling expansion is performed.
　割断抵抗Ｒは、０Ｎ／ｍｍ２超４５Ｎ／ｍｍ２以下であってよく、１０Ｎ／ｍｍ２以上又は２０Ｎ／ｍｍ２以上であってもよく、４０Ｎ／ｍｍ２以下又は３５Ｎ／ｍｍ２以下であってもよい。割断抵抗Ｒが４５Ｎ／ｍｍ２以下であると、フィルム状接着剤の強度が過度となり過ぎず、充分な分断性が得られる傾向にある。割断抵抗Ｒが０Ｎ／ｍｍ２超であると、冷却エキスパンドにおいて良好な応力伝播が生じ、より優れた分断性が得られる傾向にある。割断抵抗Ｒが２０Ｎ／ｍｍ２以上であると、この傾向がより一層顕著となる傾向にある。 The breaking resistance R may be more than 0 N/mm 2 and 45 N/mm 2 or less, may be 10 N/mm 2 or more or 20 N/mm 2 or more , and may be 40 N/mm 2 or less or 35 N/mm 2 or less. may When the breaking resistance R is 45 N/mm 2 or less, the strength of the film-like adhesive does not become excessive and there is a tendency to obtain sufficient splittability. When the breaking resistance R is more than 0 N/mm 2 , good stress propagation occurs during cooling expansion, and there is a tendency to obtain better splitting properties. This tendency tends to become more pronounced when the breaking resistance R is 20 N/mm 2 or more.
［ダイシング・ダイボンディング一体型フィルム］
　図５は、ダイシング・ダイボンディング一体型フィルムの一実施形態を示す模式断面図である。図５に示されるダイシング・ダイボンディング一体型フィルム１０は、基材層２と、粘着剤層３と、上記の接着剤組成物からなる接着剤層１Ａとをこの順に備える。接着剤層１Ａは、フィルム状接着剤１であり得る。基材層２及び粘着剤層３は、ダイシングテープ４であり得る。このようなダイシング・ダイボンディング一体型フィルム１０を用いると、半導体ウェハへのラミネート工程が１回となることから、作業の効率化が可能である。ダイシング・ダイボンディング一体型フィルムは、フィルム状、シート状、テープ状等であってもよい。 [Dicing and die bonding integrated film]
FIG. 5 is a schematic cross-sectional view showing an embodiment of a dicing/die bonding integrated film. A dicing/die-bonding integrated film 10 shown in FIG. 5 includes a substrate layer 2, an adhesive layer 3, and an adhesive layer 1A made of the adhesive composition in this order. The adhesive layer 1A may be the film adhesive 1. The base material layer 2 and the adhesive layer 3 may be a dicing tape 4 . When such a dicing/die-bonding integrated film 10 is used, the lamination process to the semiconductor wafer is reduced to one step, so that work efficiency can be improved. The dicing/die-bonding integrated film may be in the form of a film, a sheet, a tape, or the like.
　ダイシングテープ４は、基材層２と、基材層２上に設けられた粘着剤層３とを備えている。 The dicing tape 4 includes a base layer 2 and an adhesive layer 3 provided on the base layer 2 .
　基材層２としては、例えば、ポリテトラフルオロエチレンフィルム、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリメチルペンテンフィルム、ポリイミドフィルム等のプラスチックフィルムなどが挙げられる。これらの基材層２は、必要に応じて、プライマー塗布、ＵＶ処理、コロナ放電処理、研磨処理、エッチング処理等の表面処理が行われていてもよい。 Examples of the base material layer 2 include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. These substrate layers 2 may be subjected to surface treatments such as primer coating, UV treatment, corona discharge treatment, polishing treatment, etching treatment, etc., as required.
　粘着剤層３は、粘着剤からなる層である。粘着剤は、ダイシング時には半導体素子が飛散しない充分な粘着力を有し、その後の半導体素子のピックアップ工程においては半導体素子を傷つけない程度の低い粘着力を有するものであれば特に制限なく、ダイシングテープの分野で従来公知のものを使用することができる。粘着剤は、非放射線硬化型又は放射線硬化型のいずれであってもよい。非放射線硬化型粘着剤は、短時間の加圧で一定の粘着性を示す粘着剤であり、放射線（例えば、紫外線）の照射によって、粘着性が低下する性質を有しない粘着剤である。一方、放射線硬化型粘着剤は、放射線（例えば、紫外線）の照射によって、粘着性が低下する性質を有する粘着剤である。放射線硬化型粘着剤は、例えば、紫外線硬化型粘着剤であってよい。 The adhesive layer 3 is a layer made of an adhesive. The adhesive is not particularly limited as long as it has sufficient adhesive strength to prevent the semiconductor elements from scattering during dicing and has low adhesive strength to the extent that the semiconductor elements are not damaged in the subsequent step of picking up the semiconductor elements. can be used. The adhesive may be either non-radiation curable or radiation curable. A non-radiation curable adhesive is an adhesive that exhibits a certain level of adhesiveness when pressed for a short period of time, and is an adhesive that does not lose its adhesiveness when exposed to radiation (for example, ultraviolet rays). On the other hand, a radiation-curable pressure-sensitive adhesive is a pressure-sensitive adhesive that has the property of decreasing its adhesiveness when irradiated with radiation (for example, ultraviolet rays). The radiation-curable adhesive may be, for example, an ultraviolet-curable adhesive.
　ダイシングテープ４（基材層２及び粘着剤層３）の厚さは、経済性及びフィルムの取扱い性の観点から、６０～１５０μｍ又は７０～１３０μｍであってよい。 The thickness of the dicing tape 4 (base material layer 2 and adhesive layer 3) may be 60 to 150 μm or 70 to 130 μm from the viewpoint of economy and film handling.
　ダイシング・ダイボンディング一体型フィルム１０は、例えば、フィルム状接着剤１及びダイシングテープ４を準備し、フィルム状接着剤１とダイシングテープ４の粘着剤層３とを貼り合わせることによって得ることができる。また、ダイシング・ダイボンディング一体型フィルム１０は、例えば、ダイシングテープ４を準備し、上記のフィルム状接着剤１を形成する方法と同様に、接着剤組成物（接着剤ワニス）をダイシングテープ４の粘着剤層３上に塗布することによっても得ることができる。 The dicing/die bonding integrated film 10 can be obtained, for example, by preparing a film adhesive 1 and a dicing tape 4 and bonding the film adhesive 1 and the adhesive layer 3 of the dicing tape 4 together. Further, the dicing/die-bonding integrated film 10 can be obtained, for example, by preparing the dicing tape 4 and applying an adhesive composition (adhesive varnish) to the dicing tape 4 in the same manner as in the method of forming the film adhesive 1 described above. It can also be obtained by coating on the pressure-sensitive adhesive layer 3 .
　フィルム状接着剤１とダイシングテープ４の粘着剤層３とを貼り合わせる場合、ダイシング・ダイボンディング一体型フィルム１０は、ロールラミネーター、真空ラミネーター等を用いて所定条件（例えば、室温（２０℃）又は加熱状態）でダイシングテープ４にフィルム状接着剤１をラミネートすることによって形成することができる。ダイシング・ダイボンディング一体型フィルム１０は、連続的に製造ができ、効率に優れることから、加熱状態でロールラミネーターを用いて形成してもよい。 When the film adhesive 1 and the adhesive layer 3 of the dicing tape 4 are attached together, the dicing/die bonding integrated film 10 is applied under predetermined conditions (for example, room temperature (20° C.) or It can be formed by laminating the film adhesive 1 on the dicing tape 4 in a heated state). The dicing/die-bonding integrated film 10 can be continuously produced and is highly efficient, so it may be formed using a roll laminator in a heated state.
　フィルム状接着剤及びダイシング・ダイボンディング一体型フィルムは、半導体装置の製造プロセスに用いられるものであってよく、複数の半導体素子を積層してなる半導体装置の製造プロセスに用いられるものであってもよい。 The film-like adhesive and the dicing/die-bonding integrated film may be used in the manufacturing process of a semiconductor device, or may be used in the manufacturing process of a semiconductor device formed by laminating a plurality of semiconductor elements. good.
　フィルム状接着剤は、半導体素子と半導体素子を搭載する支持部材とを接着するため接着剤としても好適に用いられる。 A film-like adhesive is also suitably used as an adhesive for adhering a semiconductor element and a supporting member on which the semiconductor element is mounted.
　また、フィルム状接着剤は、複数の半導体素子を積層してなる半導体装置である積層ＭＣＰ（例えば、三次元ＮＡＮＤ型メモリ）において、半導体素子同士を接着するための接着剤としても好適に用いられる。 In addition, the film-like adhesive is also suitably used as an adhesive for bonding semiconductor elements in a laminated MCP (for example, a three-dimensional NAND memory), which is a semiconductor device formed by laminating a plurality of semiconductor elements. .
　フィルム状接着剤は、例えば、フリップチップ型半導体装置の半導体素子の裏面を保護する保護シート、フリップチップ型半導体装置の半導体素子の表面と被着体との間を封止するための封止シート等としても用いることできる。 The film adhesive is, for example, a protective sheet for protecting the back surface of the semiconductor element of the flip chip type semiconductor device, or a sealing sheet for sealing between the surface of the semiconductor element of the flip chip type semiconductor device and the adherend. etc. can also be used.
　フィルム状接着剤及びダイシング・ダイボンディング一体型フィルムを用いて製造された半導体装置について、以下、図面を用いて具体的に説明する。なお、近年は様々な構造の半導体装置が提案されており、本実施形態のフィルム状接着剤及びダイシング・ダイボンディング一体型フィルムの用途は、以下に説明する構造の半導体装置に限定されるものではない。 A semiconductor device manufactured using a film-like adhesive and a dicing/die-bonding integrated film will be specifically described below with reference to the drawings. In recent years, semiconductor devices with various structures have been proposed, and the application of the film-like adhesive and dicing/die bonding integrated film of the present embodiment is not limited to the semiconductor devices having the structures described below. do not have.
［半導体装置］
　図６は、半導体装置の一実施形態を示す模式断面図である。図６に示される半導体装置１００は、半導体素子１１と、半導体素子１１を搭載する支持部材１２と、接着部材１５とを備えている。接着部材１５は、半導体素子１１及び支持部材１２の間に設けられ、半導体素子１１と支持部材１２とを接着している。接着部材１５は、接着剤組成物の硬化物（フィルム状接着剤の硬化物）である。半導体素子１１の接続端子（図示せず）はワイヤ１３を介して外部接続端子（図示せず）と電気的に接続され、封止材１４によって封止されている。 [Semiconductor device]
FIG. 6 is a schematic cross-sectional view showing one embodiment of a semiconductor device. A semiconductor device 100 shown in FIG. 6 includes a semiconductor element 11 , a support member 12 on which the semiconductor element 11 is mounted, and an adhesive member 15 . The adhesive member 15 is provided between the semiconductor element 11 and the support member 12 and bonds the semiconductor element 11 and the support member 12 together. The adhesive member 15 is a cured product of an adhesive composition (cured film adhesive). Connection terminals (not shown) of the semiconductor element 11 are electrically connected to external connection terminals (not shown) via wires 13 and sealed with a sealing material 14 .
　図７は、半導体装置の他の実施形態を示す模式断面図である。図７に示される半導体装置１１０において、一段目の半導体素子１１ａは、接着部材１５ａ（接着剤組成物の硬化物（フィルム状接着剤の硬化物））によって、端子１６が形成された支持部材１２に接着され、一段目の半導体素子１１ａ上にさらに接着部材１５ｂ（接着剤組成物の硬化物（フィルム状接着剤の硬化物））によって二段目の半導体素子１１ｂが接着されている。一段目の半導体素子１１ａ及び二段目の半導体素子１１ｂの接続端子（図示せず）は、ワイヤ１３を介して外部接続端子と電気的に接続され、封止材１４によって封止されている。図７に示される半導体装置１１０は、図６に示される半導体装置１００において、半導体素子（１１ａ）の表面上に積層された他の半導体素子（１１ｂ）をさらに備えているともいえる。 FIG. 7 is a schematic cross-sectional view showing another embodiment of the semiconductor device. In the semiconductor device 110 shown in FIG. 7, the first semiconductor element 11a is a support member 12 having terminals 16 formed by an adhesive member 15a (cured product of adhesive composition (cured product of film adhesive)). , and the semiconductor element 11b in the second stage is further bonded onto the semiconductor element 11a in the first stage with an adhesive member 15b (cured product of adhesive composition (cured product of film-like adhesive)). Connection terminals (not shown) of the first-stage semiconductor element 11 a and the second-stage semiconductor element 11 b are electrically connected to external connection terminals via wires 13 and sealed with a sealing material 14 . It can be said that the semiconductor device 110 shown in FIG. 7 further includes another semiconductor element (11b) laminated on the surface of the semiconductor element (11a) in the semiconductor device 100 shown in FIG.
　図８は、半導体装置の他の実施形態を示す模式断面図である。図８に示される半導体装置１２０は、支持部材１２と、支持部材１２上に積層された半導体素子１１ａ，１１ｂ，１１ｃ，１１ｄとを備える。四つの半導体素子１１ａ，１１ｂ，１１ｃ，１１ｄは、支持部材１２の表面に形成された接続端子（図示せず）との接続のために、横方向（積層方向と直交する方向）に互いにずれた位置に積層されている（図８参照）。半導体素子１１ａは、接着部材１５ａ（接着剤組成物の硬化物（フィルム状接着剤の硬化物））によって支持部材１２に接着されており、三つの半導体素子１１ｂ，１１ｃ，１１ｄの間にも、接着部材１５ｂ，１５ｃ，１５ｄ（接着剤組成物の硬化物（フィルム状接着剤の硬化物））がそれぞれ介在している。図８に示される半導体装置１２０は、図６に示される半導体装置１００において、半導体素子（１１ａ）の表面上に積層された他の半導体素子（１１ｂ，１１ｃ，１１ｄ）をさらに備えているともいえる。 FIG. 8 is a schematic cross-sectional view showing another embodiment of the semiconductor device. A semiconductor device 120 shown in FIG. 8 includes a support member 12 and semiconductor elements 11 a, 11 b, 11 c, and 11 d stacked on the support member 12 . The four semiconductor elements 11a, 11b, 11c, and 11d are offset from each other in the lateral direction (direction perpendicular to the stacking direction) for connection with connection terminals (not shown) formed on the surface of the support member 12. position (see FIG. 8). The semiconductor element 11a is adhered to the support member 12 by an adhesive member 15a (cured product of adhesive composition (cured product of film adhesive)). Adhesive members 15b, 15c, and 15d (cured adhesive composition (cured film adhesive)) are interposed, respectively. It can be said that the semiconductor device 120 shown in FIG. 8 further includes other semiconductor elements (11b, 11c, 11d) laminated on the surface of the semiconductor element (11a) in the semiconductor device 100 shown in FIG. .
　以上、本開示の実施形態について半導体装置（パッケージ）を詳細に説明したが、本開示は上記実施形態に限定されるものではない。例えば、図８においては、四つの半導体素子が積層された態様の半導体装置を例示したが、積層する半導体素子の数はこれに限定されるものではない。また、図８においては、半導体素子が横方向（積層方向と直交する方向）に互いにずれた位置に積層されている態様の半導体装置を例示したが、半導体素子が横方向（積層方向と直交する方向）に互いにずれていない位置に積層されている態様の半導体装置であってもよい。 Although the semiconductor device (package) has been described in detail with respect to the embodiments of the present disclosure, the present disclosure is not limited to the above embodiments. For example, FIG. 8 illustrates a semiconductor device in which four semiconductor elements are stacked, but the number of stacked semiconductor elements is not limited to this. In addition, although FIG. 8 illustrates the semiconductor device in which the semiconductor elements are stacked at positions shifted in the lateral direction (direction orthogonal to the stacking direction), the semiconductor elements direction) may be stacked at positions that are not shifted from each other.
［半導体装置の製造方法］
　図６、図７、及び図８に示される半導体装置（半導体パッケージ）は、半導体素子と支持部材との間、又は、半導体素子（第１の半導体素子）と半導体素子（第２の半導体素子）との間に上記のフィルム状接着剤を介在させ、半導体素子及び支持部材、又は、半導体素子（第１の半導体素子）及び半導体素子（第２の半導体素子）を接着させる工程を備える方法によって得ることができる。より具体的には、半導体素子と支持部材との間、又は、半導体素子（第１の半導体素子）と半導体素子（第２の半導体素子）との間に上記のフィルム状接着剤を介在させ、これらを加熱圧着して両者を接着させ、その後、必要に応じてワイヤボンディング工程、封止材による封止工程、はんだによるリフローを含む加熱溶融工程等を経ることによって得ることができる。 [Method for manufacturing a semiconductor device]
The semiconductor device (semiconductor package) shown in FIGS. 6, 7, and 8 is provided between the semiconductor element and the supporting member, or between the semiconductor element (first semiconductor element) and the semiconductor element (second semiconductor element). By interposing the film adhesive between and bonding the semiconductor element and the supporting member, or the semiconductor element (first semiconductor element) and the semiconductor element (second semiconductor element). be able to. More specifically, interposing the film-like adhesive between the semiconductor element and the supporting member, or between the semiconductor element (first semiconductor element) and the semiconductor element (second semiconductor element), They can be obtained by bonding them together under heat and pressure, and then, if necessary, through a wire bonding process, a sealing process using a sealing material, a heat melting process including reflow using solder, and the like.
　半導体素子と支持部材との間、又は、半導体素子（第１の半導体素子）と半導体素子（第２の半導体素子）との間にフィルム状接着剤を介在させる方法としては、後述のように、予め接着剤片付き半導体素子を作製した後、支持部材又は半導体素子に貼り付ける方法であってよい。 As a method for interposing a film-like adhesive between the semiconductor element and the support member or between the semiconductor element (first semiconductor element) and the semiconductor element (second semiconductor element), as described later, A method may be employed in which a semiconductor element with an adhesive piece is prepared in advance and then attached to a supporting member or a semiconductor element.
　次に、図５に示されるダイシング・ダイボンディング一体型フィルムを用いて半導体装置の製造方法の一実施形態について説明する。なお、ダイシング・ダイボンディング一体型フィルムによる半導体装置の製造方法は、以下に説明する半導体装置の製造方法に限定されるものではない。 Next, an embodiment of a method for manufacturing a semiconductor device using the dicing/die bonding integrated film shown in FIG. 5 will be described. The method of manufacturing a semiconductor device using the dicing/die-bonding integrated film is not limited to the method of manufacturing a semiconductor device described below.
　半導体装置は、例えば、上記のダイシング・ダイボンディング一体型フィルムの接着剤層に半導体ウェハを貼り付ける工程（ラミネート工程）と、接着剤層を貼り付けた半導体ウェハをダイシングする工程（ダイシング工程）と、基材層を冷却条件下エキスパンドすることによって、複数の個片化された接着剤片付き半導体素子を作製する工程（冷却エキスパンド工程）と、接着剤片付き半導体素子を粘着剤層からピックアップする工程（ピックアップ工程）と、ピックアップされた接着剤片付き半導体素子を支持部材に接着剤片を介して接着する工程（第１の接着工程）とを備える方法によって得ることができる。半導体装置の製造方法は、他の接着剤片付き半導体素子を、支持部材に接着された半導体素子の表面に接着剤片を介して接着する工程（第２の接着工程）をさらに備えていてもよい。 A semiconductor device includes, for example, a step of attaching a semiconductor wafer to the adhesive layer of the dicing/die bonding integrated film (laminating step), and a step of dicing the semiconductor wafer to which the adhesive layer is attached (dicing step). , a step of producing a plurality of individualized semiconductor elements with adhesive pieces by expanding the base material layer under cooling conditions (cooling expansion step), and a step of picking up the semiconductor elements with adhesive pieces from the adhesive layer ( picking up step) and a step of adhering the picked up semiconductor element with an adhesive piece to a support member via the adhesive piece (first adhesion step). The method of manufacturing a semiconductor device may further include a step of bonding another semiconductor element with adhesive piece to the surface of the semiconductor element bonded to the support member via the adhesive piece (second bonding step). .
　ラミネート工程は、ダイシング・ダイボンディング一体型フィルム１０における接着剤層１Ａに半導体ウェハを圧着し、これを接着保持させて貼り付ける工程である。本工程は、圧着ロール等の押圧手段によって押圧しながら行ってもよい。なお、半導体ウェハは、上記と同様の半導体ウェハを例示することができる。 The lamination step is a step of pressing a semiconductor wafer onto the adhesive layer 1A of the dicing/die bonding integrated film 10, holding it by adhesion, and attaching it. This step may be performed while pressing with a pressing means such as a pressing roll. As for the semiconductor wafer, the same semiconductor wafer as described above can be exemplified.
　半導体ウェハとしては、例えば、単結晶シリコン、多結晶シリコン、各種セラミック、ガリウムヒ素等の化合物半導体などが挙げられる。 Examples of semiconductor wafers include monocrystalline silicon, polycrystalline silicon, various ceramics, and compound semiconductors such as gallium arsenide.
　ダイシング工程は、半導体ウェハのダイシングを行う工程である。ダイシングは、例えば、半導体ウェハの回路面側から常法に従って行うことができる。また、本工程では、例えば、半導体ウェハに半分切り込みを設けるハーフカットと呼ばれる方式、レーザーによって改質領域を形成し分断する方式（ステルスダイシング）等を採用できる。上記のダイシング・ダイボンディング一体型フィルムの接着剤層は、冷却エキスパンドによる分断性に優れることから、ステルスダイシングを採用することが好ましい。本工程で用いるダイシング装置としては、特に限定されず、従来公知のものを用いることができる。 A dicing process is a process of dicing a semiconductor wafer. Dicing can be performed, for example, from the circuit surface side of the semiconductor wafer according to a conventional method. In addition, in this step, for example, a method called half-cut in which a semiconductor wafer is cut in half, a method in which a modified region is formed and divided by laser (stealth dicing), or the like can be employed. Stealth dicing is preferably adopted for the adhesive layer of the dicing/die-bonding integrated film as described above because it is excellent in splitting property by cooling expansion. The dicing device used in this step is not particularly limited, and conventionally known devices can be used.
　冷却エキスパンド工程は、基材層を冷却条件下エキスパンドする工程である。これにより、複数の個片化された接着剤片付き半導体素子を得ることができる。冷却条件下におけるエキスパンドの条件は、任意に設定することができるが、例えば、冷却温度－３０～５℃、冷却時間３０秒～５分、突き上げ量５～２０ｍｍ、突き上げ速度５０～３００ｍｍ／秒とすることができる。 The cooling expansion step is a step of expanding the base material layer under cooling conditions. As a result, a plurality of individualized semiconductor devices with adhesive pieces can be obtained. The expansion conditions under the cooling conditions can be arbitrarily set, but for example, the cooling temperature is −30 to 5° C., the cooling time is 30 seconds to 5 minutes, the thrust amount is 5 to 20 mm, and the thrust speed is 50 to 300 mm/second. can do.
　半導体素子（半導体チップ）としては、例えば、ＩＣ（集積回路）等が挙げられる。支持部材としては、例えば、４２アロイリードフレーム、銅リードフレーム等のリードフレーム；ポリイミド樹脂、エポキシ樹脂等のプラスチックフィルム；ガラス不織布等基材にポリイミド樹脂、エポキシ樹脂等のプラスチックを含浸、硬化させた変性プラスチックフィルム；アルミナ等のセラミックスなどが挙げられる。 Examples of semiconductor elements (semiconductor chips) include ICs (integrated circuits). Examples of supporting members include lead frames such as 42 alloy lead frames and copper lead frames; plastic films such as polyimide resin and epoxy resin; glass non-woven fabrics and other substrates impregnated with plastics such as polyimide resin and epoxy resin and cured. modified plastic film; ceramics such as alumina;
　ピックアップ工程は、ダイシング・ダイボンディング一体型フィルムに接着固定された接着剤片付き半導体素子を剥離するために、接着剤片付き半導体素子同士を離間させつつ、接着剤片付き半導体素子のピックアップを行う工程である。接着剤片付き半導体素子同士を離間させるためのエキスパンドの方法としては、特に限定されず、従来公知の種々の方法を採用できる。接着剤片付き半導体素子同士を離間させる方法としては、例えば、基材層をエキスパンドする方法が挙げられる。エキスパンドは、必要に応じて、冷却条件下におけるエキスパンドであってよい。ピックアップの方法としては、特に限定されず、従来公知の種々の方法を採用できる。このような方法としては、例えば、個々の接着剤片付き半導体素子をダイシング・ダイボンディング一体型フィルム側からニードルによって突き上げ、突き上げられた接着剤片付き半導体素子をピックアップ装置によってピックアップする方法等が挙げられる。 The pick-up step is a step of picking up semiconductor elements with adhesive pieces while separating the semiconductor elements with adhesive pieces from each other in order to separate the semiconductor elements with adhesive pieces adhesively fixed to the dicing/die bonding integrated film. . The method of expanding for separating the semiconductor elements with adhesive strips is not particularly limited, and various conventionally known methods can be employed. As a method for separating the semiconductor elements with adhesive strips, for example, a method of expanding the base material layer can be mentioned. The expansion may optionally be expansion under chilled conditions. The pickup method is not particularly limited, and conventionally known various methods can be employed. Examples of such a method include a method of pushing up individual semiconductor elements with adhesive pieces from the dicing/die bonding integrated film side with a needle and picking up the pushed-up semiconductor elements with adhesive pieces with a pickup device.
　ここでピックアップ工程は、粘着剤層が放射線（例えば、紫外線）硬化型の場合、該粘着剤層に放射線を照射した後に行うことができる。これによって、粘着剤層の接着剤片に対する粘着力が低下し、接着剤片付き半導体素子の剥離が容易になる。その結果、接着剤片付き半導体素子を損傷させることなく、ピックアップが可能となる。 Here, when the adhesive layer is radiation (for example, ultraviolet) curable, the pick-up step can be performed after irradiating the adhesive layer with radiation. As a result, the adhesive strength of the pressure-sensitive adhesive layer to the adhesive piece is lowered, and the semiconductor element with the adhesive piece is easily peeled off. As a result, it is possible to pick up the semiconductor element with the adhesive piece without damaging it.
　第１の接着工程は、ピックアップされた接着剤片付き半導体素子を、半導体素子を搭載するための支持部材に接着剤片を介して接着する工程である。また、必要に応じて、他の接着剤片付き半導体素子を、支持部材に接着された半導体素子の表面に接着剤片を介して接着する工程（第２の接着工程）を備えていてもよい。接着はいずれも圧着によって行うことができる。圧着条件としては、特に限定されず、適宜必要に応じて設定することができる。圧着条件は、例えば、８０～１６０℃の温度条件、５～１５Ｎの荷重条件、１～１０秒の時間条件であってよい。なお、支持部材は、上記と同様の支持部材を例示することができる。 The first bonding step is a step of bonding the picked-up semiconductor element with the adhesive piece to a supporting member for mounting the semiconductor element via the adhesive piece. In addition, if necessary, a step (second bonding step) of bonding another semiconductor element with an adhesive piece to the surface of the semiconductor element bonded to the support member via the adhesive piece may be provided. Any bonding can be performed by crimping. The crimping conditions are not particularly limited, and can be appropriately set according to need. The crimping conditions may be, for example, a temperature condition of 80 to 160° C., a load condition of 5 to 15 N, and a time condition of 1 to 10 seconds. In addition, the support member can illustrate the same support member as the above.
　半導体装置の製造方法は、必要に応じて、接着剤片を熱硬化させる工程を備えていてもよい。上記接着工程によって、半導体素子及び支持部材、又は、半導体素子（第１の半導体素子）と半導体素子（第２の半導体素子）を接着している接着剤片を熱硬化させることによって、より強固に接着固定が可能となる。熱硬化を行う場合、圧力を同時に加えて硬化させてもよい。本工程における加熱温度は、接着剤片を構成成分によって適宜変更することができる。加熱温度は、例えば、６０～２００℃であってよい。なお、温度又は圧力は、段階的に変更しながら行ってもよい。 The method of manufacturing a semiconductor device may include a step of thermally curing the adhesive piece, if necessary. By the above bonding step, the adhesive pieces bonding the semiconductor element and the support member, or the semiconductor element (first semiconductor element) and the semiconductor element (second semiconductor element) are thermally cured, thereby making them more firmly. Adhesive fixation is possible. When heat curing is performed, pressure may be applied at the same time for curing. The heating temperature in this step can be appropriately changed depending on the composition of the adhesive piece. The heating temperature may be, for example, 60-200.degree. Note that the temperature or pressure may be changed stepwise.
　半導体装置の製造方法は、必要に応じて、支持部材の端子部（インナーリード）の先端と半導体素子上の電極パッドとをボンディングワイヤで電気的に接続する工程（ワイヤボンディング工程）を備えていてもよい。ボンディングワイヤとしては、例えば、金線、アルミニウム線、銅線等が用いられる。ワイヤボンディングを行う（ボンディングワイヤを設ける）際の温度は、８０～２５０℃又は８０～２２０℃の範囲内であってよい。加熱時間は数秒～数分であってよい。ボンディングワイヤを設ける際は、上記温度範囲内で加熱された状態で、超音波による振動エネルギーと印加加圧とによる圧着エネルギーの併用によって行ってもよい。 A method of manufacturing a semiconductor device includes, if necessary, a step (wire bonding step) of electrically connecting tips of terminal portions (inner leads) of a support member and electrode pads on a semiconductor element with bonding wires. good too. As the bonding wire, for example, gold wire, aluminum wire, copper wire, or the like is used. The temperature for wire bonding (providing bonding wires) may be in the range of 80 to 250°C or 80 to 220°C. The heating time can be from a few seconds to several minutes. When the bonding wire is provided, it may be performed in a heated state within the above-mentioned temperature range by using both vibrational energy of ultrasonic waves and crimping energy of applied pressure.
　半導体装置の製造方法は、必要に応じて、封止材によって半導体素子を封止する工程（封止工程）を備えていてもよい。本工程は、支持部材に搭載された半導体素子又はボンディングワイヤを保護するために行われる。本工程は、封止用の樹脂（封止樹脂）を金型で成型することによって行うことができる。封止樹脂としては、例えばエポキシ系の樹脂であってよい。封止時の熱及び圧力によって支持部材及び残渣が埋め込まれ、接着界面での気泡による剥離を防止することができる。 The method of manufacturing a semiconductor device may optionally include a step of sealing the semiconductor element with a sealing material (sealing step). This step is performed to protect the semiconductor element or bonding wires mounted on the support member. This step can be performed by molding resin for sealing (sealing resin) with a mold. As the sealing resin, for example, an epoxy resin may be used. The support member and residue are embedded by heat and pressure during sealing, and peeling due to air bubbles at the adhesion interface can be prevented.
　半導体装置の製造方法は、必要に応じて、封止工程で硬化不足の封止樹脂を完全に硬化させる工程（後硬化工程）を備えていてもよい。封止工程において、接着剤片が熱硬化されない場合でも、本工程において、封止樹脂の硬化とともに接着剤片を熱硬化させて接着固定が可能になる。本工程における加熱温度は、封止樹脂の種類よって適宜設定することができ、例えば、１６５～１８５℃の範囲内であってよく、加熱時間は０．５～８時間程度であってよい。 The method of manufacturing a semiconductor device may include, if necessary, a process (post-curing process) for completely curing the sealing resin that is insufficiently cured in the sealing process. Even if the adhesive piece is not heat-cured in the sealing process, the adhesive piece can be heat-cured together with the curing of the sealing resin in the present process to enable adhesive fixation. The heating temperature in this step can be appropriately set according to the type of sealing resin, and may be, for example, within the range of 165 to 185° C., and the heating time may be approximately 0.5 to 8 hours.
　半導体装置の製造方法は、必要に応じて、支持部材に接着された接着剤片付き半導体素子に対して、リフロー炉を用いて加熱する工程（加熱溶融工程）を備えていてもよい。本工程では支持部材上に、樹脂封止した半導体装置を表面実装してもよい。表面実装の方法としては、例えば、プリント配線板上に予めはんだを供給した後、温風等によって加熱溶融し、はんだ付けを行うリフローはんだ付けなどが挙げられる。加熱方法としては、例えば、熱風リフロー、赤外線リフロー等が挙げられる。また、加熱方法は、全体を加熱するものであってもよく、局部を加熱するものであってもよい。加熱温度は、例えば、２４０～２８０℃の範囲内であってよい。 The method of manufacturing a semiconductor device may include, if necessary, a step of heating the semiconductor element with the adhesive piece adhered to the support member using a reflow furnace (heating and melting step). In this step, a resin-sealed semiconductor device may be surface-mounted on the supporting member. Examples of surface mounting methods include reflow soldering in which solder is preliminarily supplied onto a printed wiring board and then heated and melted by hot air or the like for soldering. Examples of the heating method include hot air reflow and infrared reflow. Moreover, the heating method may be a method of heating the whole or a method of locally heating. The heating temperature may be within the range of 240-280° C., for example.
　以下に、本開示を実施例に基づいて具体的に説明するが、本開示はこれらに限定されるものではない。 The present disclosure will be specifically described below based on examples, but the present disclosure is not limited to these.
［フィルム状接着剤の作製］
（実施例１～１９及び比較例１～３）
＜接着剤ワニスの調製＞
　表１、表２、及び表３に示す成分及び含有量（単位：質量部）で、（Ａ）成分、（Ｂ）成分、及び（Ｄ）成分からなる混合物にシクロヘキサノンを加え、撹拌混合した。これに、表１、表２、及び表３に示す成分及び含有量（単位：質量部）で、（Ｃ）成分を加えて撹拌し、さらに（Ｅ）成分及び（Ｆ）成分を加えて、各成分が均一になるまで撹拌して、接着剤ワニスを調製した。なお、表１、表２、及び表３に示す各成分は下記のものを意味し、表１、表２、及び表３に示す数値は固形分の質量部を意味する。 [Preparation of film adhesive]
(Examples 1 to 19 and Comparative Examples 1 to 3)
<Preparation of adhesive varnish>
Cyclohexanone was added to a mixture of components (A), (B), and (D) with the components and contents (unit: parts by mass) shown in Tables 1, 2, and 3, and mixed with stirring. To this, the components and contents (unit: parts by mass) shown in Tables 1, 2, and 3, (C) component is added and stirred, and (E) component and (F) component are added, An adhesive varnish was prepared by stirring each component until uniform. In addition, each component shown in Table 1, Table 2, and Table 3 means the following, and the numerical value shown in Table 1, Table 2, and Table 3 means the mass part of solid content.
（Ａ）成分：エポキシ樹脂
（Ａ－１）Ｎ－５００Ｐ－１０（商品名、ＤＩＣ株式会社製、ｏ－クレゾールノボラック型エポキシ樹脂、エポキシ当量：２０３ｇ／ｅｑ）
（Ａ－２）ＰＧ－１００（商品名、大阪ガスケミカル株式会社製、フルオレン骨格を有するエポキシ樹脂、エポキシ当量：２６０ｇ／ｅｑ） (A) Component: Epoxy resin (A-1) N-500P-10 (trade name, manufactured by DIC Corporation, o-cresol novolac type epoxy resin, epoxy equivalent: 203 g/eq)
(A-2) PG-100 (trade name, manufactured by Osaka Gas Chemicals Co., Ltd., epoxy resin having a fluorene skeleton, epoxy equivalent: 260 g/eq)
（Ｂ）成分：硬化剤
（Ｂ－１）ＭＥＨ－７８００Ｍ（商品名、明和化学株式会社製、フェノールノボラック型フェノール樹脂、水酸基当量：１６７～１８０ｇ／ｅｑ、軟化点：６１～９０℃）
（Ｂ－２）ＧＰＨ－１０３（商品名、日本化薬株式会社製、ビフェニルアラルキル型フェノール樹脂、水酸基当量：２２０～２４０ｇ／ｅｑ、軟化点：９９～１０６℃）
（Ｂ－３）ＰＳＭ－４３２６（商品名、群栄化学工業株式会社製、フェノールノボラック型フェノール樹脂、水酸基当量：１０５ｇ／ｅｑ、軟化点：１１８～１２２℃） (B) component: curing agent (B-1) MEH-7800M (trade name, manufactured by Meiwa Chemical Co., Ltd., phenolic novolac type phenolic resin, hydroxyl equivalent: 167-180g/eq, softening point: 61-90°C)
(B-2) GPH-103 (trade name, manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl-type phenolic resin, hydroxyl equivalent: 220 to 240 g/eq, softening point: 99 to 106°C)
(B-3) PSM-4326 (trade name, manufactured by Gun Ei Chemical Industry Co., Ltd., phenol novolac type phenolic resin, hydroxyl equivalent: 105 g/eq, softening point: 118 to 122° C.)
（Ｃ）成分：エラストマー
（Ｃ－１）ＨＴＲ－８６０Ｐ（商品名、ナガセケムテックス株式会社製、アクリルゴム、重量平均分子量：８０万、Ｔｇ：－１２℃）
（Ｃ－２）ＨＴＲ－８６０Ｐ－３０Ｂ：ナガセケムテックス株式会社製、アクリルゴム、重量平均分子量：３０万、Ｔｇ：－１２℃） (C) Component: Elastomer (C-1) HTR-860P (trade name, manufactured by Nagase ChemteX Corporation, acrylic rubber, weight average molecular weight: 800,000, Tg: -12°C)
(C-2) HTR-860P-30B: manufactured by Nagase ChemteX Corporation, acrylic rubber, weight average molecular weight: 300,000, Tg: -12°C)
（Ｄ）成分：平均粒径が４００ｎｍ以下である無機フィラー
（Ｄ－１）アエロジルＲ９７２（商品名（「アエロジル」は登録商標）、日本アエロジル株式会社製、シリカ粒子、平均粒径：１６ｎｍ）
（Ｄ－２）ＹＡ０５０Ｃ－ＨＨＧ（商品名、アドマテックス株式会社製、シリカフィラー分散液、平均粒径：５０ｎｍ）
（Ｄ－３）Ｋ１８０ＳＴ（商品名、アドマテックス株式会社製、シリカフィラー分散液、平均粒径：１８０ｎｍ）
（Ｄ－４）３ＧＦ（商品名、アドマテックス株式会社製、シリカフィラー分散液、平均粒径：３００ｎｍ）
（ｄ）成分：平均粒径が４００ｎｍ超である無機フィラー
（ｄ－１）ＳＣ２０５０－ＨＬＧ（商品名、アドマテックス株式会社製、シリカフィラー分散液、平均粒径：５００ｎｍ） Component (D): Inorganic filler having an average particle size of 400 nm or less (D-1) Aerosil R972 (trade name ("Aerosil" is a registered trademark), manufactured by Nippon Aerosil Co., Ltd., silica particles, average particle size: 16 nm)
(D-2) YA050C-HHG (trade name, Admatechs Co., Ltd., silica filler dispersion, average particle size: 50 nm)
(D-3) K180ST (trade name, Admatechs Co., Ltd., silica filler dispersion, average particle size: 180 nm)
(D-4) 3GF (trade name, Admatechs Co., Ltd., silica filler dispersion, average particle size: 300 nm)
(d) Component: Inorganic filler (d-1) SC2050-HLG having an average particle size of more than 400 nm (trade name, manufactured by Admatechs Co., Ltd., silica filler dispersion, average particle size: 500 nm)
（Ｅ）成分：カップリング剤
（Ｅ－１）Ａ－１８９（商品名、日本ユニカー株式会社製、γ－メルカプトプロピルトリメトキシシラン）
（Ｅ－２）Ｙ－９６６９（商品名、モメンティブ・パフォーマンス・マテリアルズ・ジャパン製、３－フェニルアミノプロピルトリメトキシシラン） Component (E): Coupling agent (E-1) A-189 (trade name, γ-mercaptopropyltrimethoxysilane manufactured by Nippon Unicar Co., Ltd.)
(E-2) Y-9669 (trade name, manufactured by Momentive Performance Materials Japan, 3-phenylaminopropyltrimethoxysilane)
（Ｆ）成分：硬化促進剤
（Ｆ－１）２ＰＺ－ＣＮ（商品名、四国化成工業株式会社製、１－シアノエチル－２－フェニルイミダゾール） Component (F): Curing accelerator (F-1) 2PZ-CN (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-cyanoethyl-2-phenylimidazole)
＜フィルム状接着剤の作製＞
　調製した接着剤ワニスを５００メッシュのフィルターでろ過し、真空脱泡した。支持フィルムとして、厚さ３８μｍの離型処理を施したポリエチレンテレフタレート（ＰＥＴ）フィルムを用意し、真空脱泡後の接着剤ワニスをＰＥＴフィルム上に塗布した。塗布した接着剤ワニスを、９０℃で５分の条件、続いて１４０℃で５分の条件の２段階で加熱乾燥し、Ｂステージ状態にある実施例１～１９及び比較例１～３のフィルム状接着剤（厚さ：７μｍ）を得た。フィルム状接着剤においては、接着剤ワニスの塗布量によって、フィルム状接着剤の厚さが７μｍになるように調整した。 <Preparation of film adhesive>
The prepared adhesive varnish was filtered through a 500 mesh filter and vacuum degassed. A release-treated polyethylene terephthalate (PET) film having a thickness of 38 μm was prepared as a support film, and an adhesive varnish after vacuum defoaming was applied onto the PET film. The applied adhesive varnish is dried by heating in two stages: 90° C. for 5 minutes, followed by 140° C. for 5 minutes. Films of Examples 1 to 19 and Comparative Examples 1 to 3 in B stage. An adhesive (thickness: 7 μm) was obtained. In the film adhesive, the thickness of the film adhesive was adjusted to 7 μm by adjusting the coating amount of the adhesive varnish.
［冷却エキスパンドによる分断性評価］
　実施例１～１９及び比較例１～３のフィルム状接着剤からそれぞれ接着剤片（幅５ｍｍ×長さ１００ｍｍ）を切り出した。接着剤片を一対の冶具（厚紙）に固定するとともに、冶具からはみ出している接着剤片の箇所を除去した。これにより、評価対象の試料（幅５ｍｍ×長さ２３ｍｍ）を得た。－１５℃に設定された恒温槽（株式会社アイテック社製、ＴＬＦ－Ｒ３－Ｆ－Ｗ－ＰＬ－Ｓ）内において割断試験を実施した。すなわち、オートグラフ（株式会社エーアンドデイ社製、ＡＺＴ－ＣＡ０１、ロードセル５０Ｎ）を用いて圧縮モード、速度１０ｍｍ／分、押し込み距離５ｍｍの条件で割断試験を実施し、フィルム状接着剤が破断したときの割断仕事Ｗ、割断強度Ｐ、及び割断伸びＬを求めた。また、上記の式（１）及び式（２）にから、割断係数ｍ及び割断抵抗Ｒを算出した。なお、割断係数ｍ及び割断抵抗Ｒは、各実施例及び各比較例について８回以上の割断試験を実施し、その平均値である。割断係数ｍはその数値が小さくなるにつれて、冷却エキスパンドによる分断性に優れる傾向にある。割断係数ｍが７０以下である場合を、冷却エキスパンドによる分断性に特に優れるとして「Ａ」、割断係数ｍが７０超９０以下である場合を「Ｂ」、割断係数ｍが９０超である場合を「Ｃ」と評価した。結果を表１、表２、及び表３に示す。また、割断係数ｍ及び割断抵抗Ｒの数値も併せて表１、表２、及び表３に示す。 [Evaluation of splitting property by cooling expansion]
Adhesive pieces (width 5 mm×length 100 mm) were cut out from the film adhesives of Examples 1 to 19 and Comparative Examples 1 to 3, respectively. The adhesive pieces were fixed to a pair of jigs (cardboard), and portions of the adhesive pieces protruding from the jigs were removed. As a result, a sample (width 5 mm×length 23 mm) to be evaluated was obtained. A cleaving test was performed in a constant temperature bath (TLF-R3-FW-PL-S manufactured by ITEC Co., Ltd.) set at -15°C. That is, using an autograph (AZT-CA01, load cell 50N, manufactured by A&D Co., Ltd.), a breaking test was performed under the conditions of compression mode, speed of 10 mm/min, and pushing distance of 5 mm. Breaking work W, breaking strength P, and breaking elongation L were obtained. Further, the breaking modulus m and the breaking resistance R were calculated from the above formulas (1) and (2). Note that the breaking coefficient m and breaking resistance R are the average values obtained by carrying out breaking tests eight times or more for each example and each comparative example. As the value of the breaking modulus m becomes smaller, the splitting property by cooling expansion tends to be excellent. "A" when the breaking modulus m is 70 or less is particularly excellent in splittability by cooling expansion, "B" when the breaking modulus m is more than 70 and 90 or less, and when the breaking modulus m is more than 90 It was evaluated as "C". The results are shown in Tables 1, 2 and 3. Tables 1, 2 and 3 also show numerical values of the breaking modulus m and the breaking resistance R.
［薄膜性の評価（ダイシェア強度の測定）］
（ダイシング・ダイボンディング一体型フィルムの作製）
　基材と粘着層とを有するダイシングテープ（商品名：６３６３－４５、昭和電工マテリアルズ株式会社製）を用意し、実施例１～１９及び比較例１～３のフィルム状接着剤のそれぞれに、ダイシングテープの粘着層をゴムロールにて張り合わせて、基材、粘着層、及び接着剤層（フィルム状接着剤）をこの順に備える実施例１～１９及び比較例１～３のダイシング・ダイボンディング一体型フィルムを作製した。 [Evaluation of thin film properties (measurement of die shear strength)]
(Preparation of dicing/die bonding integrated film)
A dicing tape (trade name: 6363-45, manufactured by Showa Denko Materials Co., Ltd.) having a base material and an adhesive layer was prepared, and each of the film adhesives of Examples 1 to 19 and Comparative Examples 1 to 3 was coated with The adhesive layer of the dicing tape is laminated with a rubber roll, and the substrate, adhesive layer, and adhesive layer (film adhesive) are provided in this order Examples 1 to 19 and Comparative Examples 1 to 3 Dicing / die bonding integrated type A film was produced.
（ダイシェア強度の測定）
　上記で作製した実施例１～１９及び比較例１～３のダイシング・ダイボンディング一体型フィルムを用いて、厚さ７μｍのフィルム状接着剤のダイシェア強度を測定した。ダイシェア強度を測定するための評価用サンプルは、以下のようにして作製した。厚さ４００μｍの半導体ウェハを用意し、ダイシング・ダイボンディング一体型フィルムのフィルム状接着剤側を、ステージ温度７０℃で半導体ウェハにラミネートし、ダイシング用サンプルを作製した。フルオートダイサーＤＦＤ－６３６１（株式会社ディスコ製）を用いて、得られたダイシング用サンプルを切断した。切断には、２枚のブレードを用いるステップカット方式で行い、ダイシングブレードＺＨ０５－ＳＤ２０００－Ｎ１－７０－ＦＦ、及びＺＨ０５－ＳＤ４０００－Ｎ１－７０－ＥＥ（いずれも株式会社ディスコ製）を用いた。切断条件は、ブレード回転数：４０００ｒｐｍ、切断速度：５０ｍｍ／秒、チップサイズ：３ｍｍ×３ｍｍとした。切断は、半導体ウェハが２００μｍ程度残るように１段階目の切断を行い、ダイシングテープに２０μｍ程度の切り込みが入るように２段階目の切断を行った。次いで、紫外線硬化型粘着剤からなる粘着剤層に紫外線を照射して、粘着剤層を硬化させ、接着剤片付き半導体素子をピックアップした。続いて、接着剤片付き半導体素子の接着剤片を温度１２０℃、圧力０．１ＭＰａ、時間１．０秒の条件で、ＡＵＳ４１０基板（ソルダーレジスト付き有機基板）に圧着し、評価用サンプルを作製した。万能ボンドテスター（ノードソン・アドバンスト・テクノロジー株式会社製）を用いて、ＡＵＳ４１０基板と接着剤片とのダイシェア強度を室温（２５℃）下で測定した。ダイシェア強度が６ＭＰａ以上である場合を、薄膜性に特に優れるとして「Ａ」、ダイシェア強度が４ＭＰａ以上６ＭＰａ未満である場合を「Ｂ」、ダイシェア強度が４ＭＰａ未満である場合を「Ｃ」と評価した。結果を表１、表２、及び表３に示す。また、ダイシェア強度の数値も併せて表１、表２、及び表３に示す。 (Measurement of die shear strength)
Using the dicing/die-bonding integrated films of Examples 1 to 19 and Comparative Examples 1 to 3 produced above, the die shear strength of the film adhesive with a thickness of 7 μm was measured. An evaluation sample for measuring the die shear strength was produced as follows. A semiconductor wafer having a thickness of 400 μm was prepared, and the film adhesive side of the dicing/die bonding integrated film was laminated on the semiconductor wafer at a stage temperature of 70° C. to prepare a sample for dicing. The obtained sample for dicing was cut using a full-auto dicer DFD-6361 (manufactured by Disco Co., Ltd.). The cutting was performed by a step cut method using two blades, and dicing blades ZH05-SD2000-N1-70-FF and ZH05-SD4000-N1-70-EE (both manufactured by DISCO Corporation) were used. The cutting conditions were blade rotation speed: 4000 rpm, cutting speed: 50 mm/sec, and chip size: 3 mm×3 mm. The first stage of cutting was performed so that the semiconductor wafer remained about 200 μm, and the second stage of cutting was performed so that the dicing tape was cut to about 20 μm. Next, the adhesive layer made of the ultraviolet curable adhesive was irradiated with ultraviolet rays to cure the adhesive layer, and the semiconductor element with the adhesive piece was picked up. Subsequently, the adhesive piece of the semiconductor element with the adhesive piece was pressure-bonded to an AUS410 substrate (organic substrate with solder resist) under conditions of a temperature of 120° C., a pressure of 0.1 MPa, and a time of 1.0 second to prepare a sample for evaluation. . Using a universal bond tester (manufactured by Nordson Advanced Technologies, Inc.), the die shear strength between the AUS410 substrate and the adhesive piece was measured at room temperature (25° C.). A case where the die shear strength is 6 MPa or more is evaluated as being particularly excellent in thin film properties, "B" when the die shear strength is 4 MPa or more and less than 6 MPa, and "C" when the die shear strength is less than 4 MPa. . The results are shown in Tables 1, 2 and 3. Tables 1, 2 and 3 also show values of die shear strength.
［耐リフロー性の評価］
　ダイシェア強度の測定で作製した接着剤片付き半導体素子を用いて、以下の方法で耐リフロー性を作製した。まず、接着剤片付き半導体素子を用いて、図８に示すような、四段に積層された積層体をモールド用封止材（日立化成株式会社製、商品名「ＣＥＬ－９７５０ＺＨＦ１０」）で封止することによって、評価用パッケージを得た。なお、封止材の封止条件は１７５℃／６．７ＭＰａ／９０秒とし、硬化の条件は１７５℃、５時間とした。評価用パッケージを２０個準備し、これらをＪＥＤＥＣで定めた環境下（レベル３、３０℃、６０ＲＨ％、１９２時間）に曝して吸湿させた。続いて、ＩＲリフロー炉（２６０℃、最高温度２６５℃）に吸湿後の評価用パッケージを３回通過させた。以下の基準で評価を行った。結果を表１、表２、及び表３に示す。
　Ａ：評価用パッケージの破損、厚さの変化、接着剤片と半導体素子との界面での剥離等が２０個の評価用パッケージのうち１個も観察されなかった。
　Ｂ：評価用パッケージの破損、厚さの変化、接着剤片と半導体素子との界面での剥離等が２０個の評価用パッケージのうち少なくとも１個観察された。 [Evaluation of reflow resistance]
Using the semiconductor element with adhesive piece produced by measuring the die shear strength, reflow resistance was produced by the following method. First, using a semiconductor element with an adhesive piece, a laminate laminated in four stages as shown in FIG. A package for evaluation was obtained by doing. The sealing conditions of the sealing material were 175° C./6.7 MPa/90 seconds, and the curing conditions were 175° C. and 5 hours. Twenty evaluation packages were prepared and exposed to the environment defined by JEDEC (level 3, 30° C., 60 RH %, 192 hours) to absorb moisture. Subsequently, the package for evaluation after moisture absorption was passed three times through an IR reflow oven (260° C., maximum temperature 265° C.). Evaluation was performed according to the following criteria. The results are shown in Tables 1, 2 and 3.
A: None of the 20 evaluation packages was found to have damage, change in thickness, peeling at the interface between the adhesive piece and the semiconductor element, or the like.
B: At least one of the 20 evaluation packages was observed to have damage, thickness change, peeling at the interface between the adhesive piece and the semiconductor element, and the like.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１、表２、及び表３に示すとおり、実施例１～１９のフィルム状接着剤は、冷却分断性及び薄膜性の点で優れていた。一方で、比較例１～３のフィルム状接着剤は、薄膜性及び冷却分断性の少なくとも一方で充分でなかった。これらのことから、本開示のフィルム状接着剤が、冷却エキスパンドによる分断性に優れるとともに、薄膜化したときに充分なダイシェア強度を有することが確認された。 As shown in Tables 1, 2, and 3, the film adhesives of Examples 1 to 19 were excellent in terms of cooling splitting properties and thin film properties. On the other hand, the film adhesives of Comparative Examples 1 to 3 were insufficient in at least one of thin film properties and cooling splitting properties. From these, it was confirmed that the film-like adhesive of the present disclosure has excellent splittability by cooling expansion and has sufficient die shear strength when thinned.
　１…フィルム状接着剤、１Ａ…接着剤層、２…基材層、３…粘着剤層、４…ダイシングテープ、１０…ダイシング・ダイボンディング一体型フィルム、１１，１１ａ，１１ｂ，１１ｃ，１１ｄ…半導体素子、１２…支持部材、１３…ワイヤ、１４…封止材、１５，１５ａ，１５ｂ，１５ｃ，１５ｄ…接着部材、１６…端子、２０…試料固定用冶具、２０ａ…開口、２１…押し込み冶具、２１ａ…先端部、１００，１１０，１２０…半導体装置。

  DESCRIPTION OF SYMBOLS 1... Film adhesive 1A... Adhesive layer 2... Base material layer 3... Adhesive layer 4... Dicing tape 10... Dicing die-bonding integrated film 11, 11a, 11b, 11c, 11d... DESCRIPTION OF SYMBOLS Semiconductor element 12... Supporting member 13... Wire 14... Sealing material 15, 15a, 15b, 15c, 15d... Adhesive member 16... Terminal 20... Sample fixing jig 20a... Opening 21... Pushing jig , 21a... tip part, 100, 110, 120... semiconductor device.

Claims (13)

  1. 　熱硬化性樹脂と、硬化剤と、エラストマーと、平均粒径が４００ｎｍ以下である無機フィラーとを含有し、
    　前記無機フィラーの含有量が、フィルム状接着剤の全量を基準として、１８～４０質量％であり、
    　前記熱硬化性樹脂及び前記硬化剤の合計の含有量が、フィルム状接着剤の全量を基準として、２５質量％以下である、
    　フィルム状接着剤。     Containing a thermosetting resin, a curing agent, an elastomer, and an inorganic filler having an average particle size of 400 nm or less,
    The content of the inorganic filler is 18 to 40% by mass based on the total amount of the film adhesive,
    The total content of the thermosetting resin and the curing agent is 25% by mass or less based on the total amount of the film adhesive.
    Film adhesive.
  2. 　前記エラストマーの含有量が、フィルム状接着剤の全量を基準として、４０質量％以上である、
    　請求項１に記載のフィルム状接着剤。     The content of the elastomer is 40% by mass or more based on the total amount of the film adhesive.
    The film adhesive according to claim 1.
  3. 　前記無機フィラーの含有量が、前記熱硬化性樹脂、前記硬化剤、及び前記エラストマーの全量１００質量部に対して、２２質量部以上である、
    　請求項１又は２に記載のフィルム状接着剤。     The content of the inorganic filler is 22 parts by mass or more with respect to 100 parts by mass of the total amount of the thermosetting resin, the curing agent, and the elastomer.
    The film adhesive according to claim 1 or 2.
  4. 　前記エラストマーの含有量が、前記熱硬化性樹脂及び前記硬化剤の全量１００質量部に対して、２００質量部以上である、
    　請求項１又は２に記載のフィルム状接着剤。     The content of the elastomer is 200 parts by mass or more with respect to 100 parts by mass of the total amount of the thermosetting resin and the curing agent.
    The film adhesive according to claim 1 or 2.
  5. 　厚さが２０μｍ以下である、
    　請求項１又は２に記載のフィルム状接着剤。     thickness is 20 μm or less,
    The film adhesive according to claim 1 or 2.
  6. 　複数の半導体素子を積層してなる半導体装置の製造プロセスに用いられる、
    　請求項１又は２に記載のフィルム状接着剤。     Used in the manufacturing process of semiconductor devices in which multiple semiconductor elements are stacked,
    The film adhesive according to claim 1 or 2.
  7. 　前記半導体装置が三次元ＮＡＮＤ型メモリである、
    　請求項６に記載のフィルム状接着剤。     wherein the semiconductor device is a three-dimensional NAND memory;
    The film adhesive according to claim 6.
  8. 　基材層と、粘着剤層と、請求項１又は２に記載のフィルム状接着剤からなる接着剤層とをこの順に備える、
    　ダイシング・ダイボンディング一体型フィルム。     A substrate layer, an adhesive layer, and an adhesive layer made of the film adhesive according to claim 1 or 2 are provided in this order,
    Dicing and die bonding integrated film.
  9. 　半導体素子と、
    　前記半導体素子を搭載する支持部材と、
    　前記半導体素子及び前記支持部材の間に設けられ、前記半導体素子と前記支持部材とを接着する接着部材と、
    を備え、
    　前記接着部材が、請求項１又は２に記載のフィルム状接着剤の硬化物である、
    　半導体装置。     a semiconductor element;
    a support member for mounting the semiconductor element;
    an adhesive member provided between the semiconductor element and the support member for bonding the semiconductor element and the support member;
    with
    The adhesive member is a cured product of the film adhesive according to claim 1 or 2,
    semiconductor device.
  10. 　前記半導体素子の表面上に積層された他の半導体素子をさらに備える、
    　請求項９に記載の半導体装置。     Further comprising another semiconductor element laminated on the surface of the semiconductor element,
    10. The semiconductor device according to claim 9.
  11. 　半導体素子と支持部材との間、又は、第１の半導体素子と第２の半導体素子との間に請求項１又は２に記載のフィルム状接着剤を介在させ、前記半導体素子及び前記支持部材、又は、前記第１の半導体素子及び前記第２の半導体素子を接着させる工程を備える、
    　半導体装置の製造方法。     The film adhesive according to claim 1 or 2 is interposed between a semiconductor element and a supporting member, or between a first semiconductor element and a second semiconductor element, and the semiconductor element and the supporting member, Alternatively, comprising a step of bonding the first semiconductor element and the second semiconductor element,
    A method of manufacturing a semiconductor device.
  12. 　請求項８に記載のダイシング・ダイボンディング一体型フィルムの前記接着剤層を半導体ウェハに貼り付ける工程と、
    　前記接着剤層を貼り付けた前記半導体ウェハをダイシングする工程と、
    　前記基材層を冷却条件下エキスパンドすることによって、複数の個片化された接着剤片付き半導体素子を作製する工程と、
    　前記接着剤片付き半導体素子を前記粘着剤層からピックアップする工程と、
    　ピックアップされた前記接着剤片付き半導体素子を支持部材に接着剤片を介して接着する工程と、
    を備える、
    　半導体装置の製造方法。     A step of attaching the adhesive layer of the dicing and die bonding integrated film according to claim 8 to a semiconductor wafer;
    dicing the semiconductor wafer to which the adhesive layer is attached;
    fabricating a plurality of singulated semiconductor devices with adhesive strips by expanding the substrate layer under cooling conditions;
    a step of picking up the semiconductor element with the adhesive piece from the adhesive layer;
    a step of adhering the picked-up semiconductor element with adhesive piece to a support member via the adhesive piece;
    comprising
    A method of manufacturing a semiconductor device.
  13. 　他の前記接着剤片付き半導体素子を、前記支持部材に接着された前記半導体素子の表面に接着剤片を介して接着する工程をさらに備える、
    　請求項１２に記載の半導体装置の製造方法。     A step of adhering another semiconductor element with an adhesive piece to the surface of the semiconductor element adhered to the support member via an adhesive piece,
    13. The method of manufacturing a semiconductor device according to claim 12.
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Citations (4)

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JP2010074144A (en) * 2008-08-20 2010-04-02 Hitachi Chem Co Ltd Dicing-tape integral type adhesive sheet and method of manufacturing semiconductor device using the same
JP2018016673A (en) * 2016-07-25 2018-02-01 日立化成株式会社 Adhesive sheet, and method for manufacturing semiconductor device
WO2020013250A1 (en) * 2018-07-11 2020-01-16 日立化成株式会社 Method for manufacturing semiconductor device, heat-curable resin composition, and dicing-die attach film
WO2021095302A1 (en) * 2019-11-15 2021-05-20 昭和電工マテリアルズ株式会社 Semiconductor device production method, dicing die-bonding integrated film, and production method therefor

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WO2020183581A1 (en) * 2019-03-11 2020-09-17 日立化成株式会社 Adhesive agent composition, film-like adhesive agent, adhesive sheet, and semiconductor device manufacturing method

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Publication number Priority date Publication date Assignee Title
JP2010074144A (en) * 2008-08-20 2010-04-02 Hitachi Chem Co Ltd Dicing-tape integral type adhesive sheet and method of manufacturing semiconductor device using the same
JP2018016673A (en) * 2016-07-25 2018-02-01 日立化成株式会社 Adhesive sheet, and method for manufacturing semiconductor device
WO2020013250A1 (en) * 2018-07-11 2020-01-16 日立化成株式会社 Method for manufacturing semiconductor device, heat-curable resin composition, and dicing-die attach film
WO2021095302A1 (en) * 2019-11-15 2021-05-20 昭和電工マテリアルズ株式会社 Semiconductor device production method, dicing die-bonding integrated film, and production method therefor

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