CN108300370B - Temperature-sensitive adhesive sheet and method for producing wafer using same - Google Patents

Temperature-sensitive adhesive sheet and method for producing wafer using same Download PDF

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Publication number
CN108300370B
CN108300370B CN201710804561.0A CN201710804561A CN108300370B CN 108300370 B CN108300370 B CN 108300370B CN 201710804561 A CN201710804561 A CN 201710804561A CN 108300370 B CN108300370 B CN 108300370B
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temperature
adhesive layer
side chain
crystalline polymer
chain crystalline
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CN108300370A (en
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山下幸志
山田博行
河原伸一郎
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Nitta Corp
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Nitta Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C09J2301/1242—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape the opposite adhesive layers being different
    • 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
    • C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/30—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
    • C09J2301/314—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 the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a temperature-sensitive adhesive sheet, which comprises: the film-shaped base material (2), a 1 st adhesive layer (3) which is laminated on one surface of the base material (2) and is adhered to the base (100), and a 2 nd adhesive layer (4) which is laminated on the other surface of the base material (2) and is adhered to the processed object. The 1 st adhesive layer (3) contains a 1 st side chain crystalline polymer and a foaming agent, and exhibits fluidity at a temperature not lower than the melting point of the 1 st side chain crystalline polymer, and the melting point of the 1 st side chain crystalline polymer is lower than the foaming temperature of the foaming agent. The 2 nd adhesive layer (4) contains a 2 nd side chain crystalline polymer and exhibits fluidity at a temperature equal to or higher than the melting point of the 2 nd side chain crystalline polymer.

Description

Temperature-sensitive adhesive sheet and method for producing wafer using same
Technical Field
The present invention relates to a temperature-sensitive adhesive sheet used for temporarily holding a wafer when manufacturing a patterned wafer, for example, and a method for manufacturing a wafer using the same.
Background
The wafer is a material for manufacturing a semiconductor device, and is a disk-shaped plate obtained by thinly slicing a columnar ingot made of a material such as silicon, sapphire, or silicon carbide. In the production of a wafer, the wafer is bonded to a base (support substrate) using an adhesive sheet, and then the wafer is adjusted to a predetermined thickness by grinding and polishing, and then the wafer is peeled from the base together with the adhesive sheet, and then the adhesive sheet is peeled from the wafer.
In order to grind and polish a wafer, the wafer needs to be firmly held by a susceptor. If the holding of the wafer is insufficient, the wafer may shift during grinding or polishing. Further, since the thinned wafer is fragile, if the wafer is not firmly held by the susceptor, the wafer may be broken by the influence of vibration during grinding or polishing.
Further, when the adhesive sheet is peeled from the wafer, it is required that no adhesive residue is adhered to the wafer surface.
Japanese patent No. 5623125 discloses a pressure-sensitive adhesive sheet used in precision grinding and polishing processes. The adhesive sheet comprises a side chain crystalline polymer and a foaming agent, wherein the side chain crystalline polymer crystallizes at a temperature lower than the melting point and exhibits fluidity at a temperature not lower than the melting point, and an adherend bonded at a temperature not lower than the foaming temperature of the foaming agent is fixed at a temperature lower than the melting point of the side chain crystalline polymer and removed at a temperature not lower than the foaming temperature of the foaming agent.
Further, japanese patent application laid-open No. 2015-183162 describes a double-sided adhesive tape for temporary fixation. The double-sided pressure-sensitive adhesive tape for temporary fixation has a 1 st pressure-sensitive adhesive layer for bonding to a base on one surface of a substrate, and a 2 nd pressure-sensitive adhesive layer for bonding to a wafer on the other surface. The 1 st adhesive layer contains a pressure-sensitive adhesive, a side chain crystalline polymer, and a foaming agent, and the adhesive force is reduced at a temperature equal to or higher than the melting point of the side chain crystalline polymer. The 2 nd adhesive layer contains a pressure-sensitive adhesive and a side chain crystalline polymer, and the adhesive force is reduced at a temperature of the melting point of the side chain crystalline polymer or higher.
In the double-sided pressure-sensitive adhesive tape described in jp 2015-183162 a, the 1 st pressure-sensitive adhesive layer is heated to a temperature not lower than the melting point of the side chain crystalline polymer and not lower than the temperature at which the foaming agent expands and foams when peeled from the base, thereby reducing the adhesive force to the base. Then, after the wafer is peeled from the susceptor together with the adhesive tape, the 2 nd adhesive layer is heated to a temperature of not less than the melting point of the side chain crystalline polymer to lower the adhesive force of the 2 nd adhesive layer to the wafer, and the adhesive tape is peeled from the wafer.
However, it is desirable to provide an adhesive sheet that can firmly hold a wafer on a base during grinding and polishing, and that can reliably achieve both processing holding properties without displacement or breakage and residue-free properties without adhesive residue adhering to the surface of the wafer from which the adhesive tape has been peeled after grinding and polishing.
In particular, in the case of a wafer having a pattern with irregularities on the surface, such as an epitaxial wafer, it is important to peel the wafer so that no residue of the adhesive remains, since the fluidized adhesive penetrates into the pattern.
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a temperature-sensitive adhesive sheet that can be firmly held without displacement or breakage even on a workpiece such as a wafer having a pattern on the surface thereof, and that has reduced residue remaining during peeling, and a wafer manufacturing method using the same.
Means for solving the problems
The present inventors have made extensive studies to solve the above problems, and as a result, the present invention has been completed. That is, the temperature-sensitive adhesive sheet of the present invention includes a film-shaped substrate, a 1 st adhesive layer laminated on one surface of the substrate and adhered to a base, and a 2 nd adhesive layer laminated on the other surface of the substrate and adhered to a workpiece. The 1 st adhesive layer contains a 1 st side chain crystalline polymer and a foaming agent, and exhibits fluidity at a temperature above the melting point of the 1 st side chain crystalline polymer, the melting point of the 1 st side chain crystalline polymer being lower than the foaming temperature of the foaming agent. The 2 nd adhesive layer contains a 2 nd side chain crystalline polymer, and exhibits fluidity at a temperature above the melting point of the 2 nd side chain crystalline polymer.
The method for manufacturing a patterned wafer of the present invention comprises:
a step of bonding a 1 st adhesive layer of the temperature-sensitive adhesive sheet to a susceptor at a temperature of not less than the melting point of the 1 st side chain crystalline polymer and less than the foaming initiation temperature, and bonding a 2 nd adhesive layer to the uneven pattern surface of the patterned wafer at a temperature of not less than the melting point of the 2 nd side chain crystalline polymer, using the above temperature-sensitive adhesive sheet;
grinding and/or polishing a surface of the patterned wafer opposite to the surface attached to the susceptor;
a step of peeling the temperature-sensitive adhesive sheet and the patterned wafer from the base with the temperature of the temperature-sensitive adhesive sheet being equal to or higher than a foaming start temperature of the foaming agent; and
and peeling the adhesive sheet from the wafer by setting the temperature of the adhesive sheet to be not lower than the melting point of the 2 nd side chain crystalline polymer.
Effects of the invention
The temperature-sensitive adhesive sheet of the present invention has the following effects: even a workpiece such as a wafer having a pattern with irregularities on the surface thereof can be firmly held without displacement or breakage, and residue remaining on the surface of the workpiece during peeling can be reduced. Therefore, the temperature-sensitive adhesive sheet of the present invention is suitable for producing a wafer having a pattern with irregularities.
Drawings
Fig. 1 is a schematic explanatory view showing one embodiment of a temperature-sensitive adhesive sheet according to the present invention.
Fig. 2(a) to (e) are process diagrams showing a method for manufacturing a patterned wafer according to an embodiment of the present invention.
Detailed Description
< temperature-sensitive adhesive sheet >
Hereinafter, a temperature-sensitive adhesive sheet (hereinafter, may be simply referred to as an adhesive sheet) according to an embodiment of the present invention will be described in detail with reference to fig. 1.
As shown in fig. 1, the tape 1 of the present embodiment includes a base material 2, a 1 st adhesive layer 3 laminated on one surface of the base material 2, and a 2 nd adhesive layer 4 laminated on the other surface of the base material 2. Spacers 5a and 5b having releasability are disposed on the surfaces of the 1 st adhesive layer 3 and the 2 nd adhesive layer 4, respectively.
(substrate 2)
The substrate 2 of the present embodiment is film-shaped. The film shape is not limited to a film, and includes a film and a sheet as long as the effects of the present embodiment are not impaired.
Examples of the constituent material of the substrate 2 include: synthetic resins such as polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyimide, polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene polypropylene copolymer, and polyvinyl chloride.
The substrate 2 of the present embodiment may be a single layer or a multilayer body, and the thickness thereof is preferably 5 to 250 μm, more preferably 12 to 188 μm, and still more preferably 25 to 100 μm. The first surface 21 and the second surface 22 of the substrate 2 may be subjected to surface treatment such as corona discharge treatment, plasma treatment, abrasive blasting treatment, chemical etching treatment, or undercoating treatment in order to improve adhesion to the 1 st adhesive layer 3 and the 2 nd adhesive layer 4.
(adhesive layer 1 3)
The 1 st adhesive layer 3 laminated on one surface of the base material 2 is a layer to be stuck to a base, and contains the 1 st side chain crystalline polymer and a foaming agent.
The 1 st side chain crystalline polymer is a polymer having a melting point. The melting point is a temperature at which a specific portion of a polymer initially integrated into an ordered arrangement becomes disordered by a certain equilibrium process, and is a value measured by a Differential Scanning Calorimeter (DSC) under a measurement condition of 10 ℃/min. The melting point of the 1 st side chain crystalline polymer is lower than the foaming temperature of the foaming agent, and is preferably 30 to 70 ℃, and more preferably 40 to 60 ℃.
The 1 st side chain crystalline polymer crystallizes at a temperature lower than the above melting point, and changes phase at a temperature higher than the melting point to exhibit fluidity. That is, the 1 st side chain crystalline polymer has temperature sensitivity to reversibly cause a crystalline state and a fluid state in response to a temperature change.
The 1 st adhesive layer 3 in the present embodiment contains the 1 st side chain crystalline polymer as a main component, and contains a foaming agent in a proportion of 10 to 110 parts by mass, preferably 20 to 80 parts by mass, and more preferably 40 to 60 parts by mass with respect to 100 parts by mass of the 1 st side chain crystalline polymer. Thus, the adhesive sheet exhibits adhesive strength at a temperature equal to or higher than the melting point and lower than the foaming temperature of the foaming agent due to the 1 st side chain crystalline polymer exhibiting fluidity, and can be attached to a base.
The adhesive sheet penetrates into fine irregularities and voids present on the surface of the base without any gap. When the psa sheet in this state is cooled to a temperature lower than the melting point, the side chain crystalline polymer crystallizes to exhibit an anchoring effect, and thus a high fixing force can be obtained. Further, since the pressure-sensitive adhesive sheet containing the crystallized side chain crystalline polymer exhibits a high elastic modulus, the fixed state of the base can be stabilized, and a workpiece to be attached to the 2 nd adhesive layer 4, which will be described later, can be processed with high accuracy.
Further, when the adhesive sheet is heated to a temperature equal to or higher than the foaming temperature of the foaming agent, the 1 st side chain crystalline polymer exhibits fluidity, so that the cohesive force of the adhesive sheet is reduced, and the foaming agent also expands or foams, so that the fixing force can be sufficiently reduced, and the adhesive sheet can be easily removed from the base. Therefore, the pressure-sensitive adhesive sheet of the present embodiment can be used as a pressure-sensitive adhesive sheet that is adhered to a base at a temperature equal to or higher than the melting point and lower than the foaming temperature of the foaming agent, fixed at a temperature lower than the melting point, and removed at a temperature equal to or higher than the foaming temperature of the foaming agent.
The melting point can be adjusted by changing the composition of the 1 st side chain crystalline polymer and the like. Examples of the composition of the 1 st side chain crystalline polymer include: and a polymer obtained by polymerizing 30 to 70 parts by mass of a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, preferably 18 or more carbon atoms, 30 to 70 parts by mass of a (meth) acrylate having an alkyl group having 1 to 6 carbon atoms, and 1 to 10 parts by mass of a polar monomer. (meth) acrylate means acrylate or methacrylate.
Examples of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms include: (meth) acrylates having a linear alkyl group having 16 to 22 carbon atoms such as cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, and docosyl (meth) acrylate. Examples of the (meth) acrylate having an alkyl group having 1 to 6 carbon atoms include: methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and the like. Examples of the polar monomer include: ethylenically unsaturated monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; and ethylenically unsaturated monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxyhexyl (meth) acrylate. These may be used in 1 kind or in combination of 2 or more kinds.
The polymerization method of the 1 st side chain crystalline polymer is not particularly limited, and for example, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, and the like can be employed. For example, in the case of a solution polymerization method, the monomers exemplified above are mixed with a solvent and stirred at about 40 to 90 ℃ for about 2 to 10 hours to polymerize the monomers.
The weight average molecular weight of the crystalline polymer having the 1 st side chain is preferably 200,000 to 1,000,000, more preferably 300,000 to 900,000, and still more preferably 400,000 to 800,000. This can prevent the adhesive tape 1 from being peeled off from the base and generating adhesive residue. In addition, when the 1 st side chain crystalline polymer exhibits fluidity at a temperature equal to or higher than the melting point, the adhesive force of the 1 st adhesive layer 3 can be sufficiently reduced. The weight average molecular weight is a value in terms of polystyrene measured by Gel Permeation Chromatography (GPC) of the 1 st side chain crystalline polymer.
On the other hand, the blowing agent is not particularly limited, and any of a general chemical blowing agent and a physical blowing agent can be used. The chemical blowing agent includes thermally decomposable and reactive organic blowing agents and inorganic blowing agents.
Examples of the organic blowing agent of the pyrolysis type include: various azo compounds (such as azodicarbonamide), nitroso compounds (such as N, N '-dinitrosopentamethylenetetramine), hydrazine derivatives [ such as 4, 4' -oxybis (benzenesulfonylhydrazide) ], semicarbazides (such as biurea), azide compounds, tetrazole compounds, and the like, and examples of the reactive organic blowing agents include isocyanate compounds.
Examples of the pyrolysis-type inorganic foaming agent include: bicarbonate, carbonate (sodium bicarbonate, etc.), nitrite, hydride, etc., and examples of the reactive inorganic foaming agent include: combinations of sodium bicarbonate and acid, combinations of hydrogen peroxide and yeast, combinations of zinc powder and acid, and the like.
Examples of the physical blowing agent include: aliphatic hydrocarbons such as butane, pentane and hexane, chlorinated hydrocarbons such as dichloroethane and dichloromethane, chlorinated hydrocarbons such as chlorofluorocarbons, and inorganic physical foaming agents such as air, carbonic acid gas and nitrogen.
As another foaming agent, a so-called microsphere foaming agent which is a heat-expandable fine particle after microencapsulation can be used. The microsphere foaming agent is a foaming agent in which a thermally expandable substance containing a solid, liquid or gas is sealed inside a polymer shell made of a thermoplastic or thermosetting resin. In other words, the microsphere foaming agent comprises: a hollow polymer shell having an average particle diameter of the order of micrometers, and a thermally expandable material enclosed inside the polymer shell. The microsphere foaming agent expands to more than 40 times by heating volume to obtain the foam in an independent bubble form. Therefore, the microsphere foaming agent has a characteristic that the expansion ratio becomes considerably larger than that of a general foaming agent. As such a microsphere foaming agent, commercially available foaming agents can be used, and examples thereof include "461 DU 20" and "551 DU 40" manufactured by EXPANCEL corporation.
The temperature at which the blowing agent expands or even foams is a temperature higher than the melting point of the 1 st side chain crystalline polymer. The temperature at which the blowing agent expands or foams is preferably 180 ℃ or lower, and for example, it is preferable that the expansion or foaming is started at 90 ℃ and the foaming is substantially completed at 120 ℃.
The average particle diameter of the blowing agent is preferably 5 to 50 μm, more preferably 5 to 20 μm. The average particle diameter is a value measured by a particle size distribution measuring apparatus.
In order to laminate the 1 st adhesive layer 3 containing such a foaming agent and containing the 1 st side chain crystalline polymer on one surface of the substrate 2, for example, a coating solution prepared by adding the 1 st side chain crystalline polymer and the foaming agent to a solvent may be applied to one surface of the substrate 2 by a coater or the like and dried. Examples of the coating machine include: knife coaters, roll coaters, calender coaters, comma coaters, gravure coaters, bar coaters, and the like.
The thickness of the first adhesive layer 3 is preferably 10 to 50 μm, and more preferably 15 to 45 μm.
The adhesive layer 1 of the adhesive layer 3 may contain various additives such as a crosslinking agent, a tackifier, a plasticizer, an antioxidant, and an ultraviolet absorber, and among the additives listed above, a crosslinking agent is preferably added. Examples of the crosslinking agent include isocyanate compounds and the like. The crosslinking agent is preferably added in a proportion of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.3 to 3 parts by mass, in terms of solid content, relative to 100 parts by mass of the 1 st side chain crystalline polymer.
Preferable compounding of the 1 st side chain crystalline polymer, the foaming agent and the crosslinking agent in the 1 st adhesive layer 3 include: the mass ratio of the 1 st side chain crystalline polymer, the foaming agent and the crosslinking agent is 100: 40-60: 0.3-3.
(second adhesive layer)
The 2 nd adhesive layer 4 laminated on the other surface of the substrate 2 is a temperature sensitive adhesive layer in which an adherend is a processed object, contains the 2 nd side chain crystalline polymer, and has a reduced adhesive force at a temperature equal to or higher than the melting point of the 2 nd side chain crystalline polymer.
The melting point of the 2 nd side chain crystalline polymer is 30 to 70 ℃, preferably 40 to 60 ℃ as in the 1 st side chain crystalline polymer. That is, in the present embodiment, the melting point of the 1 st side chain crystalline polymer and the melting point of the 2 nd side chain crystalline polymer are both 30 to 70 ℃, preferably 40 to 60 ℃. Thus, for example, when the object is polished, the 1 st and 2 nd side chain crystalline polymers can both maintain a crystalline state, and therefore, the adhesive strength of the 1 st adhesive layer 3 and the 2 nd adhesive layer 4 can be secured, and as a result, occurrence of processing defects such as polishing defects can be suppressed.
The weight average molecular weight of the 2 nd side chain crystalline polymer is preferably 200,000 to 1,000,000, more preferably 300,000 to 900,000, and further preferably 400,000 to 800,000.
The melting point, composition, weight average molecular weight, blending amount, etc. of the 2 nd side chain crystalline polymer may be the same as or different from those of the 1 st side chain crystalline polymer described above.
That is, the 2 nd side chain crystalline polymer is obtained by polymerizing 30 to 70 parts by mass of an acrylate or methacrylate having a linear alkyl group having 16 or more carbon atoms, 30 to 70 parts by mass of an acrylate or methacrylate having an alkyl group having 1 to 6 carbon atoms, and 1 to 10 parts by mass of a polar monomer, as in the 1 st side chain crystalline polymer.
In this case, the acrylic ester or methacrylic ester having an alkyl group having 1 to 6 carbon atoms preferably contains 2 to 70 mass% of an acrylic ester or methacrylic ester having an alkyl group having 1 or 2 carbon atoms with respect to the total amount of the ester. This improves the adhesive strength of the 2 nd adhesive layer, makes the wafer less likely to peel off, and improves the hardness, so that the 2 nd adhesive layer can be prevented from being displaced or deformed, thereby improving the workability of the wafer. The other points are the same as those of the above-mentioned side chain crystalline polymer 1.
The 1 st side chain crystalline polymer may have a composition containing 2 to 70 mass% of an acrylate or methacrylate having an alkyl group having 1 or 2 carbon atoms, based on the total amount, as in the 2 nd side chain crystalline polymer.
The thickness of the 2 nd adhesive layer 4 is preferably 5 to 50 μm, more preferably 5 to 20 μm, as the thickness of the 1 st adhesive layer 3. In this case, the thickness of the 2 nd adhesive layer 4 containing the 2 nd side chain crystalline polymer may be the same as that of the 1 st adhesive layer 3 or smaller than that of the 1 st adhesive layer 3, but is preferably larger than that of the 1 st adhesive layer 3 in order to make the adhesive follow the irregularities on the surface of the object such as a wafer to firmly fix the object.
In the 2 nd adhesive layer 4, a crosslinking agent is preferably added as in the 1 st adhesive layer 3. The crosslinking agent is preferably added in a proportion of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.3 to 3 parts by mass, in terms of solid content, relative to 100 parts by mass of the 2 nd side chain crystalline polymer.
The other structure of the 2 nd adhesive layer 4 is the same as that of the 1 st adhesive layer 3 described above, and therefore, the description thereof is omitted.
(1 st adhesive layer 3 and 2 nd adhesive layer 4)
The 1 st adhesive layer 3 and the 2 nd adhesive layer 4 in the present embodiment have storage moduli lower than the melting points (usually 23 ℃) of the 1 st side chain crystalline polymer and the 2 nd side chain crystalline polymerAre all 1 × 106～1×108Pa. This stabilizes the fixed state of the workpiece to the base, and allows the workpiece to be processed with high accuracy.
At this time, the storage modulus of the 2 nd adhesive layer 4 may be the same as that of the 1 st adhesive layer 3, or less than that of the 1 st adhesive layer 3, but preferably greater than that of the 1 st adhesive layer 3. This stabilizes the fixed state of the workpiece such as a wafer, and can process the workpiece with high accuracy.
The storage modulus G' at a temperature lower than the melting point of the side chain crystalline polymer can be arbitrarily adjusted by, for example, changing the composition of the side chain crystalline polymer or the like. The storage modulus G' at each temperature is a value measured by the measurement method described in the examples described later.
On the other hand, the peel strength of the 1 st adhesive layer 3 to polyethylene terephthalate in a state lower than the melting point after passing through a temperature higher than the melting point and lower than the foaming agent temperature is preferably 0.5 to 5.0N/25 mm. Thereby, the fixing force to the base can be obtained. The peel strength of the 1 st adhesive layer 3 in a state lower than the above melting point is a value obtained by measuring the 180 ° peel strength with respect to the polyethylene terephthalate film at an atmospheric temperature of 23 ℃ in accordance with JIS Z0237.
The 2 nd adhesive layer 4 preferably has a peel strength of 0.1 to 3.0N/25mm from polyethylene terephthalate in a state of passing through a temperature of not less than the melting point and less than the temperature of the foaming agent and being lower than the melting point. This makes it possible to obtain a fixing force to a workpiece such as a wafer. The peel strength of the adhesive layer 4 of the 2 nd part is a value obtained by measuring the 180 ° peel strength with respect to the polyethylene terephthalate film at an atmospheric temperature of 23 ℃ in accordance with JIS Z0237.
In the present embodiment, the 180 ° peel strength of the 2 nd adhesive layer 4 is preferably smaller than the 180 ° peel strength of the 1 st adhesive layer 3. This means that the fixing force to the workpiece is smaller than the fixing force to the base. This can reduce the adhesion of the adhesive layer to the residue of the workpiece when the workpiece is peeled. Specifically, the 180 DEG peel strength of the 2 nd adhesive layer 4 is preferably lower than the 180 DEG peel strength of the 1 st adhesive layer 3 by about 0.1 to 3.0N/25 mm.
The adjustment of the peeling strength of each 180 ° of the 1 st adhesive layer 3 and the 2 nd adhesive layer 4 can be performed by changing the composition of each side chain crystalline polymer.
(spacer)
The spacers 5a and 5b of the present embodiment are spacers for protecting the surfaces of the 1 st adhesive layer 3 and the 2 nd adhesive layer 4.
Examples of the spacers 5a and 5b include spacers in which a release agent such as silicone or fluorine is applied to the surface of a film made of polyethylene or polyethylene terephthalate. The thickness of each of the spacers 5a and 5b is preferably 10 to 110 μm.
The spacers 5a and 5b may be identical or different in composition, thickness, and the like. In the present embodiment, the spacer 5a is formed by applying a silicone release agent to the surface of a polyethylene film, and the spacer 5b is formed by applying a silicone release agent to the surface of a polyethylene terephthalate film.
In the present embodiment, the foaming agent may be contained in the 1 st side chain crystalline polymer of the 1 st adhesive layer 3, or the foaming agent may be contained in the 2 nd side chain crystalline polymer of the 2 nd adhesive layer 4. In this case, a foaming agent having a higher foaming temperature than that of the foaming agent of the 1 st adhesive layer 3 is used as the foaming agent of the 2 nd adhesive layer 4, and the content is preferably reduced if the foaming agent is the same.
< method for producing patterned wafer >
Next, a method for manufacturing a wafer when the workpiece is a patterned wafer will be described with reference to fig. 2. Examples of the patterned wafer include an epitaxial wafer, a semiconductor device having a 3-dimensional stacked structure, and an MEMS wafer, and the patterned wafer has an uneven pattern on the surface. Examples of the material of the wafer include silicon, sapphire glass, silicon carbide (SiC), gallium nitride (GaN), and the like. Sapphire glass, silicon carbide and gallium nitride, in particular, are difficult materials to abrade.
The method for producing a wafer according to the present embodiment is a method for grinding and/or polishing a wafer using the adhesive sheet 1 described above, and includes the following steps (i) to (iv).
(i) As shown in fig. 2(a), the spacer 5a shown in fig. 1 is peeled off from the adhesive tape 1, and placed on the base 100, and the adhesive tape 1 is bonded to the base 100 while being pressed from above by the roller 6 (pressing means) at a temperature not lower than the melting point of the 1 st side chain crystalline polymer and lower than the foaming start temperature. The base 100 may be, for example, a ceramic base.
(ii) As shown in fig. 2(b), the patterned wafer 200 is bonded to the surface of the 2 nd adhesive layer 4 at a temperature not lower than the melting point of the 2 nd side chain crystalline polymer.
The order of the steps (i) and (ii) may be reversed.
(iii) As shown in fig. 2(c), the surface of the patterned wafer 200 (i.e., the surface opposite to the surface attached to the susceptor 100) is ground and/or polished. In fig. 2(c), a grinding chip is denoted by reference numeral 201.
(iv) As shown in fig. 2(d), the adhesive sheet 1 and the patterned wafer 200 are peeled from the base 100 while the temperature of the adhesive sheet 1 is set to be not lower than the foaming initiation temperature of the foaming agent contained in the 1 st adhesive layer 3. In FIG. 2(d), the 1 st adhesive layer after peeling is denoted by the reference numeral 3'.
(v) As shown in fig. 2(e), the patterned wafer 200 is placed on a heater 300, and heated so that the temperature of the adhesive sheet 1 becomes equal to or higher than the melting point of the 2 nd side chain crystalline polymer of the 2 nd adhesive layer 4, and the adhesive sheet 1 is peeled off from the wafer 200.
Since the method for manufacturing a wafer according to the present embodiment uses the adhesive sheet 1, the patterned wafer 200 can be stably and firmly fixed to the susceptor 100 in the step (i). Therefore, in the step (ii), the patterned wafer 200 can be precisely polished on the order of microns without displacement or breakage. In the case of grinding, the workpiece can be ground into a desired shape.
In the steps (IV) and (IV), since the fixing force can be sufficiently reduced, the patterned wafer 200 can be easily removed, and the adhesion of the residue of the adhesive sheet 1 to the surface of the wafer 200 can be reduced.
Examples
The present invention will be described in detail below with reference to synthesis examples and examples, but the present invention is not limited to the synthesis examples and examples below. In the following description, "parts" means parts by mass.
(Synthesis example 1: side chain crystalline Polymer 1)
These monomers were polymerized by adding 45 parts of behenyl acrylate, 50 parts of butyl acrylate, 5 parts of hydroxyethyl acrylate, and 0.5 part of Perbutyl ND (manufactured by japan oil corporation) as a polymerization initiator to 230 parts of a mixed solvent of ethyl acetate and n-heptane in a mass ratio of 7: 3, and stirring at 60 ℃ for 5 hours. The weight average molecular weight of the obtained copolymer was 550,000, and the melting point was 44 ℃.
Synthesis example 2 side chain crystalline Polymer No. 2
These monomers were polymerized by adding 45 parts of behenyl acrylate, 50 parts of butyl acrylate, 5 parts of acrylic acid, and 0.5 part of Perbutyl ND (manufactured by japan oil corporation) as a polymerization initiator to 230 parts of a mixed solvent of ethyl acetate and n-heptane in a mass ratio of 7: 3, and stirring at 60 ℃ for 5 hours. The weight average molecular weight of the obtained copolymer was 580,000, and the melting point was 45 ℃.
Synthesis example 3 side chain crystalline Polymer of 2 nd
These monomers were polymerized by adding 45 parts of behenyl acrylate, 15 parts of methacrylate, 35 parts of butyl acrylate, 5 parts of acrylic acid, and 0.5 part of Perbutyl ND (manufactured by japan oil corporation) as a polymerization initiator to 230 parts of a mixed solvent of ethyl acetate and n-heptane in a mass ratio of 7: 3, and stirring at 60 ℃ for 5 hours. The weight average molecular weight of the obtained copolymer was 600,000, and the melting point was 45 ℃.
(comparative Synthesis example 3: pressure sensitive adhesive)
These monomers were polymerized by adding 52 parts of 2-ethylhexyl acrylate, 40 parts of methyl acrylate, 8 parts of 2-hydroxyethyl acrylate, and 0.3 part of Perbutyl ND (manufactured by Nichigan Co.) as a polymerization initiator to 200 parts of a mixed solvent of ethyl acetate and toluene at a mass ratio of 7: 3, and stirring at 60 ℃ for 5 hours. The weight average molecular weight of the resulting copolymer was 450,000.
The copolymers of Synthesis examples 1 to 2 and comparative Synthesis example 3 are shown in Table 1. The melting point was measured by DSC under the measurement condition of 10 ℃ per minute. The weight average molecular weight is obtained by measuring a copolymer by GPC and converting the obtained measurement value into polystyrene.
Very good [ Table 1]
Figure BDA0001401539580000121
1) C22A: behenyl acrylate, C4A: butyl acrylate, HEA: 2-hydroxyethyl acrylate,
AA: acrylic acid, EHA: 2-ethylhexyl acrylate, C1A: acrylic acid methyl ester
[ example 1]
(preparation of temperature-sensitive adhesive sheet)
The blowing agents and crosslinking agents used are as follows.
■ foaming agent: a microsphere foaming agent "461 DU 20" manufactured by EXPANCEL corporation and having an average particle diameter of 6 to 9 μm and a foaming initiation temperature of 90 ℃ or higher "
■ crosslinking agent: isocyanate Compound "Coronate L-45E" manufactured by Nippon polyurethane industries Ltd "
(preparation of adhesive layer 1)
The side chain crystalline polymer/blowing agent/crosslinking agent obtained in synthesis example 1 was mixed in ethyl acetate at a ratio (mass ratio) of 100/50/1 so as to adjust the solid content to 30% to obtain a coating solution, and the coating solution was applied to a film-shaped substrate made of polyethylene terephthalate and having a thickness of 100 μm and dried to form a 1 st adhesive layer having a thickness of 20 μm.
(preparation of adhesive layer 2)
The side chain crystalline polymer/crosslinking agent obtained in synthesis example 2 was mixed in ethyl acetate at a ratio of 100/3 (mass ratio) and adjusted so that the solid content became 30%, to obtain a coating solution. Next, a coating solution was applied to the opposite surface of the substrate having the 1 st adhesive layer formed on one surface thereof, and the coating solution was dried to form a 2 nd adhesive layer having a thickness of 40 μm, thereby obtaining an adhesive sheet.
[ example 2]
(preparation of temperature-sensitive adhesive sheet)
The blowing agents and crosslinking agents used are as follows.
■ foaming agent: a microsphere foaming agent "461 DU 20" manufactured by EXPANCEL corporation and having an average particle diameter of 6 to 9 μm and a foaming initiation temperature of 90 ℃ or higher "
■ crosslinking agent: isocyanate Compound "Coronate L-45E" manufactured by Nippon polyurethane industries Ltd "
(preparation of adhesive layer 1)
The side chain crystalline polymer/blowing agent/crosslinking agent obtained in synthesis example 1 was mixed in ethyl acetate at a ratio (mass ratio) of 100/50/1 so as to adjust the solid content to 30% to obtain a coating solution, and the coating solution was applied to a film-shaped substrate made of polyethylene terephthalate and having a thickness of 100 μm and dried to form a 1 st adhesive layer having a thickness of 20 μm.
(preparation of adhesive layer 2)
The side chain crystalline polymer/crosslinking agent obtained in synthesis example 3 was mixed in ethyl acetate at a ratio of 100/3 (mass ratio) and adjusted so that the solid content became 30%, to obtain a coating solution. Next, a coating solution was applied to the opposite surface of the substrate on one side of which the 1 st adhesive layer was formed, and the coating solution was dried to form a 2 nd adhesive layer having a thickness of 40 μm, thereby obtaining an adhesive sheet.
Comparative example 1
(preparation of pressure-sensitive adhesive sheet)
(adjustment of adhesive layer 1)
The pressure-sensitive adhesive/foaming agent/crosslinking agent obtained in comparative synthesis example 3 was mixed with ethyl acetate at a ratio (mass ratio) of 100/30/0.5 to adjust the solid content to 30% to obtain a coating solution, and the coating solution was applied to a release film made of polyethylene terephthalate and having a thickness of 100 μm and dried to form an adhesive layer having a thickness of 40 μm.
(adjustment of adhesive layer 2)
The pressure-sensitive adhesive/crosslinking agent obtained in comparative synthesis example 3 was mixed in ethyl acetate at a ratio of 100/1 (mass ratio) and adjusted so that the solid content became 30%, to obtain a coating solution. Next, a coating solution was applied to the opposite surface of the substrate on one side of which the 1 st adhesive layer was formed, and the coating solution was dried to form a 2 nd adhesive layer having a thickness of 40 μm, thereby obtaining an adhesive sheet.
[ example 3]
(production of wafer)
The patterned wafer is fabricated as follows.
(i) The adhesive sheet 1 obtained in example 1 was peeled off from the spacer 5a shown in fig. 1, placed on a ceramic base 100 (support substrate), and the adhesive tape 1 was attached to the base 100 while being pressed from above by a roller 6 (pressing means) at a temperature of 60 ℃ (fig. 2 (a)).
(ii) The surface of the 2 nd adhesive layer 4 was bonded with the uneven pattern surface of the patterned wafer 200 at a temperature of 60 ℃ (fig. 2 (b)).
(iii) As shown in fig. 2 c, the patterned wafer 200 is ground and polished to a predetermined thickness on the surface opposite to the surface bonded to the susceptor 100 (fig. 2 c).
(iv) The adhesive sheet 1 and the patterned wafer 200 were peeled from the base 100 with the temperature of the adhesive sheet 1 set at 120 ℃ (fig. 2 (d)).
(v) The patterned wafer 200 is placed on a heater 300, heated to 60 ℃, and the adhesive sheet 1 is peeled from the wafer 200 (fig. 2 (e)).
As a result, by using the pressure-sensitive adhesive sheet 1 obtained in example 1, the wafer 200 was not observed to be misaligned or cracked by grinding or polishing in the step (iii) described above. From this, it was found that the pressure-sensitive adhesive sheet 1 had high processing retention.
In the step (v), no residue of the 2 nd adhesive layer 4 adheres to the pattern surface of the peeled wafer 200.
[ example 4]
(production of wafer)
A patterned wafer was produced in the same manner as in example 3, except that the adhesive sheet obtained in example 2 was used as the adhesive sheet 1.
As a result, by using the pressure-sensitive adhesive sheet 1 obtained in example 2, the wafer 200 was not observed to be misaligned or cracked by grinding or polishing in the same step (iii) as in example 3. From this, it was found that the adhesive sheet 1 had high work retention.
In the same step (v) as in example 3, no residue of the 2 nd adhesive layer 4 was adhered to the pattern surface of the peeled wafer 200.
Comparative example 2
A wafer was produced in the same manner as in example 3, except that the pressure-sensitive adhesive sheet obtained in comparative example 1 was used instead of the pressure-sensitive adhesive sheet obtained in example 1, and as a result, the wafer 200 was deviated by grinding and polishing, and cracked. From this, it was found that the pressure-sensitive adhesive sheet obtained in comparative example 1 had no work retention property. In the step (v), residues adhere to the pattern surface of the peeled wafer 200.
< evaluation >
Storage moduli G', 180 were evaluated with respect to the 1 st adhesive layer and the 2 nd adhesive layer of the adhesive sheets obtained in example 1 and comparative example 1, respectively. Peel strength. Further, the grinding, polishing retention properties, and adhesive residue properties of the adhesive sheet were also evaluated. The evaluation method is as follows.
(storage modulus G')
The storage modulus G' of the 1 st adhesive layer and the 2 nd adhesive layer at 23 ℃ was measured at 10Hz, 5 ℃/min and 0 to 100 ℃ in a temperature raising process using a dynamic viscoelasticity measuring apparatus "DMS 6100" manufactured by Seiko Instruments Inc.
(180 ℃ Peel Strength)
The 1 st adhesive layer was set to be an upper side, and the 2 nd adhesive layer was fixed to a stainless steel plate via a commercially available double-sided tape. Subsequently, the 1 st adhesive layer was laminated on a polyethylene terephthalate film having a thickness of 25 μm, and the laminate was subjected to a temperature of 60 ℃ (not lower than the melting point but lower than the foaming agent temperature) and then bonded at a temperature of 23 ℃ (lower than the melting point). The polyethylene terephthalate film was then peeled 180 ° from the 1 st adhesive layer using a load cell at a rate of 300 mm/min. The 180 ° peel strength at this time was measured in accordance with JIS Z0237, and the 180 ° peel strength of the 1 st adhesive layer with respect to the polyethylene terephthalate film at an atmospheric temperature of 23 ℃.
On the other hand, the 2 nd adhesive layer and the polyethylene terephthalate film were laminated, and both were bonded to each other at a temperature of 23 ℃ (lower than the melting point) after passing through a temperature of 60 ℃ (not lower than the melting point but lower than the foaming agent temperature) as described above. Then, the 180 ° peel strength with respect to the polyethylene terephthalate film was evaluated in the same manner as described above.
(grinding and polishing Retention)
First, the 1 st adhesive layer of the adhesive sheet was adhered to a base at 60 ℃ (melting point or higher and lower than foaming agent temperature) and 2kg/cm was applied2The pressure of (2) was applied to a plate-like work piece made of sapphire glass having a diameter of 100mm × a thickness of 700 μm at 60 ℃ for 5 minutes. Then, after releasing the pressure, the temperature was decreased from 60 ℃ to 23 ℃ and left for 20 minutes. Then, the workpiece is processed in the order of grinding and polishing. The grinding and polishing conditions were set as follows.
< grinding Condition >
Grinding machine: single wafer type grinding disc
Coarse grinding
Removal amount: 400 μm
Rotation speed: 1000rpm
Cutting in: 1 μm/s or less
Finish grinding
Removal amount: 200 μm
Rotation speed: 1000rpm
Cutting in: 0.5 μm/s or less
< grinding Condition >
Mold base (Japanese: PAN): copper (Cu)
Diamond grit: 5 μm
Rotation speed: 30rpm
Pressure: 300g/cm2
Under the above conditions, the workpiece was thinned to a thickness of 70 μm. At this time, the grinding and polishing retentivity was evaluated by visually observing whether or not the sapphire glass as the workpiece was broken. The visual observation was performed after the polishing. The evaluation criterion was set as follows.
O: the sapphire glass after grinding is not cracked.
X: the ground sapphire glass was broken.
(residual tackiness)
Applying 2kg/cm2The pressure of (2) was such that the 2 nd adhesive layer of the adhesive sheet was pressed against the mirror surface side of a silicone wafer having a diameter of 100mm x a thickness of 800 μm at 60 ℃ for 5 minutes. Then, after releasing the pressure, the temperature was decreased from 60 ℃ to 23 ℃ and left for 20 minutes. Then, the temperature was again raised to 60 ℃, and after standing for 5 minutes, the 2 nd adhesive layer was peeled off from the silicone wafer at 180 ° using a load cell at a speed of 300 mm/min. The mirror surface side of the silicone wafer after the peeling was observed with an electron microscope (magnification: 20 times), and the presence or absence of residual adhesive was confirmed. The evaluation criterion was set as follows.
O: no gum residue was observed.
X: residual gum was observed.
The evaluation results are shown in table 2.
Very good [ Table 2]
Figure BDA0001401539580000181
Description of the symbols
1 pressure-sensitive adhesive sheet
2 base material
3 st adhesive layer
4 adhesive layer 2
5a, 5b spacer
100 base

Claims (7)

1. A temperature-sensitive adhesive sheet comprising: a film-like base material, a 1 st adhesive layer laminated on one surface of the base material and adhered to a base, and a 2 nd adhesive layer laminated on the other surface of the base material and adhered to a workpiece,
the 1 st adhesive layer contains a 1 st side chain crystalline polymer and a foaming agent, and exhibits fluidity at a temperature equal to or higher than the melting point of the 1 st side chain crystalline polymer, the melting point of the 1 st side chain crystalline polymer being lower than the foaming temperature of the foaming agent, and,
the 2 nd adhesive layer contains a 2 nd side chain crystalline polymer and exhibits fluidity at a temperature of the 2 nd side chain crystalline polymer or higher than the melting point thereof,
the storage modulus of each of the 1 st adhesive layer and the 2 nd adhesive layer is 1X 10 below the melting point of the 1 st side chain crystalline polymer and the 2 nd side chain crystalline polymer6～1×108Pa，
The storage modulus of the 2 nd adhesive layer is greater than the storage modulus of the 1 st adhesive layer.
2. The temperature-sensitive adhesive sheet according to claim 1,
the melting points of the 1 st side chain crystalline polymer and the 2 nd side chain crystalline polymer are both lower than the foaming initiation temperature and are 30 to 70 ℃.
3. The temperature-sensitive adhesive sheet according to claim 1,
the 1 st side chain crystalline polymer and the 2 nd side chain crystalline polymer are polymers obtained by polymerizing 30 to 70 parts by mass of an acrylate or methacrylate having a linear alkyl group having 16 or more carbon atoms, 30 to 70 parts by mass of an acrylate or methacrylate having an alkyl group having 1 to 6 carbon atoms, and 1 to 10 parts by mass of a polar monomer.
4. A temperature-sensitive adhesive sheet according to claim 3,
the 2 nd side chain crystalline polymer is a polymer obtained by polymerizing 30 to 70 parts by mass of an acrylate or methacrylate having a linear alkyl group having 16 or more carbon atoms, 30 to 70 parts by mass of an acrylate or methacrylate having an alkyl group having 1 to 6 carbon atoms, and 1 to 10 parts by mass of a polar monomer,
the acrylic ester or methacrylic ester having an alkyl group with 1 to 6 carbon atoms contains 2 to 70 mass% of acrylic ester or methacrylic ester having an alkyl group with 1 or 2 carbon atoms based on the total amount of the ester.
5. The temperature-sensitive adhesive sheet according to claim 1,
the peel strength of the 1 st adhesive layer to polyethylene terephthalate, which is lower than the melting point after passing through a temperature higher than the melting point and lower than the temperature of the foaming agent, is 0.5 to 5.0N/25mm, and the peel strength of the 2 nd adhesive layer to polyethylene terephthalate, which is lower than the melting point after passing through a temperature higher than the melting point and lower than the temperature of the foaming agent, is 0.1 to 3.0N/25 mm.
6. The temperature-sensitive adhesive sheet according to claim 5,
the peel strength of the 2 nd adhesive layer is less than the peel strength of the 1 st adhesive layer.
7. A method of manufacturing a patterned wafer, comprising:
a step of using the temperature-sensitive adhesive sheet according to any one of claims 1 to 6, wherein a 1 st adhesive layer of the temperature-sensitive adhesive sheet is attached to a base at a temperature of not lower than the melting point of the 1 st side chain crystalline polymer but lower than the foaming initiation temperature, and a 2 nd adhesive layer is attached to the uneven pattern surface of the patterned wafer at a temperature of not lower than the melting point of the 2 nd side chain crystalline polymer;
grinding and/or polishing a surface of the patterned wafer opposite to the surface attached to the susceptor;
a step of peeling the temperature-sensitive adhesive sheet and the patterned wafer from the base with the temperature of the temperature-sensitive adhesive sheet being equal to or higher than a foaming start temperature of the foaming agent; and
and peeling the adhesive sheet from the wafer by setting the temperature of the adhesive sheet to be not lower than the melting point of the 2 nd side chain crystalline polymer.
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