CN116391004A - 粘合带及加工方法 - Google Patents
粘合带及加工方法 Download PDFInfo
- Publication number
- CN116391004A CN116391004A CN202180070725.6A CN202180070725A CN116391004A CN 116391004 A CN116391004 A CN 116391004A CN 202180070725 A CN202180070725 A CN 202180070725A CN 116391004 A CN116391004 A CN 116391004A
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- Prior art keywords
- adhesive tape
- polymer
- adhesive layer
- adhesive
- adherend
- Prior art date
- Legal status (The legal status 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 status listed.)
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- 239000002390 adhesive tape Substances 0.000 title claims abstract description 79
- 238000003672 processing method Methods 0.000 title claims description 10
- 239000012790 adhesive layer Substances 0.000 claims abstract description 68
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 239000010703 silicon Substances 0.000 claims abstract description 35
- 239000010410 layer Substances 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 235000012431 wafers Nutrition 0.000 claims description 56
- -1 isocyanate compound Chemical class 0.000 claims description 44
- 239000004065 semiconductor Substances 0.000 claims description 42
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 21
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- 238000012545 processing Methods 0.000 claims description 14
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- 238000001228 spectrum Methods 0.000 claims description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
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- 125000000217 alkyl group Chemical group 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 5
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 5
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
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- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BMOMBHKAYGMGCR-UHFFFAOYSA-N octadecyl 3-oxobutanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CC(C)=O BMOMBHKAYGMGCR-UHFFFAOYSA-N 0.000 description 1
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 description 1
- IKYDDBGYKFPTGF-UHFFFAOYSA-N octyl 3-oxobutanoate Chemical compound CCCCCCCCOC(=O)CC(C)=O IKYDDBGYKFPTGF-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- 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
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- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
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- C08G18/8029—Masked aromatic polyisocyanates
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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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- 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
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- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- H—ELECTRICITY
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- 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
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- 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
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- 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
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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
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- C09J2301/00—Additional features of adhesives in the form of films or foils
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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
- 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
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- 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
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- 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
- H01L2221/68336—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 involving stretching of the auxiliary support post dicing
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
粘合带,其具有基材层、和设置于该基材层上的粘合剂层,前述粘合剂层包含光自由基引发剂、和具有聚合性碳双键的聚合物A,硅晶片表面对水的接触角R0、与在将前述粘合剂层贴附于前述硅晶片并放置24小时后对前述粘合剂层照射紫外线、并将前述粘合剂层剥离后的硅晶片表面对水的接触角R1之差|R0-R1|为20°以下。
Description
技术领域
本发明涉及粘合带和加工方法。
背景技术
在将半导体封装、半导体晶片(以下,也称为“被粘物”)等单片化时,将半导体晶片加工用胶带贴附于被粘物,在划片时将被粘物临时固定。由此,在单片化时能够防止芯片飞散。另外,在划片后,使半导体晶片加工用胶带扩展(expanding),将单片化的被粘物从半导体晶片加工用胶带拾取(剥离)。
作为这样的半导体晶片加工用胶带,主要使用在对紫外线具有透过性的膜基材上涂布有利用紫外线照射而发生固化反应的粘合剂层的粘合带。在该紫外线固化型的加工用胶带中,通过在划片后对粘合剂层照射紫外线而使固化反应进行,由此可降低粘合剂层的粘合力,因此可容易地拾取经单片化的被粘物。
在这样的半导体晶片加工用粘合带中,要求在拾取时减少对被粘物的残胶、可制造高品质的电子部件的技术。
关于这点,在上述紫外线照射型的加工用带的情况下,当将粘合带贴附至被粘物时,若气泡等进入粘合带与被粘物之间,则存在在紫外线照射时由于氧阻碍等引起粘合剂的固化不良、粘合剂以未固化的状态残留在被粘物上。另外,对被粘物的粘合力不足时,划片时切削水渗入被粘物与粘合带之间而污染被粘物、进而单片化的被粘物飞散。
因此,为补偿粘合力,可考虑增加粘合剂层的厚度、降低粘合剂层的弹性模量而提高粘合力的方法。但是,在这种情况下,有时粘合剂因由划片时刀片的旋转而产生的摩擦热而熔化、被刮起,由此粘合剂屑附着在被粘物上、单片化的被粘物固定在粘合带上,导致拾取时在与被粘物的界面上不能剥离而引起粘合剂自身的破坏,产生粘合剂屑残留在被粘物上的问题。
对此,例如,专利文献1中公开了通过使用具有5~6个丙烯酰基的放射线聚合性化合物,使紫外线照射及/或电子线照射后的凝胶分率为90wt%以上等,从而抑制残胶。
现有技术文献
专利文献
专利文献1:日本特开2000-281993号公报
发明内容
发明所要解决的课题
但是,在专利文献1记载的方法中,虽然多少可抑制残胶,但反而有粘合力降低的倾向,划片时切削水渗入被粘物与粘合带之间,有可能产生背面污染、单片化的被粘物飞散。
此外,由于近年来对半导体晶片、器件的高密度化、高性能化的要求,即使是看起来没有粘合剂的残胶的半导体晶片、器件表面,有时也会被起因于粘合剂的有机物污染,这样的污染也逐渐成为问题。需要说明的是,在本说明书中,仅称为“污染”时,是指此种无法目视的污染,就可目视者而言,称为“残胶”。
本发明是鉴于上述问题点而完成的,其目的在于,提供能够减少来自粘合剂层的污染的粘合带以及使用该粘合带的加工方法。
用于解决课题的手段
为解决上述课题,本申请的发明人对粘合带的粘合剂设计进行了深入研究。结果发现,通过使用以在紫外线固化前后显示规定的接触角特性的方式构成的粘接剂层,可解决上述课题,从而完成了本发明。
即,本发明如下所述。
〔1〕
粘合带,其具有基材层、和设置于该基材层上的粘合剂层,
前述粘合剂层包含光自由基引发剂、和具有聚合性碳双键的聚合物A,
硅晶片表面对水的接触角R0、与在将前述粘合剂层贴附于前述硅晶片并放置24小时后对前述粘合剂层照射紫外线、并将前述粘合剂层剥离后的前述硅晶片表面对水的接触角R1之差|R0-R1|为20°以下
〔2〕
请求项1所述的粘合带,其中,前述聚合物A中所含的重均分子量为20000以下的成分A1的含量相对凝胶渗透色谱的图谱的总面积而言为15面积%以下。
〔3〕
如〔1〕或〔2〕所述的粘合带,其中,紫外线照射前的前述粘合剂层对硅晶片的180°剥离强度在23℃时为2.0~20.0N/20mm。
〔4〕
如〔1〕~〔3〕中任一项所述的粘合带,其中,聚合物A具有羟基。
〔5〕
如〔1〕~〔4〕中任一项所述的粘合带,其中,前述聚合物A的重均分子量为1.0×105~2.0×106。
〔6〕
如〔1〕~〔5〕中任一项所述的粘合带,其中,前述聚合物A的玻璃化转变点为-80~23℃。
〔7〕
如〔1〕~〔6〕中任一项所述的粘合带,其中,前述聚合物A包含(甲基)丙烯酸酯系共聚物,
该(甲基)丙烯酸酯系共聚物具有直链形状、支链形状或交联形状。
〔8〕
如〔1〕~〔7〕中任一项所述的粘合带,其中,前述粘合剂层还包含固化剂。
〔9〕
如〔8〕所述的粘合带,其中,前述固化剂包含异氰酸酯系化合物。
〔10〕
如〔9〕所述的粘合带,其中,前述异氰酸酯系化合物包含2官能以上的多官能异氰酸酯系化合物。
〔11〕
如〔8〕~〔10〕中任一项所述的粘合带,其中,前述固化剂的含量相对100重量份的聚合物A而言为0.1~5.0重量份。
〔12〕
如〔1〕~〔11〕中任一项所述的粘合带,其用于半导体晶片、半导体器件、各种半导体封装加工。
〔13〕
加工方法,其具有:
将〔1〕~〔12〕中任一项所述的粘合带与被粘物贴合的贴合工序;和
在将前述粘合带与前述被粘物贴合的状态下将前述被粘物单片化的划片工序,
前述被粘物为半导体晶片、半导体器件或各种半导体封装。
发明效果
根据本发明,可提供能够减少来自粘合剂层的污染的粘合带以及使用该粘合带的加工方法。
具体实施方式
以下,对本发明的实施方式(以下,称为“本实施方式”)进行详细说明,但本发明并不限定于此,在不脱离其主旨的范围内能够进行各种变形。
(粘合带)
本实施方式的粘合带具有基材层和设置于该基材层上的粘合剂层,粘合剂层包含光自由基引发剂和具有聚合性碳双键的聚合物A,硅晶片表面对水的接触角R0、与在将粘合剂层贴附于硅晶片并放置24小时后对粘合剂层照射紫外线、并将粘合剂层剥离后的硅晶片表面对水的接触角R1之差|R0-R1|为20°以下。
以往的粘合剂层例如由不具有紫外线固化性的基底聚合物和具有紫外线固化性的低分子量成分构成。因此,紫外线照射后以未反应的状态残留的低分子量成分、聚合物成分有可能污染被粘物表面。
与此相对,在本实施方式中,通过使用具有聚合性碳双键的聚合物A,利用紫外线照射而使聚合物A彼此进一步聚合、相互交联。因此,可避免低分子量成分污染被粘物表面的问题,另外,即使聚合物A的聚合性碳双键的一部分未反应,与低分子量成分相比,也仍可以避免被粘物表面的污染。进而,在使用具有聚合性碳双键的低分子量成分的情况下,低分子量成分也能够与聚合物A键合,因此变得容易留在粘合剂中,能够抑制对被粘物表面的污染。
另外,在本实施方式中,还利用接触角R0与接触角R1之差|R0-R1|表示的接触角特性来规定包含聚合物A的粘合剂层的基于紫外线照射的固化特性。通过使用具有这样的接触角特性的粘合剂层,可进一步减少来自粘合剂层的污染。以下,对本发明进行详细说明。
(接触角)
在本实施方式中,通过使用硅晶片表面对水的接触角R0、与在将粘合剂层贴附于硅晶片并放置24小时后对粘合剂层层照射紫外线、并将粘合剂层剥离后的硅晶片表面对水的接触角R1之差|R0-R1|来规定紫外线照射后的粘合剂层对硅晶片的低污染性。
更具体而言,差|R0-R1|为20°以下,优选为0~17.5°,更优选为0~15°,进一步优选为0~12.5°。差|R0-R1|越小,被粘物的污染变得越少。
特别是,通过使|R0-R1|为20°以下,污染性更显著地降低,被粘物的后续的制造步骤、实装时的良品率也提高。另一方面,差|R0-R1|大于20°时,被粘物表面容易被污染,甚至会产生对被粘物的残胶。
需要说明的是,硅晶片表面由于被空气中的氧氧化而在最外表面露出羟基,因此通常亲水性高。因此,对水的接触角R1小意味着接近贴附粘合带前的清洁的硅晶片表面的状态。另外,与此相反,如果硅晶片被粘合剂层中含有的有机成分污染,则硅晶片表面的亲水性降低,对水的接触角变大。
另外,接触角R1优选为5~25°,更优选为5~28°,进一步优选为5~32°。通过使接触角R1在上述范围内,可进一步抑制紫外线照射后的粘合剂层对硅晶片的污染。
作为使差|R0-R1|和接触角R1处于上述范围内的方法,没有特别限制,例如可举出减少粘合剂中含有的低分子量成分,减少聚合物A的低分子量成分,提高紫外线照射时的交联密度等。作为低分子量成分的减少方法,没有特别限制,例如可举出在基材层上形成粘合剂层后、在加温下进行老化的方法,使用低分子量成分的含量少的聚合物A的方法。另外,作为提高交联密度的方法,没有特别限制,例如可举出调整聚合性碳双键的数量、光自由基引发剂的含量的方法。
本说明书中记载的“接触角”是:将粘合带贴附于硅晶片,在23℃的条件下放置24小时后,利用高压汞灯以150mJ/cm2照射紫外线来进行剥离,利用液滴法测定对水的接触角而得到的接触角。
(180°剥离强度)
紫外线照射前的粘合剂层对硅晶片的180°剥离强度S在23℃时优选为2.0~20.0N/20mm,更优选为4.0~16.0N/20mm,进一步优选为6.0~12.0N/20mm。
通过使180°剥离强度S为2.0N/20mm以上,具有紫外线照射前的粘合力更优异的倾向。因此,粘合带不易从环形框上剥离,在划片工序中也不易发生芯片飞散。
另外,通过使180°剥离强度S为20N/20mm以下,具有不易产生粘合剂被划片工序的刀片刮起、被刮起的粘合剂不易附着于被粘物的侧面等的倾向。因此,存在能够进一步抑制被刮起的粘合剂在被粘物上作为残胶而残留、在该状态下发生紫外线固化而将芯片固定化、发生拾取不良、在固定化的芯片上产生缺损的倾向。
本说明书中记载的“对硅晶片的180°剥离强度”可根据JIS Z0237(2009)的粘合力的测定方法进行测定。具体而言,在清洗过表面的被粘物(硅晶片)上使用压接装置(辊的质量2kg)压接粘合剂层,在温度23℃湿度50%的环境下用万能型拉伸试验机测定相对被粘物以180°剥离时的粘合力。
(粘合剂层)
粘合剂层包含光自由基引发剂和具有聚合性碳双键的聚合物A,根据需要,也可以包含固化剂、其他成分。
(聚合物A)
聚合物A是具有聚合性碳双键的聚合物,是构成粘合剂层的主成分的成分。对粘合剂层照射紫外线时,光自由基引发剂产生自由基,由此聚合物A的聚合性碳双键各自聚合。由此,在紫外线照射后,聚合物A成为相互交联的状态。
从降低污染的观点出发,优选聚合物A中所含的低分子量成分少。更具体而言,聚合物A中所含的重均分子量为20000以下的成分A1的含量相对凝胶渗透色谱的图谱的总面积而言优选为15面积%以下,更优选为10面积%以下,进一步优选为8面积%以下,更进一步优选为5面积%以下。成分A1的含量的下限没有特别限制,为0面积%。通过使成分A1的含量为15面积%以下,紫外线照射后残存于被粘物的表面的低分子量成分变少,有污染进一步减少的倾向。
另外,聚合物A的重均分子量优选为1.0×105~2.0×106,更优选为2.0×105~1.0×106,进一步优选为2.5×105~8.0×105。通过聚合物A的重均分子量为1.0×105以上,除了高分子量成分变多以外,分子量越高则1个聚合物A与其他聚合物A以聚合性双键聚合的机会越多,因此有污染进一步减少的倾向。通过聚合物A的重均分子量为2.0×106以下,聚合物A容易移动,1个聚合物A与其他聚合物A聚合的机会变多,因此有污染进一步减少的倾向。另外,分子量越小则粘合剂的弹性模量不会变得过高,因此常态下的粘合力有进一步提高的倾向。另外,对被粘物的追随性变好,对被粘物的高度差也能追随,因此可避免由氧阻碍为原因的UV固化不良导致的污染。进而,柔软的粘合剂通过UV照射容易充分固化收缩,因此可充分降低固化后的粘合力。
本说明书中记载的“重均分子量”是使用凝胶渗透色谱分析装置对将聚合物A溶解于四氢呋喃中而成的样品进行测定而得到的分子量。成分A1的含量可以通过将聚合物A的色谱的面积设为100面积%,由标准聚苯乙烯换算的分子量的校正曲线算出重均分子量为20000以下的保持时间的色谱的面积的比例而求出。
另外,聚合物A的玻璃化转变点优选为-80~23℃,更优选为-70~10℃,进一步优选为-60~0℃。通过聚合物A的玻璃化转变点为-80℃以上,有污染进一步减少的倾向。另外,通过聚合物A的玻璃化转变点为23℃以下,具有对被粘物的粘接性进一步提高的倾向。
作为聚合物A,没有特别限制,例如可举出具有聚合性双键的(甲基)丙烯酸酯系共聚物。(甲基)丙烯酸酯系共聚物的形状没有特别限制,例如可举出直链形状、支链形状或交联形状。其中,优选具有交联形状。通过使用这样的聚合物A,具有粘合剂层的内聚力提高,对被粘物的粘接性进一步提高、并且污染进一步降低的倾向。具有交联形状或支链形状的聚合物A可以是具有直链形状的聚合物A的聚合性双键的一部分通过老化等而结合的聚合物。
作为构成(甲基)丙烯酸酯系共聚物的(甲基)丙烯酸酯的单体,没有特别限制,例如可举出具有甲基、乙基、正丙基、异丙基、正丁基、叔丁基、异丁基、戊基、异戊基、己基、庚基、环己基、2-乙基己基、辛基、异辛基、壬基、异壬基、癸基、异癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基和十二烷基等直链或支链烷基的(甲基)丙烯酸烷基酯。这些(甲基)丙烯酸烷基酯可以单独使用1种,或者也可以并用2种以上。
另外,作为上述(甲基)丙烯酸烷基酯以外的单体成分,没有特别限制,可举出例如丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、衣康酸、马来酸、富马酸和巴豆酸等含羧基单体;马来酸酐、衣康酸酐等酸酐单体;(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、(甲基)丙烯酸6-羟基己酯、(甲基)丙烯酸8-羟基辛酯、(甲基)丙烯酸1-羟基癸酯、(甲基)丙烯酸12-羟基月桂酯、(甲基)丙烯酸(4-羟甲基环己基)甲酯等含羟基单体;苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺丙酯及(甲基)丙烯酰氧基萘磺酸等含磺酸基单体;2-羟基乙基丙烯酰基磷酸酯等含磷酸基的单体等,优选(甲基)丙烯酸2-乙基己酯、甲基丙烯酸的共聚物。这些其他单体可以单独使用1种,或者也可以并用2种以上。
其中,优选包含(甲基)丙烯酸烷基酯和含羟基单体的(甲基)丙烯酸酯系共聚物、包含(甲基)丙烯酸烷基酯和含羧基单体的(甲基)丙烯酸酯系共聚物。
向(甲基)丙烯酸酯系共聚物中导入聚合性双键的方法没有特别限制,例如可举出使具有聚合性双键的改性剂与含羧基单体的羧基、酸酐单体的酸酐羧基、或含羟基单体的羟基反应的方法。
例如,通过使具有聚合性双键的异氰酸酯系化合物作为改性剂与包含含羟基单体单元的(甲基)丙烯酸酯系共聚物反应,可以经由氨基甲酸酯键将聚合性双键导入到含羟基单体单元中。另外,作为其他例子,通过使具有聚合性双键的环氧化合物作为改性剂与包含含羟基单体单元的(甲基)丙烯酸酯系共聚物反应,可以经由醚键向含羟基单体单元导入聚合性双键。
需要说明的是,作为改性剂,只要是具有与(甲基)丙烯酸酯系共聚物所具有的官能团反应的官能团且具有聚合性双键的物质即可,没有特别限制,例如可举出具有聚合性双键的异氰酸酯系化合物、具有聚合性双键的环氧化合物等。
另外,聚合性双键的导入量相对于构成聚合物A的反应性单体单元100摩尔%而言优选为20~80摩尔%,更优选为30~75摩尔%,进一步优选为40~70摩尔%。需要说明的是,在此,“反应性单体单元”是指含羧基单体、酸酐单体以及含羟基单体。通过使聚合性双键的导入量为20摩尔%以上,紫外线照射时不易残留未反应的聚合物A,有进一步抑制污染的倾向。另外,通过使聚合性双键的导入量为80摩尔%以下,可以抑制过度的交联,因此存在可抑制粘合剂层不能耐受拾取时的销的顶起所导致的粘合带的变形而破裂成销的形状、由此产生残胶的倾向。进而,通过聚合性双键的导入量为80摩尔%以下,未反应的羧基等极性基团容易残留,有紫外线照射前对被粘物的粘合力进一步提高的倾向。
聚合物A优选具有羟基。需要说明的是,该羟基可以是来自含羟基单体等的羟基,也可以是来自改性剂的羟基,还可以是通过含羟基单体与改性剂反应而产生的羟基。作为通过含羟基单体等单体单元与改性剂反应而产生的羟基,例如可举出使具有聚合性双键的环氧化合物与含羟基单体反应的例子。
通过聚合物A具有羟基,在配合后述的固化剂的情况下,可以借助羟基将多个聚合物间进一步交联,有粘合剂层的内聚力进一步提高的倾向。另外,基材膜与粘合剂层的锚固性也进一步提高,内聚破坏、锚固破坏得到抑制,有得到更稳定的粘合特性的倾向。
聚合物A的含量相对粘合剂层的总量而言优选为80~99.5质量%,更优选为85~99.5质量%,进一步优选为90~99.5质量%。通过聚合物A的含量为上述范围内,有进一步抑制污染的倾向。
(光自由基引发剂)
作为光自由基引发剂,没有特别限定,例如可举出烷基苯基酮系光聚合引发剂、酰基氧化膦系光聚合引发剂、噻吨酮系光聚合引发剂、芳香族酮类、芳香族鎓盐化合物、有机过氧化物、硫代化合物(含有苯硫基的化合物等)、α-氨基烷基苯基酮化合物、六芳基联咪唑化合物、酮肟酯化合物、硼酸盐化合物、吖嗪鎓化合物、茂金属化合物、活性酯化合物、具有碳卤键的化合物以及烷基胺化合物。
其中,优选烷基苯基酮系光聚合引发剂。
光自由基引发剂的含量相对于粘合剂层的总量而言优选为0.1~5.0质量%,更优选为0.2~4.0质量%,进一步优选为0.3~3.0质量%。通过光自由基引发剂的含量在上述范围内,具有进一步抑制污染的倾向。
(固化剂)
作为固化剂,没有特别限制,例如可举出异氰酸酯系化合物、环氧系化合物、胺系化合物等。其中,优选异氰酸酯系化合物。通过使用这样的固化剂,具有粘合剂层的内聚力进一步提高的倾向。这些固化剂可以单独使用1种、也可以并用2种以上。
作为异氰酸酯系化合物,没有特别限制,可举出例如甲苯二异氰酸酯、4,4-二苯基甲烷二异氰酸酯、苯二甲基二异氰酸酯等芳香族二异氰酸酯;异佛尔酮二异氰酸酯、亚甲基双(4-环己基异氰酸酯)等脂环族二异氰酸酯;六亚甲基二异氰酸酯、三甲基六亚甲基二异氰酸酯等脂肪族二异氰酸酯。它们可以单独使用1种,也可以并用2种以上。
其中,固化剂优选为2官能以上的多官能异氰酸酯系化合物。通过使用这样的固化剂,多个聚合物A间也可通过固化剂进行交联,因此有粘合剂层的内聚力进一步提高的倾向。另外,基材层与粘合剂层的锚固性也提高,有得到更稳定的粘合特性的倾向。
相对于100重量份的聚合物A,固化剂的含量优选为0.1~5.0重量份,更优选为0.3~4.0重量份,进一步优选为0.3~3.0重量份。通过固化剂的含量为0.1重量份以上,具有粘合剂层的交联密度进一步提高,剥离时产生的内聚破坏得到进一步抑制,起因于内聚破坏的污染得到进一步抑制的倾向。另外,通过使固化剂的含量为5.0重量份以下,交联密度进一步降低,弹性模量降低,因此有粘合力进一步提高的倾向。
另外,固化剂的含量相对于粘合剂层的总量而言优选为0.1~2.0质量%,更优选为0.2~1.5质量%,进一步优选为0.3~1.0质量%。通过固化剂的含量为上述范围内,从而有进一步抑制污染的倾向。
(其他添加剂)
本实施方式的粘合剂层根据需要可以添加增粘剂、交联延迟剂、抗氧化剂等其他添加剂。
作为增粘剂,没有特别限制,例如可举出石油系树脂、萜烯树脂、萜烯酚醛树脂、芳香族改性萜烯树脂、香豆酮-茚树脂、天然树脂松香、改性松香、甘油酯松香、季戊四醇酯松香、酚醛树脂、二甲苯树脂、脂环族系石油树脂、苯乙烯系树脂、二环戊二烯树脂等。
作为交联延迟剂,没有特别限制,例如为在含有异氰酸酯系固化剂的粘合剂组合物中,通过将固化剂所具有的异氰酸酯基封端而能够抑制粘合剂组合物的过度的粘度上升的化合物。作为这样的交联延迟剂,没有特别限制,例如可举出乙酰丙酮、己烷-2,4-二酮、庚烷-2,4-二酮、辛烷-2,4-二酮等β-二酮类;乙酰乙酸甲酯、乙酰乙酸乙酯、乙酰乙酸丙酯、乙酰乙酸丁酯、乙酰乙酸辛酯、乙酰乙酸油酯、乙酰乙酸月桂酯、乙酰乙酸硬脂酯等β-酮酯类;苯甲酰丙酮等。
作为抗氧化剂,没有特别限制,例如可举出甲基氢醌、氢醌、2,2-亚甲基-双(4-甲基-6-叔丁基苯酚)、儿茶酚、氢醌单甲醚、单叔丁基氢醌、2,5-二叔丁基氢醌、对苯醌,2,5-二苯基-对苯醌、2,5-二叔丁基对苯醌、苦味酸、柠檬酸、吩噻嗪、叔丁基儿茶酚、2-丁基-4-羟基茴香醚、2,6-二叔丁基对甲酚和4-[[4,6-双(辛硫基)-1,3,5-三嗪-2-基]氨基]-2,6-二叔丁基苯酚。
(厚度)
粘合剂层的厚度通常为1.0~250μm,优选为2.0~50μm。进一步优选为5.0~40μm。通过使粘合剂层的厚度为1.0μm以上,可以确保充分的粘合力,因此容易抑制通过扩展而被分割的半导体芯片的飞散。另外,通过使粘合剂层的厚度为250μm以下,有进一步抑制成本的倾向。
作为半导体晶片加工用胶带使用时,优选在上述范围内调节基材层和粘合剂层的厚度,以使得胶带的总厚度优选为60~250μm的范围。半导体晶片加工用胶带的厚度更优选为70~200μm,进一步优选为80~180μm的范围。
(基材层)
作为构成基材层的材料,没有特别限制,例如可举出聚氯乙烯、聚对苯二甲酸乙二醇酯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸-丙烯酸酯膜、乙烯-丙烯酸乙酯共聚物、聚乙烯、聚丙烯、丙烯系共聚物、乙烯-丙烯酸共聚物、以及将乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸-(甲基)丙烯酸酯系共聚物等用金属离子交联而得到的离聚物树脂。构成基材层的基材膜可以是这些树脂的单独、2种以上的混合物、共聚物或它们的层叠物。
基材层的厚度可以在不损害操作性的范围内适当选择。基材层的厚度通常为10~500μm,优选为50~200μm,进一步优选为70~150μm。通过将基材层的厚度调整到上述范围内,在实用上没有问题,在经济上也有效。在基材层由多层基材膜构成的情况下,优选以基材层整体的厚度成为上述范围内的方式进行调整。
为了提高与粘合剂层的密合性,基材层可以根据需要实施化学或物理表面处理。作为上述表面处理,例如可举出电晕处理、铬酸处理、臭氧暴露、火焰暴露、高压电击暴露及离子化放射线处理等。
(保护膜)
对于本实施方式的粘合带而言,为了保护粘合剂层,也可以具有贴合在粘合剂层上的保护膜。保护膜由于在粘合带的使用时被剥离,因此优选剥离性优异的保护膜。作为保护膜,没有特别限制,例如可举出由氟树脂形成的表面能低的膜、用有机硅系剥离剂对聚对苯二甲酸乙二醇酯的表面进行了处理的膜等。
(用途)
本实施方式的粘合带可以优选用于半导体晶片、半导体器件或各种半导体封装的加工用途。半导体晶片也可以是形成有电子电路等的单片之前的晶片。另外,半导体器件是指单片化后的各种半导体芯片或包含其的元件,半导体封装是指在半导体芯片上附加有用于保护其的树脂和连接半导体芯片与外部的连接端子的封装。
(粘合带的制造方法)
作为粘合带的制造方法,没有特别限制,可举出在基材层上形成粘合剂层的方法。
本实施方式的粘合带的基材层可以按照已知的技术制造。将基材层成型的方法没有特别限定,使用惯用的熔融混炼等、各种混合装置(1螺杆或2螺杆挤出机、辊、班伯里混炼机、各种捏合机等)将上述各种材料以各成分均匀分散的方式混合,将该混合物用T模法、压延法、吹塑法成型为基材。优选使用厚度精度高的利用挤出机的T模法进行制膜的方法。
本实施方式的粘合带的粘合剂层可以按照已知的技术制造。将粘合剂层成型的方法没有特别限定,将上述各种材料溶解于有机溶剂等溶剂中而形成树脂液,通过刮刀涂布法、辊涂法、喷涂法、凹版涂布法、棒涂法或帘涂法等将其涂布在保护膜上,除去溶剂,由此形成粘合剂层。通过将其贴合在基材层上,制作粘合带。
在本实施方式中,可以在形成粘合剂层后进行老化处理。在老化处理中,在规定的温度下保管所形成的粘合剂层。温度条件没有特别限制,优选为30~50℃,更优选为35~45℃。另外,保管时间没有特别限制,优选为24~150小时,更优选为48~100小时。通过进行该老化处理,粘合剂层的粘合力、固化特性发生变化。另外,紫外线照射后的拉伸弹性模量、断裂伸长率也可控制在上述优选范围内。
〔加工方法〕
本实施方式的加工方法具有将上述粘合带与被粘物贴合的贴合工序和在将粘合带与被粘物贴合的状态下对被粘物进行加工的划片工序,其是对作为被粘物的半导体晶片、半导体器件或各种半导体封装进行加工的方法。另外,本实施方式的加工方法可根据需要具有对划片工序后的粘合带照射紫外线的紫外线照射工序、从紫外线照射后的粘合带拾取单片化后的芯片的拾取工序。
利用划片工序的单片化方法没有特别限制,可以使用以往已知的方法。例如,通过使用划片装置使含有金刚石磨粒的划片刀片高速旋转,可以将硅晶片切断成半导体芯片。
紫外线照射方法没有特别限制,可使用以往已知的方法。例如,使用紫外线照射装置对划片工序的粘合带照射紫外线。
然后,拾取方法没有特别限制,可使用以往已知的方法。例如,可以使用扩展装置,将紫外线照射后的粘合带沿面方向拉伸,在使各芯片分离的状态下利用拾取装置拾取芯片。
实施例
以下,使用实施例和比较例更具体地说明本发明,但本发明并不限定于这些实施例。
(实施例1)
使丙烯酸2-乙基己酯63重量份、丙烯酸2-羟基乙酯15重量份、乙氧基乙氧基乙基丙烯酸酯22重量份、引发剂(偶氮二异丁腈)0.03重量份在乙酸乙酯中于65℃共聚24小时,得到含有丙烯酸系聚合物的溶液。
使该丙烯酸系聚合物中的丙烯酸2-羟基乙酯单元的羟基与2-甲基丙烯酰氧基乙基异氰酸酯反应,得到在侧链导入有双键的侧链双键导入型丙烯酸系聚合物。此时,以2-甲基丙烯酰氧基乙基异氰酸酯的导入量相对上述丙烯酸系聚合物的丙烯酸2-羟基乙酯单元100摩尔而言为50摩尔(50摩尔%)的方式使两者反应。
接着,向包含100重量份的侧链双键导入型丙烯酸系聚合物的溶液中,添加作为多异氰酸酯系化合物的三羟甲基丙烷改性甲苯二异氰酸酯固化剂(日本聚氨酯株式会社:Coronate L-45E)0.5重量份、光自由基引发剂(2,2-二甲氧基-2-苯基苯乙酮(BASF公司制:Omnirad 651)2.1重量份,制备作为紫外线固化型粘合剂的树脂组合物。
将该树脂组合物以使得干燥后的粘合剂层的厚度为20μm的方式涂布在预先实施了脱模处理的聚对苯二甲酸乙二醇酯保护膜的脱模处理面上,于100℃干燥1分钟后,与预先对供粘合剂层贴合的表面实施了电晕处理的乙烯-甲基丙烯酸-丙烯酸酯系共聚物的离聚物膜(基材树脂膜)的电晕处理面贴合,将粘合剂转印到基材树脂膜上。将其在40℃的气氛下老化72小时,得到粘合带。
(实施例2)
使丙烯酸丁酯67重量份、丙烯酸甲酯28重量份、丙烯酸2-羟基乙酯5重量份和引发剂(偶氮二异丁腈)0.03重量份在甲苯中于65℃共聚24小时,得到含有丙烯酸系聚合物的溶液。使该丙烯酸系聚合物中的丙烯酸2-羟基乙酯单元的羟基与2-甲基丙烯酰氧基乙基异氰酸酯反应,得到在侧链导入有双键的侧链双键导入型丙烯酸系聚合物。此时,以2-甲基丙烯酰氧基乙基异氰酸酯的导入量相对上述丙烯酸系聚合物的丙烯酸2-羟基乙酯单元100摩尔而言为70摩尔(70摩尔%)的方式使两者反应。将上述丙烯酸系聚合物溶解于乙酸乙酯:甲醇=1:20的溶液中,以固体成分浓度20%进行清洗,由此除去低分子量成分。此后与实施例1同样地得到粘合带。
(实施例3)
省略丙烯酸系聚合物的清洗工序,除此以外,与实施例2同样操作,得到粘合带。
(实施例4)
以2-甲基丙烯酰氧基乙基异氰酸酯的导入量相对丙烯酸系聚合物的丙烯酸2-羟基乙酯单元100摩尔而言为30摩尔(30摩尔%)的方式使两者反应,除此以外,与实施例1同样操作,得到粘合带。
(实施例5)
除了调整引发剂的量,使侧链双键导入型丙烯酸系聚合物的重均分子量为80万以外,与实施例1同样操作,得到粘合带。
(实施例6)
使丙烯酸2-乙基己酯92重量份、丙烯酸8重量份、引发剂(偶氮二异丁腈)0.05重量份在乙酸乙酯中于65℃共聚24小时,得到含有丙烯酸系聚合物的溶液。
使甲基丙烯酸缩水甘油酯与该丙烯酸系聚合物中的丙烯酸单元的羧基反应,得到在侧链导入有双键的侧链双键导入型丙烯酸系聚合物。此时,以甲基丙烯酸缩水甘油酯的导入量相对上述丙烯酸系聚合物的丙烯酸单元100摩尔而言为80摩尔(80摩尔%)的方式使两者反应。将上述丙烯酸系聚合物溶解于乙酸乙酯:甲醇=1:20的溶液中,以固体成分浓度20%进行清洗,由此除去低分子量成分。
接着,向包含100重量份的侧链双键导入型丙烯酸系聚合物的溶液中,添加作为多异氰酸酯系化合物的三羟甲基丙烷改性甲苯二异氰酸酯固化剂(日本聚氨酯株式会社:Coronate L-45E)0.1重量份,和作为光自由基引发剂的2,2-二甲氧基-2-苯基苯乙酮(BASF公司制:Omnirad 651)2.1重量份,制备作为紫外线固化型粘合剂的树脂组合物。此后与实施例1同样地得到粘合带。
(实施例7)
在使丙烯酸系聚合物中的丙烯酸单元的羧基与甲基丙烯酸缩水甘油酯反应,得到在侧链导入有双键的侧链双键导入型丙烯酸系聚合物时,以甲基丙烯酸缩水甘油酯的导入量相对上述丙烯酸系聚合物的丙烯酸单元100摩尔而言为60摩尔(60摩尔%)的方式使两者反应;使作为多异氰酸酯系化合物的三羟甲基丙烷改性甲苯二异氰酸酯固化剂(日本聚氨酯株式会社:Coronate L-45E)为0.5重量份,除此以外,与实施例6同样操作,得到粘合带。
(比较例1)
省略丙烯酸系聚合物的清洗工序,并且使作为多异氰酸酯系化合物的三羟甲基丙烷改性甲苯二异氰酸酯固化剂(日本聚氨酯株式会社:Coronate L-45E)为0.5重量份,除此以外,与实施例6同样操作,得到粘合带。
(比较例2)
使丙烯酸2-乙基己酯45重量份、丙烯酸2-羟基乙酯10重量份、丙烯酸甲酯40重量份、丙烯酸5.0重量份、引发剂(偶氮二异丁腈)0.03重量份在乙酸乙酯中于65℃共聚24小时,得到含有丙烯酸系聚合物的溶液。
向该丙烯酸系聚合物中另外添加紫外线聚合性氨基甲酸酯丙烯酸酯,并且调整固化剂和引发剂的量,除此以外,与实施例1同样操作,制作粘合带。
对于如上制备的各样品,对于有机物污染、接触角、分子量、180°剥离对硅晶片粘合力、划片、拾取,如下进行评价试验。将得到的结果归纳示于下述表1。
<有机物污染>
在原始晶片(prime wafer)上贴附如上制作的粘合带,放置24小时后,利用高压汞灯照射150mJ/cm2紫外线,进行剥离。然后,用TD-GC/MS测定原始晶片表面的挥发有机物成分。TD-GC/MS的测定条件如下所示。
(测定条件)
试样前处理:通过下述装置将晶片上的有机吸附物质回收到TENAX管中。
·装置:“WA2560M”(GL Sciences公司制)
·加热条件:室温→约25℃/min升温→400℃(15min保持)
·吸附条件:Tenax管(室温)
TD-GC/MS
·测定装置:“TD2530”(GL Sciences公司制)
·Agilent Technologies 7890B GC System
·Agilent Technologies 5977A MSD
·TENAX管解吸附温度:270℃
·GC导入法:-130℃冷阱后,270℃加热
·色谱柱:InertCap 1MS(Length(长):60m,Diam(直径):0.25mm,Film(膜):0.25μm)
·载气:He
·离子化法:EI法
·GC升温条件:40℃(5min保持)→10℃/min升温→280℃(11min保持)
使用的原始晶片:6inch(英寸),颗粒:0.3μm≤15个
<接触角>
将如上制作的粘合带贴附于硅晶片,在23℃的条件下放置24小时后,利用高压汞灯照射150mJ/cm2的紫外线,进行剥离。然后,用液滴法测定硅晶片表面对蒸馏水的接触角R1。对粘贴粘合带前的开封时的硅晶片对蒸馏水的接触角R0也同样地进行测定,算出差|R0-R1|。液滴法的测定条件如下所示。
(测定条件)
·水滴:3mL
·30次/1测定(1次/1秒),采用第30次的值×n3
<重均分子量>
将10mg如上合成的侧链双键导入型丙烯酸系聚合物溶解于四氢呋喃(THF,不含稳定剂,和光制药工业株式会社制)10mL中,用膜过滤器(PTFE制,0.50μm)过滤,将所得物供于分析。重均分子量的测定条件如下所示。
(分析装置)
凝胶渗透色谱分析装置(DGU-20AC等,株式会社岛津制作所制)
(测定条件)
标准物质:Shodex STANDARD(Type:SM-105,昭和电工株式会社制)
试样导入量:20μL
流动相:THF
流量:1mL/min
色谱柱:Shim-pack GPC-80M(300mm×8.0mmI.D.)
柱温:40℃
检测器:示差折射率检测器(RID)
需要说明的是,重均分子量为20000以下的成分A1的含量通过以侧链双键导入型丙烯酸系聚合物的色谱图的面积为100面积%、由标准聚苯乙烯换算的分子量的校正曲线算出重均分子量为20000以下的保持时间的色谱图的面积的比例而求出。
<玻璃化转变点>
聚合物A的玻璃化转变点的测定基于JIS K7121,通过差示扫描量热测定法(DSC法)进行测定。
<180°剥离强度>
粘合带的粘合力通过JIS Z0237(2009)的粘合力的测定方法(方法1:将带及片相对于不锈钢试验板以180°剥离的试验方法)进行测定。具体而言,使用压接装置(辊的质量2kg)将粘合带压接于已清洗过表面的硅晶片,在温度23℃湿度50%的环境下使用万能型拉伸试验机(ORIENTEC公司制Tensilon型号:RTG-1210)测定。
(测定条件)
测定模式:拉伸
拉伸速度:300mm/min
卡盘间距离:50mm
测定样品宽度:20mm
<划片工序>
使用具有辊的胶带安装装置,在直径8英寸×厚度0.1mm的硅晶片的背面贴合如上制作的粘合带。接着,用划片刀片将硅晶片划片为0.49mm×0.3mm的半导体芯片。划片的主要设定条件如下。
(设定条件)
划片装置:DISCO公司制DAD341
划片刀片:DISCO公司制NBC-ZH205O-27HEEE
划片刀片转速:40,000rpm
划片刀片进给速度:50mm/秒
切削水温度:25℃
切削水量:1.0升/分钟
<拾取工序>
在划片工序后,照射150mJ/cm2紫外线,使粘合剂层固化。然后,从粘合带上拾取半导体芯片并剥离。拾取的主要设定条件如下。
(设定条件)
拾取装置:Canon Machinery公司制造的CAP-300II
针销形状:250μmR
针销顶起高度:0.5mm
扩展量:8mm
顶起速度:10,000μm/秒
<拾取收率>
对于拾取时销高度,从0.1mm至1.5mm以0.1mm刻度进行拾取试验。更具体而言,尝试以各销高度拾取100个芯片,对每个销高度确认能够拾取的芯片的比例(拾取收率)。而且,将芯片的拾取收率达到95%以上的销高度的最小值记载于表中。
[表1]
※R0为5.0。
产业上的可利用性
本发明的粘合带作为半导体晶片加工用胶带、特别是划片工序中使用的粘合带具有产业上的可利用性。
Claims (13)
1.粘合带,其具有基材层、和设置于该基材层上的粘合剂层,
所述粘合剂层包含光自由基引发剂、和具有聚合性碳双键的聚合物A,
硅晶片表面对水的接触角R0、与在将所述粘合剂层贴附于所述硅晶片并放置24小时后对所述粘合剂层照射紫外线、并将所述粘合剂层剥离后的所述硅晶片表面对水的接触角R1之差|R0-R1|为20°以下。
2.根据权利要求1所述的粘合带,其中,所述聚合物A中所含的重均分子量为20000以下的成分A1的含量相对凝胶渗透色谱的图谱的总面积而言为15面积%以下。
3.根据权利要求1或2所述的粘合带,其中,紫外线照射前的所述粘合剂层对硅晶片的180°剥离强度在23℃时为2.0~20.0N/20mm。
4.根据权利要求1~3中任一项所述的粘合带,其中,聚合物A具有羟基。
5.根据权利要求1~4中任一项所述的粘合带,其中,所述聚合物A的重均分子量为1.0×105~2.0×106。
6.根据权利要求1~5中任一项所述的粘合带,其中,所述聚合物A的玻璃化转变点为-80~23℃。
7.根据权利要求1~6中任一项所述的粘合带,其中,所述聚合物A包含(甲基)丙烯酸酯系共聚物,
该(甲基)丙烯酸酯系共聚物具有直链形状、支链形状或交联形状。
8.根据权利要求1~7中任一项所述的粘合带,其中,所述粘合剂层还包含固化剂。
9.根据权利要求8所述的粘合带,其中,所述固化剂包含异氰酸酯系化合物。
10.根据权利要求9所述的粘合带,其中,所述异氰酸酯系化合物包含2官能以上的多官能异氰酸酯系化合物。
11.根据权利要求8~10中任一项所述的粘合带,其中,所述固化剂的含量相对100重量份的聚合物A而言为0.1~5.0重量份。
12.根据权利要求1~11中任一项所述的粘合带,其用于半导体晶片、半导体器件或各种半导体封装的加工。
13.加工方法,其具有:
将权利要求1~12中任一项所述的粘合带与被粘物贴合的贴合工序;和
在将所述粘合带与所述被粘物贴合的状态下将所述被粘物单片化的划片工序,
所述被粘物为半导体晶片、半导体器件或各种半导体封装。
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