WO2013058054A1 - Feuille thermiquement détachable - Google Patents

Feuille thermiquement détachable Download PDF

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Publication number
WO2013058054A1
WO2013058054A1 PCT/JP2012/074143 JP2012074143W WO2013058054A1 WO 2013058054 A1 WO2013058054 A1 WO 2013058054A1 JP 2012074143 W JP2012074143 W JP 2012074143W WO 2013058054 A1 WO2013058054 A1 WO 2013058054A1
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WIPO (PCT)
Prior art keywords
temperature
heat
peelable sheet
support
less
Prior art date
Application number
PCT/JP2012/074143
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English (en)
Japanese (ja)
Inventor
宇圓田　大介
裕亮 白川
寛 浜本
小田　高司
豊田　英志
松村　健
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2012143315A external-priority patent/JP2013100450A/ja
Priority claimed from JP2012143287A external-priority patent/JP2013153122A/ja
Priority claimed from JP2012143292A external-priority patent/JP2013153124A/ja
Priority claimed from JP2012143288A external-priority patent/JP2013153123A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN201280050829.1A priority Critical patent/CN103890116A/zh
Priority to KR1020147013439A priority patent/KR20140084220A/ko
Priority to US14/348,947 priority patent/US20140249269A1/en
Publication of WO2013058054A1 publication Critical patent/WO2013058054A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • 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
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H01L23/49894—Materials of the insulating layers or coatings
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
    • 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
    • H01L2221/68318—Auxiliary support including means facilitating the separation of a device or wafer from the auxiliary support
    • 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
    • H01L2221/68345—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 as a support during the manufacture of self supporting substrates
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a heat-peelable sheet.
  • Patent Document 1 describes that the heat-sensitive adhesive can be used at a temperature up to 180 ° C.
  • the first and fourth aspects of the present invention have been made in view of the above-described problems, and an object thereof is to provide a heat-peelable sheet that exhibits releasability at a higher temperature. .
  • the second aspect of the present invention has been made in view of the above-described problems, and an object thereof is to provide a solvent peelable sheet that can be easily peeled off using a solvent.
  • the present invention has been made in view of the above-described problems, and an object thereof is to provide a heat-peelable sheet having higher heat resistance.
  • the fifth aspect of the present invention has been made in view of the above-described problems, and an object thereof is to provide a heat-peelable sheet that is excellent in durability at high temperatures.
  • the sixth aspect of the present invention has been made in view of the above-described problems, and an object thereof is to provide a heat-peelable sheet that exhibits releasability at a higher temperature and whose peel temperature can be controlled. It is in.
  • the seventh aspect of the present invention has been made in view of the above-mentioned problems.
  • the purpose of the seventh aspect of the present invention is to prevent separation even when exposed to a relatively high temperature under conditions where the oxygen concentration is low, and to maintain the same oxygen concentration as the atmosphere. It is an object of the present invention to provide a heat-peelable sheet that exhibits releasability at a low temperature as compared with a low oxygen concentration condition.
  • the present inventors have already invented a method of manufacturing a semiconductor device having the following configuration (1) (for example, JP 2010-141126 A).
  • the metal support layer can be removed without being etched, and the metal support layer can be reused.
  • the manufacturing cost can be reduced.
  • the rigidity (stiffness) of the metal support layer due to the rigidity (stiffness) of the metal support layer, deformation of the printed circuit board directly under the semiconductor chip to be mounted can be prevented.
  • the method for manufacturing a semiconductor device when the method for manufacturing a semiconductor device is adopted, first, it is necessary to form a printed circuit board on a support. In the step of forming the wired circuit board, it is necessary that the wired circuit board does not peel from the metal support layer. On the other hand, after the printed circuit board is formed, it may be desired to peel the substrate without heating in consideration of damage to the wiring.
  • the heat-peelable sheet according to the first aspect of the present invention has a shear adhesive strength to the silicon wafer at the temperature after being held at 200 ° C. for 1 minute, at 0.25 kg / 5 ⁇ 5 mm or more.
  • the shear adhesive force to the silicon wafer at the temperature after holding for 3 minutes at any temperature in the temperature range higher than 200 ° C. and lower than 500 ° C. is less than 0.25 kg / 5 ⁇ 5 mm.
  • the shear adhesive force to the silicon wafer at the temperature after being held at 200 ° C. for 1 minute is 0.25 kg / 5 ⁇ 5 mm or more, and is larger than 200 ° C. and 500
  • the shear adhesive strength to the silicon wafer at the temperature after holding for 3 minutes at any temperature in the temperature range of 0 ° C. or lower is less than 0.25 kg / 5 ⁇ 5 mm. Therefore, while having a certain degree of adhesiveness at the time of 200 ° C., the peelability higher than that at the time of 200 ° C. is exhibited at a temperature higher than 200 ° C.
  • a heat-peelable sheet that exhibits releasability at a higher temperature can be provided.
  • the dynamic hardness is preferably 10 or less.
  • the adhesive force of the heat-peelable sheet to the adherend can be made sufficient.
  • the weight reduction rate after being immersed in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes is less than 1% by weight. If the weight loss after immersion in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes is less than 1% by weight, the dissolution into the 3% tetramethylammonium hydroxide aqueous solution is small, so solvent resistance (particularly , Solvent resistance to tetramethylammonium hydroxide aqueous solution can be improved.
  • the amount of increase in particles of 0.2 ⁇ m or more on the silicon wafer surface when peeled after being bonded to the silicon wafer is less than 10000/6 inch wafers before being bonded to the silicon wafer. It is preferable that When the amount of particles of 0.2 ⁇ m or more on the silicon wafer surface when peeled after being bonded to the silicon wafer is less than 10,000 / 6 inch wafers before being bonded to the silicon wafer, Later adhesive residue can be suppressed.
  • the heat-peelable sheet with a support of the first aspect of the present invention is characterized in that the heat-peelable sheet described above is provided on the support.
  • the solvent release sheet according to the second aspect of the present invention is the weight loss rate after being immersed in N-methyl-2-pyrrolidone at 50 ° C. for 60 seconds and dried at 150 ° C. for 30 minutes. Is 1.0% by weight or more.
  • the weight reduction rate after dipping in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and drying at 150 ° C. for 30 minutes is 1.0. % By weight or more. Since the weight reduction rate after immersing in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and drying at 150 ° C. for 30 minutes is 1% by weight or more, the solvent release sheet is N-methyl-2 -It can be said that it has dissolved in pyrrolidone and has been sufficiently reduced in weight. As a result, the solvent release sheet can be easily peeled with N-methyl-2-pyrrolidone.
  • NMP N-methyl-2-pyrrolidone
  • the weight reduction rate of the solvent release sheet can be controlled by, for example, the solubility of the raw material in NMP. That is, as a raw material having a higher solubility in NMP is selected, the solvent release sheet obtained using the raw material has higher solubility in NMP.
  • the dynamic hardness is preferably 10 or less.
  • the adhesive force of the solvent release sheet to the adherend can be made sufficient.
  • the weight reduction rate after being immersed in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes is less than 1% by weight. If the weight loss after immersion in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes is less than 1% by weight, the dissolution into the 3% tetramethylammonium hydroxide aqueous solution is small, so solvent resistance (particularly , Solvent resistance to tetramethylammonium hydroxide aqueous solution can be improved.
  • the amount of increase in particles of 0.2 ⁇ m or more on the silicon wafer surface when peeled after being bonded to the silicon wafer is less than 10000/6 inch wafers before being bonded to the silicon wafer. It is preferable that When the amount of particles of 0.2 ⁇ m or more on the silicon wafer surface when peeled after being bonded to the silicon wafer is less than 10,000 / 6 inch wafers before being bonded to the silicon wafer, Later adhesive residue can be suppressed.
  • the solvent peelable sheet with a support of the second aspect of the present invention is characterized in that the solvent peelable sheet described above is provided on a support in order to solve the above problems.
  • the heat-peelable sheet according to the third invention has an imide group.
  • the heat-peelable sheet according to the third aspect of the present invention since it has an imide group, it has excellent heat resistance. Whether or not the heat-peelable sheet has an imide group can be confirmed based on whether or not a spectrum having an absorption peak at 1400 to 1500 cm ⁇ 1 exists in a Fourier transform infrared (FT-IR) spectrum. That is, when there is a spectrum having an absorption peak at 1400-1500 cm ⁇ 1 , it can be determined that it has an imide group.
  • FT-IR Fourier transform infrared
  • the said structure it is preferable to have a structural unit derived from the diamine which has an ether structure.
  • a structural unit derived from a diamine having an ether structure when the heat-peelable sheet is heated to a high temperature (for example, 200 ° C. or higher), the shear adhesive force can be reduced. With respect to this phenomenon, the present inventors have inferred that the ether structure is detached from the resin constituting the heat-peelable sheet when heated to a high temperature, and the shear adhesive force is reduced by this desorption. .
  • the heat-peelable sheet has a diamine having an ether structure can be confirmed by whether or not a spectrum having an absorption peak at 2700 to 3000 cm ⁇ 1 exists in a Fourier transform infrared spectroscopy (FT-IR) spectrum. . That is, when a spectrum having an absorption peak at 2700 to 3000 cm ⁇ 1 exists, it can be determined that the diamine has an ether structure.
  • the ether structure is desorbed from the resin constituting the heat-peelable sheet, for example, by comparing FT-IR (Fourier Transform Infrared Spectroscopy) spectra before and after heating at 300 ° C. for 30 minutes. It can be confirmed that the spectrum of ⁇ 3000 cm ⁇ 1 decreases before and after heating.
  • FT-IR Fastier Transform Infrared Spectroscopy
  • the structural unit derived from the diamine having an ether structure preferably has a glycol skeleton or a glycol skeleton derived from a diamine having an alkylene glycol.
  • the peeling can be performed better by heating to a high temperature (for example, 200 ° C. or higher). Showing gender. Whether or not the heat-peelable sheet has a diamine having a glycol skeleton can be confirmed by whether or not a spectrum having an absorption peak at 2700 to 3000 cm ⁇ 1 exists in the FT-IR spectrum.
  • the diamine has a glycol skeleton.
  • whether or not the heat-peelable sheet has a diamine having a glycol skeleton derived from a diamine having an alkylene glycol depends on whether or not there is a spectrum having an absorption peak at 2700 to 3000 cm ⁇ 1 in the FT-IR spectrum. Can be confirmed.
  • the heat-peelable sheet comprises a polyimide resin obtained by imidizing polyamic acid obtained by reacting an acid anhydride, a diamine having an ether structure, and a diamine not having an ether structure.
  • a polyimide resin obtained by imidizing polyamic acid obtained by reacting an acid anhydride, a diamine having an ether structure, and a diamine not having an ether structure.
  • Mixing ratio of the diamine having the ether structure and the diamine not having the ether structure when the acid anhydride, the diamine having the ether structure, and the diamine not having the ether structure are reacted as a material
  • the molar ratio is preferably in the range of 100: 0 to 10:90.
  • the mixing ratio of the diamine having the ether structure and the diamine not having the ether structure when the acid anhydride, the diamine having the ether structure, and the diamine not having the ether structure are reacted is a molar ratio.
  • the ratio is in the range of 100: 0 to 10:90, the thermal peelability at high temperature is excellent.
  • the diamine having an ether structure preferably has a molecular weight in the range of 200 to 5,000.
  • the molecular weight of the diamine having an ether structure is a value (weight average molecular weight) measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
  • the heat-peelable sheet with a support of the third aspect of the present invention is characterized in that the above-described heat-peelable sheet is provided on a support in order to solve the above-mentioned problems.
  • the heat-peelable sheet according to the fourth aspect of the present invention substantially does not contain a foaming agent, and is held for 1 minute at any temperature in a temperature range of 200 ° C. or lower.
  • the force is less than 0.25 kg / 5 ⁇ 5 mm.
  • the shear adhesive force to the silicon wafer at the temperature after holding for 1 minute at any temperature in the temperature range of 200 ° C. or lower is 0.25 kg / 5 ⁇ 5 mm or more.
  • the shear adhesive strength to the silicon wafer at that temperature after being held for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C. is less than 0.25 kg / 5 ⁇ 5 mm. Accordingly, when held for 3 minutes at any temperature in the temperature range greater than 200 ° C.
  • the shear adhesion is greater than after holding for 1 minute at any temperature in the temperature range less than or equal to 200 ° C. descend.
  • it does not contain a foaming agent substantially, it is excellent in terms of contamination, in particular, no metal contamination derived from the foaming agent. That is, it is difficult to cause a problem of migration or corrosion due to metal contamination.
  • it is possible to provide a heat-peelable sheet that exhibits releasability at a higher temperature in a mode substantially not containing a foaming agent.
  • the content of the foaming agent is preferably 0.1% by weight or less.
  • the heat-peelable sheet according to the fifth aspect of the present invention has a heat curing rate of 80% or more.
  • the heat-peelable sheet according to the fifth aspect of the present invention has a heat curing rate of 80% or more. Therefore, when used in a high temperature environment, further thermosetting hardly occurs. As a result, it is excellent in durability at high temperatures.
  • the thermosetting rate is obtained by measuring the calorific value using DSC (differential scanning calorimetry). A specific method will be described in detail later.
  • the heat-peelable sheet according to the fifth aspect of the present invention contains a polyimide resin and has an imidization ratio of 80% or more. Therefore, further imidization hardly occurs when used in a high temperature environment. As a result, it is excellent in durability at high temperatures.
  • the imidization ratio is determined by measuring the peak intensity of the imide group using 1H-NMR (proton nuclear magnetic resonance). A specific method will be described in detail later.
  • the heat-peelable sheet according to the sixth aspect of the present invention has a shear adhesive force to the silicon wafer at the temperature after being held for 1 minute at any temperature in a temperature range of 200 ° C. or lower.
  • the shear adhesive strength to the silicon wafer at the temperature after being held for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C. is 0.25 kg / 5 ⁇ 5 mm.
  • the ratio of the structural unit derived from a diamine having an ether structure to the structural unit derived from another diamine not having an ether structure is 10:90 to 70:30 in a molar ratio.
  • the shear adhesive strength to the silicon wafer at the temperature after holding for 1 minute at any temperature in the temperature range of 200 ° C. or lower is 0.25 kg / 5 ⁇ 5 mm.
  • the shear adhesive force to the silicon wafer at the temperature after holding for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C. is less than 0.25 kg / 5 ⁇ 5 mm. Accordingly, when held for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C., the shear adhesion is greater than after holding for 1 minute at any temperature in the temperature range less than or equal to 200 ° C. descend.
  • the silicon wafer It is possible to suitably control the shearing adhesive force with respect to. Specifically, when the ratio of the structural units derived from the diamine having an ether structure is increased within the range of the molar ratio, a relatively low temperature (for example, 200 to 250 ° C.) within a temperature range higher than 200 ° C. is achieved. If held for 3 minutes, the shear adhesive strength can be reduced (less than 0.25 kg / 5 ⁇ 5 mm).
  • the shear adhesive force can be increased unless it is kept at a relatively high temperature (for example, 250 to 400 ° C.) within a temperature range higher than 200 ° C. for 3 minutes. It is possible to prevent it from being reduced (less than 0.25 kg / 5 ⁇ 5 mm).
  • a relatively high temperature for example, 250 to 400 ° C.
  • the heat-peelable sheet according to the seventh aspect of the present invention The shear adhesive strength to the silicon wafer after being held for 0.1-60 minutes at any temperature in the temperature range of greater than 200 ° C. and less than or equal to 400 ° C. under a condition where the oxygen concentration is 100 ppm or less is 0.25 kg / 5 ⁇ 5 mm or more, Shear adhesion to silicon wafer after holding for 1-30 minutes at any temperature in the temperature range of 50 ° C. or more and 300 ° C. or less under an atmospheric pressure condition where the oxygen concentration is 18-25% is 0.25 kg / 5 It is characterized by being less than 5 mm.
  • the silicon after being held for 0.1-60 minutes at any temperature in the temperature range of greater than 200 ° C. and less than or equal to 400 ° C. under an oxygen concentration of 100 ppm or less Since the shear adhesive strength to the wafer is 0.25 kg / 5 ⁇ 5 mm or more, it does not peel even when exposed to a relatively high temperature.
  • the shear adhesive strength to the silicon wafer after being held for 1-30 minutes at atmospheric temperature where the oxygen concentration is 18-25% and at any temperature in the temperature range of 50 ° C. to 300 ° C. is 0.25 kg. Since it is less than / 5 ⁇ 5 mm, it peels at a lower temperature under the condition where the oxygen concentration is the same as that of the atmosphere, compared with the condition where the oxygen concentration is low.
  • a method for manufacturing a semiconductor device is a method for manufacturing a semiconductor device having a structure in which a semiconductor chip is mounted on a printed circuit board, Preparing a support having a release layer; Forming a printed circuit board on the release layer of the support; Mounting a semiconductor chip on the wired circuit board; After the mounting, the step of peeling the support together with the release layer, using the surface of the release layer opposite to the support as an interface,
  • the release layer has a shear adhesive force with respect to the silicon wafer at the temperature after being held at 200 ° C. for 1 minute, and is in a temperature range of 200 ° C. or more and 200 ° C. or less and greater than or equal to 0.25 kg / 5 ⁇ 5 mm.
  • the shear adhesive strength to the silicon wafer at the temperature after holding at the temperature of 3 minutes is less than 0.25 kg / 5 ⁇ 5 mm.
  • the peeling layer has a shear adhesive force to the silicon wafer at the temperature after being held at 200 ° C. for 1 minute, and is 0.25 kg / 5 ⁇ 5 mm or more, and more than 200 ° C. and 500 ° C. or less. After holding for 3 minutes at any temperature in the temperature range, the shear adhesive force to the silicon wafer at that temperature is less than 0.25 kg / 5 ⁇ 5 mm. Therefore, the peeling layer does not peel even if it is exposed to a high temperature to some extent, and further peels in a higher temperature region. As a result, it is possible to prevent the support and the printed circuit board from being peeled off while the printed circuit board is formed on the support, and to peel off after mounting the semiconductor chip on the printed circuit board. Can do.
  • the release layer preferably has a dynamic hardness of 10 or less.
  • the dynamic hardness is 10 or less, the adhesion of the release layer to the adherend (support or printed circuit board) can be made sufficient.
  • the release layer preferably has a weight reduction rate of less than 1% by weight after being immersed in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes. If the weight loss after immersion in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes is less than 1% by weight, the dissolution into the 3% tetramethylammonium hydroxide aqueous solution is small, so solvent resistance (particularly , Solvent resistance to tetramethylammonium hydroxide aqueous solution can be improved.
  • the increase amount of particles of 0.2 ⁇ m or more on the surface of the silicon wafer is 10,000 / Preferably less than 6 inch wafers.
  • the amount of particles of 0.2 ⁇ m or more on the silicon wafer surface when peeled after being bonded to the silicon wafer is less than 10,000 / 6 inch wafers before being bonded to the silicon wafer, Later adhesive residue can be suppressed.
  • a method for manufacturing a semiconductor device is a method for manufacturing a semiconductor device having a structure in which a semiconductor chip is mounted on a printed circuit board, Preparing a support having a release layer; Forming a printed circuit board on the release layer of the support; Mounting a semiconductor chip on the wired circuit board; After the mounting, the step of peeling the support together with the release layer, using the surface of the release layer opposite to the support as an interface,
  • the release layer has a weight loss rate of 1.0% by weight or more after being immersed in N-methyl-2-pyrrolidone at 50 ° C. for 60 seconds and dried at 150 ° C. for 30 minutes.
  • the weight loss rate after the release layer is immersed in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and dried at 150 ° C. for 30 minutes is 1.0% by weight or more. . Since the weight loss after immersion in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and drying at 150 ° C. for 30 minutes is 1% by weight or more, the release layer is N-methyl-2-pyrrolidone. It can be said that the weight has been sufficiently reduced. As a result, the release layer can be easily peeled off with N-methyl-2-pyrrolidone.
  • NMP N-methyl-2-pyrrolidone
  • a support body can be peeled with a peeling layer using NMP, without heating.
  • the weight reduction rate of the release layer can be controlled by, for example, the solubility of the raw material in NMP. That is, as a raw material having a higher solubility in NMP is selected, the release layer obtained using the raw material has a higher solubility in NMP.
  • the release layer preferably has a dynamic hardness of 10 or less.
  • the dynamic hardness is 10 or less, the adhesion of the release layer to the adherend (support or printed circuit board) can be made sufficient.
  • the release layer preferably has a weight reduction rate of less than 1% by weight after being immersed in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes. If the weight loss after immersion in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes is less than 1% by weight, the dissolution into the 3% tetramethylammonium hydroxide aqueous solution is small, so solvent resistance (particularly , Solvent resistance to tetramethylammonium hydroxide aqueous solution can be improved.
  • the increase amount of particles of 0.2 ⁇ m or more on the surface of the silicon wafer is 10,000 / Preferably less than 6 inch wafers.
  • the amount of particles of 0.2 ⁇ m or more on the silicon wafer surface when peeled after being bonded to the silicon wafer is less than 10,000 / 6 inch wafers before being bonded to the silicon wafer, Later adhesive residue can be suppressed.
  • a semiconductor device manufacturing method is a method for manufacturing a semiconductor device having a structure in which a semiconductor chip is mounted on a printed circuit board, Preparing a support having a release layer; Forming a printed circuit board on the release layer of the support; Mounting a semiconductor chip on the wired circuit board; After the mounting, the step of peeling the support together with the release layer, using the surface of the release layer opposite to the support as an interface,
  • the release layer has a structural unit derived from a diamine having an imide group and at least partially having an ether structure.
  • a peeling layer since a peeling layer has an imide group, it is excellent in heat resistance. Whether or not the release layer has an imide group can be confirmed by checking whether or not a spectrum having an absorption peak at 1400 to 1500 cm ⁇ 1 exists in a Fourier transform infrared (FT-IR) spectrum. That is, when there is a spectrum having an absorption peak at 1400-1500 cm ⁇ 1 , it can be determined that it has an imide group.
  • FT-IR Fourier transform infrared
  • the said peeling layer has the structural unit derived from the diamine which has an ether structure
  • a shearing adhesive force can be reduced.
  • the present inventors presume that the ether structure is detached from the resin constituting the release layer when heated, and the shear adhesive force is reduced due to the removal.
  • the release layer has a diamine having an ether structure can be confirmed by whether or not a spectrum having an absorption peak at 2700 to 3000 cm ⁇ 1 exists in a FT-IR (fourier transform infrared spectroscopy) spectrum. That is, when a spectrum having an absorption peak at 2700 to 3000 cm ⁇ 1 exists, it can be determined that the diamine has an ether structure.
  • the ether structure is detached from the resin constituting the release layer, for example, by comparing FT-IR (Fourier Transform Infrared Spectroscopy) spectra before and after heating at 300 ° C. for 30 minutes, 2800 to 3000 cm. This can be confirmed by the decrease in the spectrum of ⁇ 1 before and after heating.
  • FT-IR Fastier Transform Infrared Spectroscopy
  • the release layer has higher heat resistance and has release properties at a higher temperature.
  • the structural unit derived from the diamine having an ether structure preferably has a glycol skeleton or a glycol skeleton derived from a diamine having an alkylene glycol.
  • the structural unit derived from the diamine having an ether structure has a glycol skeleton or a glycol skeleton derived from a diamine having an alkylene glycol, it exhibits better peelability when heated.
  • the release layer has a diamine having a glycol skeleton can be confirmed by whether or not a spectrum having an absorption peak at 2700 to 3000 cm ⁇ 1 exists in the FT-IR spectrum.
  • the diamine has a glycol skeleton.
  • the release layer has a diamine having a glycol skeleton derived from a diamine having an alkylene glycol is confirmed by whether or not a spectrum having an absorption peak at 2700 to 3000 cm ⁇ 1 exists in the FT-IR spectrum. it can.
  • the release layer is composed of a polyimide resin obtained by imidizing polyamic acid obtained by reacting an acid anhydride, a diamine having an ether structure, and a diamine having no ether structure.
  • the mixing ratio of the diamine having the ether structure and the diamine not having the ether structure when the acid anhydride, the diamine having the ether structure, and the diamine not having the ether structure are reacted,
  • the molar ratio is preferably in the range of 100: 0 to 10:90.
  • the mixing ratio of the diamine having the ether structure and the diamine not having the ether structure when the acid anhydride, the diamine having the ether structure, and the diamine not having the ether structure are reacted is a molar ratio. When the ratio is in the range of 100: 0 to 10:90, the thermal peelability at high temperature is excellent.
  • the diamine having an ether structure preferably has a molecular weight in the range of 200 to 5,000.
  • the molecular weight of the diamine having an ether structure is a value (weight average molecular weight) measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
  • a heat-peelable sheet that exhibits peelability at a higher temperature and a heat-peelable sheet provided with the heat-peelable sheet on a support An attached support can be provided.
  • the second aspect of the present invention it is possible to provide a solvent peelable sheet that can be easily peeled off using a solvent, and a support with a solvent peelable sheet provided with the solvent peelable sheet on the support. it can.
  • the third aspect of the present invention it is possible to provide a heat-peelable sheet having higher heat resistance and a support with a heat-peelable sheet in which the heat-peelable sheet is provided on the support.
  • a heat-peelable sheet having excellent durability at high temperatures can be provided.
  • the film when the oxygen concentration is low, the film does not peel even when exposed to a relatively high temperature, and when the oxygen concentration is the same as the atmosphere, the oxygen concentration is lower than that of the low oxygen concentration.
  • a heat-peelable sheet that exhibits peelability at low temperatures can be provided.
  • the support and the printed circuit board can be prevented from being separated, and the wiring After the semiconductor chip is mounted on the circuit board, a method for manufacturing a semiconductor device that can be peeled off can be provided.
  • the ninth aspect of the present invention it is possible to provide a method for manufacturing a semiconductor device in which the support can be peeled off together with the peeling layer without heating after the printed circuit board is formed.
  • FIG. 4 is a schematic cross-sectional view for explaining in detail an example of a method for manufacturing the semiconductor device shown in FIG. 3.
  • FIG. 4 is a schematic cross-sectional view for explaining in detail an example of a method for manufacturing the semiconductor device shown in FIG. 3.
  • FIG. 4 is a schematic cross-sectional view for explaining in detail an example of a method for manufacturing the semiconductor device shown in FIG. 3.
  • FIG. 4 is a schematic cross-sectional view for explaining in detail an example of a method for manufacturing the semiconductor device shown in FIG. 3.
  • FIG. 4 is a schematic cross-sectional view for explaining in detail an example of a method for manufacturing the semiconductor device shown in FIG. 3.
  • FIG. 4 is a schematic cross-sectional view for explaining in detail an example of a method for manufacturing the semiconductor device shown in FIG. 3.
  • FIG. 4 is a schematic cross-sectional view for explaining in detail an example of a method for manufacturing the semiconductor device shown in FIG. 3.
  • FIG. 4 is a schematic cross-sectional view for explaining in detail an example of a method for manufacturing the semiconductor device shown in FIG. 3.
  • FIG. 4 is a schematic cross-sectional view for explaining in detail an example of a method for manufacturing the semiconductor device shown in FIG. 3.
  • FIG. 4 is a schematic cross-sectional view for explaining in detail an example of a method for manufacturing the semiconductor device shown in FIG. 3.
  • the heat peelable sheet according to the first aspect of the present invention has a shear adhesive strength to the silicon wafer at the temperature after being held at 200 ° C. for 1 minute, and is 0.25 kg / 5 ⁇ 5 mm or more, and 0.30 kg / 5 ⁇ 5 mm or more. It is preferable that it is 0.50 kg / 5 ⁇ 5 mm or more. Further, the heat-peelable sheet has a shear adhesive force to the silicon wafer at the temperature after being held for 3 minutes at any temperature in the temperature range exceeding 200 ° C. and 500 ° C. or less, and less than 0.25 kg / 5 ⁇ 5 mm.
  • the shear adhesive strength to the silicon wafer at that temperature is 0.25 kg / 5 ⁇ 5 mm or more, and held for 3 minutes at any temperature in the temperature range above 200 ° C. and below 500 ° C. Since the shearing adhesive force to the silicon wafer at the temperature after being less than 0.25 kg / 5 ⁇ 5 mm, it has a certain degree of adhesion at the time of 200 ° C., while at a temperature higher than 200 ° C., It exhibits higher peelability than that at 200 ° C.
  • a heat-peelable sheet that exhibits peelability at a higher temperature can be provided.
  • the shear adhesive strength of the heat-peelable sheet can be controlled by, for example, the number of functional groups contained in the heat-peelable sheet.
  • the shear adhesion of the heat-peelable sheet to the silicon wafer is less than 0.25 kg / 5 ⁇ 5 mm (preferably less than 0.10 kg / 5 ⁇ 5 mm, more preferably less than 0.05 kg / 5 ⁇ 5 mm).
  • the temperature is not particularly limited as long as it is any temperature in the temperature range exceeding 200 ° C.
  • seat is 200 degrees C or less, if it hold
  • the shear adhesive force to the silicon wafer at the temperature after holding for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than 500 ° C. is less than 0.25 kg / 5 ⁇ 5 mm. It is an index for evaluating the property, and when “any temperature in a temperature range of greater than 200 ° C. and less than or equal to 500 ° C.” is set, it means that the shear adhesive force to the silicon wafer is immediately less than 0.25 kg / 5 ⁇ 5 mm. Not what you want. Further, unless the temperature is set to “any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C.”, this does not mean that peelability is not exhibited.
  • the thermal peelable sheet preferably has a dynamic hardness of 10 or less, more preferably 9 or less, and even more preferably 8 or less. Moreover, although the said dynamic hardness is so preferable that it is small, it is 0.001 or more, for example. When the dynamic hardness is 10 or less, the adhesive force of the heat-peelable sheet to the adherend can be made sufficient.
  • the heat-peelable sheet preferably has a surface hardness of 10 GPa or less, more preferably 8 GPa or less, and even more preferably 6 GPa or less. Moreover, although the said surface hardness is so preferable that it is small, it is 0.05 GPa or more, for example. When the surface hardness is 10 GPa or less, the adhesive force between the thermally peelable sheet and the adherend can be controlled.
  • the heat-peelable sheet preferably has a weight reduction rate of less than 1% by weight after being immersed in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes, more preferably less than 0.9% by weight, More preferably, it is less than 0.8% by weight.
  • the said weight decreasing rate is so preferable that it is small, it is 0 weight% or more and 0.001 weight% or more, for example.
  • the weight loss after immersion in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes is less than 1% by weight, the dissolution into the 3% tetramethylammonium hydroxide aqueous solution is small, so solvent resistance (particularly , Solvent resistance to tetramethylammonium hydroxide aqueous solution can be improved.
  • the weight reduction rate of the heat-peelable sheet can be controlled by, for example, the composition of the diamine used (solubility of the diamine in tetramethylammonium hydroxide aqueous solution).
  • the increase amount of particles of 0.2 ⁇ m or more on the surface of the silicon wafer is 10000/6 inches before being bonded to the silicon wafer. It is preferably less than a wafer, more preferably less than 9000/6 inch wafers, and even more preferably less than 8000/6 inch wafers.
  • the increase amount of the particles is particularly preferably less than 1000/6 inch wafer, less than 900/6 inch wafer, and less than 800/6 inch wafer, as compared with before being bonded to the silicon wafer.
  • the amount of particles of 0.2 ⁇ m or more on the silicon wafer surface when peeled after being bonded to the silicon wafer is less than 10,000 / 6 inch wafers before being bonded to the silicon wafer, Later adhesive residue can be suppressed.
  • the heat-peelable sheet preferably has a weight loss rate of 1.0% by weight or more after being immersed in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and dried at 150 ° C. for 30 minutes. 1.1% by weight or more, more preferably 1.2% by weight or more.
  • NMP N-methyl-2-pyrrolidone
  • the said weight decreasing rate is so preferable that it is large, it is 50 weight% or less and 40 weight% or less, for example.
  • the weight reduction rate after dipping in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and drying at 150 ° C. for 30 minutes is 1.0% by weight or more, the heat-peelable sheet becomes N-methyl.
  • the heat-peelable sheet can be easily peeled with N-methyl-2-pyrrolidone.
  • the weight reduction rate of the heat-peelable sheet can be controlled by, for example, the solubility of the raw material in NMP. That is, as a raw material having a higher solubility in NMP is selected, the heat-peelable sheet obtained using the raw material has higher solubility in NMP.
  • the heat peelable sheet according to the first aspect of the present invention has a shear adhesive strength to the silicon wafer at the temperature after being held at 200 ° C. for 1 minute, which is 0.25 kg / 5 ⁇ 5 mm or more, and is greater than 200 ° C. and less than 500 ° C.
  • the forming material is not particularly limited as long as the shearing adhesive force to the silicon wafer at the temperature after being held for 3 minutes at any temperature in the temperature range is less than 0.25 kg / 5 ⁇ 5 mm, but the material is not particularly limited. Resins, acrylic resins, fluororesins, epoxy resins, urethane resins, rubber resins, and the like can be given.
  • the polyimide resin can be generally obtained by imidizing (dehydrating and condensing) a polyamic acid that is a precursor thereof.
  • a method for imidizing the polyamic acid for example, a conventionally known heat imidization method, azeotropic dehydration method, chemical imidization method and the like can be employed. Of these, the heating imidization method is preferable.
  • the heat imidization method it is preferable to perform heat treatment under a nitrogen atmosphere or an inert atmosphere such as a vacuum in order to prevent deterioration of the polyimide resin due to oxidation.
  • the polyamic acid is charged in an appropriately selected solvent such that an acid anhydride and a diamine (including both a diamine having an ether structure and a diamine not having an ether structure) have a substantially equimolar ratio. Can be obtained by reaction.
  • the polyimide resin preferably has a structural unit derived from a diamine having an ether structure.
  • the diamine having an ether structure is not particularly limited as long as it is a compound having an ether structure and having at least two terminals having an amine structure.
  • a diamine having a glycol skeleton is preferable.
  • the present inventors when heated to a high temperature, cause the ether structure or the glycol skeleton to desorb from the resin constituting the heat-peelable sheet, and this debonding reduces the shear adhesive force. I guess that. Note that the ether structure or the glycol skeleton is detached from the resin constituting the heat-peelable sheet, for example, FT-IR (Fourier Transform Infrared Spectroscopy) before and after heating at 300 ° C. for 30 minutes. It can be confirmed by comparing the spectra that the spectrum of 2800 to 3000 cm ⁇ 1 decreases before and after heating.
  • FT-IR Fastier Transform Infrared Spectroscopy
  • the spectral peak intensity of 2800 to 3000 cm ⁇ 1 before heating is compared with the spectral peak of 2800 to 3000 cm ⁇ 1 after heating.
  • the amount of decrease is obtained by the following equation (3). And when the reduction
  • diamine having a glycol skeleton examples include a polypropylene glycol structure and a diamine having one amino group at each end, a polyethylene glycol structure, and one amino group at each end.
  • examples thereof include a diamine having a polytetramethylene glycol structure and a diamine having an alkylene glycol such as a diamine having one amino group at each end.
  • the diamine which has two or more of these glycol structures and has one amino group in both the ends can be mentioned.
  • the molecular weight of the diamine having an ether structure is preferably within the range of 100 to 5000, and more preferably 150 to 4800.
  • a heat-peelable sheet having high adhesive strength at 200 ° C. or lower and exhibiting releasability in a temperature range of 200 ° C. or higher is obtained.
  • other diamines having no ether structure can be used in combination with diamines having an ether structure.
  • examples of other diamines having no ether structure include aliphatic diamines and aromatic diamines.
  • the mixing ratio of the diamine having an ether structure and the diamine having no ether structure is preferably in the range of 100: 0 to 10:90, more preferably 100: 0 to 20: 80, more preferably 99: 1 to 30:70.
  • the thermal peelability at high temperature is excellent.
  • Examples of the aliphatic diamine include ethylenediamine, hexamethylenediamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 4,9-dioxa-1,12-diaminododecane, , 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane ( ⁇ , ⁇ -bisaminopropyltetramethyldisiloxane) and the like.
  • the molecular weight of the aliphatic diamine is usually 50 to 1,000,000, preferably 100 to 30,000.
  • aromatic diamine examples include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, and 4,4′-diaminodiphenylpropane.
  • the molecular weight of the aromatic diamine is usually 50 to 1000, preferably 100 to 500.
  • molecular weight means the value (weight average molecular weight) measured by GPC (gel permeation chromatography) and computed by polystyrene conversion.
  • Examples of the acid anhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,2-bis (2, 3-Dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), bis (2,3-dicarboxyphenyl) methane dianhydride Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis
  • Examples of the solvent for reacting the acid anhydride with the diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, and cyclopentanone. These may be used alone or in combination. Further, in order to adjust the solubility of raw materials and resins, a nonpolar solvent such as toluene or xylene may be appropriately mixed and used.
  • the heat-peelable sheet according to the present embodiment is produced as follows, for example. First, a solution containing the polyamic acid is prepared. The polyamic acid may optionally contain an additive. Next, the solution is applied on a substrate to a predetermined thickness to form a coating film, and then the coating film is dried under a predetermined condition.
  • the substrate include metal foil such as SUS304, 6-4 alloy, aluminum foil, copper foil, Ni foil, polyethylene terephthalate (PET), polyethylene, polypropylene, fluorine-based release agent, and long-chain alkyl acrylate-type release agent.
  • a plastic film, paper, or the like whose surface is coated with a release agent such as, can be used. Moreover, it does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, a spin coat etc. are mentioned. As drying conditions, for example, the drying temperature is 50 to 150 ° C. and the drying time is 3 to 30 minutes. Thereby, the heat exfoliation type sheet concerning this embodiment is obtained.
  • the heat-peelable sheet can be used after being peeled from the substrate. Moreover, a heat peelable sheet
  • the heat-peelable sheet may be produced by directly applying a solution containing polyamic acid to a support to form a coating film, and then drying the coating film under predetermined conditions. When used as a heat-peelable sheet with a support, the rigidity is stronger than when the heat-peelable sheet is used alone, which is preferable in terms of reinforcing the adherend.
  • the support is not particularly limited, and examples thereof include compound wafers such as silicon wafers, SiC wafers, and GaAs wafers, glass wafers, metal foils such as SUS, 6-4 Alloy, Ni foil, and Al foil.
  • compound wafers such as silicon wafers, SiC wafers, and GaAs wafers, glass wafers, metal foils such as SUS, 6-4 Alloy, Ni foil, and Al foil.
  • a silicon wafer or a glass wafer is preferable.
  • a SUS board or a glass plate is preferable.
  • the support in the heat-peelable sheet with support can be used as it is for manufacturing various semiconductor devices.
  • the support may be used alone or in combination of two or more.
  • the thickness of the support is usually about 100 ⁇ m to 20 mm.
  • the use of the heat-peelable sheet is not particularly limited, for example, it can be used in the manufacturing process of a semiconductor device. More specifically, for example, it can be used in a step of encapsulating a semiconductor chip with a resin or a step of forming a conductive through hole (TSV) penetrating a silicon chip.
  • TSV conductive through hole
  • when sealing with resin it can be attached to the back side of the lead frame and used for the purpose of preventing resin leakage. It can also be used for processing glass members (for example, lenses), color filters, touch panels, and power modules.
  • the heat-peelable sheet may be used for manufacturing a semiconductor device having a structure in which a semiconductor chip is mounted on a printed circuit board (see, for example, JP 2010-141126 A). it can. That is, it can be used as a heat-peelable sheet in the following semiconductor device manufacturing method.
  • a method of manufacturing a semiconductor device having a structure in which a semiconductor chip is mounted on a printed circuit board Preparing a support having a heat-peelable sheet; Forming a printed circuit board on the thermally peelable sheet of the support; Mounting a semiconductor chip on the wired circuit board; After the mounting, a method of manufacturing a semiconductor device comprising: a step of peeling the support together with the heat-peelable sheet with the surface of the heat-peelable sheet opposite to the support as an interface.
  • the heat-peelable sheet can also be used for fixing a semiconductor wafer having a through-silicon via when the semiconductor wafer is formed. That is, it can be used as a heat-peelable sheet in the following semiconductor device manufacturing method. Fixing the semiconductor wafer to the pedestal using a heat-peelable sheet; Performing a specific process on the semiconductor wafer fixed to the pedestal; Separating the pedestal from the semiconductor wafer after the processing.
  • the specific treatment preferably includes a step of grinding a surface of the semiconductor wafer on which the bottomed hole for forming the silicon through electrode is formed, on the side where the bottomed hole is not formed.
  • the specific treatment preferably includes a step of grinding the semiconductor wafer on which the through silicon vias are formed.
  • the solvent peelable sheet of the second invention can exhibit the same characteristics as those of the heat peelable sheet of the first invention, particularly as characteristics other than those described in the section of the second invention.
  • the solvent peelable sheet of the second aspect of the present invention has a weight reduction rate of 1.0% by weight or more after being immersed in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and dried at 150 ° C. for 30 minutes. It is preferably 1.2% by weight or more, and more preferably 1.3% by weight or more. Moreover, although the said weight decreasing rate is so preferable that it is large, it is 50 weight% or less and 30 weight% or less, for example. Since the weight loss after immersion in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and drying at 150 ° C.
  • NMP N-methyl-2-pyrrolidone
  • the solvent release sheet is N-methyl-2 -It can be said that it has dissolved in pyrrolidone and has been sufficiently reduced in weight.
  • the solvent peelable sheet can be easily peeled with N-methyl-2-pyrrolidone.
  • seat can be controlled by the solubility with respect to NMP of a raw material, for example. That is, as a raw material having a higher solubility in NMP is selected, the solvent release sheet obtained using the raw material has higher solubility in NMP.
  • the solvent peelable sheet of the second aspect of the present invention has a weight reduction rate of 1.0% by weight or more after being immersed in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and dried at 150 ° C. for 30 minutes.
  • NMP N-methyl-2-pyrrolidone
  • the forming material is not particularly limited, and examples thereof include polyimide resin, silicone resin, acrylic resin, fluorine resin, epoxy resin, urethane resin, and rubber resin.
  • the heat-peelable sheet according to the third aspect of the present invention can exhibit the same characteristics as those of the heat-peelable sheet according to the first aspect of the present invention, particularly as characteristics other than those described in the section of the third aspect of the present invention.
  • the heat-peelable sheet according to the third aspect of the present invention has an imide group.
  • the material for forming the heat-peelable sheet is not particularly limited as long as it has an imide group, and examples thereof include a polyimide resin.
  • the polyimide resin those described in the first aspect of the present invention can be used.
  • the heat-peelable sheet according to the fourth aspect of the present invention can exhibit the same characteristics as those of the heat-peelable sheet according to the first aspect of the present invention, particularly as characteristics other than those described in the section of the fourth aspect of the present invention.
  • the shear adhesive force to the silicon wafer at the temperature after holding for 1 minute at any temperature in the temperature range of 200 ° C. or lower is 0.25 kg / 5 ⁇ 5 mm or more. 0.30 kg / 5 ⁇ 5 mm or more, and more preferably 0.50 kg / 5 ⁇ 5 mm or more.
  • the heat-peelable sheet has a shear adhesive force to the silicon wafer at the temperature of less than 0.25 kg / 5 ⁇ 5 mm after being held for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C.
  • any temperature in the temperature range of 200 ° C. or lower is not particularly limited as long as it is 200 ° C. or lower.
  • the shear adhesion of the heat-peelable sheet to the silicon wafer is less than 0.25 kg / 5 ⁇ 5 mm (preferably less than 0.10 kg / 5 ⁇ 5 mm, more preferably less than 0.05 kg / 5 ⁇ 5 mm).
  • the temperature is not particularly limited as long as it is any temperature in the temperature range of 200 ° C. or more and 500 ° C. or less, preferably over 220 ° C. and 480 ° C. or less, more preferably over 240 ° C. 450 ° C. or lower. After holding for 1 minute at any temperature in the temperature range of 200 ° C.
  • the shear adhesive force to the silicon wafer at the temperature is 0.25 kg / 5 ⁇ 5 mm or higher, and in the temperature range of 200 ° C. or higher and 500 ° C. or lower. Since the shear adhesive force to the silicon wafer at the temperature after holding for 3 minutes at any temperature is less than 0.25 kg / 5 ⁇ 5 mm, the temperature is set to any temperature in the temperature range of 200 ° C. or more and 500 ° C. or less. When held for 1 minute, the shear adhesive strength is reduced as compared with the case after holding for 1 minute at any temperature in the temperature range of 200 ° C. or lower.
  • the fourth aspect of the present invention it is possible to provide a heat-peelable sheet that exhibits releasability at a higher temperature in a mode that does not substantially contain a foaming agent.
  • the shear adhesive strength of the heat-peelable sheet can be controlled by, for example, the number of functional groups contained in the heat-peelable sheet.
  • the said shearing adhesive force with respect to a silicon wafer may become less than 0.25kg / 5x5mm. is there.
  • the release sheet is kept at a temperature higher than 200 ° C. (for example, 210 to 400 ° C.), if it is a short time (for example, within 0.1 minutes), the shear adhesive force to the silicon wafer is It may not be less than 0.25 kg / 5 ⁇ 5 mm.
  • the shear adhesive force to the silicon wafer at the temperature after holding for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than 500 ° C. is less than 0.25 kg / 5 ⁇ 5 mm
  • any temperature in a temperature range greater than 200 ° C. and 500 ° C. or less is set, the shear adhesive force to the silicon wafer immediately becomes 0.25 kg / 5 ⁇ . It does not mean that it becomes less than 5 mm. Further, unless the temperature is set to “any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C.”, this does not mean that peelability is not exhibited.
  • the heat-peelable sheet does not substantially contain a foaming agent.
  • “Substantially free of foaming agent” means that the content of the foaming agent is 0.1% by weight or less, preferably 0.05% by weight or less, and 0.03% by weight or less. More preferably.
  • Examples of the foaming agent include conventionally known thermally expandable microspheres.
  • Examples of the heat-expandable microsphere include those encapsulated in microcapsules.
  • Examples of such thermally expandable microspheres include microspheres in which substances such as isobutane, propane, and pentane that are easily gasified and expanded by heating are encapsulated in an elastic shell.
  • the shell may be formed of a hot-melt material or a material that breaks due to thermal expansion.
  • the heat-peelable sheet according to the fourth aspect of the present invention is substantially free from a foaming agent, and has zero shear adhesion to the silicon wafer at that temperature after being held at any temperature in the temperature range of 200 ° C. or lower for 1 minute. .25 kg / 5 ⁇ 5 mm or more, and the shear adhesive strength to the silicon wafer at the temperature after holding for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than 500 ° C. is less than 0.25 kg / 5 ⁇ 5 mm
  • the forming material is not particularly limited, and examples thereof include polyimide resin, silicone resin, acrylic resin, fluorine resin, epoxy resin, urethane resin, and rubber resin.
  • the heat-peelable sheet according to the present embodiment is produced as follows, for example. First, a solution containing the polyamic acid (see the first aspect of the present invention) is prepared. The polyamic acid may optionally contain an additive. However, the foaming agent is not substantially contained. Next, the solution is applied on a substrate to a predetermined thickness to form a coating film, and then the coating film is dried under a predetermined condition. Examples of the substrate include metal foil such as SUS304, 6-4 alloy, aluminum foil, copper foil, Ni foil, polyethylene terephthalate (PET), polyethylene, polypropylene, fluorine-based release agent, and long-chain alkyl acrylate-type release agent.
  • metal foil such as SUS304, 6-4 alloy, aluminum foil, copper foil, Ni foil, polyethylene terephthalate (PET), polyethylene, polypropylene, fluorine-based release agent, and long-chain alkyl acrylate-type release agent.
  • a plastic film, paper, or the like whose surface is coated with a release agent such as, can be used. Moreover, it does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, etc. are mentioned. As drying conditions, for example, the drying temperature is 50 to 150 ° C. and the drying time is 3 to 30 minutes. Thereby, the heat exfoliation type sheet concerning this embodiment is obtained.
  • the heat-peelable sheet according to the fifth aspect of the present invention can exhibit the same characteristics as those of the heat-peelable sheet according to the first aspect of the present invention, particularly as characteristics other than those described in the section of the fifth aspect of the present invention.
  • the heat-peelable sheet according to the fifth aspect of the present invention has (a) a thermosetting rate of 80% or more, or (b) contains a polyimide resin and has an imidization rate of 80% or more.
  • the heat-peelable sheet according to the fifth aspect of the present invention has a thermosetting rate of 80% or more, preferably 90% or more, and more preferably 95% or more.
  • mold sheet it is so preferable that it is large, and 100% and 99.9% can be mentioned.
  • the heat peelable sheet has a heat curing rate of 80% or more (for example, 80 to 100%), further heat curing is unlikely to occur when used in a high temperature environment. As a result, it is excellent in durability at high temperatures.
  • heat-cured means that the resin constituting the heat-peelable sheet undergoes a chemical reaction due to heat and is cured by generating a three-dimensional cross-linking bond between molecules. It does not include degradation or decomposition due to oxidation.
  • the thermosetting rate is obtained by measuring the calorific value using DSC (differential scanning calorimetry). Specifically, a heating rate is applied from room temperature (23 ° C.) using a state in which a solution for producing a heat-peelable sheet (solution containing polyamic acid) is applied and dried (condition: 120 ° C. for 10 minutes). The calorific value (total calorific value) when the temperature is raised to 500 ° C. (the temperature at which the thermosetting reaction is assumed to be completely completed) is measured at 10 ° C./min.
  • DSC differential scanning calorimetry
  • the heat-peelable sheet is not particularly limited as long as the heat curing rate is 80% or more, but polyimide resin, silicone resin, acrylic resin, fluororesin, epoxy resin, urethane resin, rubber resin, etc. Can be mentioned.
  • the heat-peelable sheet according to (b) contains a polyimide resin and has an imidization rate of 80% or more.
  • the heat-peelable sheet may contain a polyimide resin. That is, the heat-peelable sheet may contain a resin other than the polyimide resin, or may be composed only of the polyimide resin.
  • the imidization rate is 80% or more, preferably 90% or more, and more preferably 95% or more. preferable.
  • the imidation ratio of the heat-peelable sheet is more preferably 98% or more (particularly 99% or more).
  • seat it is so preferable that it is large, and 100% and 99.9% can be mentioned. If the imidization ratio of the heat-peelable sheet is 80% or more (for example, 80 to 100%), further imidization hardly occurs when used in a high temperature environment. As a result, it is excellent in durability at high temperatures.
  • the imidization rate is determined by measuring the peak intensity of the imide group using 1H-NMR (proton nuclear magnetic resonance, manufactured by JEOL Ltd., LA400). Specifically, a solution for producing a heat-peelable sheet (polyamide acid-containing solution) is applied and dried (drying conditions: 50-150 ° C. for 5-30 minutes), and imidized (imidation conditions: 200- 1 hour at 450 ° C.).
  • polyimide resin that can be used for the heat-peelable sheet according to (a) and the heat-peelable sheet according to (b), those described in the first aspect of the present invention can be used.
  • other diamines having no ether structure can be used in combination with diamines having an ether structure.
  • examples of other diamines having no ether structure include aliphatic diamines and aromatic diamines.
  • the mixing ratio of the diamine having an ether structure and another diamine having no ether structure is 15:85 to 80:20 is preferable, and 20:80 to 70:30 is more preferable.
  • the blending weight part of the diamine having an ether structure is the blending weight part of the diamine having an ether structure when the total blending weight excluding the solvent is 100 parts by weight.
  • the compounding weight part of the other diamine which does not have an ether structure is a compounding weight part of the other diamine which does not have an ether structure when the total compounding weight except a solvent is 100 parts by weight.
  • the shear adhesive strength to the silicon wafer at the temperature after holding for 1 minute at any temperature in the temperature range of 200 ° C. or lower is 0.25 kg / 5 ⁇ 5 mm or more. Is preferably 0.30 kg / 5 ⁇ 5 mm or more, and more preferably 0.50 kg / 5 ⁇ 5 mm or more.
  • the heat-peelable sheet has a shear adhesive force to the silicon wafer at the temperature of less than 0.25 kg / 5 ⁇ 5 mm after being held for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C.
  • any temperature in the temperature range of 200 ° C. or lower is not particularly limited as long as it is 200 ° C. or lower.
  • the shear adhesion of the heat-peelable sheet to the silicon wafer is less than 0.25 kg / 5 ⁇ 5 mm (more preferably less than 0.10 kg / 5 ⁇ 5 mm, and even more preferably less than 0.05 kg / 5 ⁇ 5 mm).
  • the temperature is not particularly limited as long as it is any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C., preferably greater than 205 ° C. and less than or equal to 400 ° C., more preferably 210 ° C. Over 300 ° C. After holding for 1 minute at any temperature in the temperature range of 200 ° C.
  • the shear adhesive force to the silicon wafer at the temperature is 0.25 kg / 5 ⁇ 5 mm or higher, and in the temperature range of 200 ° C. or higher and 500 ° C. or lower.
  • the temperature is set to any temperature in the temperature range of 200 ° C. or more and 500 ° C. or less.
  • the shear adhesive strength of the heat-peelable sheet can be controlled by, for example, the number of functional groups contained in the heat-peelable sheet.
  • the heat-peelable sheet according to the sixth aspect of the present invention can exhibit the same characteristics as those of the heat-peelable sheet according to the first aspect of the present invention, particularly as characteristics other than those described in the section of the sixth aspect of the present invention.
  • the shear adhesive strength to the silicon wafer at the temperature after holding for 1 minute at any temperature in the temperature range of 200 ° C. or lower is 0.25 kg / 5 ⁇ 5 mm or more. 0.30 kg / 5 ⁇ 5 mm or more, and more preferably 0.50 kg / 5 ⁇ 5 mm or more.
  • the heat-peelable sheet has a shear adhesive force to the silicon wafer at the temperature of less than 0.25 kg / 5 ⁇ 5 mm after being held for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C.
  • any temperature in the temperature range of 200 ° C. or lower is not particularly limited as long as it is 200 ° C. or lower.
  • the above “any temperature in the temperature range of 200 ° C. or lower” controls the ratio of a structural unit derived from a diamine having an ether structure and a structural unit derived from another diamine not having an ether structure. Thus, a desired temperature can be obtained.
  • the “any temperature in the temperature range of 200 ° C. or lower” is not particularly limited as long as it is 200 ° C. or lower.
  • the shear adhesion of the heat-peelable sheet to the silicon wafer is less than 0.25 kg / 5 ⁇ 5 mm (preferably less than 0.10 kg / 5 ⁇ 5 mm, more preferably less than 0.05 kg / 5 ⁇ 5 mm).
  • the temperature is not particularly limited as long as it is any temperature in the temperature range of 200 ° C. or more and 500 ° C. or less, preferably over 220 ° C. and 480 ° C. or less, more preferably over 240 ° C.
  • the shear adhesive force to the silicon wafer at the temperature is 0.25 kg / 5 ⁇ 5 mm or higher, and in the temperature range of 200 ° C. or higher and 500 ° C. or lower. Since the shear adhesive force to the silicon wafer at the temperature after holding for 3 minutes at any temperature is less than 0.25 kg / 5 ⁇ 5 mm, the temperature is set to any temperature in the temperature range of 200 ° C. or more and 500 ° C. or less. When held for 1 minute, the shear adhesive strength is reduced as compared with the case after holding for 1 minute at any temperature in the temperature range of 200 ° C. or lower.
  • the molar ratio of the structural unit derived from a diamine having an ether structure and the structural unit derived from another diamine not having an ether structure is 10: 90 to 70:30, preferably 12:88 to 58:32, and more preferably 15:85 to 55:45. Since the ratio is 10:90 to 70:30, the shear adhesive force to the silicon wafer can be suitably controlled.
  • the said shearing adhesive force with respect to a silicon wafer may become less than 0.25kg / 5x5mm. is there.
  • the release sheet is kept at a temperature higher than 200 ° C. (for example, 210 to 400 ° C.), if it is a short time (for example, within 0.1 minutes), the shear adhesive force to the silicon wafer is It may not be less than 0.25 kg / 5 ⁇ 5 mm.
  • the shear adhesive force to the silicon wafer at the temperature after holding for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than 500 ° C. is less than 0.25 kg / 5 ⁇ 5 mm
  • any temperature in a temperature range greater than 200 ° C. and 500 ° C. or less is set, the shear adhesive force to the silicon wafer immediately becomes 0.25 kg / 5 ⁇ . It does not mean that it becomes less than 5 mm. Further, unless the temperature is set to “any temperature in the temperature range greater than 200 ° C. and less than or equal to 500 ° C.”, this does not mean that peelability is not exhibited.
  • the heat-peelable sheet according to the sixth aspect of the present invention is composed of a polyimide resin.
  • the polyimide resin described in the first aspect of the present invention can be used.
  • the polyimide resin has a structural unit derived from another diamine having no ether structure.
  • examples of other diamines having no ether structure include aliphatic diamines and aromatic diamines.
  • the ratio of the structural unit derived from a diamine having an ether structure to the structural unit derived from another diamine not having an ether structure is 10:90 to 70:30 in terms of a molar ratio. : 88 to 58:32 is preferable, and 15:85 to 55:45 is more preferable. Since the ratio is 10:90 to 70:30, the shear adhesive force to the silicon wafer can be suitably controlled.
  • the heat-peelable sheet according to the seventh aspect of the present invention can exhibit the same characteristics as those of the heat-peelable sheet according to the first aspect of the present invention, particularly as characteristics other than those described in the section of the seventh aspect of the present invention.
  • the heat-peelable sheet of the seventh aspect of the present invention is a silicon after being held for 0.1-60 minutes at any temperature in a temperature range of 200 ° C. or more and 400 ° C. or less under an oxygen concentration of 100 ppm or less.
  • the shear adhesive strength to the wafer is 0.25 kg / 5 ⁇ 5 mm or more, preferably 0.30 kg / 5 ⁇ 5 mm or more, and more preferably 0.50 kg / 5 ⁇ 5 mm or more.
  • the “any temperature in the temperature range of 200 ° C. to 400 ° C.” is not particularly limited as long as it is greater than 200 ° C. and no more than 400 ° C., but for example, any temperature in the temperature range of 200 to 350 ° C.
  • the above-mentioned “conditions where the oxygen concentration is 100 ppm or less” may be any conditions as long as the oxygen concentration is 100 ppm or less, for example, 50 ppm.
  • the entire pressure may be lower than atmospheric pressure (depressurized state) or may be about atmospheric pressure.
  • Examples of a method for setting the pressure to about atmospheric pressure include a method in which an atmosphere of an inert gas (for example, a rare gas element such as helium, neon, or argon, or nitrogen) is used.
  • the present inventors presume that the reason why the high shear adhesive force can be maintained even when heated to a high temperature under a condition where the oxygen concentration is low is that the heat-peelable sheet is less susceptible to oxidative degradation under a low oxygen concentration condition. is doing.
  • the heat-peelable sheet has an oxygen concentration of 18-25 vol% (volume%) under an atmospheric pressure and at any temperature within a temperature range of 50 ° C. to 300 ° C. for 0.1-60 minutes.
  • the shear adhesive force to the silicon wafer after being held is less than 0.25 kg / 5 ⁇ 5 mm, preferably less than 0.10 kg / 5 ⁇ 5 mm, and more preferably less than 0.05 kg / 5 ⁇ 5 mm. .
  • the shear adhesive strength of the heat-peelable sheet to the silicon wafer is less than 0.25 kg / 5 ⁇ 5 mm (preferably 0.10 kg / 5 ⁇ 5 mm)
  • the temperature that is less than 0.05 kg / 5 ⁇ 5 mm is not particularly limited as long as it is any temperature in the temperature range of 50 ° C. to 300 ° C., but preferably 60 ° C. More than 280 degreeC, More preferably, it exceeds 70 degreeC and is 270 degreeC or less.
  • the atmospheric pressure means 101325 Pa.
  • Shear adhesive strength to silicon wafer after holding for 0.1-60 minutes at any temperature in the temperature range of greater than 200 ° C. and less than or equal to 400 ° C. under conditions of oxygen concentration of 100 ppm or less is 0.25 kg / 5 ⁇ 5 mm or more Therefore, even if exposed to a relatively high temperature, it does not peel off.
  • the shear adhesive strength to the silicon wafer after being held for 1-30 minutes at atmospheric temperature with an oxygen concentration of 18-25 vol% and in any temperature range of 50 ° C. or higher and 300 ° C. or lower is 0.25 kg.
  • a heat-peelable sheet that exhibits releasability at a low temperature compared to conditions can be provided.
  • Such a heat-peelable sheet is particularly useful when it is not desired to peel the sheet under low oxygen concentration and high temperature conditions.
  • the heat-peelable sheet according to the seventh aspect of the present invention is a silicon after being held for 0.1-60 minutes at any temperature in a temperature range of 200 ° C. or more and 400 ° C. or less under an oxygen concentration of 100 ppm or less. 1-30 at any temperature in the temperature range of 50 ° C. or more and 300 ° C. or less under the atmospheric pressure condition where the shear adhesive strength to the wafer is 0.25 kg / 5 ⁇ 5 mm or more, the oxygen concentration is 18-25 vol%.
  • the forming material is not particularly limited, but polyimide resin, silicone resin, acrylic resin, fluorine resin, epoxy resin, urethane Examples thereof include resins and rubber resins.
  • the polyimide resin described in the first aspect of the present invention can be used.
  • other diamines having no ether structure can be used in combination with diamines having an ether structure.
  • examples of other diamines having no ether structure include aliphatic diamines and aromatic diamines.
  • the proportion of the diamine having an ether structure is preferably 15 to 80 parts by weight, and more preferably 20 to 70 parts by weight.
  • the compounding part number of the diamine having an ether structure is the compounding part number of the diamine having an ether structure when the total compounding weight excluding the solvent is 100 parts by weight.
  • Specific examples of other diamines having no ether structure are as described in the section of the first invention.
  • the release layer according to the eighth aspect of the present invention can exhibit the same characteristics as those of the heat-peelable sheet according to the first aspect of the present invention, particularly as characteristics other than those described in the section of the eighth aspect of the present invention.
  • FIG. 1 to 3 are schematic cross-sectional views for explaining an outline of a semiconductor device manufacturing method according to an embodiment of the eighth invention.
  • the outline of the manufacturing method of the semiconductor device concerning this embodiment is explained first. Note that the terms “upper surface”, “lower surface”, and the like used in the eighth aspect of the present invention are only for explaining the positional relationship of the layers, and are actually used for the printed circuit board and the semiconductor device. It does not limit the vertical posture.
  • the method for manufacturing a semiconductor device is a method for manufacturing a semiconductor device having a structure in which a semiconductor chip is mounted on a printed circuit board, the step of preparing a support having a release layer, and the support A step of forming a wiring circuit board on the release layer, a step of mounting a semiconductor chip on the wiring circuit board, and after the mounting, the surface of the release layer opposite to the support is used as an interface. And a step of peeling the support together with the release layer, and the release layer has a shear adhesive strength to the silicon wafer at the temperature after being held at 200 ° C.
  • a support 1 having a release layer 5 is prepared (see FIG. 1).
  • the printed circuit board 2 having the connecting conductor portion 21 that can be connected to the electrode 31 of the semiconductor chip 3 is formed on the release layer 5 so that the connecting conductor portion 21 is exposed on the upper surface of the printed circuit board 2.
  • the printed circuit board 2 has an external connection conductor 22 for electrical connection to the outside on the release layer 5 side.
  • FIG. 1 shows the case where the connecting conductor portion 21 is convexly exposed on the upper surface of the printed circuit board 2, but in the eighth aspect of the present invention, the connecting conductor portion is the upper surface of the printed circuit board. The upper surface of the connecting conductor portion may be flush with the upper surface of the printed circuit board.
  • the connecting conductor portion 21 of the wired circuit board 2 and the electrode 31 of the semiconductor chip 3 are connected, and the semiconductor chip 3 is mounted on the wired circuit board 2.
  • the protrusions of the connecting conductor portion 21 and the electrode 31 after mounting are omitted.
  • the support 1 is peeled together with the release layer 5 with the surface of the release layer 5 opposite to the support 1 as an interface.
  • the semiconductor device 4 in which the semiconductor chip 3 is mounted on the printed circuit board 2 is obtained.
  • FIGS. 4 to 11 are schematic cross-sectional views for explaining in detail an example of a method of manufacturing the semiconductor device shown in FIG.
  • the support body 1 is prepared (refer FIG. 4).
  • the support 1 preferably has a certain strength or more.
  • the support 1 is not particularly limited, and examples thereof include compound wafers such as silicon wafers, SiC wafers, and GaAs wafers, glass wafers, metal foils such as SUS, 6-4 Alloy, Ni foil, and Al foil.
  • compound wafers such as silicon wafers, SiC wafers, and GaAs wafers, glass wafers, metal foils such as SUS, 6-4 Alloy, Ni foil, and Al foil.
  • a silicon wafer or a glass wafer is preferable.
  • a SUS board or a glass plate is preferable.
  • Examples of the support 1 include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, and polymethylpentene.
  • Polyolefin such as ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, Ethylene-hexene copolymer, Polyester such as polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone, polyimide, polyetherimide, polyamide, wholly aromatic poly It de, polyphenyl sulphates id, aramid (paper), glass, glass cloth, fluorine resin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, also possible to use paper or the like.
  • Polyester such as polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone, polyimide, polyetherimi
  • the support 1 may be used alone or in combination of two or more.
  • the thickness of the support is not particularly limited, but is usually about 10 ⁇ m to 20 mm, for example.
  • a release layer 5 is formed on the support 1.
  • the release layer 5 has a shear adhesive strength to the silicon wafer at the temperature after being held at 200 ° C. for 1 minute, and is preferably 0.25 kg / 5 ⁇ 5 mm or more, preferably 0.30 kg / 5 ⁇ 5 mm or more. More preferably, it is 50 kg / 5 ⁇ 5 mm or more.
  • the release layer 5 has a shear adhesive force with respect to the silicon wafer at the temperature after being held for 3 minutes at any temperature in the temperature range higher than 200 ° C. and lower than 500 ° C. is less than 0.25 kg / 5 ⁇ 5 mm. , Preferably less than 0.10 kg / 5 ⁇ 5 mm, and more preferably less than 0.05 kg / 5 ⁇ 5 mm.
  • any temperature in the temperature region where the shearing adhesive force to the silicon wafer at the temperature after holding the release layer 5 at 200 ° C. for 1 minute is 0.25 kg / 5 ⁇ 5 mm or more, exceeding 200 ° C. and not more than 500 ° C.
  • the shear adhesive force to the silicon wafer at the temperature after holding for 3 minutes is less than 0.25 kg / 5 ⁇ 5 mm
  • the release layer 5 does not peel even if it is exposed to a certain high temperature, and even higher In the region, it peels off.
  • the shear adhesive force of the release layer 5 can be controlled by, for example, the number of functional groups included in the release layer 5. Further, the temperature at which the shearing adhesive force of the release layer 5 to the silicon wafer is less than 0.25 kg / 5 ⁇ 5 mm (preferably less than 0.10 kg / 5 ⁇ 5 mm, more preferably less than 0.05 kg / 5 ⁇ 5 mm). Is not particularly limited as long as it is any temperature in a temperature range exceeding 200 ° C. and 500 ° C. or less, preferably exceeding 220 ° C. and not more than 480 ° C., more preferably exceeding 240 ° C., It is 450 degrees C or less.
  • the shear adhesive force with respect to a silicon wafer may become less than 0.25 kg / 5x5 mm.
  • the shear adhesive force to the silicon wafer may not be less than 0.25 kg / 5 ⁇ 5 mm for a short time. That is, “the shear adhesive force to the silicon wafer at the temperature after holding for 3 minutes at any temperature in the temperature range greater than 200 ° C. and less than 500 ° C.
  • the heat release type sheet according to the first aspect of the present invention can be used.
  • the support 1 having the release layer 5 can be produced by transferring the release layer 5 to the support 1.
  • the support 1 having the release layer 5 may be prepared by directly applying a solution containing polyamic acid to the support 1 to form a coating film, and then drying the coating film under predetermined conditions. .
  • the printed circuit board 2 is formed on the release layer 5 of the support 1.
  • Conventionally known circuit board and interposer manufacturing techniques such as a semi-additive method and a subtractive method may be applied to the method for forming a printed circuit board on a support having a release layer.
  • the dimensional stability is improved during the manufacturing process, and the handleability of the thin printed circuit board is improved.
  • an example of a method for forming a printed circuit board will be described.
  • the base insulating layer 20 a is formed on the release layer 5 of the support 1.
  • the material of the base insulating layer 20a is not particularly limited.
  • Known synthetic resins, and those resins and synthetic fiber cloths, glass cloths, glass nonwoven cloths, and composite resins of fine particles such as TiO 2 , SiO 2 , ZrO 2 , minerals, and clays.
  • the base insulating layer 20a is preferably 3 to 50 ⁇ m.
  • an opening h1 is formed at a position where the external connection conductor portion 22 is to be formed (see FIG. 6).
  • a method for forming the opening h1 a conventionally known method can be employed.
  • the opening h1 is formed by irradiating light through a photomask in which a pattern corresponding to the opening h1 is formed and then developing. be able to.
  • the shape of the opening is not particularly limited, but a circular shape is preferable, and the diameter can be set as appropriate, but can be set to 5 ⁇ m to 500 ⁇ m, for example.
  • a contact metal film 211 is formed in the opening h1.
  • electrical connection can be performed more favorably and corrosion resistance can be improved.
  • the formation method of the metal film 211 is not particularly limited, but plating is preferable, and the material of the metal film is copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, tungsten, ruthenium, etc. These single metals or alloys composed of two or more of these can be used.
  • preferable materials include gold, tin, nickel, and the like.
  • a preferable example of the metal film includes a two-layer structure in which the base layer is Ni and the surface layer is Au.
  • a seed film (metal thin film) 23a for satisfactorily depositing a metal material is formed on the conductor layer 23 and the wall surface of the portion that should be the conduction path 25.
  • the seed film 23a can be formed by sputtering, for example.
  • a material for the seed film for example, a single metal such as copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, tungsten, ruthenium, or an alloy composed of two or more of these is used. It is done.
  • the thickness of the conductor layer 23 is not particularly limited, but may be appropriately selected within the range of 1 to 500 nm.
  • the conducting path 25 is preferably in the shape of a column, and its diameter is 5 to 500 ⁇ m, preferably 5 to 300 ⁇ m. Thereafter, the conductor layer 23 and the conduction path 25 having a predetermined wiring pattern are formed.
  • the wiring pattern can be formed by, for example, electrolytic plating. Thereafter, the seed film in the portion without the conductor layer 23 is removed.
  • the conductor layer 23 is covered with a plating resist r1 (except for a portion where a conduction path is to be formed), and the lower surface of the support 1 is entirely covered with a resist r2.
  • the conductive path 24 is formed by electrolytic plating.
  • the plating resists r1 and r2 are removed, and an adhesive layer 20b mainly composed of epoxy and polyimide is formed so as to bury the exposed conductor layer 23 and conduction path 24.
  • the adhesive layer is etched with an alkaline solution or the like so as to be exposed on the upper surface of the adhesive layer as a terminal portion (see FIG. 10).
  • the connecting conductor portion 21 is formed on the upper end surface of the conduction path 24 by, for example, electrolytic plating.
  • the connecting conductor portion 21 can be formed of, for example, a nickel film or a gold film.
  • the underfill resin may be a sheet or a liquid.
  • resin sealing is performed after mounting the chip.
  • a conventionally known flip chip type semiconductor back film is formed on the chip. It may be used.
  • the flip-chip type semiconductor back film is a film for forming on the back surface of a chip (semiconductor element) flip-chip connected on an adherend. Details are disclosed in, for example, Japanese Patent Application Laid-Open No. 2011-249739. Since it is disclosed, a description thereof is omitted here.
  • the lower limit of the temperature at the time of the peeling step can be set to 50 ° C., 80 ° C., 100 ° C., 150 ° C., and 180 ° C., for example.
  • the upper limit of the temperature at the time of the peeling step is preferably 260 ° C, more preferably 230 ° C, and further preferably 200 ° C.
  • the time for maintaining the temperature condition in the peeling step varies depending on the temperature, but is preferably 0.05 to 120 minutes, more preferably 0.1 to 30 minutes. Note that it is preferable not to be exposed to heat of 260 ° C. or higher in the steps after the mounting step. Thereby, it can suppress that solder etc. melt.
  • a method for manufacturing a semiconductor device comprising: forming a wiring circuit board on a support having a release layer (for example, a long support); and mounting a plurality of semiconductor chips on the wiring circuit board. It includes a method of performing resin sealing and then cutting to obtain a plurality of semiconductor devices. According to the method for manufacturing a semiconductor device, a printed circuit board for a plurality of semiconductor devices can be formed on one support.
  • the example of the semiconductor device manufacturing method according to the present embodiment has been described above. However, the semiconductor device manufacturing method according to the eighth aspect of the present invention is not limited to the above-described example, and is within the scope of the eighth aspect of the present invention. It can be changed as appropriate.
  • the release layer of the ninth aspect of the present invention can exhibit the same characteristics as those of the release layer of the eighth aspect of the present invention, particularly as characteristics other than those described in the section of the ninth aspect of the present invention.
  • the manufacturing method of the semiconductor device of the ninth aspect of the present invention may employ the same steps as those of the manufacturing method of the semiconductor device of the eighth aspect of the present invention, except for those described in the section of the ninth aspect of the present invention. it can.
  • the method for manufacturing a semiconductor device is a method for manufacturing a semiconductor device having a structure in which a semiconductor chip is mounted on a printed circuit board, the step of preparing a support having a release layer, and the support A step of forming a wiring circuit board on the release layer, a step of mounting a semiconductor chip on the wiring circuit board, and after the mounting, the surface of the release layer opposite to the support is used as an interface. And a step of peeling the support together with the release layer.
  • the release layer is immersed in N-methyl-2-pyrrolidone at 50 ° C. for 60 seconds and dried at 150 ° C. for 30 minutes to reduce the weight. The rate is 1.0% by weight or more.
  • the release layer 5 of the embodiment according to the eighth aspect of the present invention can be used for characteristics other than those described below.
  • the release layer 5 was immersed in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and dried at 150 ° C. for 30 minutes. % Or more, and more preferably 1.3% by weight or more. Moreover, although the said weight decreasing rate is so preferable that it is large, it is 50 weight% or less and 30 weight% or less, for example. Since the weight loss after immersion in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and drying at 150 ° C. for 30 minutes is 1% by weight or more, the release layer 5 is N-methyl-2- It can be said that it is dissolved in pyrrolidone and sufficiently reduced in weight.
  • NMP N-methyl-2-pyrrolidone
  • the peeling layer 5 can be easily peeled with N-methyl-2-pyrrolidone.
  • the said weight decreasing rate of the peeling layer 5 can be controlled by the solubility with respect to NMP of a raw material, for example. That is, as a raw material having a higher solubility in NMP is selected, the solvent release sheet obtained using the raw material has higher solubility in NMP.
  • the release layer 5 preferably has a dynamic hardness of 10 or less, more preferably 9 or less, and even more preferably 8 or less. Moreover, although the said dynamic hardness is so preferable that it is small, it is 0.001 or more, for example. When the dynamic hardness is 10 or less, the adhesive force of the release layer 5 to the adherend can be made sufficient.
  • the release layer 5 has a surface hardness of preferably 10 GPa or less, more preferably 8 GPa or less, and even more preferably 6 GPa or less. Moreover, although the said surface hardness is so preferable that it is small, it is 0.05 GPa or more, for example. When the surface hardness is 10 GPa or less, the adhesive force between the release layer 5 and the adherend can be controlled.
  • the release layer 5 preferably has a weight reduction rate of less than 1% by weight, more preferably less than 0.9% by weight after being immersed in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes. More preferably, it is less than 8% by weight. Moreover, although the said weight decreasing rate is so preferable that it is small, it is 0 weight% or more and 0.001 weight% or more, for example.
  • the weight loss after immersion in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes is less than 1% by weight, the dissolution into the 3% tetramethylammonium hydroxide aqueous solution is small, so solvent resistance (particularly , Solvent resistance to tetramethylammonium hydroxide aqueous solution can be improved.
  • the weight reduction rate of the release layer 5 can be controlled by, for example, the composition of the diamine used (solubility of the diamine in tetramethylammonium hydroxide aqueous solution).
  • the peeling layer 5 has an increase amount of particles of 0.2 ⁇ m or more on the silicon wafer surface when it is peeled after being bonded to the silicon wafer, and less than 10000/6 inch wafers before being bonded to the silicon wafer. More preferably, it is less than 9000/6 inch wafers, and more preferably less than 8000/6 inch wafers.
  • the increase amount of the particles is particularly preferably less than 1000/6 inch wafer, less than 900/6 inch wafer, and less than 800/6 inch wafer, as compared with before being bonded to the silicon wafer.
  • the release layer 5 is formed by immersing it in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 60 seconds and drying at 150 ° C. for 30 minutes.
  • NMP N-methyl-2-pyrrolidone
  • the resin include, but are not limited to, polyimide resin, silicone resin, acrylic resin, fluororesin, epoxy resin, urethane resin, and rubber resin.
  • the same steps as those for the method for manufacturing a semiconductor device according to the eighth embodiment of the present invention can be adopted except that the peeling process is different. Therefore, only the peeling process will be described below.
  • the peeling step is preferably performed by immersing for 10 to 6000 seconds using N-methyl-2-pyrrolidone (NMP) as a solvent.
  • NMP N-methyl-2-pyrrolidone
  • the immersion time is more preferably 15 to 3000 seconds.
  • the temperature of the solvent in the peeling step is preferably ⁇ 10 to 200 ° C., more preferably 20 to 120 ° C. Note that it is preferable not to be exposed to heat of 260 ° C. or higher in the steps after the mounting step. Thereby, it can suppress that solder etc. melt.
  • the manufacturing method of the semiconductor device in 9th this invention is not limited to the example mentioned above, In the range of the summary of 9th this invention It can be changed as appropriate.
  • the release layer according to the tenth aspect of the present invention can exhibit the same characteristics as those of the release layer according to the eighth aspect of the present invention, particularly as characteristics other than those described in the section of the tenth aspect of the present invention.
  • the manufacturing method of the semiconductor device according to the tenth aspect of the present invention can employ the same steps as the manufacturing method of the semiconductor device according to the eighth aspect of the present invention.
  • the method for manufacturing a semiconductor device is a method for manufacturing a semiconductor device having a structure in which a semiconductor chip is mounted on a printed circuit board, the step of preparing a support having a release layer, and the support A step of forming a wiring circuit board on the release layer, a step of mounting a semiconductor chip on the wiring circuit board, and after the mounting, the surface of the release layer opposite to the support is used as an interface. And a step of peeling the support together with the release layer, wherein the release layer has a structural unit derived from a diamine having an imide group and at least partially having an ether structure.
  • the release layer 5 of the embodiment according to the eighth aspect of the present invention can be used for characteristics other than those described below.
  • the release layer 5 is composed of a polyimide resin having an imide group and having a structural unit derived from a diamine having an ether structure at least partially.
  • the polyimide resin can be generally obtained by imidizing (dehydrating and condensing) a polyamic acid that is a precursor thereof.
  • a method for imidizing the polyamic acid for example, a conventionally known heat imidization method, azeotropic dehydration method, chemical imidization method and the like can be employed. Of these, the heating imidization method is preferable.
  • the heat imidization method it is preferable to perform heat treatment under a nitrogen atmosphere or an inert atmosphere such as a vacuum in order to prevent deterioration of the polyimide resin due to oxidation.
  • the polyamic acid is charged in an appropriately selected solvent such that an acid anhydride and a diamine (including both a diamine having an ether structure and a diamine not having an ether structure) have a substantially equimolar ratio. Can be obtained by reaction.
  • the polyimide resin has a structural unit derived from a diamine having an ether structure.
  • the diamine having an ether structure is not particularly limited as long as it is a compound having an ether structure and having at least two terminals having an amine structure.
  • a diamine having a glycol skeleton is preferable.
  • heating the release layer 5 may reduce the shear adhesive force. it can.
  • the fact that the ether structure or the glycol skeleton is detached from the resin constituting the release layer 5 is, for example, an FT-IR (Fourier Transform Infrared Spectroscopy) spectrum before and after heating at 300 ° C for 30 minutes. And the spectrum of 2800 to 3000 cm ⁇ 1 decreases before and after heating.
  • FT-IR Fastier Transform Infrared Spectroscopy
  • diamine having a glycol skeleton examples include a polypropylene glycol structure and a diamine having one amino group at each end, a polyethylene glycol structure, and one amino group at each end.
  • examples thereof include a diamine having a polytetramethylene glycol structure and a diamine having an alkylene glycol such as a diamine having one amino group at each end.
  • the diamine which has two or more of these glycol structures and has one amino group in both the ends can be mentioned.
  • the molecular weight of the diamine having an ether structure is preferably within the range of 100 to 5000, and more preferably 150 to 4800.
  • the molecular weight of the diamine having an ether structure is in the range of 100 to 5000, it is easy to obtain the release layer 5 having high adhesive strength at low temperatures and exhibiting peelability at high temperatures.
  • a diamine having no ether structure can be used in combination with a diamine having an ether structure.
  • the diamine having no ether structure include aliphatic diamines and aromatic diamines.
  • the mixing ratio of the diamine having an ether structure and the diamine having no ether structure is preferably in the range of 100: 0 to 10:90, more preferably 100: 0 to 20: 80, more preferably 99: 1 to 30:70.
  • the thermal peelability at high temperature is excellent.
  • Examples of the aliphatic diamine include ethylenediamine, hexamethylenediamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 4,9-dioxa-1,12-diaminododecane, , 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane ( ⁇ , ⁇ -bisaminopropyltetramethyldisiloxane) and the like.
  • the molecular weight of the aliphatic diamine is usually 50 to 1,000,000, preferably 100 to 30,000.
  • aromatic diamine examples include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, and 4,4′-diaminodiphenylpropane.
  • the molecular weight of the aromatic diamine is usually 50 to 1000, preferably 100 to 500.
  • the molecular weight of the aliphatic diamine and the molecular weight of the aromatic diamine are values measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene (weight average molecular weight).
  • Examples of the acid anhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,2-bis (2, 3-Dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), bis (2,3-dicarboxyphenyl) methane dianhydride Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis
  • Examples of the solvent for reacting the acid anhydride with the diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, and cyclopentanone. These may be used alone or in combination. Further, in order to adjust the solubility of raw materials and resins, a nonpolar solvent such as toluene or xylene may be appropriately mixed and used.
  • the same steps as those of the manufacturing method of the semiconductor device according to the eighth aspect of the present invention are adopted except that the peeling layer described above is used as the peeling layer. Can do. Therefore, the description here is omitted.
  • Example 1 In an atmosphere under a nitrogen stream, 12.95 g of polyether diamine (manufactured by Heinzmann, D-2000, molecular weight: 1990.8) in 123.31 g of N, N-dimethylacetamide (DMAc), 4,4′- Diaminodiphenyl ether (DDE, molecular weight: 200.2) 7.88 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.00 g were mixed and reacted at 70 ° C. to obtain a polyamic acid solution A. Obtained.
  • DMAc N, N-dimethylacetamide
  • DDE 4,4′- Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution A was applied onto the mirror surface of an 8-inch silicon wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support A with polyamic acid.
  • the support A with polyamic acid is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermal release sheet) having a thickness of 30 ⁇ m, and the support A with thermal release sheet (support with release layer) A) was obtained.
  • Example 2 In an atmosphere under a nitrogen stream, 12.32 g of polyether diamine (manufactured by Heinzmann, D-400, molecular weight: 422.6), 4,4′- in 102.64 g of N, N-dimethylacetamide (DMAc). Diaminodiphenyl ether (DDE, molecular weight: 200.2) 3.34 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.00 g were mixed and reacted at 70 ° C. to obtain a polyamic acid solution B. Obtained.
  • DDE Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution B was applied onto a SUS foil (thickness 38 ⁇ m) so that the thickness after drying was 50 ⁇ m, dried at 90 ° C for 20 minutes, and with polyamic acid A support B was obtained.
  • the support B with polyamic acid is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermal release sheet) having a thickness of 50 ⁇ m, and the support B with thermal release sheet (support with release layer) B) was obtained.
  • Example 3 In an atmosphere under a nitrogen stream, 18.90 g of polyether diamine (manufactured by Ihara Chemical Co., Elastomer 1000, molecular weight: 1229.7) in 64.41 g of N, N-dimethylacetamide (DMAc), 4,4′- Diaminodiphenyl ether (DDE, molecular weight: 200.2) 6.10 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.00 g were mixed and reacted at 70 ° C. to obtain a polyamic acid solution C. It was.
  • DMAc N, N-dimethylacetamide
  • DDE 4,4′- Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution C was applied onto an 8-inch glass wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support C with polyamic acid.
  • the support C with polyamic acid is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermal release sheet) having a thickness of 80 ⁇ m, and the support C with thermal release sheet (support with release layer) C) was obtained.
  • the support J with polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermal release sheet) having a thickness of 30 ⁇ m, and the support J with thermal release sheet (support with release layer) J) was obtained.
  • a 5 mm square (500 ⁇ m thick) silicon wafer chip is placed on a heat-peelable sheet (peeling layer) formed on a support (silicon wafer, SUS foil, or glass wafer), and 60 ° C., 10 mm / s.
  • the shear adhesive strength between the heat-peelable sheet (peel layer) and the silicon wafer chip was measured using a shear tester (Dage 4000, manufactured by Dage). The conditions of the shear test were as follows. The results are shown in Table 1.
  • the support body was peeled from the support body with a heat peelable sheet which concerns on an Example and a comparative example.
  • the heat-peelable sheets of Examples and Comparative Examples were processed to have a diameter of 6 inches, and were laminated on a wafer having a diameter of 8 inches at 60 ° C. and 10 mm / s. Then, it was left for 1 minute and peeled off.
  • a particle counter (SFS6200, manufactured by KLA), the number of particles of 0.2 ⁇ m or more on the surface of an 8-inch diameter wafer was measured.
  • the shear adhesive strength to the silicon wafer at the temperature after being held at 200 ° C. for 1 minute is 0.25 kg / 5 ⁇ 5 mm or more, and after being held at 260 ° C. for 3 minutes.
  • the shearing adhesive force to the silicon wafer at this temperature was less than 0.25 kg / 5 ⁇ 5 mm.
  • insulating base layer was formed on the support with release layer of Examples and Comparative Examples. Specifically, a solution containing photosensitive polyimide and polybenzoxazole (PBO) was applied so that the thickness after curing (after imidization) was 10 ⁇ m. Then, solvent drying was performed for 10 minutes at 150 degreeC, and it exposed with the predetermined pattern. The exposure amount was 1000 mJ / cm 2 with i-line (mercury spectral line of wavelength 365 nm). Next, post-exposure baking (PEB) was performed at 150 ° C. for 1 hour.
  • PBO photosensitive polyimide and polybenzoxazole
  • TMAH 3% aqueous tetramethylammonium hydroxide solution
  • Copper plating corresponding to the pattern of the formed resist was formed by electrolytic plating.
  • the thickness of the copper plating was 10 ⁇ m.
  • resist stripping The resist was peeled off by dipping in an alkali solution (10% KOH) at 50 ° C. for 60 seconds.
  • cover coat (adhesive layer)
  • the epoxy resin was applied so that the thickness after curing was 10 ⁇ m, and dried at 100 ° C. for 10 minutes. Next, exposure was performed to form a predetermined pattern. The exposure amount was 300 mJ / cm 2 with i-line (mercury spectrum line having a wavelength of 365 nm). Thereafter, using an alkaline solution (10% NaOH), development was performed at 50 ° C. for 60 seconds, and patterning was performed. Then, it heated at 150 degreeC for 1 hour, and the epoxy resin was hardened.
  • a nickel (Ni) layer having a thickness of 1 ⁇ m and a gold (Au) layer having a thickness of 0.5 ⁇ m were formed by plating on the portion where the terminal is to be formed. As a result, a printed circuit board having a connecting conductor (terminal) was obtained.
  • a semiconductor chip having electrodes corresponding to the formed connection conductor portions (terminals) was mounted on a printed circuit board. Thereafter, the temperature was maintained at 260 ° C. for 3 minutes.
  • Example 1 In an atmosphere under a nitrogen stream, polyether diamine (manufactured by Heinzmann, D-400, molecular weight: 422.6) 10.34 g, 4,4′- in 98.49 g of N, N-dimethylacetamide (DMAc). 4.28 g of diaminodiphenyl ether (DDE, molecular weight: 200.2) and 10.00 g of pyromellitic dianhydride (PMDA, molecular weight: 218.1) were mixed and reacted at 70 ° C. to obtain a polyamic acid solution A. Obtained.
  • DDE diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution A was applied onto the mirror surface of an 8-inch silicon wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support A with polyamic acid.
  • the support A with polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (solvent release sheet) having a thickness of 35 ⁇ m, and the support A with solvent release sheet (support with release layer) A) was obtained.
  • Example 2 In an atmosphere under a nitrogen stream, polyether diamine (manufactured by Ihara Chemical Co., Elastomer 1000, molecular weight: 1229.7) 15.39 g, 4,4′- in 66.70 g N, N-dimethylacetamide (DMAc). Diaminodiphenyl ether (DDE, molecular weight: 200.2) 6.67 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.00 g were mixed and reacted at 70 ° C. to obtain a polyamic acid solution B. Obtained.
  • DDE Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution B was applied onto a SUS foil (thickness 38 ⁇ m) so that the thickness after drying was 100 ⁇ m, dried at 90 ° C for 20 minutes, and with polyamic acid A support B was obtained.
  • the support B with polyamic acid is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (solvent release sheet) having a thickness of 100 ⁇ m, and the support B with solvent release sheet (support with release layer) B) was obtained.
  • Example 3 In an atmosphere under a nitrogen stream, polyether diamine (manufactured by Heinzmann, D-4000, molecular weight: 4023.5) 21.27 g, 4,4′- in 157.58 g of N, N-dimethylacetamide (DMAc) Diaminodiphenyl ether (DDE, molecular weight: 200.2) 8.12 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.00 g were mixed and reacted at 70 ° C. to obtain a polyamic acid solution C. It was.
  • DMAc N, N-dimethylacetamide
  • DDE Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution C was applied onto an 8-inch glass wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support C with polyamic acid.
  • the support C with polyamic acid is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (solvent release sheet) having a thickness of 30 ⁇ m, and the support C with solvent release sheet (support with release layer) C) was obtained.
  • the support J with polyamic acid is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (solvent release sheet) having a thickness of 30 ⁇ m.
  • the support J with solvent release sheet (support with release layer) J) was obtained.
  • the support body was peeled from the support body with a solvent peeling type sheet which concerns on an Example and a comparative example.
  • the solvent peelable sheets of Examples and Comparative Examples were processed into a diameter of 6 inches and laminated on a wafer of 8 inches in diameter at 60 ° C. and 10 mm / s. Then, it was left for 1 minute and peeled off.
  • a particle counter (SFS6200, manufactured by KLA), the number of particles of 0.2 ⁇ m or more on the surface of an 8-inch diameter wafer was measured.
  • the solvent peelable sheet according to the example had a weight reduction rate of 1.0% by weight or more after being immersed in N-methyl-2-pyrrolidone at 50 ° C. for 60 seconds and dried at 150 ° C. for 30 minutes.
  • insulating base layer was formed on the support with release layer of Examples and Comparative Examples. Specifically, a solution containing photosensitive polyimide and polybenzoxazole (PBO) was applied so that the thickness after curing (after imidization) was 10 ⁇ m. Then, solvent drying was performed for 10 minutes at 150 degreeC, and it exposed with the predetermined pattern. The exposure amount was 1000 mJ / cm 2 with i-line (mercury spectral line of wavelength 365 nm). Next, post-exposure baking (PEB) was performed at 150 ° C. for 1 hour.
  • PBO photosensitive polyimide and polybenzoxazole
  • TMAH 3% aqueous tetramethylammonium hydroxide solution
  • Copper plating corresponding to the pattern of the formed resist was formed by electrolytic plating.
  • the thickness of the copper plating was 10 ⁇ m.
  • resist stripping The resist was peeled off by dipping in an alkali solution (10% KOH) at 50 ° C. for 60 seconds.
  • cover coat (adhesive layer)
  • the epoxy resin was applied so that the thickness after curing was 10 ⁇ m, and dried at 100 ° C. for 10 minutes. Next, exposure was performed to form a predetermined pattern. The exposure amount was 300 mJ / cm 2 with i-line (mercury spectrum line having a wavelength of 365 nm). Thereafter, using an alkaline solution (10% NaOH), development was performed at 50 ° C. for 60 seconds, and patterning was performed. Then, it heated at 150 degreeC for 1 hour, and the epoxy resin was hardened.
  • a nickel (Ni) layer having a thickness of 1 ⁇ m and a gold (Au) layer having a thickness of 0.5 ⁇ m were formed by plating on the portion where the terminal is to be formed. As a result, a printed circuit board having a connecting conductor (terminal) was obtained.
  • a semiconductor chip having electrodes corresponding to the formed connection conductor portions (terminals) was mounted on a printed circuit board. Thereafter, it was immersed in N-methyl-2-pyrrolidone (NMP) at 50 ° C. for 600 seconds.
  • NMP N-methyl-2-pyrrolidone
  • Example 1 In an atmosphere under a nitrogen stream, 13.41 g of polyether diamine (manufactured by Heinzman, D-4000, molecular weight: 4023.5), 13.4 g, 4,4′-in 127.69 g of N, N-dimethylacetamide (DMAc). Diaminodiphenyl ether (DDE, molecular weight: 200.2) 8.51 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.00 g were mixed and reacted at 70 ° C. to obtain a polyamic acid solution A. Obtained.
  • DDE Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution A was applied onto the mirror surface of an 8-inch silicon wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support A with polyamic acid.
  • the support A with polyamic acid is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermal release sheet) having a thickness of 30 ⁇ m, and the support A with thermal release sheet (support with release layer) A) was obtained.
  • Example 2 In an atmosphere under a nitrogen stream, 16.20 g, 4,4′-polyether diamine (manufactured by Heinzmann, D-2000, molecular weight: 1990.8) in 135.00 g of N, N-dimethylacetamide (DMAc) Diaminodiphenyl ether (DDE, molecular weight: 200.2) 7.55 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.00 g were mixed and reacted at 70 ° C. Obtained.
  • DMAc N, N-dimethylacetamide
  • DDE Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution B was applied on a SUS foil (thickness 50 ⁇ m) so that the thickness after drying was 30 ⁇ m, dried at 90 ° C for 20 minutes, and with polyamic acid A support B was obtained.
  • the support B with polyamic acid is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermal release sheet) having a thickness of 30 ⁇ m, and the support B with thermal release sheet (support with release layer) B) was obtained.
  • Example 3 In an atmosphere under nitrogen flow, 107.17 g of N, N-dimethylacetamide (DMAc) was mixed with polyetherdiamine (manufactured by Heinzmann, D-400, molecular weight: 422.6) 14.47 g, 4,4′- Diaminodiphenyl ether (DDE, molecular weight: 200.2) 2.33 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.00 g were mixed and reacted at 70 ° C. to obtain a polyamic acid solution C. It was.
  • DMAc N-dimethylacetamide
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution C was applied onto a nickel foil (thickness 100 ⁇ m) so that the thickness after drying was 50 ⁇ m, dried at 90 ° C for 20 minutes, and with polyamic acid A support C was obtained.
  • the support C with polyamic acid is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermal release sheet) having a thickness of 50 ⁇ m, and the support C with thermal release sheet (support with release layer) C) was obtained.
  • a 5 mm square (500 ⁇ m thick) silicon wafer chip is placed on a heat-peelable sheet (peeling layer) formed on a support (silicon wafer, SUS foil, or glass wafer), and 60 ° C., 10 mm / s.
  • the shear adhesive strength between the heat-peelable sheet (peel layer) and the silicon wafer chip was measured using a shear tester (Dage 4000, manufactured by Dage). The conditions of the shear test were as follows. The results are shown in Table 3.
  • the support was peeled from the support with a heat-peelable sheet according to the example.
  • the heat-peelable sheet of the example was processed into a size of 6 inches in diameter, and was laminated on a wafer having a diameter of 8 inches under the conditions of 60 ° C. and 10 mm / s. Then, it was left for 1 minute and peeled off.
  • a particle counter (SFS6200, manufactured by KLA)
  • the number of particles of 0.2 ⁇ m or more on the surface of an 8-inch diameter wafer was measured.
  • the heat-peelable sheet according to the example has a high shear adhesive force to the silicon wafer at the temperature after being held at 200 ° C. for 1 minute, and the shear adhesion to the silicon wafer at the temperature after being held at 260 ° C. for 3 minutes. The force was greatly reduced compared to the case after holding at 200 ° C. for 1 minute.
  • insulating base layer was formed on the support with a release layer of the example. Specifically, a solution containing photosensitive polyimide and polybenzoxazole (PBO) was applied so that the thickness after curing (after imidization) was 10 ⁇ m. Then, solvent drying was performed for 10 minutes at 150 degreeC, and it exposed with the predetermined pattern. The exposure amount was 1000 mJ / cm 2 with i-line (mercury spectral line of wavelength 365 nm). Next, post-exposure baking (PEB) was performed at 150 ° C. for 1 hour.
  • PBO photosensitive polyimide and polybenzoxazole
  • TMAH 3% aqueous tetramethylammonium hydroxide solution
  • Copper plating corresponding to the pattern of the formed resist was formed by electrolytic plating.
  • the thickness of the copper plating was 10 ⁇ m.
  • resist stripping The resist was peeled off by dipping in an alkali solution (10% KOH) at 50 ° C. for 60 seconds.
  • cover coat (adhesive layer)
  • the epoxy resin was applied so that the thickness after curing was 10 ⁇ m, and dried at 100 ° C. for 10 minutes. Next, exposure was performed to form a predetermined pattern. The exposure amount was 300 mJ / cm 2 with i-line (mercury spectrum line having a wavelength of 365 nm). Thereafter, using an alkaline solution (10% NaOH), development was performed at 50 ° C. for 60 seconds, and patterning was performed. Then, it heated at 150 degreeC for 1 hour, and the epoxy resin was hardened.
  • a nickel (Ni) layer having a thickness of 1 ⁇ m and a gold (Au) layer having a thickness of 0.5 ⁇ m were formed by plating on the portion where the terminal is to be formed. As a result, a printed circuit board having a connecting conductor (terminal) was obtained.
  • a semiconductor chip having electrodes corresponding to the formed connection conductor portions (terminals) was mounted on a printed circuit board. Thereafter, the temperature was maintained at 260 ° C. for 3 minutes.
  • Example 1 In an atmosphere under a nitrogen stream, 13.95 g of polyether diamine (manufactured by Heinzmann, D-4000, molecular weight: 4023.5), 12,4′-in 129.73 g of N, N-dimethylacetamide (DMAc). Diaminodiphenyl ether (DDE, molecular weight: 200.2) 8.49 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.0 g were mixed and reacted at 70 ° C. to obtain a polyamic acid solution A. Obtained.
  • DDE Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution A was applied onto the mirror surface of an 8-inch silicon wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support A with polyamic acid.
  • the support A with polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermally peelable sheet) having a thickness of 30 ⁇ m, thereby obtaining a support A with a thermally peelable sheet.
  • Example 2 In an atmosphere under a nitrogen stream, 15.62 g of polyetherdiamine (manufactured by Heinzmann, D-2000, molecular weight: 1990.8), 13,4′-diamino in 132.9 g of N, N-dimethylacetamide (DMAc) 7.61 g of diphenyl ether (DDE, molecular weight: 200.2) and 10.0 g of pyromellitic dianhydride (PMDA, molecular weight: 218.1) are mixed and reacted at 70 ° C. to obtain a polyamic acid solution B It was.
  • DMAc diphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution B was applied onto a SUS foil (thickness 38 ⁇ m) so that the thickness after drying was 50 ⁇ m, dried at 90 ° C for 20 minutes, and with polyamic acid A support B was obtained.
  • the support B with polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermally peelable sheet) having a thickness of 50 ⁇ m, thereby obtaining a support B with a thermally peelable sheet.
  • Example 3 In an atmosphere under a nitrogen stream, polyether diamine (manufactured by Heinzmann, D-400, molecular weight: 422.6), 13.37 g, 4,4′- in 104.86 g of N, N-dimethylacetamide (DMAc). Diaminodiphenyl ether (DDE, molecular weight: 200.2) 2.85 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.0 g were mixed and reacted at 70 ° C. to obtain a polyamic acid solution C. It was.
  • DDE Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution C was applied onto an 8-inch glass wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support C with polyamic acid.
  • the support C with polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermally peelable sheet) having a thickness of 80 ⁇ m, thereby obtaining a support C with a thermally peelable sheet.
  • the polyamic acid solution I was applied onto the mirror surface of an 8-inch silicon wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support I with polyamic acid.
  • the support I with polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermally peelable sheet) having a thickness of 30 ⁇ m, thereby obtaining a support I with a thermally peelable sheet.
  • a 5 mm square (500 ⁇ m thick) silicon wafer chip is placed on a heat-peelable sheet formed on a support (silicon wafer, SUS foil, or glass wafer) and laminated under conditions of 60 ° C. and 10 mm / s. Then, using a shear tester (Dage, Dage 4000), the shear adhesive strength between the heat-peelable sheet and the silicon wafer chip was measured. The conditions of the shear test were as follows. The results are shown in Table 4. Note that Comparative Example 1 was not measured because it did not adhere to the silicon wafer chip.
  • the support body was peeled from the support body with a heat peelable sheet which concerns on an Example and a comparative example.
  • the heat-peelable sheets of Examples and Comparative Examples were processed to have a diameter of 6 inches, and were laminated on a wafer having a diameter of 8 inches at 60 ° C. and 10 mm / s. Then, it was left for 1 minute and peeled off.
  • a particle counter (SFS6200, manufactured by KLA), the number of particles of 0.2 ⁇ m or more on the surface of an 8-inch diameter wafer was measured.
  • Example 1 In an atmosphere under a nitrogen stream, polyether diamine (manufactured by Heinzmann, D-400, molecular weight: 422.6), 10.66 g, 4,4′- in 99.16 g of N, N-dimethylacetamide (DMAc). Diaminodiphenyl ether (DDE, molecular weight: 200.2) 4.13 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.0 g were mixed and reacted at 70 ° C. to prepare polyamic acid solution A. Obtained.
  • DDE Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution A was applied onto the mirror surface of an 8-inch silicon wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support A with polyamic acid.
  • the support A with polyamic acid was heat-treated at 300 ° C. for 4 hours in a nitrogen atmosphere (oxygen concentration: 100 ppm or less) to form a polyimide film (thermally peelable sheet) having a thickness of 30 ⁇ m. A was obtained.
  • the imidation ratio of the heat-peelable sheet according to Example 1 was 99.9%.
  • the polyamic acid solution B is applied onto a SUS foil (thickness 38 ⁇ m) so that the thickness after drying is 50 ⁇ m, dried at 90 ° C for 20 minutes, and with polyamic acid A support B was obtained.
  • the support B with polyamic acid is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere (oxygen concentration: 100 ppm or less) to form a polyimide film (thermally peelable sheet) having a thickness of 50 ⁇ m, and the support with thermally peelable sheet B was obtained.
  • the imidation ratio of the heat-peelable sheet according to Example 2 was 90%.
  • Example 3 Polyether diamine (manufactured by Heinzmann, D-4000, molecular weight: 4023.5) 18.98 g, 4,4′-diamino in 148.87 g of N, N-dimethylacetamide (DMAc) in an atmosphere under a nitrogen stream Diphenyl ether (DDE, molecular weight: 200.2) 8.24 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.0 g were mixed and reacted at 70 ° C. to obtain polyamic acid solution C. It was.
  • DDE diphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution C was applied on a SUS foil (thickness 38 ⁇ m) so that the thickness after drying was 50 ⁇ m, dried at 90 ° C for 20 minutes, and with polyamic acid A support C was obtained.
  • the support C with polyamic acid is heat-treated at 250 ° C. for 1.5 hours in a nitrogen atmosphere (oxygen concentration: 100 ppm or less) to form a polyimide film (thermally peelable sheet) having a thickness of 50 ⁇ m, with a thermally peelable sheet A support C was obtained.
  • the imidation ratio of the heat-peelable sheet according to Example 3 was 80.5%.
  • the support I with polyamic acid was heat-treated at 300 ° C. for 2 hours under a nitrogen atmosphere (oxygen concentration: 100 ppm or less) to form a polyimide film (thermally peelable sheet) having a thickness of 30 ⁇ m. I was obtained.
  • the imidation ratio of the heat-peelable sheet according to Comparative Example 1 was 75%.
  • the imidization ratios of the examples and comparative examples were determined by measuring the peak intensity of the imide group using 1H-NMR (proton nuclear magnetic resonance, manufactured by JEOL Ltd., LA400). Specifically, a solution for producing a heat-peelable sheet (solution containing polyamic acid) is applied and dried (drying condition: 90 ° C. for 20 minutes), and imide is obtained under the imidization conditions described in Examples and Comparative Examples. Make it.
  • thermosetting rate was measured as follows. The temperature was increased from room temperature (23 ° C.) using a state in which a solution for producing a heat-peelable sheet according to Examples and Comparative Examples (solution containing polyamic acid) was applied and dried (condition: 90 ° C. for 20 minutes). The calorific value (total calorific value) when the temperature was raised to 500 ° C. (the temperature at which the thermosetting reaction was assumed to be completely completed) was measured at a temperature rate of 10 ° C./min.
  • thermosetting reaction is completely completed from room temperature (23 ° C.) under a temperature rising rate of 10 ° C./min.
  • the amount of heat generated when the temperature was raised to (the temperature assumed to have been obtained) was measured.
  • the thermosetting rate was obtained by the following formula (1).
  • Formula (1) [1-((Amount of heat generated after manufacturing the heat-peelable sheet) / (Total amount of heat generated))] ⁇ 100 (%)
  • the reaction exotherm in the temperature range of ⁇ 5 ° C. of the reaction exothermic peak temperature measured with a differential scanning calorimeter is used. The results are shown in Table 5.
  • a 5 mm square (500 ⁇ m thick) silicon wafer chip is placed on a heat-peelable sheet formed on a support (silicon wafer, SUS foil, or glass wafer) and laminated under conditions of 60 ° C. and 10 mm / s. Then, using a shear tester (Dage, Dage 4000), the shear adhesive strength between the heat-peelable sheet and the silicon wafer chip was measured. The conditions of the shear test were as follows. The results are shown in Table 5.
  • the support body was peeled from the support body with a heat peelable sheet which concerns on an Example and a comparative example.
  • the heat-peelable sheets of Examples and Comparative Examples were processed to have a diameter of 6 inches, and were laminated on a wafer having a diameter of 8 inches at 60 ° C. and 10 mm / s. Then, it was left for 1 minute and peeled off.
  • a particle counter (SFS6200, manufactured by KLA), the number of particles of 0.2 ⁇ m or more on the surface of an 8-inch diameter wafer was measured.
  • Example 1 In an atmosphere under a nitrogen stream, 13.45 g of polyether diamine (manufactured by Heinzmann, D-2000, molecular weight: 1990.8) in 125.10 g of N, N-dimethylacetamide (DMAc), 4,4′- Diaminodiphenyl ether (DDE, molecular weight: 200.2) 7.83 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.0 g were mixed and reacted at 70 ° C. to prepare polyamic acid solution A. Obtained.
  • DMAc N, N-dimethylacetamide
  • DDE 4,4′- Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution A was applied onto the mirror surface of an 8-inch silicon wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support A with polyamic acid.
  • the support A with a polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermally peelable sheet) having a thickness of 30 ⁇ m, thereby obtaining a support A with a thermally peelable sheet.
  • the compounding ratio of acid anhydride (pyromellitic dianhydride), diamine (ether diamine) which has an ether structure, and other diamine (DDE) which does not have an ether structure Is a molar ratio as follows.
  • Example 2 Polyether diamine (manufactured by Heinzmann, D-4000, molecular weight: 4023.5) 18.98 g, 4,4′-diamino in 148.87 g of N, N-dimethylacetamide (DMAc) in an atmosphere under a nitrogen stream 8. 24 g of diphenyl ether (DDE, molecular weight: 200.2) and 10.0 g of pyromellitic dianhydride (PMDA, molecular weight: 218.1) are mixed and reacted at 70 ° C. to obtain a polyamic acid solution B It was.
  • DDE diphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution B is applied onto a SUS foil (thickness 38 ⁇ m) so that the thickness after drying is 50 ⁇ m, dried at 90 ° C for 20 minutes, and with polyamic acid A support B was obtained.
  • the support B with a polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermally peelable sheet) having a thickness of 50 ⁇ m to obtain a support B with a thermally peelable sheet.
  • the compounding ratio of acid anhydride (pyromellitic dianhydride), diamine (ether diamine) which has an ether structure, and other diamine (DDE) which does not have an ether structure Is a molar ratio as follows.
  • Example 3 In an atmosphere under a nitrogen stream, polyether diamine (manufactured by Heinzmann, D-400, molecular weight: 422.6), 13.37 g, 4,4′- in 104.86 g of N, N-dimethylacetamide (DMAc). Diaminodiphenyl ether (DDE, molecular weight: 200.2) 2.85 g and pyromellitic dianhydride (PMDA, molecular weight: 218.1) 10.0 g were mixed and reacted at 70 ° C. to obtain polyamic acid solution C. It was.
  • DDE Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the polyamic acid solution C was applied onto an 8-inch glass wafer with a spin coater and dried at 90 ° C. for 20 minutes to obtain a support C with polyamic acid.
  • the support C with a polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermally peelable sheet) having a thickness of 80 ⁇ m, thereby obtaining a support C with a thermally peelable sheet.
  • the compounding ratio of an acid anhydride (pyromellitic dianhydride), diamine (ether diamine) which has an ether structure, and other diamine (DDE) which does not have an ether structure Is a molar ratio as follows.
  • (Acid anhydride): (Diamine having an ether structure): (Other diamine not having an ether structure) 100: 69.0: 31.0
  • the support I with polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermally peelable sheet) having a thickness of 30 ⁇ m.
  • a support I with thermally peelable sheet was obtained.
  • the support body was peeled from the support body with a heat peelable sheet which concerns on an Example and a comparative example.
  • the heat-peelable sheets of Examples and Comparative Examples were processed to have a diameter of 6 inches, and were laminated on a wafer having a diameter of 8 inches at 60 ° C. and 10 mm / s. Then, it was left for 1 minute and peeled off.
  • a particle counter (SFS6200, manufactured by KLA), the number of particles of 0.2 ⁇ m or more on the surface of an 8-inch diameter wafer was measured.
  • Example 1 In an atmosphere under a nitrogen stream, aromatic diamine oligomer (Ihara Chemical Co., Elastomer 1000, molecular weight: 1229.7) 12.89 g, 4,4 ′ in 68.33 g of N, N-dimethylacetamide (DMAc).
  • -Polyamino acid solution A was obtained by mixing 7.08 g of diaminodiphenyl ether (DDE, molecular weight: 200.2) and 10.0 g of pyromellitic dianhydride (PMDA) at 70 ° C. and reacting them. After cooling to room temperature (23 ° C.), the polyamic acid solution A was applied onto the mirror surface of an 8-inch silicon wafer with a spin coater and dried at 90 ° C.
  • DDE diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the support A with a polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermally peelable sheet) having a thickness of 30 ⁇ m, thereby obtaining a support A with a thermally peelable sheet.
  • Example 2 In an atmosphere under a nitrogen stream, 16.29 g of polyether diamine (manufactured by Heinzmann, D-400, molecular weight: 422.6), 14,4′- in 138.6 g of N, N-dimethylacetamide (DMAc). Diaminodiphenyl ether (DDE, molecular weight: 200.2) 8.37 g and pyromellitic dianhydride (PMDA) 10.0 g were mixed and reacted at 70 ° C. to obtain a polyamic acid solution B. After cooling to room temperature (23 ° C.), the polyamic acid solution B was applied onto the mirror surface of an 8-inch silicon wafer with a spin coater and dried at 120 ° C.
  • DDE Diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the support B with a polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a 10 ⁇ m-thick polyimide film (thermally peelable sheet) to obtain a support B with a thermally peelable sheet.
  • Example 3 In an atmosphere under a nitrogen stream, polyether diamine (Heinzmann, D-2000, molecular weight: 1990.8) 18.07 g, 4,4 ′ in 141.7 g of N-methyl-2-pyrrolidone (NMP)
  • NMP N-methyl-2-pyrrolidone
  • a polyamic acid solution C was obtained by mixing 7.36 g of diaminodiphenyl ether (DDE, molecular weight: 200.2) and 10.0 g of pyromellitic dianhydride (PMDA) at 70 ° C. and reacting them. After cooling to room temperature (23 ° C.), the polyamic acid solution C was applied onto the mirror surface of an 8-inch silicon wafer with a spin coater and dried at 100 ° C.
  • DDE diaminodiphenyl ether
  • PMDA pyromellitic dianhydride
  • the support C with a polyamic acid was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a polyimide film (thermally peelable sheet) having a thickness of 15 ⁇ m, thereby obtaining a support C with a thermally peelable sheet.
  • the support D with a polyamic acid was heat-treated at 400 ° C. for 2 hours in a nitrogen atmosphere to form a 10 ⁇ m-thick polyimide film (thermally peelable sheet) to obtain a support D with a thermothermally peelable sheet.
  • a silicon wafer chip of 5 mm square (thickness 500 ⁇ m) is placed on a heat-peelable sheet formed on a support (silicon wafer) and laminated under conditions of 60 ° C. and 10 mm / s, and then a shear tester (Dage The shear adhesive strength between the heat-peelable sheet and the silicon wafer chip was measured using a Dage 4000).
  • the conditions of the shear test were as follows. The results are shown in Table 7. In addition, in order to control oxygen concentration, the shear tester was put in the glove box and evaluated.
  • the support body was peeled from the support body with a heat peelable sheet which concerns on an Example and a comparative example.
  • the heat-peelable sheets of Examples and Comparative Examples were processed to have a diameter of 6 inches, and were laminated on a wafer having a diameter of 8 inches at 60 ° C. and 10 mm / s. Then, it was left for 1 minute and peeled off.
  • a particle counter (SFS6200, manufactured by KLA), the number of particles of 0.2 ⁇ m or more on the surface of an 8-inch diameter wafer was measured.

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Abstract

Pour obtenir une feuille thermiquement détachable qui se détache à des températures plus élevées, la feuille thermiquement détachable selon l'invention a une résistance de liaison au cisaillement par rapport à une plaquette de silicium de 0,25 kg/5 × 5 mm ou plus, à une température de 200°C, après que ladite température a été maintenue pendant une minute, et une résistance de liaison au cisaillement par rapport à une plaquette de silicium de 0,25 kg/moins de 5 × 5 mm, à une température quelconque dans une plage supérieure à 200°C mais inférieure ou égale à 500°C, après que ladite température a été maintenue pendant trois minutes.
PCT/JP2012/074143 2011-10-20 2012-09-21 Feuille thermiquement détachable WO2013058054A1 (fr)

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CN106133077A (zh) * 2014-03-31 2016-11-16 日产化学工业株式会社 剥离层形成用组合物

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JP2009074067A (ja) * 2007-08-29 2009-04-09 Hitachi Chem Co Ltd 半導体素子固定用接着フィルム及び接着シート
WO2010051212A2 (fr) * 2008-10-31 2010-05-06 Brewer Science Inc. Compositions d'oléfines cycliques permettant une liaison de plaquettes temporaire

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JPH08311415A (ja) * 1995-05-23 1996-11-26 Nitto Denko Corp 転写用シート
JP2009074067A (ja) * 2007-08-29 2009-04-09 Hitachi Chem Co Ltd 半導体素子固定用接着フィルム及び接着シート
WO2010051212A2 (fr) * 2008-10-31 2010-05-06 Brewer Science Inc. Compositions d'oléfines cycliques permettant une liaison de plaquettes temporaire

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Publication number Priority date Publication date Assignee Title
CN106133062A (zh) * 2014-03-31 2016-11-16 日产化学工业株式会社 剥离层形成用组合物
CN106133077A (zh) * 2014-03-31 2016-11-16 日产化学工业株式会社 剥离层形成用组合物
CN108690495A (zh) * 2014-03-31 2018-10-23 日产化学工业株式会社 剥离层形成用组合物
CN108690494A (zh) * 2014-03-31 2018-10-23 日产化学工业株式会社 剥离层形成用组合物
CN108690495B (zh) * 2014-03-31 2021-05-25 日产化学工业株式会社 剥离层形成用组合物

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