WO2015152010A1 - Film protecteur et procédé de production de dispositif à semi-conducteur au moyen de ce film protecteur - Google Patents

Film protecteur et procédé de production de dispositif à semi-conducteur au moyen de ce film protecteur Download PDF

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Publication number
WO2015152010A1
WO2015152010A1 PCT/JP2015/059459 JP2015059459W WO2015152010A1 WO 2015152010 A1 WO2015152010 A1 WO 2015152010A1 JP 2015059459 W JP2015059459 W JP 2015059459W WO 2015152010 A1 WO2015152010 A1 WO 2015152010A1
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WIPO (PCT)
Prior art keywords
protective film
semiconductor wafer
adhesive layer
grinding
heating
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PCT/JP2015/059459
Other languages
English (en)
Japanese (ja)
Inventor
誠 助川
木下　仁
田原　修二
Original Assignee
三井化学東セロ株式会社
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Filing date
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Application filed by 三井化学東セロ株式会社 filed Critical 三井化学東セロ株式会社
Priority to CN201580007736.4A priority Critical patent/CN105981137B/zh
Priority to JP2016511600A priority patent/JP6106332B2/ja
Publication of WO2015152010A1 publication Critical patent/WO2015152010A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
    • H01L2221/68386—Separation by peeling

Definitions

  • the present invention relates to a protective film and a method for manufacturing a semiconductor device using the protective film. Specifically, the present invention relates to a protective film that is used in a manufacturing process of a semiconductor device such as a discrete device or an IGBT element and protects a circuit forming surface of a semiconductor wafer, and a method of manufacturing a semiconductor device using the protective film.
  • wafer backside a step of grinding a circuit non-formed surface of a semiconductor wafer (hereinafter referred to as “wafer backside” as appropriate), a step of etching a work-affected layer on the backside of a wafer with a chemical solution, Various processes are performed on the back side of the wafer, such as a step of forming a metal electrode on the back side of the wafer, and in the case of an IGBT element, a step of ion implantation into the back side of the wafer and an annealing step of activating the implanted dopant.
  • an adhesive layer is applied to the circuit forming surface of the semiconductor wafer (hereinafter referred to as “wafer surface” as appropriate) in order to prevent damage and contamination of the semiconductor wafer.
  • wafer surface the circuit forming surface of the semiconductor wafer
  • a protective film with is attached.
  • Examples of such a protective film include the following.
  • Japanese Patent Application Laid-Open No. 2010-287819 discloses that “an intermediate resin layer formed by curing an intermediate resin layer composition containing an adhesive component and a curing component on a base film and a radiation curable adhesive layer”
  • a semiconductor wafer processing pressure-sensitive adhesive tape in which and are laminated in this order is disclosed.
  • Japanese Patent Application Laid-Open No. 2011-249608 discloses that “a pressure-sensitive adhesive tape for protecting a semiconductor wafer surface comprising a pressure-sensitive adhesive layer made of a radiation-curable resin composition on a base resin film containing a polyester resin”. Is disclosed.
  • the film provided with the adhesive layer is a film for sticking to a semiconductor to protect it during the processing of the semiconductor having a reduced pressure heating process.
  • Japanese Patent Application Laid-Open No. 2012-109585 discloses “A semiconductor processing tape is disclosed which includes a pressure-sensitive adhesive layer containing a photocurable pressure-sensitive adhesive, silica fine particles having a specific particle diameter, and a gas generating agent on at least one surface of a substrate.
  • a sheet for fixing a semiconductor wafer whose adhesive strength is reduced by heating for example, in JP-A-10-025456, “sheet-like support and support In the semiconductor wafer fixing sheet, the main part of which is formed of a pressure-sensitive adhesive laminated on top thereof, the main component of the adhesive is 100 parts by weight of the base polymer, 10 to 900 parts by weight of the thermosetting compound, and heat polymerization is started.
  • a semiconductor wafer fixing sheet characterized by being formed with 0.1 to 10 parts by mass of an agent is disclosed.
  • JP-A-8-302301 discloses a thickness of 500 ⁇ m having an oxygen transmission coefficient of “1 ⁇ 10 8 cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg or more.
  • a heat-peelable pressure-sensitive adhesive sheet formed by forming a curable pressure-sensitive adhesive layer that does not cure or is delayed in the presence of oxygen in the following film-like substrate but is cured by heating is disclosed.
  • the curable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is based on 100 parts by weight of the pressure-sensitive rubber resin (A), 50 to 150 parts by weight of the ethylenically unsaturated group-containing compound (B), and 0% of the organic peroxide (C). It is also disclosed that 1 to 15 parts by mass, 0.01 to 5.00 parts by mass of a crosslinking agent (D) and 0.001 to 1.0 parts by mass of a polymerization inhibitor (E) are blended. Yes.
  • This pressure-sensitive adhesive sheet has a feature that it can be easily peeled off by heating.
  • the various processes performed on the wafer back side described above include a step of heating the semiconductor wafer under vacuum.
  • the semiconductor wafer is heated to 200 ° C. or higher under vacuum in a vacuum apparatus.
  • the film may be lifted or peeled off from the semiconductor wafer.
  • the adhesive strength may increase. If the film floats, it may be difficult to convey. That is, the present situation is that a film having a conventional adhesive layer cannot be applied to a process in which heating at 200 ° C. or higher is performed under vacuum.
  • heating at 200 ° C. or higher under vacuum is appropriately referred to as “vacuum heating”.
  • an object of the present invention is to apply a process that is performed under vacuum heating while being adhered to a semiconductor wafer after being adhered to a circuit forming surface of a semiconductor wafer and thermosetting the thermosetting adhesive layer.
  • An object of the present invention is to provide a protective film that, when applied to a method for manufacturing a semiconductor device, suppresses the occurrence of floating while protecting the circuit forming surface of the semiconductor wafer and is excellent in releasability when peeling from the semiconductor wafer. .
  • the other subject of this invention is providing the manufacturing method of the semiconductor device including the process performed under vacuum heating using the said protective film.
  • the means for solving the above-mentioned problems are as follows.
  • a polyimide base material A composition comprising an acrylic polymer (a), a thermal radical generator (b) having a half-life temperature of 140 ° C. or more and 200 ° C. or less, and a crosslinking agent (c) provided on one surface of the polyimide substrate.
  • a thermosetting adhesive layer obtained from the product, A protective film that is attached to a circuit forming surface of a semiconductor wafer.
  • ⁇ 2> The protective film according to ⁇ 1>, wherein the thermal radical generator (b) has a molecular weight of 200 or more and 1000 or less.
  • the thermal radical generator (b) has a molecular weight of 200 or more and 1000 or less.
  • the composition further contains a bifunctional or higher functional acrylic oligomer (d).
  • ⁇ 4> The protective film according to any one of ⁇ 1> to ⁇ 3>, wherein the acrylic polymer (a) is a polymer having a radical-reactive double bond in a side chain.
  • thermosetting adhesive layer is in contact with the circuit forming surface.
  • Pasting process (B) a grinding step of grinding a non-circuit-formed surface of the semiconductor wafer; (C) a heating step of heating the semiconductor wafer to which the protective film is attached and the non-circuit-formed surface is ground at a temperature of 120 ° C. or higher and 180 ° C. or lower; (D) after the heating step of (C), a standing step of standing the semiconductor wafer to which the protective film is stuck under vacuum; (E) After the standing step of (D), under vacuum and at a temperature of 200 ° C.
  • a method for manufacturing a semiconductor device comprising:
  • ⁇ 10> The method according to any one of ⁇ 6> to ⁇ 9>, wherein the grinding step (B) is a step of grinding an inner peripheral portion while leaving an outer peripheral portion of a circuit non-formed surface in the semiconductor wafer.
  • the grinding step (B) is a step of grinding an inner peripheral portion while leaving an outer peripheral portion of a circuit non-formed surface in the semiconductor wafer.
  • a method for manufacturing a semiconductor device including a step of applying a vacuum heating while being attached to a semiconductor wafer after being attached to a circuit forming surface of a semiconductor wafer and thermosetting the thermosetting adhesive layer.
  • a protective film that suppresses the occurrence of floating while protecting the circuit forming surface of the semiconductor wafer and is excellent in releasability when peeling from the semiconductor wafer.
  • the manufacturing method of the semiconductor device including the process performed under vacuum heating using the said protective film can be provided.
  • the protective film of the present invention is a polyimide base and a thermal radical generator (a) provided on one surface of the polyimide base and having an acrylic polymer (a) and a one-minute half-life temperature of 140 ° C. or higher and 200 ° C.
  • thermosetting adhesive layer obtained from a composition containing a crosslinking agent (c), and forming a circuit on a semiconductor wafer It is a protective film affixed to the surface.
  • the thermal radical generator (b) having a one-minute half-life temperature of 140 ° C. or more and 200 ° C. or less contained in the thermosetting adhesive layer is suitable for storage at room temperature or when forming a thermosetting adhesive layer. Decomposition is difficult to start under dry conditions, and it has the property of decomposing even without heating conditions that develop adhesive strength that makes it difficult to peel from the semiconductor wafer. In addition, the polyimide base material is unlikely to be softened by heating, can maintain a high elastic modulus even at a high temperature, has a property such that the thermal expansion coefficient is close to that of a semiconductor wafer, and the thermal contraction ratio is low.
  • the protective film of the present invention is applied to the circuit forming surface of a semiconductor wafer, and the thermosetting adhesive
  • thermosetting the layer it is estimated that it is difficult to expand even at a high temperature, and that it can be a pressure-sensitive adhesive layer (after thermosetting) having peelability from the semiconductor wafer.
  • the protective film of the present invention suppresses the occurrence of floating even when subjected to a process performed in a harsh environment such as under vacuum heating, and protects the circuit forming surface of the semiconductor wafer. Can be continued, and after that, excellent peelability can also be exhibited when peeling from the semiconductor wafer.
  • thermosetting adhesive layer The thermosetting pressure-sensitive adhesive layer in the present invention (hereinafter sometimes abbreviated as “pressure-sensitive adhesive layer”) is an acrylic polymer (a), a one-minute half-life temperature of 140 ° C. or higher and 200 ° C. or lower. It is obtained from the composition containing (b) and a crosslinking agent (c).
  • the acrylic polymer (a) is a binder resin that serves as a base for the pressure-sensitive adhesive in the pressure-sensitive adhesive layer, and can be obtained by copolymerizing several general (meth) acrylic acid ester monomers.
  • the (meth) acrylic acid ester monomer constituting the acrylic polymer (a) those known for pressure-sensitive adhesives can be applied.
  • the acrylic polymer (a) preferably has a high thermal decomposition temperature.
  • an acrylic polymer polymerized from an acrylate monomer is more heat resistant than an acrylic polymer polymerized from a methacrylic acid ester monomer (thermally decomposable). 50 mol% or more) is more preferable.
  • Suitable monomers for obtaining the acrylic polymer (a) are, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl.
  • Examples include methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, dodecyl acrylate, dodecyl methacrylate, and the like.
  • the side chain alkyl group of these monomers may be linear or branched. Moreover, you may use together 2 or more types of said acrylic acid alkylester monomers according to the objective.
  • the acrylic polymer (a) preferably has a functional group that reacts with a cross-linking agent (c) described later from the viewpoint of adjusting the properties (eg, adhesiveness) of the adhesive layer.
  • the functional group that reacts with the crosslinking agent (c) of the acrylic polymer (a) is preferably a carboxylic acid group, a hydroxyl group, a glycidyl group, or the like.
  • a carboxylic acid group, a hydroxyl group, a glycidyl group, etc. react with polyisocyanate and polyfunctional epoxy resin which are crosslinking agents (c).
  • a (meth) acrylic acid ester monomer having such a functional group may be copolymerized.
  • the (meth) acrylic acid ester monomer having a functional group that reacts with the crosslinking agent (c) include monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; And monomers having a hydroxyl group such as ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; monomers having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate;
  • an acrylic polymer (a) has a radical reactive double bond in a side chain from the point which hardens an adhesion layer.
  • a (meth) acrylic acid ester monomer having such a radical reactive double bond may be added to the copolymerized main polymer side chain.
  • a well-known technique in which glycidyl (meth) acrylate is copolymerized in the main chain, and (meth) acrylic acid is added to the glycidyl group of the main chain as a secondary reaction.
  • the method of making it react; etc. are mentioned.
  • the reaction of acid and glycidyl is more effective than the reaction of isocyanate and hydroxyl group.
  • the acrylic polymer (a) has a radical-reactive double bond in the side chain so that the radicals generated from the specific thermal radical generator (b) react with each other between the acrylic polymers (a).
  • the reaction between the acrylic polymer (a) and the later-described bifunctional or higher acrylic oligomer becomes possible.
  • the acrylic polymer (a) is preferably contained in the composition in the range of 50% by mass to 99.5% by mass, and more preferably in the range of 65% by mass to 99% by mass.
  • the specific thermal radical generator (b) used in the present invention is a component selected from the following points. That is, in the present invention, an adhesive layer formed by dissolving each component (including the acrylic polymer (a), the specific thermal radical generator (b), and the crosslinking agent (c)) used in obtaining the adhesive layer in a solvent.
  • the coating liquid is applied on a polyimide substrate (or separator) and dried to produce a protective film. Since heat is applied during the drying, it is preferable to select a temperature at which the decomposition is difficult to start at the drying temperature. Also, those having a high decomposition temperature are preferable in terms of storage stability at room temperature.
  • the specific thermal radical generator (b) used in the present invention needs to have a one-minute half-life temperature of 140 ° C. or higher and 200 ° C. or lower.
  • the 1 minute half-life temperature of the specific thermal radical generator is preferably 145 ° C. or higher and 180 ° C. or lower.
  • the molecular weight of the specific thermal radical generator is preferably 200 to 1000, more preferably 200 to 700, and further preferably 300 to 700.
  • specific thermal radical generator (b) known peroxides, azo compounds and the like having a 1 minute half-life temperature in the above range are used.
  • Specific examples of the specific thermal radical generator (b) include the following, but the present invention is not limited thereto.
  • a commercial product name (all manufactured by NOF Corporation), molecular weight, and 1-minute half-life temperature are also shown.
  • Specific commercial products of the specific thermal radical generator (b) include, for example, Perhexa MC, Perhexa TMH, Perhexa HC, Perhexa C, Pertetra A, Perhexyl I, Perbutyl 355, Perbutyl L, Perbutyl manufactured by NOF Corporation.
  • E perhexyl Z, perhexa 25Z, perhexa 22, perhexa V, perbutyl P, park mill D, perhexyl D, perhexa 25B, perbutyl C, perhexine 25B, and the like are preferable.
  • the amount of the specific thermal radical generator (b) added is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of monomers constituting the acrylic polymer (a). Preferably they are 0.2 mass part or more and 2 mass parts or less, More preferably, they are 0.3 mass part or more and 1 mass part or less. If the amount of the specific thermal radical generator added is too small, there may be a problem that the adhesive layer is not sufficiently cured by heat and the tackiness is increased.
  • XPS X-ray photoelectron spectroscopy
  • the crosslinking agent (c) in the present invention is a component that can react with the acrylic polymer (a) to form a crosslinked body (three-dimensional crosslinked body) of the acrylic polymer (a).
  • a crosslinked body three-dimensional crosslinked body
  • the acrylic polymer (a) By adjusting the acrylic polymer (a) to a crosslinked product, adjustment of the initial adhesive strength of the adhesive layer, ease of cutting of the tape (easiness of cutting the adhesive layer on the cut surface), pressure deformation, etc. are adjusted. Furthermore, thermal decomposition of the main chain of the acrylic polymer (a) can be suppressed.
  • an isocyanate-based or epoxy-based crosslinking agent which is a general crosslinking agent for an acrylic pressure-sensitive adhesive, is used.
  • thermo decomposability a crosslinking agent having high heat resistance (thermal decomposability) from the viewpoint of improving the heat resistance (thermal decomposability) of the acrylic polymer (a).
  • preferred crosslinking agents (c) include those shown below, but the present invention is not limited thereto. That is, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol diglycidyl ether, resorcin diglycidyl ether Examples include chemical epoxy compounds such as tetrad C and tetrad X; isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate triadduct of trimethylolpropane, polyisocyanate, isocyanurate type isocyanate, and the like.
  • the pressure-sensitive adhesive layer before curing becomes soft and fluid and tends to be excellent in wettability and unevenness followability to the wafer surface.
  • shape stability will worsen and there exists a possibility that a level
  • the protective film of this invention is cut, there exists a possibility that the cut of an adhesive may worsen.
  • the amount of the crosslinking agent is large, the adhesive layer before curing becomes hard, it is difficult to obtain wettability and unevenness followability to the wafer surface, and the protective film may float under vacuum heating.
  • the addition amount of the crosslinking agent (c) may be determined in consideration of the above points.
  • the proper addition amount of the crosslinking agent is preferably increased because the tendency to become a soft adhesive is promoted when there are many bifunctional or higher acrylic oligomers added to the composition of the present invention.
  • the addition amount of the crosslinking agent (c) is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of monomers constituting the acrylic polymer (a). 2 parts by mass or more and 10 parts by mass or less are more preferable.
  • the composition for obtaining the thermosetting adhesive layer in the present invention further contains a bifunctional or higher functional acrylic oligomer (d).
  • the bifunctional or higher-functional acrylic oligomer (d) is an acrylic oligomer having two or more radical-reactive double bonds, and reacts with radicals generated by the specific thermal radical generator (b). It is a component that contributes to curing.
  • the above-mentioned acrylic polymer (a) does not have a radical reactive double bond in the side chain, it becomes essential as a component for thermosetting the adhesive layer.
  • the pressure-sensitive adhesive layer after heat curing is hard and brittle, the pressure-sensitive adhesive layer may break while it is biting into the irregularities on the wafer surface, and a part of the pressure-sensitive adhesive layer may remain on the wafer surface (also referred to as residue). For this reason, it is good to adjust the addition amount, the number of functional groups, etc. of bifunctional or more acrylic oligomer (d) so that the elongation at the time of the tensile fracture of the adhesion layer after thermosetting may become large. If a large number of functional groups having a large molecular weight is added, it may be hard and brittle.
  • the bifunctional or higher acrylic oligomer (d) is preferably hexafunctional or lower, more preferably trifunctional or higher and pentafunctional or lower. Since the protective film of the present invention requires heat resistance, it is preferable to select a bifunctional or higher acrylic oligomer (d) having a structure with high heat resistance (not easily thermally decomposed). From the viewpoint of heat resistance, those having an ester bond are preferable to those having a urethane bond.
  • the molecular weight of the acrylic oligomer (d) is preferably from 200 to 10,000, more preferably from 300 to 5,000, from the viewpoint of cured properties.
  • bifunctional or higher acrylic oligomer (d) include commercially available urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, pentaerythritol polyacrylate, dipentaerythritol polyacrylate, ethoxylated isocyanuric acid triacrylate, tri Examples include methylolpropane triacrylate and ditrimethylolpropane tetraacrylate.
  • the bifunctional or higher functional acrylic oligomer (d) may be added in the case where the acrylic polymer (a) has a radical reactive double bond in the side chain.
  • the acrylic oligomer (d) functions as a low molecular weight component, and the unevenness followability and wettability of the pressure-sensitive adhesive layer before thermosetting to the wafer surface are improved.
  • the cured adhesive layer becomes hard and brittle, and the adhesive layer described above may break.
  • the addition amount of the bifunctional or higher-functional acrylic oligomer (d) is 0 to 100 parts by mass, more preferably 0 to 50 parts by mass with respect to 100 parts by mass of the acrylic polymer (a). Less than parts by mass is appropriate.
  • the acrylic polymer (a) does not have a radical-reactive double bond in the side chain, it is essential as a component for thermally curing the adhesive layer, but a bifunctional or higher-functional acrylic oligomer (d ) Is insufficient, the thermosetting of the adhesive layer is insufficient, and a part of the adhesive layer may remain (cohesive failure) on the wafer surface.
  • the adhesive layer may break.
  • the amount of addition when the bifunctional or higher functional acrylic oligomer (d) is essential is 1 to 100 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the acrylic polymer (a). 20 mass parts or more and 50 mass parts or less are suitable.
  • the thickness of the pressure-sensitive adhesive layer obtained from the composition containing each component as described above is preferably formed to a thickness that can sufficiently follow the irregularities on the wafer surface.
  • the thickness of the adhesive layer is suitably 10 ⁇ m or more and 100 ⁇ m or less, more preferably 20 ⁇ m or more and 50 ⁇ m or less.
  • the polyimide base material in the present invention is selected from the following points. That is, when the base material is subjected to vacuum heating, if the base material is softened, it is not preferable because the base material is fixed to the contacting member. Moreover, it is preferable that a high elastic modulus can be maintained even at high temperatures.
  • the semiconductor wafer (silicon wafer) to which the protective film of the present invention is attached is processed to be as thin as 150 ⁇ m or less, and in some cases, 100 ⁇ m or less. When such a thin semiconductor wafer and a protective film are applied and then heated, if the linear expansion coefficient of the base material is greatly deviated from the thermal expansion coefficient of silicon of the semiconductor wafer, the semiconductor wafer is warped. .
  • a drying process for reducing the moisture contained in the protective film is performed before the process performed under vacuum heating.
  • a drying process for reducing the moisture contained in the protective film is performed.
  • the adhesive strength between the pressure-sensitive adhesive layer and the polyimide base material is obtained by subjecting the polyimide base material to a surface treatment (such as a known discharge treatment (corona, plasma) or a coupling agent treatment) or an adhesive layer. Is preferably increased.
  • the thickness of the polyimide base material is preferably 25 ⁇ m or more and 100 ⁇ m or less, and more preferably 38 ⁇ m or more and 50 ⁇ m or less. If the polyimide base material is too thin, wrinkles may be easily formed at the time of sticking. On the other hand, if it is too thick, the water vapor permeability may be deteriorated or the followability to the irregularities on the surface of the semiconductor wafer may be deteriorated. .
  • a commercially available polyimide substrate may be used as the polyimide substrate.
  • Kapton registered trademark of Toray DuPont
  • Apical registered trademark of Kaneka
  • Upilex registered trademark of Ube Industries, etc. have been commercialized and can be used. .
  • the protective film is produced as follows. First, each component which comprises the composition used in order to obtain an adhesion layer is melt
  • a protective film of the laminate may be peeled off before being attached to the semiconductor wafer.
  • the temperature and the residence time in the drying furnace in consideration of sufficiently removing the volatile component such as a solvent so that the protective film can be prevented from floating under vacuum heating.
  • the temperature in the drying step is preferably 60 ° C. or higher and 130 ° C. or lower, and the residence time is preferably 1 minute or longer and 10 minutes or shorter.
  • the protective film of the present invention is preferably used as a protective film in a method for producing a semiconductor device including the following steps (1) to (4).
  • the protective film is attached. Heating step of heating the semiconductor wafer at a temperature of 120 ° C. or higher and 180 ° C.
  • step (1) is described later in (A) a sticking step
  • step (2) is described in (C) a heating step
  • step (3) is described in (D) static.
  • step (4) corresponds to the (E) processing step under vacuum heating described later. The details of each step are the same as the corresponding (A) sticking step, (C) heating step, (D) standing step, and (E) processing step under vacuum heating, and thus are omitted here.
  • a method for manufacturing a semiconductor device of the present invention includes: (A) An attaching step of attaching the protective film of the present invention to the circuit forming surface of the semiconductor wafer so that the thermosetting adhesive layer is in contact with the circuit forming surface; (B) a grinding step of grinding a non-circuit-formed surface of the semiconductor wafer; (C) a heating step of heating the semiconductor wafer to which the protective film is attached and the non-circuit-formed surface is ground at a temperature of 120 ° C. or higher and 180 ° C.
  • the sticking step in the present invention the sticking is performed so that the thermosetting adhesive layer in the protective film of the present invention is in contact with the circuit forming surface of the semiconductor wafer.
  • This (A) sticking process is performed before or after the (B) grinding process.
  • the semiconductor wafer to which the protective film of the present invention is stuck is applied to the (B) grinding step as it is.
  • a sticking process is performed after (B) a grinding process, it sticks so that the adhesion layer in a well-known protective film may contact
  • the process of peeling a well-known protective film from a semiconductor wafer is performed. Since the number of steps is small and there is no need to replace the protective film, it is preferable to perform the (A) pasting step before the (B) grinding step.
  • a known tape applicator can be applied to the protective film of the present invention applied to the semiconductor wafer.
  • a vacuum applicator In order to apply air to the irregularities of the circuit on the wafer surface without applying air, it is preferable to use a vacuum applicator. It is not preferable to bite air because (E) the protective film floats in the processing step performed under vacuum heating.
  • the non-circuit-formed surface (wafer back surface) of the semiconductor wafer is ground.
  • a semiconductor wafer to which the protective film of the present invention or the conventional protective film is attached is fixed to a chuck table of a grinding machine via a polyimide base material, and a circuit is not formed on the semiconductor wafer. Grind the surface (wafer back). After the grinding is finished, when the conventional protective film is stuck on the semiconductor wafer, the protective film is peeled off.
  • the semiconductor wafer with the protective film attached may be subjected to an etching process step using a chemical solution such as chemical etching or polishing of the back surface of the wafer.
  • the semiconductor wafer to which the protective film of the present invention is attached is preheated to remove moisture in the protective film.
  • the protective film of the present invention is composed of an acrylic pressure-sensitive adhesive and a polyimide base material, both of which are materials having a high moisture absorption rate. Since the grinding process and the etching process are processes using water, the protective film of the present invention is in a moisture-absorbing state. When the moisture-absorbing protective film is heated in the heating step (C), floating may occur due to rapid expansion of moisture absorbed.
  • an oven or the like and preheat and dry the semiconductor wafer to which the protective film of the present invention is attached at 60 ° C. or higher and 100 ° C. or lower for several minutes to several tens of minutes.
  • the semiconductor wafer to which the protective film of the present invention is attached and the non-circuit-formed surface is ground is heated at a temperature of 120 ° C. or higher and 180 ° C. or lower.
  • This step may be carried out under reduced pressure or under increased pressure, but if it is carried out under reduced pressure, floating may occur due to the generated gas accompanying decomposition of the peroxide. It is preferable to carry out at atmospheric pressure from the viewpoint that a general-purpose oven can be used.
  • the adhesive layer of the protective film of the present invention is thermally cured.
  • the heating conditions in the (C) heating step may be set according to the 1-minute half-life temperature of the used specific thermal radical generator (b).
  • the specific thermal radical generator (b ) Preferably within ⁇ 30 ° C. (more preferably within ⁇ 20 ° C.).
  • the heating step is performed at a temperature of 120 ° C. or higher and 180 ° C. or lower (preferably 130 ° C. or higher and 170 ° C. or lower) at atmospheric pressure, and several minutes or longer and 1 hour or shorter (preferably 1). It is preferable to carry out heating for a period of 1 minute to 1 hour, more preferably 3 minutes to 30 minutes, still more preferably 5 minutes to 30 minutes, particularly preferably 10 minutes to 30 minutes.
  • a vacuum deposition apparatus is applied to metal deposition
  • a sputtering apparatus is applied to metal sputtering
  • an ion implantation apparatus is applied to ion implantation.
  • Vacuum equipment In these vacuum apparatuses, generally, a semiconductor wafer is allowed to stand in a preliminary exhaust chamber, and after reaching a certain degree of vacuum (for example, 1 Pa or less), the semiconductor wafer is transferred to this apparatus. The standing in the preliminary exhaust chamber is the above-described (D) standing step.
  • metal vapor deposition, metal sputtering, or ion implantation is performed under vacuum, and the semiconductor wafer in the apparatus at that time is heated to 200 ° C. or higher.
  • the upper limit of the heating in the processing step (E) under vacuum heating is determined by the type of the processing, the heating / cooling mechanism of the apparatus, etc., specifically, it is about 300 ° C.
  • (E) the protective film of the present invention is peeled from the semiconductor wafer after the treatment process under vacuum heating.
  • an automatic peeling machine Takatori Co., Ltd., model: ATRM-2000B, ATRM-2100, Teikoku Seiki Co., Ltd., model: STP series, Nitto Seiki Co., Ltd., model: HR-8500II Etc.
  • an adhesive tape called a peeling tape used when peeling the protective film of the present invention from the wafer surface by the automatic peeling machine for example, Sumitomo 3M Co., Ltd., Highland Mark Filament Tape No. 897 or the like can be used.
  • the temperature at which the protective film of the present invention is peeled off from the wafer surface is usually performed at room temperature of about 25 ° C. However, when the above-described automatic peeling machine has a function of heating the wafer, the semiconductor wafer The protective film may be peeled off while the temperature is raised to a predetermined temperature (usually about 40 ° C. to 90 ° C.).
  • the wafer surface after peeling off the protective film of the present invention is cleaned as necessary.
  • the cleaning method include wet cleaning such as water cleaning and solvent cleaning, and dry cleaning such as plasma cleaning.
  • wet cleaning ultrasonic cleaning may be used in combination. These cleaning methods are appropriately selected depending on the contamination state of the wafer surface.
  • the semiconductor device manufacturing method of the present invention preferably further includes the following steps.
  • the polyimide base material is hard, and when the thickness of the adhesive layer is thin, the unevenness on the wafer surface may not be absorbed. In this case, the back surface of the convex portion may be excessively ground during grinding in the (B) grinding step. From the standpoint of preventing this, a method of applying a known semiconductor wafer grinding film to the surface of the polyimide base material (non-adhesive surface of the adhesive layer) in the protective film of the present invention is employed.
  • the step of attaching the semiconductor wafer grinding film to the surface of the polyimide base material of the protective film applied to the semiconductor wafer ((i) ))
  • a method of applying a semiconductor wafer grinding film in advance to the surface of the polyimide base material of the protective film (B) the step of attaching the semiconductor wafer grinding film to the surface of the polyimide base material of the protective film applied to the semiconductor wafer ((i) ))
  • a method of applying a semiconductor wafer grinding film in advance to the surface of the polyimide base material of the protective film preferably includes a soft / stress relaxation layer that absorbs irregularities on the wafer surface.
  • the semiconductor wafer grinding film is preferably peeled off from the protective film of the present invention after the (B) grinding step and before the (C) heating step ((ii) step).
  • the grinding step is a step of grinding the inner peripheral portion while leaving the outer peripheral portion of the circuit non-formed surface in the semiconductor wafer.
  • the (B) grinding step it is preferable to use a so-called Tyco process, in which the outer peripheral edge of the semiconductor wafer is left thick and the strength is increased while the center is ground to a predetermined thickness.
  • the polyimide base material in the protective film of the present invention does not cause thermal expansion and does not completely match the thermal expansion coefficient with the silicon wafer.
  • the above-described Tyco process is used in combination with the protective film of the present invention applied.
  • Semiconductor wafers to which the method for manufacturing a semiconductor device of the present invention can be applied are not limited to silicon wafers, but include semiconductor wafers such as gallium nitride, germanium, gallium-arsenic, gallium-phosphorus, and gallium-arsenic-aluminum.
  • a compounding quantity is a mass part with respect to 100 mass parts of monomers in an acrylic polymer, and is a mass ratio of solid content.
  • Polymers 1 and 2 oligomers 1 and 2, peroxides 1 to 5, and crosslinking agent 1 abbreviated in Table 2 are as follows.
  • Polymer 1 82 parts of ethyl acrylate, 10 parts of methyl methacrylate, 8 parts of hydroxybutyl acrylate and 0.5 parts by weight of benzoyl peroxide as a polymerization initiator are mixed, 65 parts by weight of toluene, 50 parts by weight of ethyl acetate was added dropwise at 80 ° C. over 5 hours while stirring in a nitrogen-substituted flask containing, and the reaction was further stirred for 5 hours to obtain an acrylate copolymer solution. This was designated as Polymer 1.
  • Polymer 2 48 parts by mass of ethyl acrylate, 27 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate, and 0.5 parts by mass of benzoyl peroxide as a polymerization initiator
  • the mixture was added dropwise to a nitrogen-substituted flask containing 65 parts by mass of toluene and 50 parts by mass of ethyl acetate with stirring at 80 ° C. over 5 hours, and further stirred for 5 hours to be reacted.
  • Oligomer 1 AD-TMP (manufactured by Shin-Nakamura Chemical, ditrimethylolpropane tetraacrylate)
  • Oligomer 2 Allonics M-402 (Toagosei, dipentaerythritol pentaacrylate and hexaacrylate)
  • Peroxide 1 Pertetra A (manufactured by NOF, 2,2-Di (4,4-di- (t-butylperoxy) cyclohexyl) propane, molecular weight 561, 1 minute half-life temperature 154 ° C.)
  • Peroxide 2 Niper BMT (manufactured by NOF, 1 minute half-life temperature 131 ° C)
  • Peroxide 3 Parroyl TCP (manufactured by NOF, molecular weight 399, half-life temperature 92 ° C.
  • Peroxide 4 Perbutyl C (manufactured by NOF, t-Butyl cumyl peroxide, molecular weight 208, 1 minute half-life temperature 173 ° C.)
  • Peroxide 5 Parkmill P (manufactured by NOF, molecular weight 194, 1 minute half-life temperature 233 ° C.)
  • Crosslinking agent 1 Olester P49-75S (Mitsui Chemicals)
  • the protective films of Examples 1 to 4 were prepared from the acrylic polymer (a), the specific thermal radical generator (b), the crosslinking agent (c), and the bifunctional or higher acrylic in the present invention. Because it has a pressure-sensitive adhesive layer obtained from a coating solution containing an oligomer (d), the protective film does not float even when subjected to vacuum heating after thermosetting, and no residue remains I understand.
  • Example A After the protective film of Example 1 was attached to the mirror surface of a 6-inch silicon wafer, this was heated in an oven at 80 ° C. for 10 minutes (preliminary heating), and then heated in an oven at 150 ° C. for 15 minutes. Then, the adhesive layer was thermally cured. Subsequently, this was put into a vacuum oven and placed under vacuum, and then heated at 250 ° C. for 30 minutes. Note that the preheating and the heating during the thermosetting of the adhesive layer were performed under atmospheric pressure.
  • Examples B to D, Comparative Examples a to f, and Reference Example Except that the protective film used in Example A was replaced with the protective film described in Table 3 below, and the heating described in Table 3 was performed. Same as Example A. When vacuum heating was performed in Examples A to D, Comparative Examples a to f, and Reference Examples, the presence or absence of occurrence of floating of the protective film was visually confirmed in the oven. Moreover, after returning to room temperature after vacuum heating, the protective film was peeled from the silicon wafer, and it was visually confirmed whether or not the adhesive layer remained on the silicon wafer. The results are shown in Table 3.
  • thermosetting of the adhesive layer is insufficient.
  • Comparative Example d using the protective film of Comparative Example 4 after preheating, without performing the thermosetting of the adhesive layer and leaving it under vacuum and at 200 ° C. or higher, did not cause a residue, The protective film was lifted. This is because a coating solution containing a large amount of a crosslinking agent is used, so that it is a hard adhesive layer, has low wettability with respect to the silicon wafer, and was unable to maintain adhesion to the silicon wafer during vacuum heating. Presumed to be.
  • Comparative Example e in which the protective film of Comparative Example 5 was used, and after the preliminary heating, the adhesive layer was not thermally cured, and was left in a vacuum at 200 ° C. or higher, the protective film did not float. However, it was found that there was a residue. This is because it uses a coating solution with a small amount of crosslinking agent added, it is a soft adhesive layer, excellent wettability to the silicon wafer, and was able to maintain adhesion to the silicon wafer even under vacuum heating, It is presumed that the adhesiveness has increased due to the high temperature, and the residue remains.
  • Example E The protective film of Example 1 was affixed to the mirror surface of an 8-inch silicon wafer (mirror) ((A) affixing process). Subsequently, the back surface of the wafer was ground to a thickness of 100 ⁇ m using a disco back grinder ((B) grinding step). After grinding, the wafer was not cracked and warpage was 1 mm or less. Next, the wafer was dried in an oven at 80 ° C. for 10 minutes (preliminary heating), and then further heated in an oven at 150 ° C. for 15 minutes to cure the adhesive layer ((C) heating step). Note that the preheating and the heating during the thermosetting of the adhesive layer were performed under atmospheric pressure.
  • the warpage of the wafer was about 2 mm, which was the amount of warpage that could be handled by the wafer transfer device. Subsequently, the wafer was put into a vacuum oven and placed under vacuum, and then heated at 250 ° C. for 30 minutes. No floating occurred in the vacuum oven. Thereafter, when the protective film of Example 1 was peeled off from the wafer returned to the atmospheric pressure and room temperature environment, no residue was observed on the wafer surface.

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Abstract

Film protecteur collé à une surface de formation de circuit d'une tranche de semi-conducteur, présentant un substrat de polyimide et comportant une couche adhésive thermodurcissable qui est appliquée sur une surface du substrat de polyimide et qui est obtenue à partir d'une composition comprenant un polymère acrylique (a), un générateur thermique de radicaux (b) possédant une demi-vie d'une minute à une température de 140 à 200 °C, et un agent de réticulation (c).
PCT/JP2015/059459 2014-03-31 2015-03-26 Film protecteur et procédé de production de dispositif à semi-conducteur au moyen de ce film protecteur WO2015152010A1 (fr)

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CN201580007736.4A CN105981137B (zh) 2014-03-31 2015-03-26 保护膜以及使用该保护膜的半导体装置的制造方法
JP2016511600A JP6106332B2 (ja) 2014-03-31 2015-03-26 保護フィルム、及び、該保護フィルムを用いる半導体装置の製造方法

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WO2022030604A1 (fr) * 2020-08-07 2022-02-10 日東電工株式会社 Élément de revêtement protecteur et feuille d'alimentation en élément

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JP6777233B2 (ja) * 2017-07-12 2020-10-28 富士電機株式会社 半導体装置の製造方法
KR20210141929A (ko) * 2019-03-15 2021-11-23 린텍 가부시키가이샤 점착 시트 및 반도체 장치의 제조 방법

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JP7247419B2 (ja) 2020-08-07 2023-03-28 日東電工株式会社 保護カバー部材及び部材供給用シート

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JPWO2015152010A1 (ja) 2017-04-13
TW201546148A (zh) 2015-12-16

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