TWI838470B - Semiconductor back side bonding film and wafer-cutting tape integrated semiconductor back side bonding film - Google Patents

Abstract

The present invention provides a semiconductor back-side adhesive film suitable for suppressing warping of a semiconductor wafer bonded with a semiconductor back-side adhesive film during the manufacturing process of a semiconductor device, and a wafer-cut tape-type semiconductor back-side adhesive film. The difference between the heat release amount in the range of 50 to 200°C in the differential scanning calorimetry at a heating rate of 10°C/min and the heat release amount in the range of 50 to 200°C in the differential scanning calorimetry at a heating rate of 10°C/min after heating at 130°C for 2 hours is 50 J/g or less. The wafer-cut tape-type semiconductor back-side adhesive film X of the present invention comprises a film 10 and a wafer-cut tape 20. The wafer-cut tape 20 has a laminated structure including a substrate 21 and an adhesive layer 22. The film 10 is releasably attached to the adhesive layer 22 of the diced ribbon 20.

Description

Semiconductor back side bonding film and wafer-cutting tape integrated semiconductor back side bonding film

The present invention relates to a semiconductor back side bonding film and a wafer-cutting-ribbon-integrated semiconductor back side bonding film which can be used in the manufacturing process of semiconductor devices.

In the manufacture of semiconductor devices having flip-chip mounted semiconductor chips, a film for forming a protective film on the so-called back side of the chip, i.e., a semiconductor back side adhesion film, is sometimes used.

The semiconductor back-side adhesive film is attached to the back side of a semiconductor wafer as a workpiece during the manufacturing process of a semiconductor device having a semiconductor chip mounted by flip-chip mounting. Thereafter, various information such as text information or graphic information is printed on the surface of the semiconductor back-side adhesive film (the surface on the side opposite to the wafer) by laser marking, corresponding to each semiconductor element formed on the wafer to be singulated into semiconductor chips. The semiconductor wafer is singulated into chips by, for example, cutting with a blade while the film is attached. The semiconductor chip with a protective film thus obtained is flip-chip mounted on a specific substrate. The technology regarding this type of semiconductor back-side adhesive film is described, for example, in the following patent document 1. [Prior art document] [Patent document]

[Patent Document 1] International Publication No. 2014/092200

[The problem the invention is trying to solve]

The steps that a semiconductor wafer with a semiconductor back-side adhesive film attached to it undergoes during the semiconductor device manufacturing process include placing the wafer under relatively high temperature conditions. Previously, semiconductor wafers with a semiconductor back-side adhesive film attached to them sometimes warp under the high temperature conditions. The thinner the wafer, the more likely it is to warp.

The present invention is conceived based on the above situation, and its purpose is to provide a semiconductor back side adhesive film suitable for suppressing the warping of a semiconductor wafer bonded with a semiconductor back side adhesive film during the semiconductor device manufacturing process, and a wafer-cutting-ribbon-integrated semiconductor back side adhesive film. [Technical means to solve the problem]

According to the first aspect of the present invention, a semiconductor back surface adhesive film is provided. The difference between the heat release (first heat release) of the semiconductor back surface adhesive film in the range of 50 to 200°C in differential scanning calorimetry at a heating rate of 10°C/min and the heat release (second heat release) in the range of 50 to 200°C in differential scanning calorimetry at a heating rate of 10°C/min after heating at 130°C for 2 hours (calorie obtained by subtracting the second heat release from the first heat release) is 50 J/g or less. The semiconductor back surface adhesive film described above can be used to obtain a semiconductor chip with a chip back surface protective film in the manufacturing process of a semiconductor device.

The so-called first heat release in the present invention refers to the heat release in the range of 50 to 200°C of the semiconductor back surface adhesive film that has not been subjected to the heat treatment under the condition of 130°C for 2 hours in the differential scanning calorimetry at a heating rate of 10°C/min. The so-called second heat release in the present invention refers to the heat release in the range of 50 to 200°C of the semiconductor back surface adhesive film that has been subjected to the heat treatment under the condition of 130°C for 2 hours in the differential scanning calorimetry at a heating rate of 10°C/min. The inventors of the present invention have found that a structure in which the difference in the heat release (the heat obtained by subtracting the second heat release from the first heat release) in the semiconductor back surface adhesive film is 50 J/g or less is preferable in terms of suppressing the warping of the semiconductor wafer bonded with the film when the semiconductor wafer is exposed to a high temperature environment. This is shown, for example, in the following examples and comparative examples.

The above-mentioned respective heat releases in the range of 50 to 200°C in differential scanning calorimetry of the semiconductor back surface adhesive film are mainly accounted for by the heat release (reaction heat) generated by the reaction between the constituent components in the film. The configuration in which the difference between the above-mentioned first heat release of the semiconductor back surface adhesive film not subjected to the above-mentioned heat treatment and the above-mentioned second heat release of the semiconductor back surface adhesive film subjected to the above-mentioned heat treatment is 50 J/g or less means that a reaction of a degree of heat release or reaction heat of 50 J/g or less occurs in the semiconductor back surface adhesive film by the above-mentioned heat treatment. That is, the structure means that the more the reaction carried out in the semiconductor back surface adhesive film by the above-mentioned heat treatment is equivalent to the degree of heat release of 50 J/g or less, the more it means that the reaction has already been carried out in the semiconductor back surface adhesive film before the above-mentioned heat treatment (the reaction rate in the film is higher) or the reaction is difficult to be carried out in the semiconductor back surface adhesive film by the above-mentioned heat treatment. Such a structure in the semiconductor back surface adhesive film is suitable for reducing the shrinkage degree of the film due to the reaction caused by exposure to a high temperature environment, and is therefore suitable for suppressing the warping of the semiconductor wafer when the semiconductor wafer bonded with the film is exposed to a high temperature environment.

As described above, the semiconductor back surface adhesive film of the first aspect of the present invention is suitable for suppressing warping of a semiconductor wafer bonded with the semiconductor back surface adhesive film during the semiconductor device manufacturing process. From the viewpoint of suppressing such warping, the above heat release difference is preferably 30 J/g or less, more preferably 20 J/g or less, and even more preferably 10 J/g or less.

In the semiconductor back surface adhesive film, relative to the tensile storage modulus at 150°C measured for a semiconductor back surface adhesive film sample having a width of 10 mm under the conditions of an initial nip distance of 20 mm, a frequency of 1 Hz and a heating rate of 10°C/min (elastic modulus measurement conditions), the ratio of the tensile storage modulus at 150°C measured under the elastic modulus measurement conditions after heat treatment at 130°C for 2 hours is preferably 20 or less, more preferably 10 or less, more preferably 5 or less, more preferably 3 or less, and more preferably 1.5 or less. This structure is suitable for reducing the degree of shrinkage caused by exposing the film to a high temperature environment, and is therefore suitable for suppressing warping of the wafer when the semiconductor wafer bonded with the film is exposed to a high temperature environment.

The semiconductor back-side adhesive film preferably contains an inorganic filler. In this case, the inorganic filler content of the semiconductor back-side adhesive film is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. Such a structure is preferred in terms of suppressing the above-mentioned warping in the semiconductor back-side adhesive film or the semiconductor wafer bonded thereto. In addition, from the perspective of ensuring the printability based on laser marking in the semiconductor back-side adhesive film, the inorganic filler content of the semiconductor back-side adhesive film is preferably less than 75% by mass.

The glass transition temperature of the semiconductor back side adhesive film is preferably 100-200° C. This structure is suitable for reducing the stress caused by thermal shrinkage of the semiconductor back side adhesive film during the manufacturing process of semiconductor devices using the semiconductor back side adhesive film, and seeking stress relaxation by shrinking the high elastic area.

The semiconductor back surface adhesive film preferably contains an epoxy resin with an epoxy equivalent of 150 to 900 g/eq at a ratio of 2 to 20 mass %. This structure is suitable for suppressing the number of crosslinking points in the constituent resin material in the semiconductor back surface adhesive film and ensuring good adhesion. The fewer the crosslinking points in the constituent resin material in the semiconductor back surface adhesive film, the more the tendency of shrinkage due to the crosslinking reaction when heated is suppressed.

According to the second aspect of the present invention, a wafer-cut tape-type semiconductor back-side bonding film is provided. The wafer-cut tape-type semiconductor back-side bonding film comprises a wafer-cut tape and the semiconductor back-side bonding film of the first aspect of the present invention. The wafer-cut tape has a layered structure including a substrate and an adhesive layer. The semiconductor back-side bonding film can be peelably bonded to the adhesive layer of the wafer-cut tape. This wafer-cut tape-type semiconductor back-side bonding film can be used to obtain a semiconductor chip with a film for forming a chip back protective film during the manufacturing process of a semiconductor device.

The present wafer-cut ribbon integrated semiconductor back surface adhesive film has the semiconductor back surface adhesive film of the first aspect of the present invention as described above. According to this wafer-cut ribbon integrated semiconductor back surface adhesive film, it is suitable for suppressing the generation of warp of a semiconductor wafer bonded with the semiconductor back surface adhesive film during the semiconductor device manufacturing process.

FIG. 1 and FIG. 2 show a wafer-cut tape-type semiconductor back-side adhesive film X in an embodiment of the present invention. FIG. 1 is a top view of the wafer-cut tape-type semiconductor back-side adhesive film X, and FIG. 2 is a cross-sectional schematic diagram of the wafer-cut tape-type semiconductor back-side adhesive film X. The wafer-cut tape-type semiconductor back-side adhesive film X can be used in the process of obtaining a semiconductor chip with a chip back protective film, and has a laminated structure including a film 10 and a wafer-cut tape 20. The film 10 is a semiconductor back-side adhesive film in an embodiment of the present invention, and is a film that is attached to the circuit non-forming surface, i.e., the reverse surface or the back surface, of a semiconductor wafer as a workpiece. The wafer-cut tape 20 has a laminated structure including a substrate 21 and an adhesive layer 22. The adhesive layer 22 has an adhesive surface 22a on the side of the film 10. The film 10 is releasably adhered to the adhesive layer 22 or its adhesive surface 22a. The wafer-cut tape-integrated semiconductor back surface adhesive film X has a disk shape having a size corresponding to the semiconductor wafer as a workpiece.

The film 10 as a semiconductor back-side bonding film has a laminated structure including a laser marking layer 11 and a bonding layer 12. The laser marking layer 11 is located on the side of the cut ribbon 20 in the film 10 and is in close contact with the cut ribbon 20 or its adhesive layer 22. Laser marking is performed on the surface of the laser marking layer 11 on the side of the cut ribbon 20 during the manufacturing process of the semiconductor device. In this embodiment, the laser marking layer 11 is in a state where the thermosetting resin composition layer has been thermoset. The bonding layer 12 is located on the side of the film 10 for bonding the workpiece, and has a workpiece bonding surface 12a. In this embodiment, it is a thermoplastic non-thermosetting resin composition layer. The film 10 having the layered structure including the laser marking layers 11 and the bonding layer 12 is a non-thermosetting film that does not substantially have thermosetting properties.

The laser marking layer 11 in the film 10 may have a composition including a thermosetting resin and a thermoplastic resin as resin components, or may have a composition including a thermoplastic resin having a thermosetting functional group that can react with a curing agent to form a bond.

When the laser marking layer 11 has a composition including a thermosetting resin and a thermoplastic resin, the thermosetting resin may be, for example, epoxy resin, phenolic resin, amino resin, unsaturated polyester resin, polyurethane resin, polysilicone resin, and thermosetting polyimide resin. The laser marking layer 11 may contain one thermosetting resin or two or more thermosetting resins. Epoxy resin has a tendency to contain less ionic impurities that may cause corrosion to the semiconductor chip to be protected by the back protective film formed by the film 10 in the following manner, so the thermosetting resin in the laser marking layer 11 of the film 10 is preferred. The laser marking layer 11 preferably contains an epoxy resin having an epoxy equivalent of preferably 150 to 900 g/eq, more preferably 150 to 700 g/eq, at a ratio of preferably 2 to 20 mass %. In addition, a phenolic resin is preferably used as a hardener for making the epoxy resin exhibit thermosetting properties.

Examples of epoxy resins include bifunctional epoxy resins or polyfunctional epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, brominated bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol AF type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, fluorene type epoxy resins, phenol novolac type epoxy resins, o-cresol novolac type epoxy resins, trihydroxyphenylmethane type epoxy resins, and tetraphenolethane type epoxy resins. Examples of epoxy resins include hydantoin type epoxy resins, triglycidyl isocyanurate type epoxy resins, and glycidylamine type epoxy resins. The laser marking layer 11 may contain one type of epoxy resin or two or more types of epoxy resins.

The phenolic resin can function as a hardener for the epoxy resin. Examples of such phenolic resins include phenol novolac resins, phenol aralkyl resins, cresol novolac resins, tertiary butylphenol novolac resins, and nonylphenol novolac resins. Examples of the phenolic resins include soluble phenolic resins and polyhydroxystyrenes such as poly(p-hydroxystyrene). The phenolic resin in the laser marking layer 11 is preferably a phenol novolac resin or a phenol aralkyl resin. Furthermore, the laser marking layer 11 may contain one kind of phenolic resin as a hardener for the epoxy resin, or may contain two or more kinds of phenolic resins.

When the laser marking layer 11 contains an epoxy resin and a phenolic resin as a curing agent, the two resins are mixed in a ratio of preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.2 equivalents of hydroxyl groups in the phenolic resin to 1 equivalent of epoxy groups in the epoxy resin. This configuration is preferred in that the curing reaction of the epoxy resin and the phenolic resin proceeds sufficiently when the laser marking layer 11 is cured.

From the viewpoint of appropriately curing the laser marking layer 11, the content ratio of the total amount of the thermosetting resin in the laser marking layer 11 is preferably 15 to 60 mass %, more preferably 20 to 55 mass %.

The thermoplastic resin in the laser marking layer 11 is, for example, one that functions as an adhesive. When the laser marking layer 11 has a composition including a thermosetting resin and a thermoplastic resin, the thermoplastic resin may include, for example, acrylic resin, natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, The laser marking layer 11 may contain one thermoplastic resin or two or more thermoplastic resins. Acrylic resins are preferably used as the thermoplastic resin in the laser marking layer 11 because of their low ionic impurities and high heat resistance.

When the laser marking layer 11 contains an acrylic resin as the thermoplastic resin, the acrylic resin preferably contains the largest amount of monomer units derived from (meth)acrylate in terms of mass ratio. "(Meth)acrylic" means "acrylic acid" and/or "methacrylic acid".

Examples of (meth)acrylates as monomer units for forming the acrylic resin, i.e., (meth)acrylates as constituent monomers of the acrylic resin, include alkyl (meth)acrylates, cycloalkyl (meth)acrylates, and aryl (meth)acrylates. Examples of alkyl (meth)acrylates include methyl (meth)acrylates, ethyl (meth)acrylates, propyl (meth)acrylates, isopropyl (meth)acrylates, butyl (meth)acrylates, isobutyl (meth)acrylates, sec-butyl (meth)acrylates, tert-butyl (meth)acrylates, pentyl (meth)acrylates, isopentyl (meth)acrylates, hexyl (meth)acrylates, heptyl (meth)acrylates, octyl (meth)acrylates, 2-ethylhexyl (meth)acrylates, isooctyl (meth)acrylates, nonyl (meth)acrylates, decyl (meth)acrylates, isodecyl (meth)acrylates, undecyl (meth)acrylates, dodecyl (meth)acrylates, tridecyl (meth)acrylates, tetradecyl (meth)acrylates, hexadecyl (meth)acrylates, octadecyl (meth)acrylates, and eicosyl (meth)acrylates. Examples of cycloalkyl (meth)acrylates include cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate. Examples of aryl (meth)acrylates include phenyl (meth)acrylate and benzyl (meth)acrylate. As monomers constituting the acrylic resin, one (meth)acrylate may be used, or two or more (meth)acrylates may be used. The acrylic resin may be obtained by polymerizing the raw material monomers used to form the acrylic resin. Examples of polymerization techniques include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization.

Acrylic resins may also use one or more other monomers copolymerizable with (meth)acrylate as constituent monomers, for example, in order to improve their cohesive force or heat resistance. Examples of such monomers include carboxyl-containing monomers, acid anhydride monomers, hydroxyl-containing monomers, epoxy-containing monomers, sulfonic acid-containing monomers, phosphoric acid-containing monomers, acrylamide, and acrylonitrile. Examples of carboxyl-containing monomers include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, and butenoic acid. Examples of acid anhydride monomers include maleic anhydride and itaconic anhydride. Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)methyl (meth)acrylate. Examples of epoxy group-containing monomers include glycidyl (meth)acrylate and methylglycidyl (meth)acrylate. Examples of sulfonic acid group-containing monomers include styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, and (meth)acryloyloxynaphthalenesulfonic acid. As the phosphoric acid group-containing monomer, for example, 2-hydroxyethylacryloyl phosphate can be mentioned.

In the case where the laser marking layer 11 has a composition including a thermoplastic resin with a thermosetting functional group, as the thermoplastic resin, for example, an acrylic resin containing a thermosetting functional group can be used. The acrylic resin used to form the acrylic resin containing a thermosetting functional group preferably contains the most monomer units derived from (meth)acrylate in terms of mass ratio. As such a (meth)acrylate, for example, the same (meth)acrylate as described above as the constituent monomer of the acrylic resin contained in the laser marking layer 11 can be used. The acrylic resin used to form the acrylic resin containing a thermosetting functional group can also contain monomer units derived from one or more other monomers that can be copolymerized with (meth)acrylate, for example, in order to improve its cohesion or heat resistance. As such a monomer, for example, the monomers described above as other monomers copolymerizable with the (meth)acrylate used to form the acrylic resin in the laser marking layer 11 can be used. On the other hand, as thermosetting functional groups used to form the acrylic resin containing thermosetting functional groups, for example, there can be listed: glycidyl group, carboxyl group, hydroxyl group, and isocyanate group. Among them, glycidyl group and carboxyl group can be preferably used. That is, as the acrylic resin containing thermosetting functional groups, it is preferable to use an acrylic resin containing glycidyl group or an acrylic resin containing carboxyl group. In addition, according to the type of thermosetting functional group in the acrylic resin containing thermosetting functional groups, a curing agent that can react with it is selected. When the thermosetting functional group of the thermosetting functional group-containing acrylic resin is a glycidyl group, the same phenolic resin as described above as the hardener for the epoxy resin can be used as the hardener.

The composition for forming the laser marking layer 11 contains a heat-curing catalyst in this embodiment. The heat-curing catalyst in the composition for forming the laser marking layer is preferably formulated so that the curing reaction of the resin component can proceed sufficiently or the curing reaction speed can be increased when the laser marking layer 11 is cured. Examples of such heat-curing catalysts include imidazole compounds, triphenylphosphine compounds, amine compounds, and trihaloborane compounds. Examples of the imidazole compounds include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methyl]imidazole, triazole, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazole, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazole, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Examples of triphenylphosphine compounds include triphenylphosphine, tri(butylphenyl)phosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, diphenyltolylphosphine, tetraphenylphosphonium bromide, methyltriphenylphosphonium bromide, methyltriphenylphosphonium chloride, methoxymethyltriphenylphosphonium chloride, and benzyltriphenylphosphonium chloride. Triphenylphosphine compounds also include compounds having a triphenylphosphine structure and a triphenylborane structure. Examples of such compounds include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, benzyltriphenylphosphonium tetraphenylborate, and triphenylphosphine triphenylborane. Examples of amine compounds include monoethanolamine trifluoroborate and dicyanamide. Examples of trihaloborane compounds include trichloroborane. The laser marking layer forming composition may contain one kind of thermosetting catalyst, or may contain two or more kinds of thermosetting catalysts.

The laser marking layer 11 may also contain fillers. The blending of fillers in the laser marking layer 11 is preferred in terms of adjusting the elastic modulus, yield point strength, elongation at break, and other physical properties of the laser marking layer 11. Fillers include inorganic fillers and organic fillers. Materials constituting the inorganic fillers include, for example: aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, boron nitride, crystalline silicon dioxide, and amorphous silicon dioxide. As constituent materials of inorganic fillers, there can also be listed: single metals such as aluminum, gold, silver, copper, nickel, or alloys, amorphous carbon, graphite, etc. As constituent materials of organic fillers, there can be listed, for example: polymethyl methacrylate (PMMA), polyimide, polyamide imide, polyetheretherketone, polyetherimide, and polyesterimide. The laser marking layer 11 may contain one filler, or may contain two or more fillers. The filler may have various shapes such as spherical, needle-shaped, and thin flake-shaped. When the laser marking layer 11 contains a filler, the average particle size of the filler is preferably 30 to 1000 nm, more preferably 40 to 800 nm, and more preferably 50 to 600 nm. That is, the laser marking layer 11 preferably contains a nanofiller. The laser marking layer 11 contains nanofillers of such a particle size as fillers, which is preferable in terms of ensuring a higher dissociation property for the film 10 that is to be fragmented. The average particle size of the filler can be obtained, for example, using a photometric particle size distribution meter (trade name "LA-910", manufactured by Horiba, Ltd.). In addition, when the laser marking layer 11 contains a filler, the content of the filler is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. The content is preferably less than 75% by mass.

The laser marking layer 11 contains a colorant in this embodiment. The colorant may be a pigment or a dye. Examples of the colorant include black colorants, cyan colorants, magenta colorants, and yellow colorants. In order to achieve higher visibility of the information engraved on the laser marking layer 11 by laser marking, the laser marking layer 11 preferably contains a black colorant. Examples of black coloring agents include carbon black, graphite (black lead), Vantablack, carbon nanotubes, copper oxide, manganese dioxide, azo black and other azo pigments, aniline black, perylene black, titanium black, cyanine black, activated carbon, ferrite, magnetite, chromium oxide, iron oxide, molybdenum disulfide, complex oxide black pigments, anthraquinone organic black dyes, and azo organic black dyes. Examples of carbon black include furnace black, soot black, acetylene black, thermal black, and lamp black. Examples of black colorants include C.I. Solvent Black 3, C.I. Solvent Black 7, C.I. Solvent Black 22, C.I. Solvent Black 27, C.I. Solvent Black 29, C.I. Solvent Black 34, C.I. Solvent Black 43, and C.I. Solvent Black 70. Examples of black colorants include C.I. Direct Black 17, C.I. Direct Black 19, C.I. Direct Black 22, C.I. Direct Black 32, C.I. Direct Black 38, C.I. Direct Black 51, and C.I. Direct Black 71. As black colorants, there are C.I. Acid Black 1, C.I. Acid Black 2, C.I. Acid Black 24, C.I. Acid Black 26, C.I. Acid Black 31, C.I. Acid Black 48, C.I. Acid Black 52, C.I. Acid Black 107, C.I. Acid Black 109, C.I. Acid Black 110, C.I. Acid Black 119, and C.I. Acid Black 154. As black colorants, there are C.I. Disperse Black 1, C.I. Disperse Black 3, C.I. Disperse Black 10, and C.I. Disperse Black 24. As black colorants, there are C.I. Pigment Black 1 and C.I. Pigment Black 7. The laser marking layer 11 may contain one coloring agent or two or more coloring agents. In addition, the content of the coloring agent in the laser marking layer 11 is preferably 0.5% by weight or more, more preferably 1% by weight or more, and more preferably 2% by weight or more. The content is preferably 10% by weight or less, more preferably 8% by weight or less, and more preferably 5% by weight or less. Such compositions of the coloring agent content are preferred in terms of achieving higher visibility of the information engraved on the laser marking layer 11 by laser marking.

The laser marking layer 11 may contain one or more other components as required. Examples of the other components include flame retardants, silane coupling agents, and ion scavengers.

The thickness of the laser marking layer 11 is, for example, 2-100 μm.

The bonding layer 12 in the film 10 may have a composition including a thermosetting resin and a thermoplastic resin as resin components, or may have a composition not including a thermosetting resin.

When the bonding layer 12 has a composition including a thermosetting resin and a thermoplastic resin, the thermosetting resin may include, for example, epoxy resin, phenolic resin, amino resin, unsaturated polyester resin, polyurethane resin, polysilicone resin, and thermosetting polyimide resin. The bonding layer 12 may contain one thermosetting resin or two or more thermosetting resins. Epoxy resins tend to contain less ionic impurities that may cause corrosion of the semiconductor wafer to be protected by the back protective film formed by the film 10 as described below, and are therefore preferably used as thermosetting resins in the bonding layer 12 of the film 10. Examples of epoxy resins in the bonding layer 12 include the epoxy resins described above as the thermosetting resin in the case where the laser marking layer 11 has a composition including a thermosetting resin and a thermoplastic resin.

The thermoplastic resin in the bonding layer 12 functions as an adhesive, for example. When the bonding layer 12 has a composition including a thermosetting resin and a thermoplastic resin, for example, the thermoplastic resin described above as the thermoplastic resin when the laser marking layer 11 has a composition including a thermosetting resin and a thermoplastic resin can be cited. The bonding layer 12 may contain one thermoplastic resin or two or more thermoplastic resins. Acrylic resins are preferred as the thermoplastic resin in the bonding layer 12 because they have fewer ionic impurities and higher heat resistance.

When the following layer 12 contains an acrylic resin as a thermoplastic resin, the acrylic resin preferably contains the largest number of monomer units derived from (meth)acrylate in terms of mass ratio. As the (meth)acrylate used to form the monomer unit of such an acrylic resin, for example, the (meth)acrylate described above as the constituent monomer of the acrylic resin when the laser marking layer 11 contains an acrylic resin as a thermoplastic resin can be used. As the constituent monomer of the acrylic resin in the following layer 12, one (meth)acrylate can be used, or two or more (meth)acrylates can be used. In addition, the acrylic resin can also contain one or more other monomers copolymerizable with (meth)acrylate as constituent monomers, for example, in order to improve its cohesive force or heat resistance. As such a monomer, for example, those mentioned above as other monomers copolymerizable with (meth)acrylate for forming the acrylic resin in the laser marking layer 11 can be used.

The connecting layer 12 may also contain fillers. The formulation of the filler in the connecting layer 12 is preferred in terms of adjusting the elastic modulus, yield point strength, elongation at break and other physical properties of the connecting layer 12. As fillers in the connecting layer 12, for example, those described above as fillers in the laser marking layer 11 can be cited. The connecting layer 12 may contain one filler, or may contain two or more fillers. The filler may have various shapes such as spheres, needles, and flakes. When the connecting layer 12 contains a filler, the average particle size of the filler is preferably 30 to 500 nm, more preferably 40 to 400 nm, and more preferably 50 to 300 nm. That is, the connecting layer 12 preferably contains a nanofiller. The connecting layer 12 contains nanofillers of such a particle size as fillers, which is preferably used to avoid or suppress damage to the workpiece bonded or mounted on the film 10 due to the fillers contained in the connecting layer 12, and is also preferably used to ensure a higher disjunction for the film 10 that may be fragmented. In addition, when the connecting layer 12 contains fillers, the content of the fillers is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. The content is preferably less than 75% by mass.

The bonding layer 12 may also contain a colorant. As the colorant in the bonding layer 12, for example, those mentioned above as the colorant in the laser marking layer 11 can be cited. In order to ensure a high contrast between the laser-marked imprinted portion on the laser marking layer 11 side of the film 10 and the portion other than the laser marking layer 11, and to achieve good visibility of the imprinted information, the bonding layer 12 preferably contains a black colorant. The bonding layer 12 may contain one colorant, or may contain two or more colorants. In addition, the content of the colorant in the bonding layer 12 is preferably 0.5% by weight or more, more preferably 1% by weight or more, and more preferably 2% by weight or more. The content is preferably 10 wt % or less, more preferably 8 wt % or less, and even more preferably 5 wt % or less. These compositions of the coloring agent content are preferred in terms of achieving the above-mentioned good visibility of the laser-marked engraved information.

The next layer 12 may contain one or more other components as needed. Examples of the other components include flame retardants, silane coupling agents, and ion scavengers.

The thickness of the bonding layer 12 is, for example, 2-100 μm.

The film 10 having the above structure as a semiconductor back side adhesive film has a difference (calorie obtained by subtracting the second heat release from the first heat release) between the heat release in the range of 50 to 200°C in differential scanning calorimetry at a heating rate of 10°C/min (first heat release) and the heat release in the range of 50 to 200°C in differential scanning calorimetry at a heating rate of 10°C/min after heat treatment at 130°C for 2 hours (second heat release) of 50 J/g or less, preferably 30 J/g or less, more preferably 20 J/g or less, and even more preferably 10 J/g or less.

Regarding film 10, relative to the tensile storage modulus at 150°C measured for a sample piece of film 10 with a width of 10 mm under the conditions of an initial clip distance of 20 mm, a frequency of 1 Hz and a heating rate of 10°C/min (elastic modulus measurement conditions), the ratio of the tensile storage modulus at 150°C measured under the above elastic modulus measurement conditions after heat treatment at 130°C for 2 hours is preferably 20 or less, more preferably 10 or less, more preferably 5 or less, more preferably 3 or less, and more preferably 1.5 or less.

The content of the inorganic filler in the entire film 10 is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. In addition, the content of the inorganic filler in the entire film 10 is preferably less than 75% by mass.

When the film 10 has the above-mentioned laser marking layer 11 (hardened thermosetting layer), the glass transition temperature of the entire film 10 is preferably 100-200°C.

The substrate 21 of the wafer ribbon 20 in the wafer ribbon integrated semiconductor back surface adhesion film X is an element that functions as a support in the wafer ribbon 20 or the wafer ribbon integrated semiconductor back surface adhesion film X, and is, for example, a plastic film. Examples of the constituent material of the substrate 21 include: polyolefin, polyester, polyurethane, polycarbonate, polyetheretherketone, polyimide, polyetherimide, polyamide, wholly aromatic polyamide, polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, polyarylamide, fluororesin, cellulose-based resin, and polysilicone resin. Examples of polyolefins include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-butene copolymer, and ethylene-hexene copolymer. Examples of polyesters include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. The substrate 21 may include one material or two or more materials. The substrate 21 may have a single-layer structure or a multi-layer structure. Furthermore, when the substrate 21 includes a plastic film, it may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film. The substrate 21 may include one material or two or more materials. When the adhesive layer 22 on the substrate 21 is UV-curable as described below, the substrate 21 is preferably UV-transmissive.

The surface of the adhesive layer 22 side of the substrate 21 may also be subjected to physical treatment, chemical treatment, or primer treatment to improve the adhesion with the adhesive layer 22. Examples of physical treatment include: corona treatment, plasma treatment, sand mat processing, ozone exposure treatment, flame exposure treatment, high-voltage electric shock exposure treatment, and ionizing radiation treatment. Examples of chemical treatment include chromic acid treatment.

From the viewpoint of ensuring the strength for the substrate 21 to function as a support in the wafer ribbon 20 or the wafer ribbon integrated semiconductor back surface adhesion film X, the thickness of the substrate 21 is preferably 40 μm or more, preferably 50 μm or more, and more preferably 60 μm or more. Furthermore, from the viewpoint of achieving appropriate flexibility in the wafer ribbon 20 or the wafer ribbon integrated semiconductor back surface adhesion film X, the thickness of the substrate 21 is preferably 200 μm or less, more preferably 180 μm or less, and more preferably 150 μm or less.

The adhesive layer 22 of the wafer ribbon 20 contains an adhesive. The adhesive may be an adhesive whose adhesive force can be intentionally reduced by external action (adhesion-reducible adhesive), or an adhesive whose adhesive force is hardly or not reduced at all by external action (adhesion-non-reducing adhesive).

As the adhesive with reduced adhesion, for example, there can be mentioned an adhesive that can be cured by radiation irradiation (radiation curing adhesive). In the adhesive layer 22 of this embodiment, one type of adhesive with reduced adhesion can be used, or two or more types of adhesive with reduced adhesion can be used.

As the radiation-curable adhesive used for the adhesive layer 22, for example, there can be cited adhesives of a type that can be cured by irradiation with electron beams, ultraviolet rays, α rays, β rays, γ rays, or X-rays. It is particularly preferable to use an adhesive of a type that can be cured by irradiation with ultraviolet rays (ultraviolet-curable adhesive).

Examples of the radiation-curable adhesive used for the adhesive layer 22 include an additive-type radiation-curable adhesive containing a base polymer such as an acrylic polymer as an acrylic adhesive and a radiation-polymerizable monomer component or oligomer component having a functional group such as a radiation-polymerizable carbon-carbon double bond.

The acrylic polymer described above preferably contains the most monomer units derived from (meth)acrylate in terms of mass ratio. (Meth)acrylates used as monomer units for forming the acrylic polymer, i.e., (meth)acrylates used as constituent monomers of the acrylic polymer, include, for example, alkyl (meth)acrylates, cycloalkyl (meth)acrylates, and aryl (meth)acrylates. More specifically, the same (meth)acrylates as those described above for the acrylic resin in the laser marking layer 11 of the film 10 can be listed. As constituent monomers of the acrylic polymer, one (meth)acrylate can be used, or two or more (meth)acrylates can be used. In addition, in order to appropriately express basic properties such as adhesion based on (meth)acrylates in the adhesive layer 22, the ratio of (meth)acrylates in the entire constituent monomers of the acrylic polymer is, for example, 40% by mass or more.

The acrylic polymer may also contain monomer units derived from one or more other monomers copolymerizable with (meth)acrylate, for example, in order to improve its cohesive force or heat resistance. Examples of such monomers include carboxyl group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, epoxy group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, acrylamide, and acrylonitrile. More specifically, the monomers described above as other monomers copolymerizable with (meth)acrylate of the acrylic resin in the laser marking layer 11 used to form the film 10 may be cited.

The acrylic polymer may also contain monomer units derived from multifunctional monomers copolymerizable with monomer components such as (meth)acrylates in order to form a cross-linked structure in its polymer backbone. Examples of such multifunctional monomers include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, poly(meth)acrylate glycidyl ester, polyester (meth)acrylate, and (meth)acrylate urethane. "(Meth)acrylate" means "acrylate" and/or "methacrylate". As a constituent monomer of the acrylic polymer, one type of multifunctional monomer may be used, or two or more types of multifunctional monomers may be used. In order to appropriately express the basic characteristics such as adhesiveness based on (meth)acrylate in the adhesive layer 22, the ratio of the multifunctional monomer in the entire monomers constituting the acrylic polymer is, for example, 40 mass % or less.

The acrylic polymer can be obtained by polymerizing the raw material monomers used to form the acrylic polymer. Examples of the polymerization method include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization.

The adhesive layer 22 or the adhesive used to form it may also contain an external crosslinking agent, for example, in order to increase the average molecular weight of the base polymer such as acrylic polymer. Examples of the external crosslinking agent that reacts with the base polymer such as acrylic polymer to form a crosslinked structure include: polyisocyanate compounds, epoxy compounds, polyol compounds, aziridine compounds, and melamine-based crosslinking agents. The content of the external crosslinking agent in the adhesive layer 22 or the adhesive used to form it is, for example, 0.1 to 5 parts by mass relative to 100 parts by mass of the base polymer.

Examples of the radiation-polymerizable monomer component used to form the radiation-curable adhesive include urethane (meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and 1,4-butanediol di(meth)acrylate. Examples of the radiation-polymerizable oligomer component used to form the radiation-curable adhesive include urethane-based, polyether-based, polyester-based, polycarbonate-based, polybutadiene-based, and other oligomers, preferably having a molecular weight of about 100 to 30,000. The total content of the radiation-polymerizable monomer component or oligomer component in the radiation-curable adhesive is determined within a range that can appropriately reduce the adhesive force of the formed adhesive layer 22, and is, for example, 5 to 500 parts by mass relative to 100 parts by mass of the base polymer such as the acrylic polymer. In addition, as an additive-type radiation-curable adhesive, for example, the one disclosed in Japanese Patent Laid-Open No. 60-196956 can be used.

As the radiation-curable adhesive used for the adhesive layer 22, for example, there can be mentioned an intrinsic radiation-curable adhesive containing a base polymer having a functional group such as a radiation-polymerizable carbon-carbon double bond in the polymer side chain or in the polymer main chain or at the end of the polymer main chain. Such an intrinsic radiation-curable adhesive is preferred in terms of suppressing unintended changes in adhesive properties over time caused by the migration of low molecular weight components in the formed adhesive layer 22.

As the base polymer contained in the intrinsic radiation-curable adhesive, it is preferred that the basic skeleton is an acrylic polymer. As the acrylic polymer forming such a basic skeleton, the acrylic polymer described above in relation to the additive radiation-curable adhesive can be used. As a method for introducing radiation-polymerizable carbon-carbon double bonds into the acrylic polymer, for example, the following method can be cited: after copolymerizing a raw material monomer containing a monomer having a specific functional group (first functional group) to obtain an acrylic polymer, a compound having a specific functional group (second functional group) that can react with the first functional group to form a bond and a radiation-polymerizable carbon-carbon double bond is subjected to a condensation reaction or an addition reaction with the acrylic polymer while maintaining the radiation polymerizability of the carbon-carbon double bond.

As the combination of the first functional group and the second functional group, for example, there can be listed: carboxyl and epoxy, epoxy and carboxyl, carboxyl and aziridine, aziridine and carboxyl, hydroxyl and isocyanate, isocyanate and hydroxyl. Among these combinations, from the viewpoint of the ease of reaction tracking, the combination of hydroxyl and isocyanate, or the combination of isocyanate and hydroxyl is preferred. In addition, since the technical difficulty of preparing a polymer having an isocyanate with high reactivity is high, from the viewpoint of the ease of preparing or obtaining an acrylic polymer, it is more preferred that the first functional group on the acrylic polymer side is a hydroxyl and the second functional group is an isocyanate. In this case, examples of the isocyanate compound having a radiation polymerizable carbon-carbon double bond and an isocyanate group as the second functional group, that is, an isocyanate compound containing a radiation polymerizable unsaturated functional group include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate (MOI), and m-isopropenyl-α,α-dimethylbenzyl isocyanate.

The radiation-curable adhesive used for the adhesive layer 22 preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include α-ketol compounds, acetophenone compounds, benzoin ether compounds, ketal compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, benzophenone compounds, 9-oxysulfide compounds, Series compounds, camphorquinone, halogenated ketones, acylphosphine oxides, and acylphosphonates. Examples of α-ketoalcohol series compounds include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, and 1-hydroxycyclohexylphenylketone. Examples of acetophenone series compounds include methoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxyacetophenone, and 2-methyl-1-[4-(methylthio)-phenyl]-2-oxo-1-ol-1-propane. Examples of benzoin ether series compounds include benzoin ethyl ether, benzoin isopropyl ether, and anisole methyl ether. Examples of ketal compounds include benzil dimethyl ketal. Examples of aromatic sulfonyl chloride compounds include 2-naphthalenesulfonyl chloride. Examples of photoactive oxime compounds include 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Examples of benzophenone compounds include benzophenone, benzoylbenzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone. Examples of 9-oxosulfuronium compounds include 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Compounds such as 9-oxosulfuron , 2-chloro-9-oxysulfuron , 2-methyl-9-oxosulfuron , 2,4-dimethyl-9-oxosulfuron , isopropyl-9-oxysulfide , 2,4-dichloro-9-oxysulfuron , 2,4-diethyl-9-oxysulfide , and 2,4-diisopropyl-9-oxysulfide The content of the photopolymerization initiator in the radiation-curable adhesive in the adhesive layer 22 is, for example, 0.05 to 20 parts by mass based on 100 parts by mass of the base polymer such as the acrylic polymer.

As the above-mentioned adhesive with non-reducing adhesive force, for example, a pressure-sensitive adhesive can be cited. As the pressure-sensitive adhesive used for the adhesive layer 22, for example, an acrylic adhesive or a rubber adhesive using an acrylic polymer as a base polymer can be used. In the adhesive layer 22 of this embodiment, one type of adhesive with non-reducing adhesive force can be used, and two or more types of adhesive with non-reducing adhesive force can also be used.

When the adhesive layer 22 contains an acrylic adhesive as a pressure-sensitive adhesive, the acrylic polymer as the base polymer of the acrylic adhesive preferably contains the most monomer units derived from (meth)acrylate in terms of mass ratio. Examples of such acrylic polymers include the acrylic polymers described above for the radiation-curable adhesive.

The adhesive layer 22 or the adhesive used to form it may contain, in addition to the above-mentioned components, a crosslinking promoter, an adhesion imparting agent, an anti-aging agent, a coloring agent such as a pigment or a dye, etc. The coloring agent may also be a compound that is colored by radiation. Examples of such compounds include stealth dyes.

The thickness of the adhesive layer 22 is, for example, 2 to 20 μm. This structure is preferred, for example, when the adhesive layer 22 includes a radiation-curable adhesive in order to achieve a balance in the adhesive force of the adhesive layer 22 to the film 10 before and after radiation curing.

The wafer-cut tape-integrated semiconductor back surface adhesion film X having the above-described structure can be manufactured, for example, in the following manner.

In the preparation of the film 10 in the wafer-cut ribbon-type semiconductor back-side adhesion film X, first, a film that will form the laser marking layer 11 and a film that will form the bonding layer 12 are separately prepared. The film that will form the laser marking layer 11 can be prepared by applying a resin composition for forming the laser marking layer on a specific insulating material to form a resin composition layer, and then drying and curing the composition layer by heating. Examples of insulating materials include polyethylene terephthalate (PET) films, polyethylene films, polypropylene films, and plastic films or papers coated with a stripping agent such as a fluorine-based stripping agent or a long-chain alkyl acrylate-based stripping agent. Examples of coating techniques for the resin composition include roller coating, screen coating, and gravure coating. In the production of the film that will form the laser marking layer 11, the heating temperature is, for example, 90 to 160°C, and the heating time is, for example, 2 to 4 minutes. On the other hand, the film that will form the connecting layer 12 can be produced by coating a resin composition for forming the connecting layer on a specific insulating member to form a resin composition layer, and then drying the composition layer by heating. In the production of the film that will form the connecting layer 12, the heating temperature is, for example, 90 to 150°C, and the heating time is, for example, 1 to 2 minutes. The above two films can be produced in the form of each with an insulating member attached as described above. Then, the exposed surfaces of the films are bonded to each other, thereby manufacturing a film 10 (double-sided spacer) having a laminated structure of a laser marking layer 11 and a bonding layer 12.

The wafer tape 20 of the wafer tape-type semiconductor back surface bonding film X can be produced by providing an adhesive layer 22 on a prepared substrate 21. For example, the resin substrate 21 can be produced by a film-making method such as a rolling film-making method, a casting method in an organic solvent, a blown extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, and a dry lamination method. For the film or substrate 21 after film-making, a specific surface treatment is performed as needed. In the formation of the adhesive layer 22, for example, after preparing an adhesive composition for forming the adhesive layer, first, the composition is applied on the substrate 21 or on a specific isolation member to form an adhesive composition layer. As the coating technique of the adhesive composition, for example, there can be listed: roller coating, screen coating, and gravure coating. Then, in the adhesive composition layer, by heating, it is dried as needed, and a cross-linking reaction is caused as needed. The heating temperature is, for example, 80 to 150°C, and the heating time is, for example, 0.5 to 5 minutes. When the adhesive layer 22 is formed on the isolation member, the adhesive layer 22 attached to the isolation member is adhered to the substrate 21, and then the isolation member is peeled off. In this way, a wafer-cutting tape 20 having a layered structure of the substrate 21 and the adhesive layer 22 is produced.

In the production of the wafer-tape-type semiconductor back-side bonding film X, the film 10 with the spacer is punched into a disk shape of a specific diameter, and then the spacer is peeled off from the laser marking layer 11 side of the film 10, and the laser marking layer 11 side of the film 10 is bonded to the adhesive layer 22 side of the wafer tape 20. The bonding temperature is, for example, 30 to 50°C, and the bonding pressure (linear pressure) is, for example, 0.1 to 20 kgf/cm. Then, the wafer tape 20 thus bonded to the film 10 is punched into a disk shape of a specific diameter in such a manner that the center of the wafer tape 20 is consistent with the center of the film 10. When the adhesive layer 22 includes the radiation-curable adhesive as described above, the adhesive layer 22 may be irradiated with radiation such as ultraviolet rays before the bonding, or may be irradiated with radiation such as ultraviolet rays from the side of the substrate 21 after the bonding. Alternatively, such radiation irradiation may not be performed during the manufacturing process of the wafer-cut tape-integrated semiconductor back surface adhesive film X (in this case, the adhesive layer 22 may be radiation-cured during the use of the wafer-cut tape-integrated semiconductor back surface adhesive film X). When the adhesive layer 22 is of the ultraviolet-curable type, the cumulative amount of ultraviolet irradiation used to cure the adhesive layer 22 is, for example, 50 to 500 mJ/ ^cm2 .

The wafer-cut ribbon-type semiconductor back surface adhesion film X can be manufactured in the above manner. The spacer is peeled off from the wafer-cut ribbon-type semiconductor back surface adhesion film X when the film is used.

The film 10 may also have a single-layer structure instead of the multi-layer structure described above. When the film 10 has a single-layer structure, the film 10 includes a non-thermosetting resin composition that does not substantially produce thermal curing. Such a film 10 may have a composition including a thermosetting resin and a thermoplastic resin, or may have a composition without a thermosetting resin.

When the film 10 as a single layer has a composition including a thermosetting resin and a thermoplastic resin, for example, the thermosetting resin may include epoxy resins, phenolic resins, amino resins, unsaturated polyester resins, polyurethane resins, polysilicone resins, and thermosetting polyimide resins. The film 10 may include one thermosetting resin or two or more thermosetting resins. As the epoxy resin in the film 10, for example, the epoxy resin as the thermosetting resin in the case where the laser marking layer 11 has a composition including a thermosetting resin and a thermoplastic resin may be included. The monolayer film 10 preferably contains an epoxy resin having an epoxy equivalent of 150 to 900 g/eq at a ratio of 2 to 20 mass %. The epoxy equivalent is preferably 150 to 700 g/eq. In addition, a phenolic resin is preferably used as a hardener for making the epoxy resin exhibit thermosetting properties.

The thermoplastic resin in the single-layer film 10 functions as an adhesive, for example. When the film 10 has a composition including a thermosetting resin and a thermoplastic resin, for example, the thermoplastic resin described above as the thermoplastic resin when the laser marking layer 11 has a composition including a thermosetting resin and a thermoplastic resin can be cited. The film 10 may contain one thermoplastic resin or two or more thermoplastic resins.

When the single-layer film 10 contains an acrylic resin as a thermoplastic resin, the acrylic resin preferably contains the largest number of monomer units derived from (meth)acrylates in terms of mass ratio. As the (meth)acrylate used to form the monomer unit of such an acrylic resin, for example, the (meth)acrylate described above as the constituent monomer of the acrylic resin when the laser marking layer 11 contains an acrylic resin as a thermoplastic resin can be used. As the constituent monomer of the acrylic resin in the film 10, one (meth)acrylate can be used, or two or more (meth)acrylates can be used. In addition, the acrylic resin can also contain one or more other monomers that can be copolymerized with (meth)acrylates as constituent monomers, for example, in order to improve its cohesive force or heat resistance. As such a monomer, for example, those mentioned above as other monomers copolymerizable with (meth)acrylate for forming the acrylic resin in the laser marking layer 11 can be used.

The film 10 composed of a single layer may also contain fillers. The formulation of the filler in the film 10 is preferred in terms of adjusting the elastic modulus, yield point strength, elongation at break and other physical properties of the film 10. As fillers in the film 10, for example, those described above as fillers in the laser marking layer 11 can be cited. The film 10 may contain one filler or two or more fillers. The filler may be in various shapes such as spheres, needles, and flakes. When the film 10 contains a filler, the average particle size of the filler is preferably 30 to 1000 nm, more preferably 40 to 800 nm, and more preferably 50 to 600 nm. That is, the film 10 preferably contains nanofillers. The film 10 containing nanofillers of such a particle size as fillers is preferably used to avoid or suppress damage to the workpiece attached or mounted on the film 10 due to the fillers contained in the film 10, and is also preferably used to ensure high dissociation for the film 10 that may be fragmented. In addition, when the film 10 contains fillers, the content of the fillers is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. The content is preferably less than 75% by mass.

When the film 10 has a single-layer structure, the film 10 contains a colorant. As the colorant in the film 10, for example, those mentioned above as the colorant in the laser marking layer 11 can be cited. In terms of ensuring a high contrast between the laser-marked engraved portion on the laser marking layer 11 side of the film 10 and the portion other than the laser marking layer 11, and realizing good visibility of the engraved information, the film 10 preferably contains a black colorant. The film 10 may contain one colorant, or may contain two or more colorants. In addition, the content of the colorant in the film 10 is preferably 0.5% by weight or more, more preferably 1% by weight or more, and more preferably 2% by weight or more. The content is preferably 10 wt % or less, more preferably 8 wt % or less, and even more preferably 5 wt % or less. These compositions of the coloring agent content are preferred in terms of achieving the above-mentioned good visibility of the laser-marked engraved information.

The single-layer film 10 may contain one or more other components as needed. Examples of the other components include flame retardants, silane coupling agents, and ion scavengers.

When the film 10 has a single-layer structure, the thickness of the film 10 is, for example, 2 to 100 μm.

3 to 7 show an example of a method for manufacturing a semiconductor device using the above-mentioned wafer-cutting tape-integrated semiconductor back surface adhesion film X.

In the present semiconductor device manufacturing method, first, as shown in FIG. 3(a) and FIG. 3(b), the wafer W is thinned by grinding (wafer thinning step). The grinding can be performed using a grinding device equipped with a grinding stone. The wafer W is a semiconductor wafer having a first surface Wa and a second surface Wb. Various semiconductor elements have been implanted on the side of the first surface Wa of the wafer W (not shown in the figure), and the wiring structure necessary for the semiconductor element has been formed on the first surface Wa (not shown in the figure). The second surface Wb is the so-called reverse side or back side. In this step, after the wafer processing tape T1 having the adhesive surface T1a is attached to the first surface Wa of the wafer W, the wafer W is ground from the second surface Wb while being held on the wafer processing tape T1 until the wafer W reaches a specific thickness, thereby obtaining a thinned wafer 30.

Next, as shown in FIG. 4( a ), the wafer 30 and the annular frame 41 are bonded with the wafer tape-type semiconductor back surface adhesive film X. Specifically, the wafer 30 held by the wafer processing tape T1 and the annular frame 41 arranged to surround the wafer 30 are bonded with the film 10 of the wafer processing tape-type semiconductor back surface adhesive film X on the wafer 30, and the wafer tape 20 or its adhesive layer 22 is bonded to the annular frame 41. Then, as shown in FIG. 4( b ), the wafer processing tape T1 is peeled off from the wafer 30. Thereafter, a baking step for improving the wettability or adhesiveness of the film 10 to the wafer 30 may be performed, for example, before the dicing step described below. In the baking step, it is preferred to heat the wafer 30 holding the wafer 30 with the integrated semiconductor back surface adhesive film X or the film 10 at a temperature below 100° C. for a few hours.

Next, laser marking is performed by irradiating the laser marking layer 11 of the film 10 in the semiconductor back contact film X of the wafer 20 (i.e., from the side of the substrate 21 of the wafer 20) with laser (laser marking step). By means of the laser marking, various information such as text information or graphic information is engraved on each semiconductor element that is subsequently singulated into a semiconductor chip. In this step, laser marking can be performed on multiple semiconductor elements in the wafer 30 at one time in a laser marking process with high efficiency. As the laser used in this step, gas lasers and solid lasers can be listed, for example. As the gas laser, carbon dioxide gas lasers ( _CO2 lasers) and excimer lasers can be listed, for example. As a solid laser, for example, there is Nd:YAG laser.

Next, the wafer 30 and the ring-shaped frame 41 are held by the ring-shaped frame 41 in the holder 42 of the device, and then, as shown in FIG5, the dicing blade provided in the wafer dicing device is used for cutting (cutting step). In FIG5, the cutting part is schematically represented by a thick solid line. In this step, the wafer 30 is singulated into chips 31, and at the same time, the film 10 of the semiconductor back side adhesive film X is cut into small pieces of film 10'. In this way, a chip 31 with a film 10' for forming a chip back protective film, that is, a chip 31 with a film 10' is obtained.

In the case where the adhesive layer 22 of the wafer-cutting tape 20 contains a radiation-curing adhesive, the adhesive layer 22 may be irradiated with radiation such as ultraviolet rays from the substrate 21 side after the above-mentioned dicing step instead of the above-mentioned radiation irradiation in the manufacturing process of the wafer-cutting tape-type semiconductor back surface adhesive film X. The cumulative irradiation light amount is, for example, 50 to 500 mJ/ ^cm2 . In the wafer-cutting tape-type semiconductor back surface adhesive film X, the area to be irradiated as a measure to reduce the adhesion of the adhesive layer 22 is, for example, as shown in FIG. 2, an area R in the adhesive layer 22 except for its peripheral portion within the film 10 bonding area.

Next, after a cleaning step of cleaning the wafer 31 side of the wafer 31 with the film 10' in the wafer tape 20 with a cleaning liquid such as water or a widening step of widening the separation distance between the wafers 31 with the film 10', as shown in FIG6, the wafer 31 with the film 10' is picked up from the wafer tape 20 (picking up step). For example, after the wafer tape-type semiconductor back surface adhesive film X with the ring-shaped frame 41 is held by the ring-shaped frame 41 on the holder 43 of the device, the lifting pin member 44 of the picking up mechanism is raised at the lower side of the wafer tape 20 in the figure, and the wafer 31 with the film 10' to be picked up is lifted up through the wafer tape 20, and then held by the suction jig 45. In the picking-up step, the lifting speed of the lifting pin component 44 is, for example, 1 to 100 mm/s, and the lifting amount of the lifting pin component 44 is, for example, 50 to 3000 μm.

Next, as shown in FIG7 , the chip 31 with the film 10' is flip-chip mounted on the mounting substrate 51. Examples of the mounting substrate 51 include: a lead frame, a TAB (Tape Automated Bonding) film, and a wiring substrate. The chip 31 is electrically connected to the mounting substrate 51 via a bump 52. Specifically, the electrode pad (not shown) on the circuit forming surface of the chip 31 and the terminal portion (not shown) of the mounting substrate 51 are electrically connected via the bump 52. The bump 52 is, for example, a solder bump. In addition, a thermosetting bottom filler 53 is interposed between the chip 31 and the mounting substrate 51.

As described above, a semiconductor device can be manufactured using the wafer-cutting tape-integrated semiconductor back surface adhesion film X.

As described above, the difference between the heat release amount (first heat release amount) of the film 10 as the semiconductor back side contact film in the differential scanning calorimetry at a temperature increase rate of 10°C/min and the heat release amount (second heat release amount) in the range of 50 to 200°C after heat treatment at 130°C for 2 hours in the differential scanning calorimetry at a temperature increase rate of 10°C/min (heat obtained by subtracting the second heat release amount from the first heat release amount) is 50 J/g or less. The so-called first heat release amount is the heat release amount in the range of 50 to 200°C in the differential scanning calorimetry at a temperature increase rate of 10°C/min with respect to the film 10 which has not been heat treated at 130°C for 2 hours. The so-called second heat release refers to the heat release in the range of 50 to 200°C in the differential scanning calorimetry at a temperature increase rate of 10°C/min for the film 10 that has been heat treated at 130°C for 2 hours. The inventors of the present invention have found that a configuration in which the difference in the heat release in the film 10 (the heat obtained by subtracting the second heat release from the first heat release) is 50 J/g or less is preferred in terms of suppressing the warping of the semiconductor wafer bonded with the film when the semiconductor wafer is exposed to a high temperature environment. This is shown, for example, in the following embodiments and comparative examples.

The above-mentioned heat release amounts in the range of 50-200°C in the differential scanning calorimetry of the film 10 are mainly accounted for by the heat release amount (reaction heat) generated by the reaction between the constituent components in the film. The configuration in which the difference between the above-mentioned first heat release amount of the film 10 not subjected to the above-mentioned heat treatment and the above-mentioned second heat release amount of the film 10 subjected to the above-mentioned heat treatment is 50 J/g or less means that a reaction of a degree equivalent to the heat release amount or reaction heat of 50 J/g or less occurs in the film 10 by the above-mentioned heat treatment. That is, this structure means that the more the reaction progresses in the film 10 by the above-mentioned heat treatment to the extent that the heat release is less than 50 J/g, the more it means that the reaction has already progressed in the film 10 before the above-mentioned heat treatment (the reaction rate in the film is high) or the reaction is difficult to proceed in the film 10 by the above-mentioned heat treatment. Such a structure in the film 10 is suitable for reducing the degree of shrinkage caused by the reaction of the film 10 when it is exposed to a high temperature environment, and is therefore suitable for suppressing the warping of the semiconductor wafer when the semiconductor wafer bonded with the film is exposed to a high temperature environment. In a film 10 including a hardened thermosetting layer (in the above-mentioned embodiment, the laser marking layer 11), the reactivity of the film 10 as a semiconductor back side contact film can be increased by, for example, adjusting the amount of a thermosetting catalyst (reaction accelerator) in the thermosetting layer, or adjusting the heating temperature and heating time used for thermosetting when the film 10 is produced.

As described above, the film 10 of the wafer-cut ribbon integrated semiconductor back surface adhesion film X is suitable for suppressing warping of the semiconductor wafer bonded with the film 10 during the semiconductor device manufacturing process. From the viewpoint of suppressing such warping, the heat release difference is preferably 30 J/g or less, more preferably 20 J/g or less, and even more preferably 10 J/g or less.

As described above, with respect to the film 10, relative to the tensile storage modulus at 150°C measured for a sample piece of the film 10 having a width of 10 mm under the conditions of an initial clamp distance of 20 m, a frequency of 1 Hz and a heating rate of 10°C/min (elastic modulus measurement conditions), the ratio of the tensile storage modulus at 150°C measured under the above elastic modulus measurement conditions after heat treatment at 130°C for 2 hours is preferably 20 or less, more preferably 10 or less, more preferably 5 or less, more preferably 3 or less, and more preferably 1.5 or less. This structure is suitable for reducing the degree of shrinkage caused by exposing the film 10 to a high temperature environment, and is therefore suitable for suppressing warping of the semiconductor wafer when the semiconductor wafer bonded with the film 10 is exposed to a high temperature environment.

As described above, the content of the inorganic filler in the entire film 10 is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. This structure is preferred in terms of suppressing the warp in the film 10 or the semiconductor wafer bonded thereto.

As described above, the content ratio of the inorganic filler in the entire film 10 is preferably less than 75% by mass. This structure is preferable in terms of ensuring the printability of the film 10 by laser marking.

When the film 10 of the wafer-cut ribbon-type semiconductor back-side adhesive film X has the above-mentioned laser marking layer 11 (hardened heat-hardening layer), as mentioned above, the glass transition temperature of the entire film 10 is preferably 100-200° C. This structure is suitable for reducing the stress generated by thermal contraction in the film 10 and seeking stress relaxation by shrinking the high elastic region.

Furthermore, as described above, the film 10 in the wafer-cut ribbon-type semiconductor back-side bonding film X preferably contains an epoxy resin with an epoxy equivalent of 150 to 900 g/eq at a ratio of 2 to 20 mass %, and the epoxy equivalent is preferably 150 to 700 g/eq. This structure is suitable for suppressing the number of crosslinking points in the constituent resin material in the film 10 and ensuring good adhesion. The fewer crosslinking points in the constituent resin material in the film 10, the more the tendency of shrinkage due to the crosslinking reaction during heating is suppressed. [Example]

[Example 1] In the preparation of the semiconductor back surface adhesion film of Example 1, first, a first film that will form a laser marking layer (LM layer) and a second film that will form an adhesion layer (AH layer) are separately prepared.

In the preparation of the first film, first, 7 parts by weight of the first epoxy resin (trade name "JER YL980", manufactured by Mitsubishi Chemical Co., Ltd.), 7 parts by weight of the second epoxy resin (trade name "KI-3000-4", manufactured by Tohto Chemical Co., Ltd.), 15 parts by weight of the phenolic resin (trade name "MEH-7851SS", manufactured by Meiwa Chemical Co., Ltd.), 15 parts by weight of the acrylic resin (trade name "TEISANRESIN SG-P3", manufactured by Nagase ChemteX Co., Ltd.), 50 parts by weight of the filler (trade name "SO-25R", manufactured by Admatechs Co., Ltd.), 4 parts by weight of the thermosetting catalyst (trade name "Curezol 2PHZ", manufactured by Shikoku Chemical Industries Co., Ltd.), and 10 parts by weight of the black dye (trade name "OIL BLACK BS", manufactured by Orient Chemical Industries Co., Ltd.) was added to methyl ethyl ketone in an amount of 2 parts by mass and mixed to obtain a resin composition having a solid content concentration of 28% by mass. Then, the resin composition was applied to the silicone release-treated surface of a PET separator having a silicone release-treated surface using an applicator to form a resin composition layer. Then, the composition layer was dried by heating at 130°C for 2 minutes to form a first film (a film that would form a laser marking layer as a cured heat-curing layer) having a thickness of 15 μm on the PET separator.

In the preparation of the second film, first, 7.5 parts by weight of the first epoxy resin (trade name "JER YL980", manufactured by Mitsubishi Chemical Co., Ltd.), 7.5 parts by weight of the second epoxy resin (trade name "KI-3000-4", manufactured by Tohto Chemical Co., Ltd.), 16.5 parts by weight of the phenolic resin (trade name "MEH-7851SS", manufactured by Meiwa Chemical Co., Ltd.), 16.5 parts by weight of the acrylic resin (trade name "TEISANRESIN SG-P3", manufactured by Nagase ChemteX Co., Ltd.), 50 parts by weight of the filler (trade name "SO-25R", manufactured by Admatechs Co., Ltd.), and 100 parts by weight of the black dye (trade name "OIL BLACK BS", manufactured by Orient Chemical Co., Ltd.) were mixed with the mixture. Industries Co., Ltd.) was added to methyl ethyl ketone in an amount of 2 parts by mass and mixed to obtain a resin composition having a solid content concentration of 28% by mass. Then, the resin composition was applied to the silicone release treatment surface of a PET separator having a silicone release treatment surface using an applicator to form a resin composition layer. Then, the composition layer was dried by heating at 130°C for 2 minutes to form a second film (a film that will form a non-thermosetting adhesive layer) with a thickness of 10 μm on the PET separator.

Then, a laminating machine is used to laminate the first film on the PET separator produced as described above and the second film on the PET separator. Specifically, the exposed surfaces of the first and second films are laminated to each other at a temperature of 100°C and a pressure of 0.6 MPa. The semiconductor back surface adhesive film of Example 1 is produced in the above manner. The composition of each film in Example 1 and the following examples and comparative examples is disclosed in Table 1 (in Table 1, the composition of each layer is represented by the mass ratio of the components).

[Example 2] In the preparation of the semiconductor back surface adhesive film of Example 2, first, 7.5 parts by weight of the first epoxy resin (trade name "JER YL980", manufactured by Mitsubishi Chemical Co., Ltd.), 7.5 parts by weight of the second epoxy resin (trade name "KI-3000-4", manufactured by Tohto Chemical Co., Ltd.), 16.5 parts by weight of the phenolic resin (trade name "MEH-7851SS", manufactured by Meiwa Chemical Co., Ltd.), 16.5 parts by weight of the acrylic resin (trade name "TEISANRESIN SG-P3", manufactured by Nagase ChemteX Co., Ltd.), 50 parts by weight of the filler (trade name "SO-25R", manufactured by Admatechs Co., Ltd.), and 100 parts by weight of the black dye (trade name "OIL BLACK BS", manufactured by Orient Chemical Industries Co., Ltd.) was added to methyl ethyl ketone in an amount of 2 parts by mass and mixed to obtain a resin composition having a solid content concentration of 28% by mass. Then, the resin composition was applied to the silicone release-treated surface of a PET separator having a silicone release-treated surface using an applicator to form a resin composition layer. Then, the composition layer was heated at 130° C. for 2 minutes to dry it. A semiconductor back-side bonding film (a non-thermosetting single-layer film) of Example 2 with a thickness of 25 μm was prepared on the PET separator in the same manner as above.

[Example 3] In the preparation of the semiconductor back-side adhesive film of Example 3, first, 25 parts by mass of a phenolic resin (trade name "MEH-7851SS", manufactured by Meiwa Chemical Co., Ltd.), 13 parts by mass of an acrylic resin (trade name "TEISANRESIN SG-P3", manufactured by Nagase ChemteX Co., Ltd.), 60 parts by mass of a filler (trade name "SO-25R", manufactured by Admatechs Co., Ltd.), and 2 parts by mass of a black dye (trade name "OIL BLACK BS", manufactured by Orient Chemical Industries Co., Ltd.) were added to methyl ethyl ketone and mixed to obtain a resin composition having a solid content concentration of 28% by mass. Then, the resin composition was applied to the silicone release treated surface of the PET separator with a silicone release treated surface using an applicator to form a resin composition layer. Then, the composition layer was dried by heating at 130° C. for 2 minutes. In the above manner, a semiconductor back surface adhesive film (non-thermosetting single-layer film) of Example 3 with a thickness of 25 μm was prepared on the PET separator.

[Example 4] The semiconductor back side adhesive film of Example 4 (thickness 25 mm) was prepared in the same manner as the semiconductor back side adhesive film of Example 2 except that the blending amount of the first epoxy resin (trade name "JER YL980") was set to 3.5 parts by mass instead of 7.5 parts by mass, the blending amount of the second epoxy resin (trade name "KI-3000-4") was set to 3.5 parts by mass instead of 7.5 parts by mass, the blending amount of the phenolic resin (trade name "MEH-7851SS") was set to 8 parts by mass instead of 16.5 parts by mass, the blending amount of the acrylic resin (trade name "TEISANRESIN SG-P3") was set to 8 parts by mass instead of 16.5 parts by mass, and the blending amount of the filler (trade name "SO-25R") was set to 75 parts by mass instead of 50 parts by mass. μm non-thermosetting single-layer film).

[Comparative Example 1] The semiconductor back surface adhesion film (cured thermosetting single-layer film) of Comparative Example 1 was prepared in the same manner as the first film of Example 1, except that the amount of the thermosetting catalyst (trade name "Curezol 2PHZ") was set to 0.5 parts by mass instead of 4 parts by mass and the film thickness was set to 25 μm instead of 12.5 μm.

<Difference in heat release> The heat release Q 1 of each semiconductor back surface adhesive film of Examples 1 to 4 and Comparative Example 1 was investigated by differential scanning calorimetry using a differential scanning calorimeter (trade name "DSC Q2000", manufactured by TA Instruments). In addition, the heat release Q ₂ of each semiconductor back surface adhesive film of each composite film of Examples 1 to 4 and Comparative Example 1 was investigated by differential scanning calorimetry using a differential scanning calorimeter (trade name "DSC Q2000", manufactured by TA Instruments) after heat treatment (standing in a constant temperature chamber at 130°C for ₂ hours). In each differential scanning calorimetry, the measurement environment was set to a nitrogen atmosphere, the measurement temperature range was set to -30°C to 300°C, and the heating rate was set to 10°C/min. In addition, for the exothermic peak appearing in the range of 50-200°C in the DSC chart obtained by each measurement, the cumulative value of the heat above the baseline of 50-200°C in the chart was calculated as the exothermic amount (J/g). For each semiconductor back surface adhesive film, the exothermic amount Q ₁ (J/g), the exothermic amount Q ₂ (J/g), and the exothermic amount difference Q ₁ -Q ₂ (J/g) are shown in Table 1.

[Tensile Storage Modulus] The tensile storage modulus E 1 at 150°C was determined for each semiconductor back surface adhesive film of Examples 1 to 4 and Comparative Example 1 based on dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring apparatus (trade name "RSA3", manufactured by TA Instruments). Furthermore, the tensile storage modulus E ₂ at 150°C was determined for each semiconductor back surface adhesive film of Examples 1 to 4 and Comparative Example 1 based on dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring apparatus (trade name "RSA3", manufactured by TA Instruments) after heat treatment (standing in a constant temperature chamber at 130°C for ₂ hours). The sample pieces (width 10 mm × length 30 mm) for measurement were prepared by cutting out from a semiconductor back side adhesive film that had not been subjected to heat treatment or a semiconductor back side adhesive film that had been subjected to heat treatment. In addition, in each measurement, the initial chuck distance of the chucks used to hold the sample pieces was set to 20 mm, the measurement mode was set to the tensile mode, the measurement environment was set to a nitrogen atmosphere, the measurement temperature range was set to 0°C to 200°C, the frequency was set to 1 Hz, the dynamic strain was set to 0.05%, and the heating rate was set to 10°C/min. For each semiconductor back side adhesive film, the tensile storage modulus _E1 (MPa), the tensile storage modulus _E2 (MPa), and the ratio of these tensile storage moduli _E2 / _E1 are disclosed in Table 1.

<Glass transition temperature> Regarding each semiconductor back-side adhesive film of Example 1 and Comparative Example 1, the glass transition temperature was investigated by differential scanning calorimetry using a differential scanning calorimeter (trade name "DSC Q2000", manufactured by TA Instruments). In each differential scanning calorimetry, the measurement environment was set to a nitrogen atmosphere, the measurement temperature range was set to -30°C to 300°C, and the heating rate was set to 10°C/min. The glass transition temperature Tg (°C) of each semiconductor back-side adhesive film of Example 1 and Comparative Example 1 is disclosed in Table 1.

<Wafer warp> Regarding each semiconductor back surface adhesive film of Examples 1 to 4 and Comparative Example 1, the degree of warp induced when the film was subjected to a heating test together with a silicon wafer was investigated. Specifically, it is as follows.

First, a semiconductor back-side adhesive film is attached to a silicon wafer (thickness 100 μm, diameter 300 mm). Then, the silicon wafer with the semiconductor back-side adhesive film is heated in a constant temperature bath at 130°C for 2 hours (heating test). The wafer with the semiconductor back-side adhesive film that has undergone the heating test is placed on a laboratory table with a horizontal table with the semiconductor back-side adhesive film on the upper surface side and left to stand for 2 hours. Afterwards, the distance between the highest position from the table surface on the surface opposite to the table of the wafer periphery is measured with a ruler. The measured value is set as the warp amount (mm). The measured value is disclosed in Table 1.

<Printing property evaluation> Regarding each semiconductor back-contact film of Examples 1 to 4 and Comparative Example 1, the printing property was investigated in the following manner. First, a laser marking device (trade name "MD-S9920", manufactured by KEYENCE Co., Ltd.) was used to irradiate the semiconductor back-contact film with laser to perform printing using laser marking (for the semiconductor back-contact film of Example 1, printing was performed on the surface of its laser marking layer). In the laser marking, the laser power was 0.23 W, the marking speed was 300 mm/s, and the laser frequency was 10 kHz. Next, a microscope (trade name "Digital Microscope VHX-500", manufactured by KEYENCE Co., Ltd.) was used to observe the printed area using laser marking (bright field observation). Regarding the characters (printed characters) engraved by laser marking, the cases that fully meet both the contrast being clear and easy to see (the first criterion) and the maximum depth of the engraved characters being 1 μm or more (the second criterion) are evaluated as "good" in printing quality, and the cases that do not fully meet at least one of the first and second criteria are evaluated as "poor" in printing quality. The evaluation results are shown in Table 1.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparison Example 1 Layer structure of semiconductor back side adhesive film LM layer AH layer Single layer Single layer Single layer Single layer No. 1 Epoxy Resin (JER YL980) 7 7.5 7.5 - 3.5 7 Second epoxy resin (KI-3000-4) 7 7.5 7.5 - 3.5 7 Phenolic resin (MEH-7851SS) 15 16.5 16.5 25 8 15 Acrylic resin (TEISANRESIN SG-P3) 15 16.5 16.5 13 8 15 Packing (SO-25R) 50 50 50 60 75 50 Heat curing catalyst (Curezol 2PHZ) 4 - - - - 0.5 Black dye (OIL BLACK BS) 2 2 2 2 2 2 Heat release Q ₁ (J/g) 13 2 4 1 110 Heat release Q ₂ (J/g) 4 2 4 1 3 Heat release difference Q ₁ -Q ₂ (J/g) 9 0 0 1 107 Tensile storage modulus E ₁ (MPa) 8 0.04 0.06 0.8 0.3 Tensile storage modulus E ₂ (MPa) 8 0.04 0.06 0.8 200 _E2 / _E1 1.0 1 1 1 667 Glass transition temperature Tg(℃) 120 - - - 120 Wafer warp Less than 1 mm Less than 1 mm Less than 1 mm Less than 1 mm 7 mm Printing evaluation good good good bad good

10,10': Film (semiconductor back-side bonding film) 11: Laser marking layer 12: Adhesive layer 12a: Workpiece bonding surface 20: Cutting tape 21: Substrate 22: Adhesive layer 22a: Adhesive surface 30,W: Wafer 31: Chip 41: Ring frame 42,43: Holder 44: Ejector component 45: Adsorption fixture 51: Mounting substrate 52: Bump 53: Bottom filler R: Area T1: Wafer processing tape T1a: Adhesive surface Wa: 1st surface Wb: 2nd surface X: Cutting tape integrated semiconductor back-side bonding film

FIG. 1 is a top view of a wafer-strip-type semiconductor back-side bonding film in one embodiment of the present invention. FIG. 2 is a cross-sectional schematic diagram of a wafer-strip-type semiconductor back-side bonding film in one embodiment of the present invention. FIG. 3(a) and (b) show a part of the steps in a method for manufacturing a semiconductor device using the wafer-strip-type semiconductor back-side bonding film shown in FIG. 1 and FIG. 2. FIG. 4(a) and (b) show a step following the step shown in FIG. 3. FIG. 5 shows a step following the step shown in FIG. 4. FIG. 6 shows a step following the step shown in FIG. 5. FIG. 7 shows a step following the step shown in FIG. 6.

10: Film (semiconductor back side adhesion film)

11: Laser marking layer

12: Next layer

12a: Workpiece close contact surface

20: Cutting ribbon

21: Base material

22: Adhesive layer

22a: Adhesive surface

R: Region

X: Cut-crystal ribbon-type semiconductor back-side bonding film

Claims (7)

A semiconductor back-side adhesive film, the difference between the heat release in the range of 50-200°C in differential scanning calorimetry at a heating rate of 10°C/min and the heat release in the range of 50-200°C in differential scanning calorimetry at a heating rate of 10°C/min after heating at 130°C for 2 hours is less than 20 J/g. For example, the semiconductor back-side adhesive film of claim 1, after being heat-treated at 130°C for 2 hours, the ratio of the tensile storage modulus at 150°C measured for a semiconductor back-side adhesive film sample with a width of 10 mm under the conditions of an initial clip distance of 20 mm, a frequency of 1 Hz and a heating rate of 10°C/min to the tensile storage modulus at 150°C measured for a semiconductor back-side adhesive film sample with a width of 10 mm under the conditions of an initial clip distance of 20 mm, a frequency of 1 Hz and a heating rate of 10°C/min is less than 20. The semiconductor back surface adhesive film of claim 1 or 2 contains an inorganic filler at a ratio of 30% by mass or more. The semiconductor back surface adhesive film of claim 1 or 2 contains an inorganic filler at a ratio of 75% by mass or less. For semiconductor backside adhesive film in claim 1 or 2, the glass transition temperature is 100~200℃. The semiconductor back surface adhesive film of claim 1 or 2 contains an epoxy resin with an epoxy equivalent of 150 to 900 g/eq at a ratio of 2 to 20 mass %. A wafer-tape-integrated semiconductor back-side bonding film, comprising: a wafer tape having a multilayer structure including a substrate and an adhesive layer, and a semiconductor back-side bonding film as claimed in any one of claims 1 to 6 which is releasably bonded to the adhesive layer of the wafer tape.