TW201838082A - Adhesive tape for semiconductor wafer surface protection, and semiconductor wafer processing method - Google Patents
Adhesive tape for semiconductor wafer surface protection, and semiconductor wafer processing method Download PDFInfo
- Publication number
- TW201838082A TW201838082A TW107111327A TW107111327A TW201838082A TW 201838082 A TW201838082 A TW 201838082A TW 107111327 A TW107111327 A TW 107111327A TW 107111327 A TW107111327 A TW 107111327A TW 201838082 A TW201838082 A TW 201838082A
- Authority
- TW
- Taiwan
- Prior art keywords
- semiconductor wafer
- adhesive
- resin layer
- surface protection
- adhesive tape
- Prior art date
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- 239000002390 adhesive tape Substances 0.000 title claims abstract description 71
- 238000003672 processing method Methods 0.000 title abstract description 8
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- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- VZDDUFFXSBGRMP-UHFFFAOYSA-N 9h-fluoren-1-ylphosphane Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2P VZDDUFFXSBGRMP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000509639 Agama Species 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 229920002873 Polyethylenimine Chemical class 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- AVUYXHYHTTVPRX-UHFFFAOYSA-N Tris(2-methyl-1-aziridinyl)phosphine oxide Chemical compound CC1CN1P(=O)(N1C(C1)C)N1C(C)C1 AVUYXHYHTTVPRX-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- SJRQIUVIXTUQLI-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate;prop-2-enoic acid Chemical compound OC(=O)C=C.C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 SJRQIUVIXTUQLI-UHFFFAOYSA-N 0.000 description 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- HXTBYXIZCDULQI-UHFFFAOYSA-N bis[4-(methylamino)phenyl]methanone Chemical compound C1=CC(NC)=CC=C1C(=O)C1=CC=C(NC)C=C1 HXTBYXIZCDULQI-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- WPCPXPTZTOMGRF-UHFFFAOYSA-K di(butanoyloxy)alumanyl butanoate Chemical compound [Al+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O WPCPXPTZTOMGRF-UHFFFAOYSA-K 0.000 description 1
- DYHSMQWCZLNWGO-UHFFFAOYSA-N di(propan-2-yloxy)alumane Chemical compound CC(C)O[AlH]OC(C)C DYHSMQWCZLNWGO-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group 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
- 229920002601 oligoester Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- 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
- C09J7/29—Laminated material
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- C—CHEMISTRY; METALLURGY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本發明係關於一種半導體晶圓表面保護用黏著帶及半導體晶圓之加工方法。 The invention relates to a semiconductor wafer surface protection adhesive tape and a method for processing a semiconductor wafer.
半導體組件係將高純度矽單晶等切片而製成半導體晶圓後,藉由離子注入、蝕刻等在該晶圓表面形成積體電路而製造。藉由對形成有積體電路之半導體晶圓之背面進行研削、研磨等,而將半導體晶圓加工成想要的厚度。此時,為了保護形成於半導體晶圓表面之積體電路,而使用半導體晶圓表面保護用黏著帶(以下亦簡稱為「表面保護帶」)。 A semiconductor device is manufactured by slicing a high-purity silicon single crystal into a semiconductor wafer, and then forming an integrated circuit on the surface of the wafer by ion implantation, etching, or the like. The semiconductor wafer is processed to a desired thickness by grinding, polishing, etc. the back surface of the semiconductor wafer on which the integrated circuit is formed. At this time, in order to protect the integrated circuit formed on the surface of the semiconductor wafer, an adhesive tape for protecting the surface of a semiconductor wafer (hereinafter also simply referred to as a "surface protection tape") is used.
經背面研削之半導體晶圓於背面研削結束後被收納至晶圓匣中,並被搬送至切晶步驟,而加工成半導體晶片。 After the back grinding is completed, the semiconductor wafer is stored in a wafer cassette, and is transferred to a dicing step to be processed into a semiconductor wafer.
先前要求藉由背面研削等將半導體晶圓之厚度製成200~400μm左右。但是,隨著近年來高密度構裝技術之進步,產生將半導體晶片小型化之需求,半導體晶圓之薄膜化亦隨之發展。根據半導體晶片之種類,需要將半導體晶圓減薄至100μm左右。另一方面,為了增加藉由一次加工能夠製造之半導體晶片之數量,而有將原半導體晶圓大徑化之傾向。迄今為止,直徑為5英吋或6英吋之半導體晶圓為主流,相對於此,近年來對直徑8~12英吋之半導體晶圓進行半導體晶片化的加工成為主流。 Previously, the thickness of a semiconductor wafer was required to be about 200 to 400 μm by back grinding. However, with the progress of high-density packaging technology in recent years, there has been a demand for miniaturization of semiconductor wafers, and the thinning of semiconductor wafers has also developed accordingly. Depending on the type of semiconductor wafer, the semiconductor wafer needs to be thinned to about 100 μm. On the other hand, in order to increase the number of semiconductor wafers that can be manufactured by one process, there is a tendency to increase the diameter of the original semiconductor wafer. So far, semiconductor wafers with a diameter of 5 inches or 6 inches have become the mainstream. In contrast, in recent years, semiconductor wafer processing has been performed on semiconductor wafers with a diameter of 8 to 12 inches.
使半導體晶圓薄膜化同時大徑化之趨勢於存在NAND型或NOR型之快閃記憶體領域或為揮發性記憶體之DRAM等領域尤其明顯。例如將直徑12英吋之半 導體晶圓研削至150μm以下之厚度之情況亦不少見。 The trend of thinning and large-diameter semiconductor wafers is particularly evident in areas such as NAND-type or NOR-type flash memories or volatile memory DRAMs. For example, it is not uncommon to grind a 12-inch diameter semiconductor wafer to a thickness of 150 m or less.
此外,尤其是近年來,隨著智慧型手機之普及或行動電話之性能提升及音樂播放器之小型化且性能提升等,對於使用有考慮過耐衝擊性等之附帶電極之半導體晶圓的覆晶構裝所使用之晶圓,對於薄膜化之要求亦逐漸增加。另外,對於附帶凸塊之半導體晶圓,亦產生對半導體晶圓部分進行100μm以下之薄膜研削的需求。用以進行覆晶連接之凸塊為了提升傳輸速度而逐漸高密度化,凸塊之高度(自半導體晶圓表面之突出高度)逐漸降低,凸塊間距隨之逐漸變短。另外,近年來對DRAM亦開始實施覆晶連接,因此晶圓之薄膜化亦加速推進。 In addition, especially in recent years, with the popularization of smart phones or the improvement of the performance of mobile phones and the miniaturization and performance of music players, the use of semiconductor wafers with electrodes that have been considered for impact resistance has been used. The wafers used in crystal structure mounting have gradually increased the requirements for thin films. In addition, for semiconductor wafers with bumps, there is also a demand for thin-film grinding of semiconductor wafers below 100 μm. The bumps used for the flip-chip connection are gradually increased in density in order to increase the transmission speed, the height of the bumps (the protruding height from the surface of the semiconductor wafer) is gradually reduced, and the bump pitch is gradually shortened. In addition, in recent years, flip-chip connections have also been implemented for DRAM, so the thinning of wafers has also accelerated.
覆晶構裝作為針對近年來電子機器之小型化、高密度化能夠將半導體元件以最小面積加以構裝之方法而逐漸受到關注。於該覆晶構裝所使用之半導體元件的電極上形成有凸塊,將凸塊與電路基板上之配線電性地接合。作為該等凸塊之組成,主要使用有焊料或金屬。該焊料凸塊或金屬凸塊係藉由蒸鍍或鍍覆而形成於與晶片內部配線連接之露出的鋁端子上等。 Flip-chip mounting has gradually attracted attention as a method capable of mounting semiconductor devices with a minimum area in response to miniaturization and high density of electronic devices in recent years. A bump is formed on an electrode of a semiconductor element used in the flip-chip structure, and the bump is electrically bonded to the wiring on the circuit board. As the composition of these bumps, solder or metal is mainly used. The solder bump or metal bump is formed on an exposed aluminum terminal connected to the internal wiring of the chip by evaporation or plating, or the like.
但是,附帶凸塊之半導體晶圓由於其表面具有大的凹凸,故而難以進行薄膜加工,若使用通常之表面保護帶進行背面研削,則半導體晶圓會產生破裂或半導體晶圓之厚度精確度會變差。因此,附帶凸塊之半導體晶圓之研削係使用特殊設計之表面保護帶而進行(例如參照專利文獻1)。 However, semiconductor wafers with bumps have large irregularities on the surface, which makes it difficult to perform thin-film processing. If conventional surface protection tapes are used for back grinding, the semiconductor wafers may be cracked or the thickness accuracy of the semiconductor wafers may be reduced. Worse. Therefore, the grinding of the semiconductor wafer with bumps is performed using a specially designed surface protection tape (for example, refer to Patent Document 1).
然而,利用該等表面保護帶時會充分地吸收凸塊而確保研削性,因此非常難以兼顧剝離性。迄今為止進行覆晶構裝之晶片的最後加工厚度為200μm以上之某程度的厚度,而保持剛性,因此勉強能夠剝離。然而,近來半導體晶圓最後加工厚度進一步薄膜化,凸塊密度亦逐漸變高,因此表面保護帶會引起無法容易地剝離、糊劑殘留等問題。另外,相反若確保剝離性,則密接會變得不充分,而會於背面研削時引起滲漏(例如灰塵或研削水之滲入)。 However, when these surface protective tapes are used, the bumps are sufficiently absorbed to ensure the grindability. Therefore, it is very difficult to balance the peelability. The final processing thickness of a wafer that has been subjected to a flip-chip structure so far is a certain thickness of 200 μm or more, while maintaining rigidity, so that it can barely be peeled off. However, recently, the final processing thickness of semiconductor wafers has been further thinned, and the bump density has gradually increased. Therefore, the surface protective tape may cause problems such as difficulty in peeling, and residual paste. On the other hand, if the releasability is ensured, the adhesion becomes insufficient, and leakage (eg, penetration of dust or grinding water) is caused during grinding on the back surface.
另一方面,晶圓級組件所使用之附帶凸塊之半導體晶圓的凸塊高度依然較高,亦搭載有高度250μm以上之凸塊。對於晶圓級組件而言,由於無需堆疊晶片,因此不存在如記憶體系半導體晶圓般進行50μm以下之極薄研削之情況,但由於附有較高之凸塊,故而即便為厚膜研削,亦非常容易破裂,厚度150μm以下之研削厚度時容易產生半導體晶圓破裂之問題。 On the other hand, the bump height of the semiconductor wafer with bumps used for wafer-level components is still high, and bumps with a height of 250 μm or more are also mounted. For wafer-level components, there is no need to stack wafers, so there is no such thing as ultra-thin grinding of less than 50 μm like memory system semiconductor wafers. However, even with thick film grinding, high bumps are attached. It is also very easy to crack. When the thickness is less than 150 μm, the problem of semiconductor wafer cracking is easy to occur.
針對此種半導體晶圓,業界提出有專用表面保護帶(參照專利文獻2~4)。專利文獻2中記載有一種半導體晶圓表面保護用黏著帶,其能夠於半導體晶圓加工時與半導體晶圓牢固地密接,並且剝離時於無半導體晶圓之破損或糊劑殘留之狀況下剝離。該表面保護帶於基材膜上具有將層厚及收縮值設為特定範圍內之輻射硬化型黏著劑層。另外,專利文獻3中揭示有一種半導體晶圓表面保護用黏著帶,其係凸塊高度較高之凸塊晶圓之背面研削所使用的表面保護用黏著帶,即便對晶圓進行研削,亦會防止晶圓之破損或不會產生滲漏,而可抑制剝離力之下降及糊劑殘留。該表面保護帶具有特定黏著力及層厚。另外,專利文獻4中揭示有一種半導體晶圓保護用黏著片之貼合方法,其係將晶圓之背面研削至形成於晶圓表面之凸凹之高低差以下時,能夠實現晶圓表面凸凹之保護、防止研削屑或研削水等滲入至晶圓表面及防止研削後之晶圓破損。該方法所使用之表面保護片具有將50℃~100℃之損耗正切設為特定範圍內的中間層及黏著劑層。 For such semiconductor wafers, a dedicated surface protection tape has been proposed in the industry (see Patent Documents 2 to 4). Patent Document 2 describes an adhesive tape for protecting the surface of a semiconductor wafer, which can be firmly adhered to the semiconductor wafer during the processing of the semiconductor wafer, and can be peeled off without the semiconductor wafer being damaged or the paste remaining during the peeling. . The surface protective tape has a radiation-curable adhesive layer on a substrate film, the layer thickness and the shrinkage value being set within a specific range. In addition, Patent Document 3 discloses an adhesive tape for surface protection of a semiconductor wafer, which is an adhesive tape for surface protection used for back surface grinding of a bump wafer having a high bump height. It can prevent the wafer from being damaged or leaking, and can suppress the decrease in peeling force and the residue of paste. The surface protective tape has a specific adhesive force and a layer thickness. In addition, Patent Document 4 discloses a method for bonding an adhesive sheet for protecting a semiconductor wafer, which is capable of realizing a bump on the wafer surface when the back surface of the wafer is ground to a level difference between bumps and depressions formed on the wafer surface. Protect and prevent grinding chips or grinding water from penetrating to the wafer surface and prevent wafer damage after grinding. The surface protection sheet used in this method has an intermediate layer and an adhesive layer with a loss tangent of 50 ° C to 100 ° C within a specific range.
[先前技術文獻] [Prior technical literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開2001-203255號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2001-203255
[專利文獻2]日本專利第5242830號公報 [Patent Document 2] Japanese Patent No. 5242830
[專利文獻3]日本專利第5117630號公報 [Patent Document 3] Japanese Patent No. 5117630
[專利文獻4]日本專利特開2010-258426號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2010-258426
專利文獻2所記載之表面保護帶能夠一定程度地抑制半導體晶圓破損或糊劑殘留。另外,專利文獻3所記載之表面保護帶之剝離性良好。但是,為了應用於以更窄之間距具有更高之凸塊的半導體晶圓,專利文獻2所記載之表面保護帶尚存進一步改善剝離性或糊劑殘留之空間。另外,專利文獻3所記載之表面保護帶尚存進一步提升密接性、抑制滲漏、改善糊劑殘留之空間。 The surface protective tape described in Patent Document 2 can suppress damage to the semiconductor wafer or residue of the paste to some extent. In addition, the surface protective tape described in Patent Document 3 has good peelability. However, in order to apply it to semiconductor wafers having higher bumps with a narrower pitch, there is room for the surface protective tape described in Patent Document 2 to further improve peelability or paste residue. In addition, the surface protective tape described in Patent Document 3 has room for further improvement of adhesion, suppression of leakage, and improvement of paste residue.
專利文獻4所記載之方法所使用的表面保護帶因追隨性極其良好,故而有時會於追隨高度250μm以上之凸塊時,表面保護變形為凹凸狀,導致在進行抽吸搬送之加工裝置內搬送中之半導體晶圓掉落而破損。 The surface protective tape used in the method described in Patent Document 4 has extremely good followability. Therefore, when following a bump having a height of 250 μm or more, the surface protection may be deformed into a concave-convex shape, leading to a suction device in a processing device. The semiconductor wafer being transported dropped and damaged.
本發明鑒於上述問題,其課題在於提供一種能夠於半導體晶圓加工時與半導體晶圓牢固地密接並抑制滲漏、加工裝置內之搬送錯誤、半導體晶圓破損,於剝離時於無糊劑殘留之狀況下剝離之半導體晶圓表面保護用黏著帶及使用其之半導體晶圓之加工方法。 The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a semiconductor wafer that can be tightly adhered to the semiconductor wafer during semiconductor wafer processing to prevent leakage, transfer errors in a processing device, breakage of the semiconductor wafer, and no paste residue during peeling In this case, an adhesive tape for protecting the surface of a semiconductor wafer that has been peeled off and a processing method of a semiconductor wafer using the same.
本發明人等為了解決上述課題而進行潛心研究後,結果發現:於具有基材膜、中間樹脂層及黏著劑層之半導體晶圓表面保護用黏著帶中,藉由將構成上述中間樹脂層之樹脂的熔點或菲卡(Vicat)軟化點及熔體質量流率(MFR)分別設為特定範圍內,並將該表面保護帶以特定溫度加熱貼合於具有特定凹凸差之半導體晶圓表面,而能夠使表面保護帶牢固地密接於半導體晶圓之電路面,從而能夠於半導體晶圓加工時,抑制滲漏、加工裝置內之搬送錯誤、半導體晶圓破損,且能夠於剝離時,於無糊劑殘留之狀況下剝離,進而能 夠抑制貼合於半導體晶圓表面之狀態下的翹曲。本發明係基於此見解而完成者。 The present inventors conducted diligent research in order to solve the above-mentioned problems, and as a result, found that in a semiconductor wafer surface protection adhesive tape having a substrate film, an intermediate resin layer, and an adhesive layer, The melting point of the resin, the softening point of Vicat, and the melt mass flow rate (MFR) are set within specific ranges, respectively, and the surface protective tape is heated and bonded at a specific temperature to the surface of a semiconductor wafer having a specific unevenness. The surface protection tape can be tightly adhered to the circuit surface of the semiconductor wafer, so that during the semiconductor wafer processing, leakage can be suppressed, transportation errors in the processing device, and the semiconductor wafer can be damaged. When the paste is peeled off, it is possible to suppress warpage in a state of being bonded to the surface of the semiconductor wafer. The present invention has been completed based on this knowledge.
即,上述課題係藉由以下之方法而解決。 That is, the above-mentioned problems are solved by the following methods.
<1> <1>
一種半導體晶圓表面保護用黏著帶,其係於40℃~90℃之條件下加熱貼合於具有20μm以上之凹凸差的半導體晶圓表面而使用者,上述半導體晶圓表面保護用黏著帶具有基材膜、黏著劑層及位於該基材膜與該黏著劑層間之中間樹脂層,上述中間樹脂層之厚度為上述凹凸差以上,構成該中間樹脂層之樹脂的熔點或菲卡軟化點為40℃~90℃,構成該中間樹脂層之樹脂的熔體質量流率為10g/min~100g/min。 A semiconductor wafer surface protection adhesive tape is used for heating and bonding a surface of a semiconductor wafer having an unevenness of more than 20 μm at a temperature of 40 ° C. to 90 ° C. and the user. The semiconductor wafer surface protection adhesive tape has The base film, the adhesive layer, and the intermediate resin layer located between the base film and the adhesive layer. The thickness of the intermediate resin layer is equal to or greater than the unevenness. The melting point or the softening point of the resin constituting the intermediate resin layer is: From 40 ° C to 90 ° C, the melt mass flow rate of the resin constituting the intermediate resin layer is 10 g / min to 100 g / min.
<2> <2>
如<1>中所記載之半導體晶圓表面保護用黏著帶,其中,照射紫外線後之上述黏著劑層對於23℃之SUS280研磨面的黏著力為0.5N/25mm以上5.0N/25mm以下,且對於50℃之SUS280研磨面的黏著力為0.3N/25mm以上7.0N/25mm以下。 The adhesive tape for protecting the surface of a semiconductor wafer as described in <1>, wherein the adhesive force of the above-mentioned adhesive layer to the SUS280 polished surface at 23 ° C. is 0.5N / 25mm or more and 5.0N / 25mm or less after irradiation with ultraviolet rays, and The adhesion to the 50 ° C SUS280 polished surface is 0.3N / 25mm or more and 7.0N / 25mm or less.
<3> <3>
如<1>或<2>中所記載之半導體晶圓表面保護用黏著帶,其中上述基材膜之厚度與上述中間樹脂層之厚度的比為基材膜之厚度:中間樹脂層之厚度=0.5:9.5~7:3。 The adhesive tape for semiconductor wafer surface protection as described in <1> or <2>, wherein the ratio of the thickness of the substrate film to the thickness of the intermediate resin layer is the thickness of the substrate film: the thickness of the intermediate resin layer = 0.5: 9.5 ~ 7: 3.
<4> <4>
如<1>至<3>中任一項所記載之半導體晶圓表面保護用黏著帶,其中構成上述中間樹脂層之樹脂為乙烯-丙烯酸甲酯共聚物樹脂、乙烯-丙烯酸乙酯共聚物樹脂及乙烯-丙烯酸丁酯共聚物樹脂中之至少1種。 The adhesive tape for semiconductor wafer surface protection according to any one of <1> to <3>, wherein the resin constituting the intermediate resin layer is an ethylene-methyl acrylate copolymer resin or an ethylene-ethyl acrylate copolymer resin And at least one of ethylene-butyl acrylate copolymer resin.
<5> <5>
如<1>至<4>中任一項所記載之半導體晶圓表面保護用黏著帶,其中上 述基材膜之構成材料的熔點為90℃~150℃。 The adhesive tape for semiconductor wafer surface protection according to any one of <1> to <4>, wherein a melting point of the constituent material of the base film is 90 ° C to 150 ° C.
<6> <6>
如<1>至<5>中任一項所記載之半導體晶圓表面保護用黏著帶,其中上述中間樹脂層之厚度為100μm~400μm。 The adhesive tape for semiconductor wafer surface protection according to any one of <1> to <5>, wherein the thickness of the intermediate resin layer is 100 μm to 400 μm.
<7> <7>
如<1>至<6>中任一項所記載之半導體晶圓表面保護用黏著帶,其中上述黏著劑層之厚度為5μm~40μm。 The adhesive tape for protecting a semiconductor wafer surface according to any one of <1> to <6>, wherein the thickness of the adhesive layer is 5 μm to 40 μm.
<8> <8>
如<1>至<7>中任一項所記載之半導體晶圓表面保護用黏著帶,其中上述基材膜之厚度為25μm~100μm。 The adhesive tape for semiconductor wafer surface protection according to any one of <1> to <7>, wherein the thickness of the substrate film is 25 μm to 100 μm.
<9> <9>
一種半導體晶圓之加工方法,其包括將半導體晶圓表面保護用黏著帶於40℃~90℃之條件下加熱貼合於具有20μm以上之凹凸差的半導體晶圓表面並對半導體晶圓背面進行研削,上述半導體晶圓表面保護用黏著帶具有基材膜、黏著劑層及位於該基材膜與該黏著劑層間之中間樹脂層,該中間樹脂層之厚度為上述凹凸差以上,構成該中間樹脂層之樹脂的熔點或菲卡軟化點為40℃~90℃,構成該中間樹脂層之樹脂的熔體質量流率為10g/min~100g/min。 A method for processing a semiconductor wafer, comprising heating and bonding the adhesive tape for protecting the surface of a semiconductor wafer to a surface of a semiconductor wafer having an unevenness of more than 20 μm at a temperature of 40 ° C. to 90 ° C. The above-mentioned adhesive tape for semiconductor wafer surface protection has a base film, an adhesive layer and an intermediate resin layer located between the base film and the adhesive layer. The melting point or the softening point of the resin of the resin layer is 40 ° C. to 90 ° C., and the melt mass flow rate of the resin constituting the intermediate resin layer is 10 g / min to 100 g / min.
於本發明之說明中,半導體晶圓表面係指半導體晶圓具有凹凸之面,即形成有積體電路之面。另外,將該表面之相反側之面稱為背面。 In the description of the present invention, the surface of a semiconductor wafer refers to a surface on which a semiconductor wafer has unevenness, that is, a surface on which an integrated circuit is formed. In addition, the surface on the opposite side of this surface is called a back surface.
於本發明之說明中,凹凸差係指凸部中之最高部至晶圓表面的距離或凹部 中之最深部至半導體晶圓表面的距離。例如於半導體晶圓上形成有金屬電極(凸塊)之情形時,最高部係指最高之凸塊之頂點部,自該頂點部至半導體晶圓表面的距離即凸塊之高度為凹凸差。或者,於半導體晶圓上形成有劃線(切割線)之情形時,最深部係指劃線中之最深位置,自該最深位置至半導體晶圓表面之距離稱為凹凸差。 In the description of the present invention, the unevenness means the distance from the highest portion of the convex portion to the surface of the wafer or the distance from the deepest portion of the concave portion to the surface of the semiconductor wafer. For example, when a metal electrode (bump) is formed on a semiconductor wafer, the highest portion refers to the vertex portion of the highest bump, and the distance from the vertex portion to the surface of the semiconductor wafer, that is, the height of the bump is the unevenness. Alternatively, when a scribe line (cut line) is formed on a semiconductor wafer, the deepest part refers to the deepest position in the scribe line, and the distance from the deepest position to the surface of the semiconductor wafer is called the unevenness.
於本發明之說明中,使用「~」表示之數值範圍係指包括「~」之前後所記載之數值作為下限值及上限值的範圍。 In the description of the present invention, a numerical range indicated by "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value.
本發明之半導體晶圓表面保護用黏著帶於半導體晶圓加工時藉由牢固地密接於半導體晶圓而減少滲漏之產生,另外,能夠抑制加工裝置內之搬送錯誤或半導體晶圓破損,且於剝離時不易產生糊劑殘留。進而,本發明之半導體晶圓表面保護用黏著帶能夠抑制貼合於半導體晶圓表面之狀態下之翹曲。另外,根據本發明之半導體晶圓之加工方法,使用上述半導體晶圓表面保護用黏著帶能夠獲得以窄間距具有高凸塊的薄膜狀半導體晶圓。 The adhesive tape for protecting the surface of a semiconductor wafer according to the present invention reduces the occurrence of leakage by tightly adhering to the semiconductor wafer during the processing of the semiconductor wafer, and furthermore, it is possible to suppress a transfer error in the processing device or damage to the semiconductor wafer, and It is not easy to generate paste residue when peeling. Furthermore, the adhesive tape for semiconductor wafer surface protection of this invention can suppress the curvature in the state stuck to the surface of a semiconductor wafer. In addition, according to the method for processing a semiconductor wafer of the present invention, a thin film semiconductor wafer having a high pitch at a narrow pitch can be obtained by using the above-mentioned adhesive tape for semiconductor wafer surface protection.
10‧‧‧半導體晶圓表面保護用黏著帶 10‧‧‧ Adhesive tape for semiconductor wafer surface protection
1‧‧‧黏著劑層 1‧‧‧adhesive layer
2‧‧‧中間樹脂層 2‧‧‧ intermediate resin layer
3‧‧‧基材膜 3‧‧‧ substrate film
圖1係本發明之晶圓表面保護用黏著帶之示意性概略剖面圖。 FIG. 1 is a schematic cross-sectional view of an adhesive tape for wafer surface protection according to the present invention.
以下,對本發明之較佳之實施形態進行詳細說明。 Hereinafter, preferred embodiments of the present invention will be described in detail.
[半導體晶圓表面保護用黏著帶] [Adhesive tape for semiconductor wafer surface protection]
本發明之半導體晶圓表面保護用黏著帶係於40℃~90℃之條件下加熱貼合於具有20μm以上之凹凸差的半導體晶圓表面者,該半導體晶圓表面保護用黏著帶具有基材膜及黏著劑層,進而於該基材膜與該黏著劑層之間至少具有中間 樹脂層。上述中間樹脂層之厚度為上述凹凸差以上。另外,構成上述中間樹脂層之樹脂的熔點或菲卡軟化點為40℃~90℃,該中間樹脂層之熔體質量流率為10g/min~100g/min。 The adhesive tape for protecting the surface of a semiconductor wafer according to the present invention is one which is heated and bonded to a surface of a semiconductor wafer having an unevenness of more than 20 μm under the conditions of 40 ° C to 90 ° C. A film and an adhesive layer, and further comprising at least an intermediate resin layer between the substrate film and the adhesive layer. The thickness of the intermediate resin layer is equal to or greater than the unevenness. In addition, the melting point or the softening point of the resin constituting the intermediate resin layer is 40 ° C. to 90 ° C., and the melt mass flow rate of the intermediate resin layer is 10 g / min to 100 g / min.
上述黏著劑層並無特別限制,較佳為輻射硬化型黏著劑層,「輻射硬化型黏著劑層」係指藉由輻射[例如紫外線之類的光線(包括雷射光線)、電子束等游離輻射]之照射而硬化的黏著劑層。所照射之輻射較佳為紫外線。 The above-mentioned adhesive layer is not particularly limited, and is preferably a radiation-curable adhesive layer. The "radiation-curable adhesive layer" refers to radiation (eg, light such as ultraviolet rays (including laser light), electron beams, etc. Radiation] and hardened adhesive layer. The radiation irradiated is preferably ultraviolet rays.
<基材膜> <Substrate film>
本發明之半導體晶圓表面保護用黏著帶所使用之基材膜並無特別限制。於本發明之半導體晶圓表面保護用黏著帶中,構成基材膜之材料之熔點較佳為90℃~150℃之範圍,更佳為100℃~140℃之範圍,進而較佳為110℃~130℃之範圍。藉由使基材膜之熔點為上述範圍,能夠防止於貼合表面保護帶之步驟中熔接至貼合輥或夾頭台(chuck table)之情況,而能夠充分地貼合於具有20μm以上之凹凸的半導體晶圓。另外,於貼合切晶接合一體型膜(DDF)之情形時,亦能夠防止熔接至夾頭台之情況而能夠進行DDF之貼合。為了藉由對中間樹脂層施加熱而使中間樹脂層之流動性提升,確保對具有20μm以上之凹凸差的半導體晶圓之充分密接性,本發明之半導體晶圓表面保護用黏著帶係於夠高之溫度即40℃~90℃之條件下進行加熱貼合。因此,若構成基材膜之材料之熔點過低,則有基材膜之背面熔化而與貼合輥或夾頭台發生熔接之虞。基材膜例如於如苯乙烯般由非結晶性之樹脂構成的情形時,不存在熔點,因此菲卡軟化點成為指標。即,較佳為菲卡軟化點處於上述熔點之範圍。若菲卡軟化點過高,則基材背面(與中間樹脂層相接之面的相反側之面)會產生流動性,因此有進入夾頭台之多孔部之虞。 The substrate film used for the adhesive tape for semiconductor wafer surface protection of the present invention is not particularly limited. In the adhesive tape for semiconductor wafer surface protection of the present invention, the melting point of the material constituting the base film is preferably in the range of 90 ° C to 150 ° C, more preferably in the range of 100 ° C to 140 ° C, and further preferably 110 ° C. Range of ~ 130 ℃. By setting the melting point of the base film to the above range, it is possible to prevent welding to a bonding roller or a chuck table in the step of bonding the surface protective tape, and it is possible to adequately bond a film having a thickness of 20 μm or more. Bump semiconductor wafer. In addition, in the case of bonding the die-cutting integrated film (DDF), it is also possible to prevent the case of welding to the chuck table and perform DDF bonding. In order to improve the fluidity of the intermediate resin layer by applying heat to the intermediate resin layer, and to ensure sufficient adhesion to a semiconductor wafer having unevenness of 20 μm or more, the adhesive tape for protecting the surface of a semiconductor wafer of the present invention is sufficient. High temperature, that is, heating and bonding under the conditions of 40 ° C to 90 ° C. Therefore, if the melting point of the material constituting the base film is too low, there is a possibility that the back surface of the base film is melted and welded to the bonding roller or the chuck table. When the base film is made of, for example, an amorphous resin such as styrene, there is no melting point, so the softening point of the Ficca is used as an index. That is, it is preferable that the Ficca softening point is in the range of the melting point. If the Ficca softening point is too high, the back surface of the substrate (the surface opposite to the surface in contact with the intermediate resin layer) will have fluidity, so there is a possibility that it may enter the porous portion of the chuck table.
本發明之半導體晶圓表面保護用黏著帶所使用之基材膜較佳為由樹脂構成者,作為此種樹脂,可使用本發明所屬技術領域中通常使用之塑 膠、橡膠等。例如可列舉:聚烯烴系樹脂(例如由聚乙烯、聚丙烯、乙烯-丙烯共聚物、聚丁烯-1、聚-4-甲基戊烯-1、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物或離子聚合物等含有乙烯性不飽和基之單體的均聚物或共聚物構成之樹脂)、聚酯樹脂(例如由聚對酞酸乙二酯或聚萘二甲酸乙二酯(polyethylene naphthalate)構成之樹脂)、聚碳酸酯樹脂、聚胺酯樹脂(polyurethane resin)、工程塑膠(例如聚甲基丙烯酸甲酯)、合成橡膠類(例如苯乙烯-乙烯-丁烯或戊烯系共聚物)、熱塑性彈性體(例如聚醯胺-多元醇共聚物)。本發明之表面保護帶所使用的基材膜可為由1種上述樹脂單獨構成之膜,亦可為將2種以上組合而成之膜。另外,本發明之表面保護帶所使用的基材膜可使用單層,亦可使用製成多層者。此外,多層之基材膜較佳為構成與中間樹脂層為相反側之最外層的材料之熔點處於上述範圍。 The base film used in the adhesive tape for protecting the surface of a semiconductor wafer of the present invention is preferably made of a resin. As such a resin, plastics, rubbers, and the like generally used in the technical field to which the present invention belongs can be used. Examples include polyolefin resins (for example, polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene- Ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, or ionic polymer (e.g., homopolymers or copolymers of monomers containing ethylenically unsaturated groups), polyester resins (such as Resin consisting of polyethylene terephthalate or polyethylene naphthalate), polycarbonate resin, polyurethane resin, engineering plastics (such as polymethyl methacrylate), synthetic Rubbers (for example, styrene-ethylene-butene or pentene-based copolymers), and thermoplastic elastomers (for example, polyamide-polyol copolymers). The base film used in the surface protection tape of the present invention may be a film composed of one of the above-mentioned resins alone, or may be a film composed of a combination of two or more. In addition, the base film used in the surface protection tape of the present invention may be a single layer or a multilayer film. In addition, the multilayer base film is preferably such that the melting point of the material constituting the outermost layer on the opposite side from the intermediate resin layer is in the above range.
於本發明之表面保護帶中,基材膜較佳為由聚酯樹脂或聚烯烴系樹脂構成之膜。 In the surface protective tape of the present invention, the base film is preferably a film made of a polyester resin or a polyolefin resin.
若考慮半導體晶圓翹曲之矯正力與表面保護帶之剝離性的平衡、成本或可製造性等方面,則基材膜之厚度較佳為25μm以上,進而較佳為50μm以上。上限較佳為200μm以下,更佳為150μm以下,尤佳為100μm以下。藉由使基材膜之厚度處於上述範圍,即便於將半導體晶圓薄膜研削至50μm以下之情形時,亦能夠抑制搬送錯誤並且進行研削,而能夠提升表面保護帶之剝離性。此外,「將半導體晶圓薄膜研削至50μm以下之情形」對於具有凸塊之半導體晶圓而言,意指將除凸塊以外之半導體晶圓本身的厚度背面研削至50μm以下。另外,對於形成有劃線之半導體晶圓而言,意指上述最深部至背面之距離。 Considering the balance between the correction force of the semiconductor wafer warpage and the peelability of the surface protective tape, cost, and manufacturability, the thickness of the substrate film is preferably 25 μm or more, and more preferably 50 μm or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less. By making the thickness of the base film within the above range, even when the semiconductor wafer thin film is ground to 50 μm or less, it is possible to suppress conveying errors and perform grinding, thereby improving the peelability of the surface protective tape. In addition, "the case where the semiconductor wafer thin film is ground to 50 µm or less" means that, for a semiconductor wafer having bumps, the thickness of the semiconductor wafer other than the bump itself is ground to 50 µm or less. In addition, the semiconductor wafer on which the scribe lines are formed means the distance from the deepest portion to the back surface.
<中間樹脂層> <Intermediate resin layer>
本發明之半導體晶圓表面保護用黏著帶必須具有中間樹脂層。藉由將表面保護帶於40~90℃之溫度條件下加熱貼合於半導體晶圓表面,中間樹脂層發生熔融,從而黏著劑層及中間樹脂層之形狀追隨具有20μm以上之凹凸差的半導體晶圓表面之形狀。進而由於貼合後加以冷卻,故而於黏著劑層密接於半導體晶圓表面之狀態下固定表面保護帶,而能夠抑制灰塵侵入等。本發明之表面保護帶所使用之構成中間樹脂層之樹脂的熔點或菲卡軟化點為40℃~90℃之範圍,更佳為60℃~80℃之範圍。由於必須將表面保護帶於40℃~90℃之範圍進行加熱貼合以使黏著劑層密接於半導體晶圓表面,故而中間樹脂層之拉伸彈性模數必須於該溫度範圍較大地發生變化。即,半導體晶圓研削時為通常之溫度,若樹脂於該溫度流動,則研削時之厚度精確度會極端惡化,因此較佳為高彈性。另一方面,為了於進行加熱貼合時充分地追隨半導體晶圓表面,而必須為低彈性,因此對中間樹脂層要求相反之性能。為了實現該相反之性能,較大地影響拉伸彈性模數及流動性之熔點或菲卡軟化點必須為40~90℃。熔點及菲卡軟化點係藉由實施例中所記載之方法進行測定。於本發明中,中間樹脂層亦較佳為熔點或菲卡軟化點之兩者為40~90℃。 The adhesive tape for semiconductor wafer surface protection of the present invention must have an intermediate resin layer. The surface protective tape is heated and bonded to the surface of the semiconductor wafer at a temperature of 40 to 90 ° C, and the intermediate resin layer is melted, so that the shape of the adhesive layer and the intermediate resin layer follows the semiconductor crystal with an unevenness of 20 μm or more. The shape of a round surface. Furthermore, since it is cooled after bonding, the surface protection tape is fixed in a state where the adhesive layer is in close contact with the surface of the semiconductor wafer, and dust intrusion can be suppressed. The melting point or softening point of the resin constituting the intermediate resin layer used in the surface protective tape of the present invention is in the range of 40 ° C to 90 ° C, and more preferably in the range of 60 ° C to 80 ° C. Since the surface protection tape must be heated and bonded in the range of 40 ° C to 90 ° C so that the adhesive layer is in close contact with the surface of the semiconductor wafer, the tensile elastic modulus of the intermediate resin layer must be greatly changed within this temperature range. That is, the semiconductor wafer is at a normal temperature during grinding, and if the resin flows at this temperature, the thickness accuracy during grinding is extremely deteriorated, and therefore high elasticity is preferred. On the other hand, in order to sufficiently follow the surface of the semiconductor wafer during heating bonding, it is necessary to have low elasticity, and therefore, the reverse performance is required for the intermediate resin layer. In order to achieve the opposite performance, the melting point or Ficah softening point that greatly affects the tensile elastic modulus and fluidity must be 40 to 90 ° C. Melting points and Fica softening points were measured by the methods described in the examples. In the present invention, it is also preferred that the intermediate resin layer has a melting point or a Ficca softening point of 40 to 90 ° C.
於構成中間樹脂層之樹脂的熔點及菲卡軟化點未達40℃之情形時,難以進行成形,另外,厚度精確度亦會變差。即,中間樹脂層之厚度會變得不均勻。另一方面,於構成中間樹脂層之樹脂的熔點及菲卡軟化點超過90℃之情形時,即便於40~90℃之條件下進行加熱貼合亦不會充分地追隨半導體晶圓表面之形狀,因此容易產生灰塵侵入或晶圓破裂。 When the melting point of the resin constituting the intermediate resin layer and the softening point of the Ficca do not reach 40 ° C., it is difficult to perform molding, and the thickness accuracy is also deteriorated. That is, the thickness of the intermediate resin layer becomes uneven. On the other hand, when the melting point of the resin constituting the intermediate resin layer and the softening point of the Ficca exceed 90 ° C, the shape of the surface of the semiconductor wafer will not be sufficiently followed even if the heat bonding is performed at 40 to 90 ° C. Therefore, it is easy to produce dust intrusion or wafer cracking.
本發明之表面保護帶所使用之構成中間樹脂層之樹脂的熔點或菲卡軟化點為40~90℃,進而熔體質量流率(MFR)為10g/min~100g/min。熔點或菲卡軟化點處於上述範圍內之中間樹脂層若如上所述般將表面保護帶於40~90℃之條件下貼合於半導體晶圓,則中間樹脂層及黏著劑層之形狀 會追隨半導體晶圓表面之形狀。其結果為,黏著劑層充分地密接於半導體晶圓表面。但是,僅憑構成中間樹脂層之樹脂的熔點或菲卡軟化點處於上述範圍內,若半導體晶圓之凹凸差成為250μm以上,則表面保護帶本身變形為凹凸狀,而誘發搬送錯誤。藉由將MFR設為10g/min~100g/min之範圍,加熱貼合時之中間樹脂層會產生適度之流動性,能夠使追隨凹凸而變形之表面保護帶恢復至平坦之狀態。藉此,能夠防止由搬送錯誤及半導體晶圓掉落所引起之破損。若中間樹脂層之熔體質量流率(MFR)未達10g/min,則流動性不足,會於表面保護帶本身變形之狀態下被加工,因此會產生搬送錯誤或半導體晶圓之破損。另一方面,若構成中間樹脂層之樹脂的熔體質量流率(MFR)超過100g/min,則維持作為基材之厚度精確度(厚度之均勻性)之狀況下之製膜變得困難。另外,研削後之半導體晶圓之厚度精確度亦會變差。本發明之表面保護帶藉由使構成中間樹脂層之樹脂的熔點或菲卡軟化點處於上述範圍內,進而使MFR處於10g/min~100g/min之範圍,而亦可應用於半導體晶圓之凹凸差為250μm以上之半導體晶圓之加工。實際上能夠應用本發明之表面保護帶之半導體晶圓之凹凸差的上限為300μm以下。 The melting point or softening point of the resin constituting the intermediate resin layer used in the surface protection tape of the present invention is 40 to 90 ° C, and the melt mass flow rate (MFR) is 10 g / min to 100 g / min. If the intermediate resin layer whose melting point or Ficca softening point is within the above range, if the surface protective tape is bonded to a semiconductor wafer at 40 to 90 ° C as described above, the shape of the intermediate resin layer and the adhesive layer will follow The shape of the surface of a semiconductor wafer. As a result, the adhesive layer is sufficiently in close contact with the surface of the semiconductor wafer. However, only when the melting point or the softening point of the resin constituting the intermediate resin layer is within the above-mentioned range, if the unevenness of the semiconductor wafer becomes 250 μm or more, the surface protective tape itself is deformed into an uneven shape, thereby causing a transfer error. By setting the MFR to a range of 10 g / min to 100 g / min, the intermediate resin layer during heating and bonding will have moderate fluidity, and the surface protective tape deformed following the unevenness can be restored to a flat state. Thereby, it is possible to prevent damage due to a transfer error and a fall of the semiconductor wafer. If the melt mass flow rate (MFR) of the intermediate resin layer is less than 10 g / min, the fluidity is insufficient, and the surface protection tape itself will be processed while it is deformed. Therefore, transportation errors or damage to the semiconductor wafer may occur. On the other hand, if the melt mass flow rate (MFR) of the resin constituting the intermediate resin layer exceeds 100 g / min, it becomes difficult to form a film while maintaining the thickness accuracy (thickness uniformity) of the substrate. In addition, the precision of the thickness of the semiconductor wafer after grinding will also deteriorate. The surface protective tape of the present invention can also be applied to semiconductor wafers by making the melting point or softening point of the resin constituting the intermediate resin layer within the above-mentioned range, and then the MFR in the range of 10 g / min to 100 g / min. Processing of semiconductor wafers with unevenness of 250 μm or more. Actually, the upper limit of the unevenness of the semiconductor wafer to which the surface protection tape of the present invention can be applied is 300 μm or less.
此外,MFR係藉由實施例中所記載之方法進行測定。 The MFR is measured by the method described in the examples.
由於中間樹脂層並非以黏著為目的,故而較佳為非黏著性。非黏著性係指於常溫下不黏膩之狀態。 Since the intermediate resin layer is not intended for adhesion, it is preferably non-adhesive. Non-adhesive refers to a state that is not sticky at room temperature.
作為構成此種樹脂層或樹脂膜之樹脂,例如可列舉:由為選自自由基聚合性酸共聚單體、丙烯酸酯共聚單體、甲基丙烯酸酯共聚單體及羧酸乙烯酯共聚單體中之至少1種共聚單體與乙烯之共聚物的乙烯系共聚物構成之樹脂、由離子聚合物等包含乙烯性不飽和基之單體的均聚物或共聚物構成之樹脂、由聚乙烯(例如低密度聚乙烯)構成之樹脂。本發明之表面保護帶所使用的中間樹脂層中可將該等樹脂單獨使用1種,亦可將2種以上組合使用。另外,上述中間樹 脂層亦可具有2層以上。 Examples of the resin constituting such a resin layer or a resin film include a resin selected from a radical polymerizable acid comonomer, an acrylate comonomer, a methacrylate comonomer, and a vinyl carboxylate comonomer. Resin composed of at least one of a comonomer and an ethylene-based copolymer of ethylene; resin composed of a homopolymer or copolymer of a monomer containing an ethylenically unsaturated group such as an ionic polymer; polyethylene (Such as low density polyethylene). Among the intermediate resin layers used in the surface protective tape of the present invention, these resins may be used alone or in combination of two or more thereof. The intermediate resin layer may have two or more layers.
作為上述自由基聚合性酸共聚單體,具體而言,可列舉:馬來酸、富馬酸、檸康酸、伊康酸等α,β-不飽和二羧酸或該等之酸酐;丙烯酸、甲基丙烯酸、丁烯酸、乙烯乙酸、戊烯酸等不飽和單羧酸等,其中較佳為馬來酸酐、丙烯酸、甲基丙烯酸。 Specific examples of the radical polymerizable acid comonomer include α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and iconic acid, or anhydrides thereof; acrylic acid; And unsaturated monocarboxylic acids such as methacrylic acid, butenoic acid, ethylene acetic acid, and pentenoic acid. Among them, maleic anhydride, acrylic acid, and methacrylic acid are preferred.
作為上述丙烯酸酯共聚單體,具體而言,可列舉:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯等,其中較佳為丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯。 Specific examples of the acrylate comonomer include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Among them, methyl acrylate, ethyl acrylate, and butyl acrylate are preferred.
作為上述甲基丙烯酸酯共聚單體,具體而言,可列舉:甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯等,其中較佳為甲基丙烯酸甲酯、甲基丙烯酸乙酯。 Specific examples of the methacrylate comonomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Among them, methyl methacrylate is preferred. Esters, ethyl methacrylate.
作為上述羧酸乙烯酯共聚單體,具體而言,可列舉:甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯等,其中較佳為乙酸乙烯酯。 Specific examples of the vinyl carboxylate comonomer include vinyl formate, vinyl acetate, vinyl propionate, and vinyl butyrate, and among these, vinyl acetate is preferred.
作為乙烯系共聚物之具體例,作為二元共聚物,例如可列舉:乙烯-丙烯酸共聚物、乙烯-甲基丙烯酸共聚物、乙烯-馬來酸酐共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-甲基丙烯酸乙酯共聚物、乙烯-乙酸乙烯酯共聚物。 As specific examples of the ethylene-based copolymer, examples of the binary copolymer include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic anhydride copolymer, ethylene-methyl acrylate copolymer, and ethylene. -Ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-vinyl acetate copolymer.
作為三元共聚物,例如可列舉:乙烯-丙烯酸-丙烯酸甲酯共聚物、乙烯-丙烯酸-丙烯酸乙酯共聚物、乙烯-丙烯酸-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸-甲基丙烯酸甲酯共聚物、乙烯-甲基丙烯酸-甲基丙烯酸乙酯共聚物、乙烯-甲基丙烯酸-乙酸乙烯酯共聚物、乙烯-馬來酸酐-丙烯酸甲酯共聚物、乙烯-馬來酸酐-丙烯酸乙酯共聚物、乙烯-馬來酸酐-甲基丙烯酸甲酯共聚物、乙烯-馬來酸酐-甲基丙烯酸乙酯共聚物、乙烯-馬來酸酐-乙酸乙烯酯共聚物。 Examples of the terpolymer include ethylene-acrylic acid-methyl acrylate copolymer, ethylene-acrylic acid-ethyl acrylate copolymer, ethylene-acrylic acid-vinyl acetate copolymer, and ethylene-methacrylic acid-methyl methacrylate Ester copolymer, ethylene-methacrylic acid-ethyl methacrylate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer, ethylene-maleic anhydride-methyl acrylate copolymer, ethylene-maleic anhydride-ethyl acrylate Ester copolymer, ethylene-maleic anhydride-methyl methacrylate copolymer, ethylene-maleic anhydride-ethyl methacrylate copolymer, ethylene-maleic anhydride-vinyl acetate copolymer.
進而,亦可舉將上述共聚單體組合而成之多元共聚物。 Further, a multi-component copolymer obtained by combining the above-mentioned comonomers may be mentioned.
上述共聚物中,尤佳為乙烯-丙烯酸共聚物、乙烯-甲基丙烯酸共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-馬來酸酐-丙烯酸甲酯共聚物、乙烯-馬來酸酐-丙烯酸乙酯共聚物、乙烯-馬來酸酐-甲基丙烯酸甲酯共聚物及乙烯-馬來酸酐-甲基丙烯酸乙酯共聚物,較佳為乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物及乙烯-丙烯酸丁酯共聚物。 Among the above-mentioned copolymers, particularly preferred are ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, and ethylene-malay. Anhydride-methyl acrylate copolymer, ethylene-maleic anhydride-ethyl acrylate copolymer, ethylene-maleic anhydride-methyl methacrylate copolymer, and ethylene-maleic anhydride-ethyl methacrylate copolymer, preferably It is an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-butyl acrylate copolymer.
乙烯系共聚物之合成所使用之乙烯與共聚單體的合計質量中,共聚單體之比率較佳為10質量%~50質量%,進而較佳為15質量%~40質量%。 Of the total mass of ethylene and comonomer used in the synthesis of the ethylene-based copolymer, the ratio of the comonomer is preferably 10% by mass to 50% by mass, and more preferably 15% by mass to 40% by mass.
中間樹脂層如上述般可為單層,亦可為多層。就製造性之方面而言,與單層相比,多層更容易膜化。於製成多層之情形時,基材膜側之層較佳為由低密度聚乙烯或乙烯-乙酸乙烯酯共聚物構成之樹脂層或樹脂膜,藉由擠出而能夠於多層之中間樹脂層之製膜時降低不良率且能夠廉價地進行製造。中間樹脂層為多層之情形時之熔點或菲卡軟化點表示構成與黏著劑層相接之層或膜之樹脂的熔點或菲卡軟化點。 The intermediate resin layer may be a single layer or a plurality of layers as described above. In terms of manufacturability, multilayers are easier to form than monolayers. In the case of making multiple layers, the layer on the base film side is preferably a resin layer or resin film composed of low-density polyethylene or an ethylene-vinyl acetate copolymer, and an intermediate resin layer capable of forming multiple layers by extrusion. It can reduce the defect rate at the time of film formation and can manufacture it cheaply. When the intermediate resin layer is multilayered, the melting point or the softening point of the Feika means the melting point or the softening point of the resin constituting the layer or film in contact with the adhesive layer.
樹脂層或樹脂膜之積層方法只要為不會對樹脂層或樹脂膜之厚度之精確度或該樹脂層或樹脂膜之缺陷產生影響之範圍,則無特別限制。例如可舉利用共擠出之製膜或利用接著劑之貼合等。 The method of laminating a resin layer or a resin film is not particularly limited as long as it does not affect the accuracy of the thickness of the resin layer or the resin film or the defects of the resin layer or the resin film. For example, film formation by coextrusion or lamination by an adhesive agent can be mentioned.
關於基材膜之厚度與中間樹脂層之厚度的比,就黏著劑層及中間樹脂層對半導體晶圓表面形狀之追隨性的方面而言,較佳為基材膜之厚度:中間樹脂層之厚度=0.5:9.5~3:7之範圍。基材膜與中間樹脂層之積層方法只要不會對成為一體之膜的缺陷產生影響,則無特別限制,可進行利用共擠出之製膜或利用接著劑之貼合。 Regarding the ratio of the thickness of the substrate film to the thickness of the intermediate resin layer, in terms of the followability of the adhesive layer and the intermediate resin layer to the surface shape of the semiconductor wafer, the thickness of the substrate film is preferably: Thickness = 0.5: 9.5 ~ 3: 7. The method of laminating the substrate film and the intermediate resin layer is not particularly limited as long as it does not affect the defects of the integrated film, and film formation by coextrusion or lamination by an adhesive can be performed.
本發明之表面保護帶所使用之中間樹脂層之厚度必須為半導體 晶圓之凹凸差以上,就製造性或厚度精確度之方面而言,較佳為100μm~400μm。若薄於半導體晶圓之凹凸差,則黏著劑層不會充分地密接於半導體晶圓,因此會產生灰塵侵入或晶圓破裂。本發明之表面保護帶所使用之中間樹脂層之厚度較佳為較半導體晶圓之凹凸差厚10μm~30μm。若中間樹脂層過厚,則有半導體晶圓之厚度精確度變差之虞,另外,製造成本亦會增加。另外,由於製造附帶凸塊之半導體晶圓之凸塊部分時會產生10μm左右之誤差,故而若除平均凸塊高度以外另具有10μm之厚度,則能夠充裕地進行追隨。 The thickness of the intermediate resin layer used in the surface protection tape of the present invention must be equal to or greater than the unevenness of the semiconductor wafer. In terms of manufacturability or thickness accuracy, it is preferably 100 m to 400 m. If the unevenness is thinner than the semiconductor wafer, the adhesive layer will not be sufficiently in close contact with the semiconductor wafer, so dust intrusion or wafer cracking will occur. The thickness of the intermediate resin layer used in the surface protection tape of the present invention is preferably 10 μm to 30 μm thicker than the unevenness of the semiconductor wafer. If the intermediate resin layer is too thick, the thickness accuracy of the semiconductor wafer may deteriorate, and in addition, the manufacturing cost may increase. In addition, since an error of about 10 μm occurs when manufacturing a bump portion of a semiconductor wafer with bumps, if it has a thickness of 10 μm in addition to the average bump height, it can be adequately followed.
<黏著劑層> <Adhesive layer>
本發明之表面保護帶所具有之黏著劑層所使用之黏著劑並無特別限制,較佳為輻射硬化型黏著劑。 The adhesive used in the adhesive layer of the surface protective tape of the present invention is not particularly limited, and a radiation-curable adhesive is preferred.
輻射硬化型黏著劑具有藉由輻射硬化而三維網狀化之性質即可,大致分為:1)由側鏈具有乙烯性不飽和基(由於具有輻射聚合性碳-碳雙鍵故而亦稱為乙烯性雙鍵)之基底樹脂(聚合物)構成的黏著劑;及2)對通常之橡膠系或(甲基)丙烯酸系之基底樹脂(聚合物)摻合分子中具有至少2個乙烯性不飽和基之低分子量化合物(以下稱為輻射聚合性低分子量化合物)及光聚合起始劑的黏著劑。 Radiation-hardening adhesives have the property of three-dimensional network formation by radiation hardening, which can be roughly divided into: 1) The ethylenically unsaturated group has a side chain (because it has a radiation polymerizable carbon-carbon double bond, it is also called Adhesive consisting of a base resin (polymer) of an ethylene-based double bond); and 2) A common rubber-based or (meth) acrylic base resin (polymer) has at least two ethylenic compounds in the molecule. Saturated low molecular weight compounds (hereinafter referred to as radiation polymerizable low molecular weight compounds) and adhesives for photopolymerization initiators.
對於本發明之表面保護帶而言,較佳為上述2)。 For the surface protective tape of the present invention, the above 2) is preferred.
1)由側鏈具有乙烯性不飽和基之基底樹脂構成的黏著劑 1) Adhesive composed of a base resin with an ethylenically unsaturated group in the side chain
側鏈具有乙烯性不飽和基的黏著劑較佳為(甲基)丙烯酸系黏著劑,更佳為基底樹脂含有(甲基)丙烯酸聚合物或(甲基)丙烯酸聚合物作為主成分者。 The adhesive having an ethylenically unsaturated group in the side chain is preferably a (meth) acrylic adhesive, and more preferably the base resin contains a (meth) acrylic polymer or a (meth) acrylic polymer as a main component.
此處,「含有(甲基)丙烯酸聚合物作為主成分」係指構成基底樹脂之聚合物或樹脂中(甲基)丙烯酸系聚合物之含量至少為50質量%以上,較佳為80質量%以上(100質量%以下)。 Here, "containing a (meth) acrylic polymer as a main component" means that the content of the (meth) acrylic polymer in the polymer constituting the base resin or the resin is at least 50% by mass, preferably 80% by mass. Above (less than 100% by mass).
(甲基)丙烯酸聚合物藉由至少於側鏈具有乙烯性不飽和基,能 夠藉由照射輻射而硬化。(甲基)丙烯酸聚合物亦可進而具有環氧基或羧基等官能基。 The (meth) acrylic polymer has an ethylenically unsaturated group at least in the side chain, and can be hardened by irradiation of radiation. The (meth) acrylic polymer may further have a functional group such as an epoxy group or a carboxyl group.
側鏈具有乙烯性不飽和基之(甲基)丙烯酸聚合物可為藉由任意方式製造者,例如較佳為使側鏈具有官能基(α)之(甲基)丙烯酸聚合物與如下化合物進行反應而獲得者,該化合物具有(甲基)丙烯醯基、(甲基)(甲基)丙烯醯氧基等具有乙烯性不飽和基之基且具有能夠與該(甲基)丙烯酸聚合物之側鏈之官能基(α)進行反應的官能基(β)。 The (meth) acrylic polymer having an ethylenically unsaturated group in the side chain may be produced by any method. For example, the (meth) acrylic polymer having a functional group (α) in the side chain is preferably prepared with the following compound. The compound obtained by the reaction has a group having an ethylenically unsaturated group such as a (meth) acrylfluorenyl group, a (meth) (meth) acrylfluorenyloxy group, and a compound capable of interacting with the (meth) acrylic polymer. A functional group (β) that reacts with a functional group (α) of a side chain.
具有乙烯性不飽和基之基只要具有非芳香族性之乙烯性雙鍵,則可為任意基,較佳為(甲基)丙烯醯基、(甲基)丙烯醯氧基、(甲基)丙烯醯胺基、烯丙基、1-丙烯基、乙烯基(包括苯乙烯或取代苯乙烯),更佳為(甲基)丙烯醯基、(甲基)丙烯醯氧基。 The group having an ethylenically unsaturated group may be any group as long as it has a non-aromatic ethylenic double bond, and is preferably (meth) acrylfluorenyl, (meth) acrylfluorenyloxy, (meth) Acrylamino, allyl, 1-propenyl, and vinyl (including styrene or substituted styrene), more preferably (meth) acrylfluorenyl and (meth) acrylfluorenyl.
作為官能基(α)、(β),可列舉:羧基、羥基、胺基、氫硫基、環狀酸酐基、環氧基、異氰酸基(-N=C=O)等。 Examples of the functional groups (α) and (β) include a carboxyl group, a hydroxyl group, an amine group, a hydrogen thio group, a cyclic acid anhydride group, an epoxy group, and an isocyanate group (-N = C = O).
此處,於官能基(α)與官能基(β)中之一個官能基為羧基、羥基、胺基、氫硫基或環狀酸酐基之情形時,另一個官能基可列舉:環氧基、異氰酸基。於一個官能基為環狀酸酐基之情形時,另一個官能基可列舉:羧基、羥基、胺基、氫硫基。此外,於一個官能基為環氧基之情形時,另一個官能基亦可為環氧基。 Here, when one functional group of the functional group (α) and the functional group (β) is a carboxyl group, a hydroxyl group, an amine group, a hydrogen thio group, or a cyclic acid anhydride group, the other functional group may be an epoxy group: , Isocyanate. In the case where one functional group is a cyclic acid anhydride group, the other functional group includes a carboxyl group, a hydroxyl group, an amine group, and a hydrogenthio group. In addition, when one functional group is an epoxy group, the other functional group may be an epoxy group.
作為官能基(α),較佳為羧基、羥基,尤佳為羥基。 The functional group (α) is preferably a carboxyl group or a hydroxyl group, and particularly preferably a hydroxyl group.
側鏈具有官能基(α)之(甲基)丙烯酸系聚合物可藉由將具有官能基(α)之(甲基)丙烯酸系單體(較佳為(甲基)丙烯酸酯[尤其於醇部具有官能基(α)者])用於單體成分而獲得。 The (meth) acrylic polymer having a functional group (α) in the side chain can be obtained by combining a (meth) acrylic monomer (preferably a (meth) acrylic acid ester (particularly alcohol) having a functional group (α) A moiety having a functional group (α)]) is used for a monomer component.
側鏈具有官能基(α)之(甲基)丙烯酸系聚合物較佳為共聚物,該共聚合成分較佳為(甲基)丙烯酸烷基酯,其中較佳為於醇部具有官能基(α)或乙烯性不 飽和基之基未經取代的(甲基)丙烯酸烷基酯。 The (meth) acrylic polymer having a functional group (α) in the side chain is preferably a copolymer, and the copolymerization component is preferably an alkyl (meth) acrylate, and among them, it is preferable to have a functional group in the alcohol part ( α) or an ethylenically unsaturated group is an unsubstituted alkyl (meth) acrylate.
作為(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯及(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸癸酯丙烯酸己酯。 Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and iso (meth) acrylate Butyl, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (formyl) Dodecyl acrylate, decyl (meth) acrylate, hexyl acrylate.
(甲基)丙烯酸酯可單獨使用1種,亦可將2種以上組合使用,較佳將醇部之碳數為5以下者與碳數為6~12者併用。 The (meth) acrylate may be used singly or in combination of two or more kinds. It is preferable to use a combination of a carbon number of 5 or less and a carbon number of 6 to 12 in the alcohol portion.
此外,由於越使用醇部之碳數大的單體,玻璃轉移點(Tg)越低,因此能夠獲得想要的玻璃轉移點者。另外,除玻璃轉移點以外,亦較佳為以提高相溶性及各種性能之目的而摻合乙酸乙烯酯、苯乙烯、丙烯腈等具有碳-碳雙鍵之低分子化合物,於該情形時,該等單體成分之含量較佳為5質量%以下之範圍內。 Further, the more the monomer having a larger carbon number in the alcohol portion is used, the lower the glass transition point (Tg), and therefore a person having a desired glass transition point can be obtained. In addition to the glass transition point, it is also preferable to blend low-molecular compounds having carbon-carbon double bonds such as vinyl acetate, styrene, and acrylonitrile for the purpose of improving compatibility and various properties. In this case, The content of these monomer components is preferably within a range of 5% by mass or less.
作為具有官能基(α)之(甲基)丙烯酸系單體,可列舉:丙烯酸、甲基丙烯酸、桂皮酸、伊康酸、富馬酸、酞酸、丙烯酸2-羥基烷基酯類、甲基丙烯酸2-羥基烷基酯類、二醇單丙烯酸酯類、二醇單甲基丙烯酸酯類、N-羥甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺、烯丙醇、丙烯酸N-烷基胺基乙酯類、甲基丙烯酸N-烷基胺基乙酯類、丙烯醯胺類、甲基丙烯醯胺類、馬來酸酐、伊康酸酐、富馬酸酐、酞酸酐、丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、烯丙基縮水甘油醚、將多異氰酸酯化合物之一部分異氰酸基利用具有羥基或羧基及乙烯性不飽和基之單體進行胺酯化而成者等。 Examples of the (meth) acrylic monomer having a functional group (α) include acrylic acid, methacrylic acid, cinnamic acid, itaconic acid, fumaric acid, phthalic acid, 2-hydroxyalkyl acrylates, and formic acid. 2-hydroxyalkyl acrylates, diol monoacrylates, diol monomethacrylates, N-methylol acrylamide, N-methylol acrylamide, allyl alcohol, N-alkylaminoethyl acrylate, N-alkylaminoethyl methacrylate, acrylamide, methacrylamidine, maleic anhydride, itaconic anhydride, fumaric anhydride, phthalic anhydride , Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, amine esterification of a part of the polyisocyanate compound with an isocyanate group using a monomer having a hydroxyl or carboxyl group and an ethylenically unsaturated group Are waiting.
該等中,較佳為丙烯酸、甲基丙烯酸、丙烯酸2-羥基烷基酯類、甲基丙烯酸2-羥基烷基酯類、丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯,更佳為丙烯酸、甲基丙烯酸、丙烯酸2-羥基烷基酯類、甲基丙烯酸2-羥 基烷基酯類,進而較佳為甲基丙烯酸、丙烯酸2-羥基烷基酯類、甲基丙烯酸2-羥基烷基酯類。 Among these, acrylic acid, methacrylic acid, 2-hydroxyalkyl acrylate, 2-hydroxyalkyl methacrylate, glycidyl acrylate, and glycidyl methacrylate are preferred, and acrylic acid, Methacrylic acid, 2-hydroxyalkyl acrylate, 2-hydroxyalkyl methacrylate, more preferably methacrylic acid, 2-hydroxyalkyl acrylate, 2-hydroxyalkyl methacrylate class.
作為具有乙烯性不飽和基及官能基(β)之化合物中的官能基(β),較佳為異氰酸基,例如可舉於醇部具有異氰酸(-N=C=O)基之(甲基)丙烯酸酯,其中較佳為取代有異氰酸(-N=C=O)基之(甲基)丙烯酸烷基酯。作為此種單體,例如可列舉:甲基丙烯酸2-異氰酸基乙酯、丙烯酸2-異氰酸基乙酯等。 The functional group (β) in the compound having an ethylenically unsaturated group and a functional group (β) is preferably an isocyanate group. For example, an isocyanate (-N = C = O) group can be mentioned in the alcohol part. Among these (meth) acrylates, alkyl (meth) acrylates substituted with an isocyanate (-N = C = O) group are preferred. Examples of such a monomer include 2-isocyanatoethyl methacrylate and 2-isocyanatoethyl acrylate.
另外,官能基(β)為異氰酸基以外之情形時之較佳的化合物可舉以具有官能基(α)之(甲基)丙烯酸系單體所例示的化合物。 Moreover, as a compound preferable when the functional group ((beta)) is other than an isocyanate group, the compound illustrated by the (meth) acrylic-type monomer which has a functional group ((alpha)) is mentioned.
具有乙烯性不飽和基及官能基(β)之化合物除於側鏈具有官能基(α)之(甲基)丙烯酸系聚合物以外,可藉由與聚合物之側鏈之官能基(α)(較佳為羥基)進行反應而將聚合性基置入共聚物,從而能夠降低照射輻射後之黏著力。 A compound having an ethylenically unsaturated group and a functional group (β) can be added to the functional group (α) of the polymer's side chain in addition to the (meth) acrylic polymer having a functional group (α) in the side chain. It is preferred that the (hydroxyl group) be reacted to place a polymerizable group in the copolymer, thereby reducing the adhesive force after irradiation with radiation.
於(甲基)丙烯酸系共聚物之合成中,作為使反應藉由溶液聚合進行之情形時之有機溶劑,可使用酮系、酯系、醇系、芳香族系者,其中較佳為甲苯、乙酸乙酯、異丙醇、苯甲賽璐蘇、乙賽璐蘇、丙酮、甲基乙基酮等通常為(甲基)丙烯酸系聚合物之良溶劑且沸點為60~120℃之溶劑。作為聚合起始劑,通常使用α,α'-偶氮雙異丁腈等偶氮雙系、苯甲醯基過氧化物等有機過氧化物系等自由基產生劑。此時,視需要可併用觸媒、聚合抑制劑,並調節聚合溫度及聚合時間,藉此能夠獲得想要的分子量之(甲基)丙烯酸系共聚物。另外,關於調節分子量,較佳使用硫醇、四氯化碳等溶劑。此外,該反應並不限定於溶液聚合,亦可藉由塊狀聚合、懸浮聚合等其他方法而進行。 In the synthesis of the (meth) acrylic copolymer, as the organic solvent in the case where the reaction is carried out by solution polymerization, ketone, ester, alcohol, and aromatic ones can be used. Among them, toluene, Ethyl acetate, isopropanol, benzocellulose, ethcelulose, acetone, methyl ethyl ketone, etc. are generally good solvents for (meth) acrylic polymers and solvents with a boiling point of 60 to 120 ° C. As the polymerization initiator, an azobis system such as α, α′-azobisisobutyronitrile, and an organic peroxide system such as benzamyl peroxide are generally used. In this case, if necessary, a catalyst and a polymerization inhibitor may be used in combination, and the polymerization temperature and the polymerization time may be adjusted to obtain a (meth) acrylic copolymer having a desired molecular weight. For the adjustment of the molecular weight, solvents such as thiol and carbon tetrachloride are preferably used. The reaction is not limited to solution polymerization, and may be performed by other methods such as block polymerization and suspension polymerization.
側鏈具有乙烯性不飽和基之基底樹脂[較佳為(甲基)丙烯酸系共聚物]的質量平均分子量較佳為20萬~100萬左右。 The mass average molecular weight of the base resin [preferably (meth) acrylic copolymer] having an ethylenically unsaturated group in the side chain is preferably about 200,000 to 1 million.
若質量平均分子量過大,則於照射輻射之情形時,照射輻射後之黏著劑無可撓性而變脆,因此會於剝離時於半導體晶片面產生糊劑殘留。若質量平均分子量過小,則照射輻射前之凝聚力小,黏著力弱,因此有於切晶時無法充分地保持半導體晶片而產生晶片飛散之虞。另外,照射輻射後,硬化亦不充分,而會於剝離時於半導體晶片面產生糊劑殘留。為了儘量防止該等情況,質量平均分子量較佳為20萬以上。 If the mass average molecular weight is too large, when the radiation is irradiated, the adhesive after the radiation has no flexibility and becomes brittle, so a paste residue may be generated on the surface of the semiconductor wafer when peeled. If the mass average molecular weight is too small, the cohesive force before radiation irradiation is small and the adhesive force is weak, so there is a possibility that the semiconductor wafer cannot be sufficiently held during the crystal cutting and the wafer may be scattered. In addition, after irradiation, the curing is not sufficient, and a paste residue may be generated on the surface of the semiconductor wafer during peeling. In order to prevent such cases as much as possible, the mass average molecular weight is preferably 200,000 or more.
此外,於本發明之說明中,質量平均分子量係藉由常規方法所獲得之聚苯乙烯換算的質量平均分子量。 In addition, in the description of the present invention, the mass average molecular weight is a polystyrene equivalent mass average molecular weight obtained by a conventional method.
側鏈具有乙烯性不飽和基之基底樹脂的玻璃轉移點較佳為-70~-10℃,更佳為-50~-10℃。若玻璃轉移點過低,則黏著劑之流動性高,導致糊劑殘留,若過高,則流動性不充分而不易適應半導體晶圓之背面,導致於半導體晶圓之研削加工時研削水滲入至晶圓表面。 The glass transition point of the base resin having an ethylenically unsaturated group in a side chain is preferably -70 to -10 ° C, and more preferably -50 to -10 ° C. If the glass transition point is too low, the fluidity of the adhesive is high, resulting in paste residue. If it is too high, the fluidity is insufficient and it is not easy to adapt to the back surface of the semiconductor wafer, which causes the infiltration of grinding water during the semiconductor wafer grinding process. To the wafer surface.
側鏈具有乙烯性不飽和基之基底樹脂的酸值[將存在於基底樹脂1g中之游離脂肪酸加以中和所需之氫氧化鉀的毫克數]較佳為0.5~30,更佳為1~20。 The acid value of the base resin having an ethylenically unsaturated group in the side chain [the number of milligrams of potassium hydroxide required to neutralize the free fatty acid present in 1 g of the base resin] is preferably 0.5 to 30, and more preferably 1 to 20.
側鏈具有乙烯性不飽和基之基底樹脂的羥值[將基底樹脂1g進行乙醯化時,將與羥基鍵結之乙酸加以中和所需之氫氧化鉀的毫克數]較佳為5~100,更佳為10~80。 The hydroxyl value of the base resin having an ethylenically unsaturated group in the side chain [the number of milligrams of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when acetating 1 g of the base resin, and neutralizing it] is preferably 5 to 100, more preferably 10 ~ 80.
藉由作上述設定,可進一步使得剝離半導體晶圓表面保護用黏著帶時防止糊劑殘留之效果優異。 By setting the above, it is possible to further improve the effect of preventing the residue of the paste when peeling the adhesive tape for protecting the surface of a semiconductor wafer.
此外,酸值或羥值之調整可藉由如下方式進行:於使側鏈具有官能基(α)之(甲基)丙烯酸系聚合物與如下化合物進行反應之階段殘留未反應之官能基,而調整為想要的酸值或羥值,所述化合物具有乙烯性不飽和基且具有能夠與該(甲基)丙烯酸系聚合物之側鏈之官能基(α)進行反應的官能基 (β)。 In addition, the adjustment of the acid value or the hydroxyl value can be performed by leaving unreacted functional groups at the stage where a (meth) acrylic polymer having a functional group (α) in a side chain reacts with the following compound, and It is adjusted to a desired acid value or hydroxyl value, and the compound has an ethylenically unsaturated group and a functional group (β) capable of reacting with a functional group (α) of a side chain of the (meth) acrylic polymer. .
於藉由照射輻射使側鏈具有乙烯性不飽和基之基底樹脂硬化的情形時,視需要可使用光聚合起始劑,例如可使用異丙基安息香醚、異丁基安息香醚、二苯甲酮、苯基二甲氧基乙醯苯、米其勒酮、氯-9-氧硫、十二烷基-9-氧硫、二甲基-9-氧硫、二乙基-9-氧硫、苄基二甲基縮酮、α-羥基環己基苯基酮、2-羥基甲基苯基丙烷等。 When the base resin having an ethylenically unsaturated group in the side chain is hardened by radiating radiation, a photopolymerization initiator may be used as necessary, for example, isopropyl benzoin ether, isobutyl benzoin ether, and dibenzoyl may be used. Ketones, Phenyldimethoxyacetophenone, Michelin, Chlor-9-oxosulfur Dodecyl-9-oxysulfur Dimethyl-9-oxysulfur Diethyl-9-oxysulfur , Benzyl dimethyl ketal, α-hydroxycyclohexylphenyl ketone, 2-hydroxymethylphenylpropane and the like.
該等光聚合起始劑之摻合量相對於基底樹脂100質量份,較佳為0.01~10質量份,更佳為0.01~5質量份。若摻合量過少,則反應不充分,若摻合量過多,則低分子成分會增加,而會對污染性產生影響。 The blending amount of these photopolymerization initiators is preferably 0.01 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the base resin. If the blending amount is too small, the reaction is insufficient, and if the blending amount is too large, the low-molecular component will increase, which will affect the pollution.
由側鏈具有乙烯性不飽和基之基底樹脂構成之黏著劑較佳為含有交聯劑。 It is preferable that the adhesive agent which consists of a base resin which has an ethylenically unsaturated group in a side chain contains a crosslinking agent.
此種交聯劑可為任意者,較佳為選自多異氰酸酯類、三聚氰胺-甲醛樹脂及環氧樹脂之群中之交聯劑。 Such a cross-linking agent may be any one, and is preferably a cross-linking agent selected from the group consisting of polyisocyanates, melamine-formaldehyde resins, and epoxy resins.
該等中,對於本發明之表面保護帶而言,較佳為多異氰酸酯類。 Among these, the surface protective tape of the present invention is preferably a polyisocyanate.
作為多異氰酸酯類,並無特別限制,例如可列舉:4,4'-二苯基甲烷二異氰酸酯、甲伸苯基二異氰酸酯、伸茬基二異氰酸酯、4,4'-二苯基醚二異氰酸酯、4,4'-[2,2-雙(4-苯氧基苯基)丙烷]二異氰酸酯等芳香族異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、異佛酮二異氰酸酯、4,4'-二環己基甲烷二異氰酸酯、2,4,-二環己基甲烷二異氰酸酯、離胺酸二異氰酸酯、離胺酸三異氰酸酯等。具體而言,可使用Coronate L(Nippon Polyurethane股份有限公司製造,商品名)等。 The polyisocyanates are not particularly limited, and examples thereof include 4,4'-diphenylmethane diisocyanate, methylenediphenyl diisocyanate, succinic diisocyanate, and 4,4'-diphenyl ether diisocyanate. Aromatic isocyanates such as 4,4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene Diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4, -dicyclohexylmethane diisocyanate, lysine diisocyanate, lysine triisocyanate, etc. Specifically, Coronate L (manufactured by Nippon Polyurethane Co., Ltd., trade name) can be used.
作為三聚氰胺-甲醛樹脂,具體而言,可使用NIKALAC MX-45(SANWA CHEMICAL公司製造,商品名)、Melan(日立化成工業公司製造,商品名)等。 Specific examples of the melamine-formaldehyde resin include NIKALAC MX-45 (manufactured by SANWA Chemical Co., Ltd., trade name), Melan (manufactured by Hitachi Chemical Co., Ltd., trade name), and the like.
作為環氧樹脂,可使用TETRAD-X(三菱化學公司製造,商品名)等。 As the epoxy resin, TETRAD-X (manufactured by Mitsubishi Chemical Corporation, trade name) can be used.
交聯劑之摻合量相對於基底樹脂100質量份,較佳為0.1~10質量份,更佳為1~10質量份。 The blending amount of the crosslinking agent is preferably 0.1 to 10 parts by mass, and more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the base resin.
可於塗佈黏著劑後,利用交聯劑使基底樹脂形成交聯結構,而提升黏著劑之凝聚力。 After the adhesive is applied, the cross-linking agent can be used to make the base resin form a cross-linked structure, thereby improving the cohesive force of the adhesive.
若交聯劑之摻合量過少,則因凝聚力提升效果不足,而使得黏著劑之流動性高,導致糊劑殘留。若交聯劑之摻合量過多,則黏著劑彈性模數變得過高,而無法保護半導體晶圓表面。 If the blending amount of the cross-linking agent is too small, the cohesive force improving effect is insufficient, and the fluidity of the adhesive is high, resulting in a paste residue. If the blending amount of the crosslinking agent is too large, the elastic modulus of the adhesive becomes too high, and the surface of the semiconductor wafer cannot be protected.
2)含有輻射聚合性低分子量化合物之黏著劑 2) Adhesives containing radiation polymerizable low molecular weight compounds
作為含有輻射聚合性低分子量化合物之黏著劑的主成分,並無特別限定,可使用黏著劑所使用之通常的氯化聚丙烯樹脂、丙烯酸樹脂[(甲基)丙烯酸樹脂]、聚酯樹脂、聚胺酯樹脂、環氧樹脂等。 The main component of the adhesive containing a radiation polymerizable low molecular weight compound is not particularly limited, and a general chlorinated polypropylene resin, an acrylic resin [(meth) acrylic resin], a polyester resin, Polyurethane resin, epoxy resin, etc.
對於本發明之表面保護帶而言,作為黏著劑之基底樹脂,較佳為丙烯酸樹脂[(甲基)丙烯酸樹脂],尤佳為合成上述側鏈具有乙烯性不飽和基之基底樹脂時的原料亦即側鏈具有官能基(α)之(甲基)丙烯酸系聚合物。 For the surface protective tape of the present invention, the base resin used as an adhesive is preferably an acrylic resin [(meth) acrylic resin], and particularly preferably a raw material when synthesizing the above-mentioned base resin having an ethylenically unsaturated group in a side chain. That is, the (meth) acrylic polymer which has a functional group ((alpha)) in a side chain.
作為該情形時之黏著劑,較佳除作為基底樹脂之丙烯酸樹脂及輻射聚合性低分子量化合物以外,亦適當摻合光聚合起始劑、硬化劑或交聯劑等,來製備黏著劑。 As the adhesive in this case, in addition to the acrylic resin and the radiation polymerizable low-molecular-weight compound as the base resin, a photopolymerization initiator, a hardener, or a cross-linking agent is preferably blended to prepare the adhesive.
黏著劑之基底樹脂的質量平均分子量較佳為20萬~200萬左右。 The mass average molecular weight of the base resin of the adhesive is preferably about 200,000 to 2 million.
黏著劑較佳除基底樹脂以外,亦含有至少1種質量平均分子量為1,000~20,000之低聚物。低聚物之質量平均分子量更佳為1,100~20,000,進而較佳為1,300~20,000,尤佳為1,500~10,000。 In addition to the base resin, the adhesive preferably contains at least one oligomer having a mass average molecular weight of 1,000 to 20,000. The mass average molecular weight of the oligomer is more preferably 1,100 to 20,000, more preferably 1,300 to 20,000, and even more preferably 1,500 to 10,000.
作為輻射聚合性低分子量化合物,可使用能夠藉由照射輻射而 三維網狀化之分子內具有至少2個以上之乙烯性不飽和基(輻射聚合性碳-碳雙鍵)且具有官能基(β)中之至少1種(較佳為羥基)的低分子量化合物。 As the radiation-polymerizable low-molecular-weight compound, an ethylenically unsaturated group (radiation-polymerizable carbon-carbon double bond) having at least two or more in the molecule capable of being three-dimensionally networked by irradiation with radiation and a functional group (β ) At least one (preferably hydroxyl) low molecular weight compound.
尤其對於本發明之表面保護帶而言,較佳為上述低聚物為具有乙烯性不飽和基之輻射聚合性低分子量化合物之情形。 Especially in the surface protective tape of the present invention, it is preferable that the oligomer is a radiation polymerizable low molecular weight compound having an ethylenically unsaturated group.
作為輻射聚合性低分子量化合物,具體而言,可應用三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇單羥基五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯或寡酯(甲基)丙烯酸酯(oligoester(meth)acrylate)等(甲基)丙烯酸酯系化合物。 As the radiation polymerizable low-molecular-weight compound, specifically, trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate can be applied. Dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanedi (Meth) acrylate compounds such as alcohol di (meth) acrylate, polyethylene glycol di (meth) acrylate, or oligoester (meth) acrylate.
另外,除如上所述之(甲基)丙烯酸酯系化合物以外,作為輻射聚合性低分子量化合物,亦可使用胺酯(甲基)丙烯酸酯(urethane(meth)acrylate)系低聚物。胺酯(甲基)丙烯酸酯系低聚物係使具有羥基之(甲基)丙烯酸酯(例如丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯、甲基丙烯酸2-羥基丙酯、聚乙二醇丙烯酸酯、聚乙二醇甲基丙烯酸酯等)與末端異氰酸酯胺酯預聚物進行反應而獲得,該末端異氰酸酯胺酯預聚物係使聚酯型或聚醚型等多元醇化合物和多元異氰酸酯化合物(例如2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、1,3-伸茬基二異氰酸酯、1,4-伸茬基二異氰酸酯、二苯基甲烷-4,4-二異氰酸酯等)進行反應而獲得。 In addition to the (meth) acrylate-based compound described above, as the radiation-polymerizable low-molecular-weight compound, an urethane (meth) acrylate-based oligomer may be used. An amine (meth) acrylate-based oligomer is a (meth) acrylate having a hydroxyl group (e.g. 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, methyl 2-hydroxypropyl acrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, etc.) are obtained by reacting with a terminal isocyanate amine prepolymer, which is a polyester type Polyol compounds and polyisocyanate compounds such as polyether type (e.g., 2,4-methylphenyl diisocyanate, 2,6-methylphenyl diisocyanate, 1,3-methyl diisocyanate, 1,4- Stubyl diisocyanate, diphenylmethane-4,4-diisocyanate, etc.) are obtained by reaction.
輻射聚合性低分子量化合物可使用1種,亦可將2種以上併用。 The radiation polymerizable low-molecular-weight compound may be used singly or in combination of two or more kinds.
於輻射硬化型黏著劑,視需要,可含有光聚合起始劑。光聚合起始劑只要為藉由透過基材之輻射進行反應者,則無特別限制,可使用通常之光聚合起始劑。例如可列舉:二苯甲酮、4,4'-二甲基胺基二苯甲酮、4,4'-二乙基胺基二苯甲酮、4,4'-二氯二苯甲酮等二苯甲酮類;苯乙酮、二乙氧基苯 乙酮、苯基二甲氧基乙醯苯等苯乙酮類;2-乙基蒽醌、三級丁基蒽醌等蒽醌類;2-氯-9-氧硫、安息香***、安息香異丙醚、二苯乙二酮、2,4,5-三芳基咪唑二聚物(咯吩二聚物)、吖啶系化合物、醯基膦氧化物類等,該等可單獨使用或將2種以上組合使用。 For radiation-curable adhesives, a photopolymerization initiator may be contained if necessary. The photopolymerization initiator is not particularly limited as long as it reacts by radiation passing through the substrate, and a general photopolymerization initiator can be used. Examples include: benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 4,4'-dichlorobenzophenone And other benzophenones; acetophenones such as acetophenone, diethoxyacetophenone, phenyldimethoxyacetophenone; anthraquinones such as 2-ethylanthraquinone and tertiary butyl anthraquinone Class; 2-chloro-9-oxysulfur , Benzoin diethyl ether, benzoin isopropyl ether, diphenylethylene dione, 2,4,5-triarylimidazole dimer (rophen dimer), acridine compounds, fluorenylphosphine oxides, etc., etc. They can be used alone or in combination of two or more.
光聚合起始劑之添加量相對於基底樹脂100質量份,較佳為0.1~10質量份,更佳為0.3~7.5質量份,進而較佳為0.5~5質量份。若光聚合起始劑之添加量過多,則由於輻射硬化會於多處急遽地產生,故而會導致輻射硬化收縮增大,因此與以往之輻射硬化型表面保護用黏著帶相比,減少光聚合起始劑之量就抑制輻射硬化收縮之方面而言亦有用。 The addition amount of the photopolymerization initiator is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the base resin, more preferably 0.3 to 7.5 parts by mass, and still more preferably 0.5 to 5 parts by mass. If the addition amount of the photopolymerization initiator is too large, radiation hardening will occur rapidly in many places, which will lead to an increase in radiation hardening shrinkage. Therefore, compared with the conventional radiation hardening surface protection adhesive tape, the photopolymerization is reduced. The amount of the initiator is also useful in terms of suppressing radiation hardening shrinkage.
較佳於黏著劑含有硬化劑或交聯劑。 It is preferable that the adhesive contains a hardener or a crosslinking agent.
作為硬化劑或交聯劑,可列舉:多元異氰酸酯化合物、多元環氧化合物、多元氮丙啶化合物、螯合化合物等。 Examples of the curing agent or the crosslinking agent include polyisocyanate compounds, polyepoxide compounds, polyaziridine compounds, and chelate compounds.
作為多元異氰酸酯化合物,並無特別限制,例如可列舉:4,4'-二苯基甲烷二異氰酸酯、甲伸苯基二異氰酸酯、伸茬基二異氰酸酯、4,4'-二苯基醚二異氰酸酯、4,4'-[2,2-雙(4-苯氧基苯基)丙烷]二異氰酸酯等芳香族異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、異佛酮二異氰酸酯、4,4'-二環己基甲烷二異氰酸酯、2,4,-二環己基甲烷二異氰酸酯、離胺酸二異氰酸酯、離胺酸三異氰酸酯等。具體而言,可使用Coronate L[日本聚氨酯工業(股份)製造,商品名]等。 The polyisocyanate compound is not particularly limited, and examples thereof include 4,4'-diphenylmethane diisocyanate, methylenephenyl diisocyanate, succinic diisocyanate, and 4,4'-diphenylether diisocyanate. Aromatic isocyanates such as 4,4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene Diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4, -dicyclohexylmethane diisocyanate, lysine diisocyanate, lysine triisocyanate, etc. Specifically, Coronate L [manufactured by Japan Polyurethane Industry (Stock Co., Ltd.), trade name] can be used.
作為多元環氧化合物,可舉環氧樹脂,例如可列舉:乙二醇二縮水甘油醚、對苯二甲酸二縮水甘油酯丙烯酸酯、N原子上取代有2個二縮水甘油基之苯胺類等。另外,亦可使用上述TETRAD-X。 Examples of the polyvalent epoxy compound include epoxy resins, and examples thereof include ethylene glycol diglycidyl ether, diglycidyl terephthalate acrylate, and anilines having two diglycidyl groups substituted on the N atom. . Alternatively, the above-mentioned TETRAD-X may be used.
此外,作為苯胺類,可舉N,N'-四縮水甘油基間苯二胺。 Examples of the anilines include N, N'-tetraglycidyl-m-phenylenediamine.
多元氮丙啶化合物可列舉:2,4,6-三(1-氮丙啶基)-1,3,5-三 、三[1-(2-甲基)氮丙啶基]膦氧化物、六[1-(2-甲基)氮丙啶基]三磷三(triphosphatriazine)等。另外,作為螯合化合物,可列舉:乙醯乙酸乙酯二異丙醇鋁、三(乙醯乙酸乙酯)鋁等。 Polyvalent aziridine compounds can be listed as: 2,4,6-tris (1-aziridinyl) -1,3,5-tris , Tris [1- (2-methyl) aziridinyl] phosphine oxide, hexa [1- (2-methyl) aziridinyl] triphosphotris (triphosphatriazine) and so on. Examples of the chelate compound include ethyl acetoacetate, aluminum diisopropoxide, and tris (ethyl acetate) aluminum.
硬化劑或交聯劑之摻合量相對於基底樹脂100質量份,較佳為0.1~10質量份,更佳為0.1~5.0質量份,進而較佳為0.5~4.0質量份。 The blending amount of the hardener or the crosslinking agent is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass, and still more preferably 0.5 to 4.0 parts by mass with respect to 100 parts by mass of the base resin.
(黏著劑層之厚度) (Thickness of adhesive layer)
黏著劑層之厚度就製造性之方面而言,較佳為5μm以上,更佳為10μm以上,進而較佳為20μm以上。上限較佳為75μm以下,更佳為50μm以下,尤佳為40μm以下。黏著劑層亦可為多層,於該情形時,較佳為至少與半導體晶圓表面相接之最外層的黏著劑為輻射硬化型黏著劑。 In terms of manufacturability, the thickness of the adhesive layer is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 20 μm or more. The upper limit is preferably 75 μm or less, more preferably 50 μm or less, and even more preferably 40 μm or less. The adhesive layer may also have multiple layers. In this case, it is preferable that the adhesive at least the outermost layer which is in contact with the surface of the semiconductor wafer is a radiation-curable adhesive.
(黏著劑層或黏著劑之特性) (Characteristics of adhesive layer or adhesive)
[輻射硬化型黏著劑層中所具有之乙烯性不飽和基的含量] [Content of ethylenically unsaturated groups in the radiation-curable adhesive layer]
於本發明之表面保護帶中,構成黏著劑層之輻射硬化型黏著劑所具有之乙烯性不飽和基(輻射聚合性碳-碳雙鍵)的含量較佳為0.2~2.0mmol/g。 In the surface protective tape of the present invention, the content of the ethylenically unsaturated group (radiation polymerizable carbon-carbon double bond) contained in the radiation-hardening adhesive constituting the adhesive layer is preferably 0.2 to 2.0 mmol / g.
輻射硬化型黏著劑所具有之乙烯性不飽和基的含量係輻射硬化型黏著劑所含有之具有乙烯性不飽和基之化合物所具有之全部乙烯性不飽和基的總和,係輻射硬化型黏著劑之每g單位之乙烯性不飽和基的總和莫耳數。此外,具有乙烯性不飽和基之化合物例如係指側鏈具有乙烯性不飽和基之基底樹脂之類的聚合物、輻射聚合性低分子量化合物。 The content of the ethylenically unsaturated group in the radiation-hardening adhesive is the sum of all the ethylenically unsaturated groups in the compound having the ethylenically unsaturated group contained in the radiation-hardening adhesive, and it is the radiation-hardening adhesive. Total moles of ethylenically unsaturated groups per g unit. The compound having an ethylenically unsaturated group refers to, for example, a polymer such as a base resin having an ethylenically unsaturated group in a side chain, or a radiation polymerizable low molecular weight compound.
輻射硬化型黏著劑所具有之乙烯性不飽和基的含量較佳為0.2~1.8mmol/g,更佳為0.2~1.5mmol/g,更佳為0.5~1.5mmol/g。 The content of the ethylenically unsaturated group in the radiation-hardening adhesive is preferably 0.2 to 1.8 mmol / g, more preferably 0.2 to 1.5 mmol / g, and still more preferably 0.5 to 1.5 mmol / g.
於黏著劑層為多層之情形時,較佳於將全部黏著劑層視作1層時,構成黏著劑層之輻射硬化型黏著劑所具有之乙烯性不飽和基的含量滿足上述範圍,更佳為各層滿足上述範圍。 In the case where the adhesive layer is multilayered, it is preferable that when all the adhesive layers are regarded as one layer, the content of the ethylenically unsaturated group in the radiation-hardening adhesive constituting the adhesive layer satisfies the above range, and it is more preferable. The above range is satisfied for each layer.
輻射硬化型黏著劑所具有之乙烯性不飽和基的含量可藉由具有上述官能基(β)之化合物及輻射聚合性低分子量化合物所具有之乙烯性不飽和基的數量或該等化合物的摻合量加以調節。 The content of the ethylenically unsaturated group in the radiation-hardening adhesive can be determined by the number of ethylenically unsaturated groups in the compound having the functional group (β) and the radiation-polymerizable low-molecular-weight compound or the blending of these compounds. Adjust the total amount.
輻射硬化型黏著劑所具有之乙烯性不飽和基的含量可根據如上所述使用之化合物量或該等化合物所具有之乙烯性不飽和基數而求出。另外,求出輻射硬化型黏著劑之碘值[對基底樹脂及輻射聚合性低分子量化合物之合計100g所加成之碘(I2)的g數],I2之分子量為253.8,因此將該值之單位轉換為mmol/g,藉此求出。 The content of the ethylenically unsaturated group in the radiation-hardening adhesive can be determined based on the amount of the compound used as described above or the number of ethylenically unsaturated groups in the compound. In addition, the iodine value [g number of iodine (I 2 ) added to the total of 100 g of the base resin and the radiation polymerizable low-molecular-weight compound] was determined for the radiation-curable adhesive, and the molecular weight of I 2 was 253.8. The unit of the value is converted to mmol / g, and it is calculated | required by this.
[對於SUS板之紫外線硬化後的黏著力] [For the adhesion of SUS board after UV curing]
關於本發明之表面保護帶中之黏著劑層於照射紫外線後之黏著力,對於23℃之SUS研磨面較佳為0.5N/25mm以上,更佳為0.7N/25mm以上。上限較佳為5.0N/25mm以下,更佳為3.0N/25mm以下,進而較佳為1.5N/25mm以下。另外,關於上述黏著劑層於照射紫外線後之黏著力,對於50℃之SUS研磨面較佳為0.3N/25mm以上,更佳為0.5N/25mm以上。上限較佳為7.0N/25mm以下,更佳為4.0N/25mm以下,進而較佳為2.5N/25mm以下。該黏著力係表面保護帶本身之特性。 Regarding the adhesive force of the adhesive layer in the surface protective tape of the present invention after irradiating ultraviolet rays, it is preferably 0.5N / 25mm or more, and more preferably 0.7N / 25mm or more for the SUS abrasive surface at 23 ° C. The upper limit is preferably 5.0 N / 25 mm or less, more preferably 3.0 N / 25 mm or less, and still more preferably 1.5 N / 25 mm or less. In addition, regarding the adhesive force of the above-mentioned adhesive layer after irradiating ultraviolet rays, it is preferably 0.3N / 25mm or more, and more preferably 0.5N / 25mm or more for a SUS polished surface at 50 ° C. The upper limit is preferably 7.0 N / 25 mm or less, more preferably 4.0 N / 25 mm or less, and still more preferably 2.5 N / 25 mm or less. The adhesion is a characteristic of the surface protection tape itself.
此外,照射紫外線後係指以累計照射量成為500mJ/cm2之方式對黏著劑層整體照射紫外線而使之硬化後。 In addition, after the ultraviolet rays are irradiated, it means that the entire adhesive layer is irradiated with ultraviolet rays so that the cumulative irradiation amount becomes 500 mJ / cm 2 and cured.
具體而言,可藉由如下方式求出。 Specifically, it can be calculated | required as follows.
自照射輻射前之表面保護帶分別採取3點之寬度25mm×長度150mm之試片。將2kg之橡膠輥施加3個往返而將該等試片壓合於利用JIS R 6253規定之第280號耐水研磨紙最後加工成JIS G 4305規定之厚度1.5mm~2.0mm的SUS銅板上。於常溫(25℃)放置1小時後,照射累計照射量500mJ/cm2之紫外線而使黏著劑層硬化。使黏著劑層硬化後,使用測定值落入該容量之15~85%之範圍 之適於JIS B 7721之拉伸試驗機,求出3點之黏著力之平均值。黏著力之測定係以拉伸速度50mm/min且藉由90°剝離法於常溫、濕度50%下進行。於該試驗中,於將試片壓合於SUS銅板前,預先使用加熱板等將SUS銅板調整為特定溫度(23℃、50℃)。此外,作為上述拉伸試驗機,例如可使用Instron公司製造之拉伸試驗機:雙柱台式5567(商品名)。 Surface protection tapes before self-irradiation were taken at three points with a width of 25 mm x a length of 150 mm. A 2 kg rubber roller was applied for 3 round trips, and the test pieces were pressed and laminated on a SUS copper plate having a thickness of 1.5 mm to 2.0 mm as specified in JIS G 4305 using water-resistant abrasive paper No. 280 specified in JIS R 6253. After being left at room temperature (25 ° C) for 1 hour, ultraviolet rays with a cumulative irradiation amount of 500 mJ / cm 2 were irradiated to harden the adhesive layer. After the adhesive layer is hardened, a tensile tester suitable for JIS B 7721 is used to determine the average value of the three points of adhesion using a tensile tester suitable for JIS B 7721 when the measured value falls within the range of 15 to 85% of the capacity. The measurement of the adhesive force was performed at a tensile speed of 50 mm / min and a 90 ° peeling method at normal temperature and 50% humidity. In this test, the SUS copper plate was adjusted to a specific temperature (23 ° C, 50 ° C) using a heating plate or the like before pressing the test piece onto the SUS copper plate. In addition, as the tensile tester, for example, a tensile tester manufactured by Instron: a two-column bench 5567 (trade name) can be used.
對於SUS研磨面之紫外線硬化後的黏著力可藉由適當調節黏著劑所使用之化合物的種類或量、交聯劑等添加劑的種類或量、黏著劑層的厚度等而成為本發明之較佳範圍。 For the UV-curing adhesion of the SUS abrasive surface, it can be made better by appropriately adjusting the type or amount of the compound used in the adhesive, the type or amount of additives such as a cross-linking agent, and the thickness of the adhesive layer. range.
若過度減小對於SUS研磨面之上述黏著力,則因交聯反應引起之硬化收縮變大,因此自凸塊晶圓等表面凹凸大之被黏著體的剝離力反而變大。若對SUS研磨面之表觀黏著力過大,則輻射硬化不充分而會產生剝離不良或糊劑殘留。 If the above-mentioned adhesive force to the SUS polished surface is excessively reduced, the hardening shrinkage due to the crosslinking reaction becomes large, and thus the peeling force from the adherend with large unevenness on the surface such as a bump wafer becomes larger. If the apparent adhesion to the SUS abrasive surface is too large, radiation hardening is insufficient and peeling failure or paste residue may occur.
<剝離襯墊(release liner)> <Release liner>
半導體晶圓表面保護用黏著帶亦可於黏著劑層上具有剝離襯墊。剝離襯墊係使用經聚矽氧脫模處理之聚對酞酸乙二酯膜等。另外,視需要亦可使用未經聚矽氧脫模處理之聚丙烯膜等。 The adhesive tape for semiconductor wafer surface protection may have a release liner on the adhesive layer. For the release liner, a polyethylene terephthalate film or the like which has been subjected to a polysiloxane release treatment is used. In addition, polypropylene film without silicone release treatment can be used if necessary.
<<半導體晶圓之加工方法>> << Semiconductor wafer processing method >>
本發明之半導體晶圓加工方法係使用本發明之半導體晶圓表面保護用黏著帶的半導體晶圓加工方法。 The semiconductor wafer processing method of the present invention is a semiconductor wafer processing method using the semiconductor wafer surface protection adhesive tape of the present invention.
本發明之半導體晶圓表面保護用黏著帶只要為半導體晶圓之加工步驟則可於任何步驟中使用。例如可較佳地列舉:半導體晶圓背面研削步驟、切晶步驟、切晶接合步驟等。 The adhesive tape for semiconductor wafer surface protection of the present invention can be used in any step as long as it is a processing step of a semiconductor wafer. For example, a semiconductor wafer back surface grinding step, a dicing step, a dicing bonding step, and the like can be preferably cited.
本發明之半導體晶圓表面保護用黏著帶係貼合於具有20μm以上之凹凸差的半導體晶圓表面而使用。 The adhesive tape for protecting the surface of a semiconductor wafer of the present invention is used by being bonded to a surface of a semiconductor wafer having an unevenness of 20 μm or more.
更佳為應用於凹凸差[凸塊(電極)之高度或劃線之深度]為20~400μm之 半導體晶圓,進而較佳為應用於50~250μm之半導體晶圓。 It is more preferably applied to a semiconductor wafer having a bump unevenness [the height of a bump (electrode) or the depth of a scribe line] of 20 to 400 μm, and more preferably to a semiconductor wafer of 50 to 250 μm.
半導體晶圓表面之凸塊的配設密度(高密度)並無特別限定,可應用於凸塊高度之0.5~3倍以下、較佳為1~2倍以下之間距(自凸塊高度方向之頂點至所配置之下一凸塊高度方向之頂點為止的距離)者。另外,亦可用於整個面均勻地配置有凸塊之半導體晶圓。 The arrangement density (high density) of the bumps on the surface of the semiconductor wafer is not particularly limited, and can be applied to a distance of 0.5 to 3 times or less, preferably 1 to 2 times or less (from the height direction of the bumps) The distance from the vertex to the vertex in the height direction of the next bump). It can also be used for semiconductor wafers where bumps are uniformly arranged on the entire surface.
關於半導體晶圓之厚度,就經藉由使用半導體晶圓表面保護用黏著帶之加工方法進行背面研削的半導體晶圓之厚度而言,較佳為20~500μm,更佳為50~200μm,進而較佳為80~200μm。 The thickness of the semiconductor wafer is preferably 20 to 500 μm, more preferably 50 to 200 μm in terms of the thickness of the semiconductor wafer that has been back-grinded by a processing method using an adhesive tape for protecting the surface of a semiconductor wafer. It is preferably 80 to 200 μm.
藉由使用本發明之半導體晶圓表面保護用黏著帶,能夠以高產率獲得薄膜半導體晶圓。該半導體晶圓之加工方法適合作為薄膜研削至50μm以下的附帶電極之半導體晶圓之製造方法。 By using the adhesive tape for semiconductor wafer surface protection of the present invention, a thin-film semiconductor wafer can be obtained at a high yield. The processing method of the semiconductor wafer is suitable as a method for manufacturing a semiconductor wafer with an electrode and an electrode with a thickness of 50 μm or less.
本發明之半導體晶圓之加工方法較佳包括如下步驟:於將本發明之半導體晶圓表面保護用黏著帶貼合於半導體晶圓表面後,進行輻射(尤其是紫外線)照射,並將半導體晶圓表面保護用黏著帶剝離。 The method for processing a semiconductor wafer of the present invention preferably includes the following steps: after the adhesive tape for protecting the surface of a semiconductor wafer of the present invention is adhered to the surface of a semiconductor wafer, radiation (especially ultraviolet rays) is irradiated, and the semiconductor crystal is irradiated; Adhesive tape for round surface protection is peeled off.
具體而言,首先於半導體晶圓之電路圖案面(表面)以黏著劑層成為貼合面之方式貼合本發明之半導體晶圓表面保護用黏著帶。繼而,對半導體晶圓之無電路圖案之面側進行研削直至半導體晶圓之厚度成為特定厚度,例如10~200μm。然後,亦可以貼合有該半導體晶圓表面保護用黏著帶之面為下側而載於加熱吸附台,於該狀態下,於半導體晶圓之無電路圖案之經研削的面側貼合切晶-接合膜。 Specifically, first, the semiconductor wafer surface protection adhesive tape of the present invention is bonded on the circuit pattern surface (surface) of the semiconductor wafer such that the adhesive layer becomes a bonding surface. Then, the surface side of the semiconductor wafer without a circuit pattern is ground until the thickness of the semiconductor wafer becomes a specific thickness, for example, 10 to 200 μm. Then, the surface on which the adhesive tape for surface protection of a semiconductor wafer is attached may be placed on a heating adsorption table as a lower side, and in this state, the surface side of the semiconductor wafer without a circuit pattern may be attached and cut. Crystal-bonding film.
進行切晶步驟,然後於半導體晶圓表面保護用黏著帶之基材膜的背面接著熱密封型(熱熔接型)或黏著型之剝離帶,並自半導體晶圓將半導體晶圓表面保護用黏著帶剝離。 The crystal cutting step is performed, and then a heat-sealing (heat-welding) or adhesive-type release tape is attached to the back surface of the base film of the adhesive tape for semiconductor wafer surface protection, and the semiconductor wafer surface is adhered for protection from the semiconductor wafer. Tape peeling.
[實施例] [Example]
以下,基於實施例更詳細地說明本發明,但本發明並不限定於該等。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these.
(黏著劑組成物之製備) (Preparation of adhesive composition)
藉由如下方式製備黏著劑組成物1A~1C。 The adhesive composition 1A ~ 1C was prepared as follows.
1)黏著劑組成物1A之製備 1) Preparation of adhesive composition 1A
由丙烯酸2-乙基己酯78質量份、丙烯酸2-羥基乙酯17質量份、甲基丙烯酸5質量份,獲得質量平均分子量達到55萬之共聚物。相對於該共聚物100質量份,添加丙烯酸酯為5官能且具有羥基作為官能基(β)之質量平均分子量3,000的胺酯丙烯酸酯(urethane acrylate)低聚物100質量份及作為多異氰酸酯之Coronate L[商品名,日本聚氨酯工業公司製造]5.0質量份、作為光聚合起始劑之SPEEDCURE BKL[商品名,DKSH Japan公司製造]5.0質量份,並進行混合,而獲得黏著劑組成物1A。 A copolymer having a mass average molecular weight of 550,000 was obtained from 78 parts by mass of 2-ethylhexyl acrylate, 17 parts by mass of 2-hydroxyethyl acrylate, and 5 parts by mass of methacrylic acid. With respect to 100 parts by mass of the copolymer, 100 parts by mass of an urethane acrylate oligomer having a mass average molecular weight of 3,000 having a 5-functional acrylate and having a hydroxyl group as a functional group (β) and Coronate as a polyisocyanate are added. L [trade name, manufactured by Japan Polyurethane Industry Co., Ltd.] 5.0 parts by mass, SPEEDCURE BKL [trade name, manufactured by DKSH Japan] as a photopolymerization initiator, and 5.0 parts by mass were mixed to obtain an adhesive composition 1A.
2)黏著劑組成物1B之製備 2) Preparation of adhesive composition 1B
使丙烯酸2-乙基己酯70質量份、丙烯酸2-羥基乙酯7質量份、甲基丙烯酸23質量份於乙酸乙酯中進行聚合,而獲得所獲得之質量平均分子量為100萬之甲基丙烯酸系聚合物。相對於該甲基丙烯酸系聚合物100質量份,混合環氧系硬化劑2.0質量份,而獲得黏著劑組成物B。 70 parts by mass of 2-ethylhexyl acrylate, 7 parts by mass of 2-hydroxyethyl acrylate, and 23 parts by mass of methacrylic acid were polymerized in ethyl acetate to obtain a methyl group having a mass average molecular weight of 1 million. Acrylic polymer. With respect to 100 parts by mass of the methacrylic polymer, 2.0 parts by mass of an epoxy-based hardener was mixed to obtain an adhesive composition B.
3)黏著劑組成物1C之製備 3) Preparation of adhesive composition 1C
由丙烯酸2-乙基己酯78質量份、丙烯酸2-羥基乙酯13質量份、甲基丙烯酸9質量份,獲得質量平均分子量達到60萬之共聚物。相對於該共聚物100質量份,添加丙烯酸酯為3官能且具有羥基作為官能基(β)之質量平均分子量1,500的胺酯丙烯酸酯低聚物100質量份及作為多異氰酸酯之Coronate L 3.0質量份、作為環氧樹脂之TETRAD-X[三菱瓦斯化學公司製造]0.5質量份、作為光聚合起始劑之SPEEDCURE BKL 5.0質量份,並進行混合,而獲得黏著劑組成物 1C。 A copolymer having a mass average molecular weight of 600,000 was obtained from 78 parts by mass of 2-ethylhexyl acrylate, 13 parts by mass of 2-hydroxyethyl acrylate, and 9 parts by mass of methacrylic acid. With respect to 100 parts by mass of the copolymer, 100 parts by mass of an amine acrylate oligomer having a mass average molecular weight of 1,500 having a trifunctional acrylate and having a hydroxyl group as a functional group (β), and 3.0 parts by mass of Coronate L as a polyisocyanate are added. 0.5 parts by mass of TETRAD-X [manufactured by Mitsubishi Gas Chemical Co., Ltd.] as an epoxy resin and 5.0 parts by mass of SPEEDCURE BKL as a photopolymerization initiator, and mixed to obtain an adhesive composition 1C.
(基材膜及中間樹脂層之製膜) (Film formation of base film and intermediate resin layer)
以如下方式製膜中間樹脂層及基材膜2A~2G。 The intermediate resin layer and the base film 2A to 2G were formed as follows.
1)膜2A之製作 1) Production of film 2A
使用乙烯-丙烯酸共聚物(EEA)樹脂(日本聚乙烯公司製造,商品名:Rexpearl ET6200)作為構成中間樹脂層之樹脂,使用低密度聚乙烯(LDPE)樹脂(東曹公司製造,商品名:Petrothene 212)作為構成基材膜之樹脂。利用擠出機將該等樹脂擠出成形,藉此製作具有中間樹脂層之基材膜(膜2A)。LDPE層之厚度為12.5μm,EEA之厚度為237.5μm。 An ethylene-acrylic acid copolymer (EEA) resin (manufactured by Japan Polyethylene Corporation, trade name: Rexpearl ET6200) was used as a resin constituting the intermediate resin layer, and a low density polyethylene (LDPE) resin (manufactured by Tosoh Corporation, trade name: Petrothene) was used. 212) As a resin constituting the base film. These resins are extruded and molded using an extruder, thereby producing a base film (film 2A) having an intermediate resin layer. The thickness of the LDPE layer is 12.5 μm, and the thickness of the EEA is 237.5 μm.
2)膜2B之製作 2) Production of film 2B
使用乙烯-丙烯酸甲酯共聚物(EMA)樹脂(日本聚乙烯公司製造,商品名:Rexpearl EB330H)作為構成中間樹脂層之樹脂,使用低密度聚乙烯(LDPE)樹脂(東曹公司製造,商品名:Petrothene 212)作為構成基材膜之樹脂。利用擠出機將該等樹脂擠出成形,藉此製作具有中間樹脂層之基材膜(膜2B)。LDPE層之厚度為140.0μm,EEA之厚度為210.0μm。 An ethylene-methyl acrylate copolymer (EMA) resin (manufactured by Japan Polyethylene Corporation, trade name: Rexpearl EB330H) was used as a resin constituting the intermediate resin layer, and a low density polyethylene (LDPE) resin (manufactured by Tosoh Corporation, trade name) was used. : Petrothene 212) as a resin constituting the base film. These resins are extruded and molded using an extruder, thereby producing a base film (film 2B) having an intermediate resin layer. The thickness of the LDPE layer is 140.0 μm, and the thickness of the EEA is 210.0 μm.
3)膜2C之製作 3) Production of film 2C
使用乙烯系特殊共聚物樹脂(日本聚乙烯公司製造,商品名:Rexpearl ET720X)作為構成中間樹脂層之樹脂,使用低密度聚乙烯(LDPE)樹脂(東曹公司製造,商品名:Petrothene 212)作為構成基材膜之樹脂。利用擠出機將該等樹脂擠出成形,藉此製作具有中間樹脂層之基材膜(膜2C)。LDPE層之厚度為50.0μm,乙烯系特殊共聚物樹脂層之厚度為200.0μm。 An ethylene-based special copolymer resin (manufactured by Japan Polyethylene Corporation, trade name: Rexpearl ET720X) was used as a resin constituting the intermediate resin layer, and a low-density polyethylene (LDPE) resin (manufactured by Tosoh Corporation, trade name: Petrothene 212) was used as the resin. Resin constituting the base film. These resins are extruded and molded with an extruder, thereby producing a base film (film 2C) having an intermediate resin layer. The thickness of the LDPE layer was 50.0 μm, and the thickness of the ethylene-based special copolymer resin layer was 200.0 μm.
4)膜2D之製作 4) Film 2D production
使用茂金屬塑性體樹脂(日本聚乙烯公司製造,商品名:KERNEL KJ640T)作為構成中間樹脂層之樹脂,使用低密度聚乙烯(LDPE)樹脂(日 本聚乙烯公司製造,商品名:NOVATEC LL UJ580)作為構成基材膜之樹脂。利用擠出機將該等樹脂擠出成形,藉此製作具有中間樹脂層之基材膜(膜2D)。LDPE層之厚度為90.0μm,乙烯系特殊共聚物樹脂層之厚度為210.0μm。 A metallocene plastomer resin (manufactured by Japan Polyethylene Corporation, trade name: KERNEL KJ640T) was used as a resin constituting the intermediate resin layer, and a low density polyethylene (LDPE) resin (manufactured by Japan Polyethylene Corporation, trade name: NOVATEC LL UJ580) was used. As a resin constituting a base film. These resins are extruded using an extruder to produce a base film (film 2D) having an intermediate resin layer. The thickness of the LDPE layer was 90.0 μm, and the thickness of the ethylene-based special copolymer resin layer was 210.0 μm.
5)膜2E之製作 5) Production of membrane 2E
使用乙烯系特殊聚合物樹脂(日本聚乙烯公司製造,商品名:Rexpearl ET220X)作為構成中間樹脂層之樹脂,使用低密度聚乙烯(LDPE)樹脂(東曹公司製造,商品名:Petrothene 212)作為構成基材膜之樹脂。利用擠出機將該等樹脂擠出成形,藉此製作具有中間樹脂層之基材膜(膜2E)。LDPE層之厚度為150.0μm,乙烯系特殊共聚物樹脂層之厚度為150.0μm。 A vinyl-based special polymer resin (manufactured by Japan Polyethylene Corporation, trade name: Rexpearl ET220X) was used as a resin constituting the intermediate resin layer, and a low-density polyethylene (LDPE) resin (manufactured by Tosoh Corporation, trade name: Petrothene 212) was used as the resin. Resin constituting the base film. These resins are extruded and molded with an extruder to produce a base film (film 2E) having an intermediate resin layer. The thickness of the LDPE layer was 150.0 μm, and the thickness of the ethylene-based special copolymer resin layer was 150.0 μm.
6)膜2F之製作 6) Production of film 2F
使用乙烯-丙烯酸丁酯共聚物樹脂(愛克瑪公司製造,商品名:LOTRYL 28BA175)作為構成中間樹脂層之樹脂,使用低密度聚乙烯(LDPE)樹脂(日本聚乙烯公司製造,商品名:NOVATEC LL UJ580)作為構成基材膜之樹脂。利用擠出機將該等樹脂擠出成形,藉此製作具有中間樹脂層之基材膜(膜2F)。LDPE層之厚度為90.0μm,乙烯-丙烯酸丁酯共聚物樹脂層之厚度為210.0μm。 An ethylene-butyl acrylate copolymer resin (manufactured by Agama, trade name: LOTRYL 28BA175) was used as a resin constituting the intermediate resin layer, and a low density polyethylene (LDPE) resin (manufactured by Japan Polyethylene Corporation, trade name: NOVATEC) was used. LL UJ580) as the resin constituting the base film. These resins are extruded and molded with an extruder to produce a base film (film 2F) having an intermediate resin layer. The thickness of the LDPE layer was 90.0 μm, and the thickness of the ethylene-butyl acrylate copolymer resin layer was 210.0 μm.
7)膜2G之製膜 7) Film 2G
使用乙烯-丙烯酸甲酯共聚物樹脂(日本聚乙烯公司製造,商品名:EB240H)作為構成中間樹脂層之樹脂,使用低密度聚乙烯(LDPE)樹脂(東曹公司製造,商品名:Petrothene 212)作為構成基材膜之樹脂。利用擠出機將該等樹脂擠出成形,藉此製作具有中間樹脂層之基材膜(膜2G)。LDPE層之厚度為90.0μm,乙烯-丙烯酸甲酯共聚物樹脂層之厚度為210.0μm。 An ethylene-methyl acrylate copolymer resin (manufactured by Japan Polyethylene Corporation, trade name: EB240H) was used as a resin constituting the intermediate resin layer, and a low density polyethylene (LDPE) resin (manufactured by Tosoh Corporation, trade name: Petrothene 212) was used. As a resin constituting a base film. These resins were extruded and molded using an extruder to produce a base film (film 2G) having an intermediate resin layer. The thickness of the LDPE layer was 90.0 μm, and the thickness of the ethylene-methyl acrylate copolymer resin layer was 210.0 μm.
8)膜2H之製膜 8) Film 2H
使用低密度聚乙烯(LDPE)樹脂(東曹公司製造,商品名:Petrothene 180)作為構成中間樹脂層之樹脂,使用低密度聚乙烯(LDPE)樹脂(東曹公司製造,商品名:Petrothene 212)作為構成基材膜之樹脂。利用擠出機將該等樹脂擠出成形,藉此製作具有中間樹脂層之基材膜(膜2H)。用作中間樹脂層之LDPE層之厚度為90.0μm,用作基材膜之LDPE層的厚度為210.0μm。 Low-density polyethylene (LDPE) resin (manufactured by Tosoh Corporation, trade name: Petrothene 180) was used as the resin constituting the intermediate resin layer, and low-density polyethylene (LDPE) resin (manufactured by Tosoh Corporation, trade name: Petrothene 212) was used. As a resin constituting a base film. These resins were extruded and molded using an extruder to produce a base film (film 2H) having an intermediate resin layer. The thickness of the LDPE layer used as the intermediate resin layer was 90.0 μm, and the thickness of the LDPE layer used as the base film was 210.0 μm.
(實施例1) (Example 1)
以乾燥後之厚度成為30μm之方式將黏著劑組成物1A塗敷於透明之剝離襯墊上,並使之乾燥。以剝離襯墊上之黏著劑層與膜2A之中間樹脂層相接的方式進行貼合,並去除剝離襯墊,而獲得圖1所示之構成的半導體晶圓表面保護用黏著帶。 The adhesive composition 1A was applied to a transparent release liner so that the thickness after drying became 30 μm, and dried. The adhesive layer on the release liner was bonded to the intermediate resin layer of the film 2A, and the release liner was removed to obtain a semiconductor wafer surface protection adhesive tape having the structure shown in FIG. 1.
(實施例2) (Example 2)
於實施例1中,將黏著劑組成物1A變更為黏著劑組成物1B,並將膜2A變更為膜2B,除此以外,以與實施例1相同之方式獲得圖1所示之構成的半導體晶圓表面保護用黏著帶。 In Example 1, the semiconductor shown in FIG. 1 was obtained in the same manner as in Example 1 except that the adhesive composition 1A was changed to the adhesive composition 1B, and the film 2A was changed to the film 2B. Adhesive tape for wafer surface protection.
(實施例3) (Example 3)
於實施例1中,將黏著劑組成物1A變更為黏著劑組成物1C,並將膜2A變更為膜2C,除此以外,以與實施例1相同之方式獲得圖1所示之構成的半導體晶圓表面保護用黏著帶。 In Example 1, the semiconductor shown in FIG. 1 was obtained in the same manner as in Example 1 except that the adhesive composition 1A was changed to the adhesive composition 1C, and the film 2A was changed to the film 2C. Adhesive tape for wafer surface protection.
(實施例4) (Example 4)
於實施例1中,將黏著劑組成物1A變更為黏著劑組成物1B,並將膜2A變更為膜2D,除此以外,以與實施例1相同之方式獲得圖1所示之構成的半導體晶圓表面保護用黏著帶。 In Example 1, the semiconductor shown in FIG. 1 was obtained in the same manner as in Example 1 except that the adhesive composition 1A was changed to the adhesive composition 1B, and the film 2A was changed to the film 2D. Adhesive tape for wafer surface protection.
(比較例1) (Comparative example 1)
於實施例1中,將黏著劑組成物1A變更為黏著劑組成物1C,並將膜2A變更 為膜2E,除此以外,以與實施例1相同之方式獲得半導體晶圓表面保護用黏著帶。 In Example 1, the adhesive tape for semiconductor wafer surface protection was obtained in the same manner as in Example 1 except that the adhesive composition 1A was changed to the adhesive composition 1C, and the film 2A was changed to the film 2E. .
(比較例2) (Comparative example 2)
於實施例1中,將黏著劑組成物1A變更為黏著劑組成物1B,並將膜2A變更為膜2F,除此以外,以與實施例1相同之方式獲得半導體晶圓表面保護用黏著帶。 In Example 1, the adhesive tape for semiconductor wafer surface protection was obtained in the same manner as in Example 1 except that the adhesive composition 1A was changed to the adhesive composition 1B, and the film 2A was changed to the film 2F. .
(比較例3) (Comparative example 3)
於實施例1中,將膜2A變更為膜2G,除此以外,以與實施例1相同之方式獲得半導體晶圓表面保護用黏著帶。 Except that the film 2A was changed to the film 2G in Example 1, the adhesive tape for semiconductor wafer surface protection was obtained in the same manner as in Example 1.
(比較例4) (Comparative Example 4)
於實施例1中,將膜2A變更為膜2H,除此以外,以與實施例1相同之方式獲得半導體晶圓表面保護用黏著帶。 Except that the film 2A was changed to the film 2H in Example 1, the adhesive tape for semiconductor wafer surface protection was obtained in the same manner as in Example 1.
針對上述實施例及比較例中製作之半導體晶圓表面保護用黏著帶進行以下之試驗,並對其性能進行評價。將評價結果記載於下述表1。此外,針對實施例2~4及比較例1~3中製作之表面保護帶,亦以與實施例1相同之方式進行試驗。 The following tests were performed on the semiconductor wafer surface protection adhesive tapes produced in the above examples and comparative examples, and their performance was evaluated. The evaluation results are described in Table 1 below. In addition, the surface protection tapes produced in Examples 2 to 4 and Comparative Examples 1 to 3 were also tested in the same manner as in Example 1.
<試驗例1>密接性試驗 <Test Example 1> Adhesion test
(1)對高度50μm之凸塊之密接性 (1) Adhesion to bumps with a height of 50 μm
於具有高度50μm且凸塊間距100μm之Cu柱凸塊的直徑8英吋附帶凸塊之矽晶圓(矽晶圓本身之厚度為725μm)之表面,使用日東精機公司製造之DR8500III(商品名),於工作臺面溫度(table temperature)80℃及輥溫度60℃、貼合壓0.35MPa、貼合速度低速(9mm/sec)之條件下,將上述實施例1中製作之表面保護帶貼合於上述晶圓。以此方式製作25片附表面保護帶之晶圓(凸塊高度:50μm)。於該貼合條件下,以由熔點80℃以下之樹脂所組成之中間 樹脂層為構成層之表面保護帶之中間樹脂層發生熔融(於以下之試驗例2之情形時亦相同)。目視確認此時之密接性,調查表面保護帶與上述晶圓之間有無空氣混入。 On a surface of a silicon wafer with bumps (the thickness of the silicon wafer itself is 725 μm) having a diameter of 8 inches and a Cu pillar bump having a height of 50 μm and a bump pitch of 100 μm, a DR8500III (trade name) manufactured by Nitto Seiki Corporation Under the conditions of a table temperature of 80 ° C and a roll temperature of 60 ° C, a bonding pressure of 0.35MPa, and a low bonding speed (9mm / sec), the surface protective tape produced in the above embodiment 1 was bonded to The above wafer. In this way, 25 wafers (bump height: 50 μm) with surface protection tape were produced. Under these bonding conditions, the intermediate resin layer of the surface protective tape comprising the intermediate resin layer composed of a resin having a melting point of 80 ° C or lower as a constituent layer is fused (the same is true in the case of the following Test Example 2). The tightness at this time was visually confirmed, and it was investigated whether air was mixed between the surface protection tape and the wafer.
(2)對高度200μm之凸塊之密接性 (2) Adhesion to bumps with a height of 200 μm
於具有高度200μm且凸塊間距400μm之焊接凸塊之直徑8英吋之附帶凸塊之矽晶圓(除凸塊以外之部分之厚度為725μm)之表面,使用日東精機公司製造之DR8500III(商品名),於工作台面溫度80℃及輥溫度60℃、貼合壓0.35MPa、貼合速度低速(9mm/sec)之條件下,將上述實施例1中製作之表面保護帶貼合於上述晶圓。以此方式製作5片附表面保護帶之晶圓(凸塊高度:200μm)。目視確認此時之密接性,調查表面保護帶與上述晶圓之間有無空氣混入。將評價基準示於以下。A及B為合格。 On the surface of a 8-inch diameter silicon wafer with bumps (the thickness of the part other than the bumps is 725 μm) with solder bumps with a height of 200 μm and a bump pitch of 400 μm, the Nitto Seiki Corporation DR8500III (commodity Name), under the conditions of a table surface temperature of 80 ° C., a roll temperature of 60 ° C., a bonding pressure of 0.35 MPa, and a low bonding speed (9 mm / sec), the surface protective tape prepared in Example 1 was bonded to the crystal. circle. In this way, five wafers (bump height: 200 μm) with surface protection tape were produced. The tightness at this time was visually confirmed, and it was investigated whether air was mixed between the surface protection tape and the wafer. The evaluation criteria are shown below. A and B are qualified.
(評價基準) (Evaluation criteria)
A:貼合後,於室溫(25℃)靜置,即便超過72小時,全部附表面保護帶之晶圓亦未觀察到空氣混入。 A: After lamination, it was left to stand at room temperature (25 ° C), and even if it exceeded 72 hours, no air intrusion was observed on all the wafers with surface protection tape.
B:貼合後,於室溫下靜置,於超過48小時且72小時以內,全部附表面保護帶之晶圓未觀察到空氣混入。 B: After lamination, it was left to stand at room temperature, and no air intrusion was observed in all wafers with surface protection tape within 48 hours and 72 hours.
C:貼合後,於室溫下靜置,於至少1片附表面保護帶之晶圓,於貼合後48時間以內觀察到空氣。 C: After lamination, it was left to stand at room temperature, and at least one wafer with a surface protective tape was used, and air was observed within 48 hours after lamination.
<試驗例2>研削試驗 <Test Example 2> Grinding test
(1)灰塵侵入 (1) Dust intrusion
以與上述相同之方式將表面保護帶貼合於上述晶圓,而製作實施例1之附表面保護帶之晶圓(凸塊高度:50μm)5片及實施例1之附表面保護帶之晶圓(凸塊高度:200μm)5片。將表面保護帶貼合於上述晶圓後靜置48小時後,進行背面研削。該背面研削係使用具有直列式機構之研磨機[迪思科股份有限公 司製造之DFG8760(商品名)]。然後,針對研削後之附表面保護帶之晶圓,目視確認晶圓與表面保護帶間有無矽塵之侵入。此外,針對實施例1之附表面保護帶之晶圓(凸塊高度:50μm),進行背面研削直至晶圓之最後研削厚度成為50μm。另一方面,針對實施例1之附表面保護帶之晶圓(凸塊高度:200μm),進行背面研削直至矽之最後研削厚度成為200μm,並按照以下之評價基準進行評價。 The surface protection tape was bonded to the wafer in the same manner as described above, and 5 wafers (bump height: 50 μm) with the surface protection tape and the crystal with the surface protection tape of Example 1 were produced. Round (bump height: 200 μm) 5 pieces. After the surface protective tape was attached to the wafer, it was allowed to stand for 48 hours, and then the back surface was ground. This back grinding was performed using a grinder [DFG8760 (trade name) manufactured by Disco Corporation) with an in-line mechanism. Then, for the wafer with the surface protection tape after the grinding, visually confirm whether there is intrusion of silicon dust between the wafer and the surface protection tape. In addition, for the wafer with a surface protection tape (bump height: 50 μm) in Example 1, the back grinding was performed until the final grinding thickness of the wafer became 50 μm. On the other hand, the wafer with a surface protection tape (bump height: 200 μm) in Example 1 was subjected to back grinding until the final grinding thickness of silicon became 200 μm, and evaluated according to the following evaluation criteria.
(評價基準) (Evaluation criteria)
合格:附表面保護帶之晶圓(凸塊高度:50μm)及附表面保護帶之晶圓(凸塊高度:200μm)均未見到灰塵侵入。 Pass: No intrusion of dust was observed on the wafer with surface protection tape (bump height: 50 μm) and the wafer with surface protection tape (bump height: 200 μm).
不合格:附表面保護帶之晶圓(凸塊高度:50μm)及附表面保護帶之晶圓(凸塊高度:200μm)均至少1片見到灰塵侵入。 Failure: At least one wafer with surface protection tape (bump height: 50 μm) and wafer with surface protection tape (bump height: 200 μm) saw dust intrusion.
(2)搬送錯誤 (2) Transfer error
將評價基準示於以下。A及B為合格。 The evaluation criteria are shown below. A and B are qualified.
A:於研削試驗中,全部晶圓均未產生研削裝置內之搬送錯誤。 A: In the grinding test, no wafer transfer error occurred in the grinding device.
B:於研削試驗中,1片產生了研削裝置內之搬送錯誤。 B: In the grinding test, one piece produced a transport error in the grinding device.
C:於研削試驗中,2片以上產生了研削裝置內之搬送錯誤。 C: In the grinding test, two or more pieces caused a transport error in the grinding device.
「搬送錯誤」係指基材膜變形而無法進行真空吸附以搬送附表面保護帶之晶圓。 "Transfer error" means that the substrate film is deformed and cannot be vacuum-adsorbed to transport a wafer with a surface protection tape.
(3)晶圓破損之評價 (3) Evaluation of wafer damage
目視確認經研削之各附表面保護帶之晶圓整體,利用光學顯微鏡進行晶圓端部之觀察,調查有無晶圓破損。將評價基準示於以下。「無(A)」為合格。 Visually confirm the entire wafer with the surface protection tape after grinding, observe the wafer end with an optical microscope, and check for wafer damage. The evaluation criteria are shown below. "None (A)" is a pass.
(評價基準) (Evaluation criteria)
無(A):以目視及顯微鏡觀察並無破損。 None (A): No damage was observed by visual inspection and microscope.
B:目視無破損但利用顯微鏡確認到破損。 B: No damage was observed visually, but damage was confirmed with a microscope.
C:目視確認到破損。 C: Damage was visually confirmed.
(4)翹曲評價 (4) Evaluation of warpage
針對灰塵侵入之評價中使用之實施例1的附表面保護帶之晶圓(凸塊高度:50μm)5片,測定翹曲高度(將附表面保護帶之晶圓放置於平板之上,自平板表面至翹曲之晶圓之最高點之下表面為止的高度)。將評價基準示於以下。A為合格。 Five wafers with surface protection tape (bump height: 50 μm) used in the evaluation of dust invasion were measured, and the warpage height was measured. Height from the surface to the surface below the highest point of the warped wafer). The evaluation criteria are shown below. A is qualified.
(評價基準) (Evaluation criteria)
A:翹曲高度之平均值未達5mm A: The average value of warpage height is less than 5mm
B:翹曲高度之平均值為5mm以上且未達10mm B: The average value of warpage height is 5mm or more and less than 10mm
C:翹曲高度之平均值為10mm以上 C: The average value of warpage height is 10 mm or more
(5)剝離性評價 (5) Evaluation of peelability
於表面具有高度75μm之凸塊(凸塊間距150μm)的8英吋徑半導體晶圓表面,於90℃之貼合溫度下貼合上述製造之各半導體晶圓表面保護用黏著帶。然後,使用迪思科股份有限公司製造之DFG8760(商品名),對貼合有上述半導體晶圓表面保護用黏著帶之附帶凸塊之半導體晶圓的背面各2片進行研削加工直至厚度成為200μm。對研削後之附帶半導體晶圓表面保護用黏著帶之半導體晶圓照射500mJ/cm2之紫外線,使用Instron公司製造之拉伸試驗機(雙柱台式5567(商品名))將半導體晶圓表面保護用黏著帶剝離,針對剝離時寬度成為最大(200mm)時之剝離力,按照以下之基準進行評價。A及B為合格。 On the surface of an 8-inch-diameter semiconductor wafer having bumps with a height of 75 μm (bump pitch 150 μm), each of the semiconductor wafer surface protection adhesive tapes manufactured above was bonded at a bonding temperature of 90 ° C. Then, using the DFG8760 (trade name) manufactured by Disco Corporation, grinding the back surface of each of the semiconductor wafers with bumps to which the above-mentioned adhesive tape for semiconductor wafer surface protection was bonded, until the thickness became 200 μm. After the grinding, the semiconductor wafer with the adhesive tape for protecting the surface of the semiconductor wafer was irradiated with 500 mJ / cm 2 of ultraviolet rays, and the surface of the semiconductor wafer was protected by a tensile tester (double column table 5567 (trade name)) manufactured by Instron Corporation. It peeled with the adhesive tape, and evaluated the peeling force when the width | variety at the time of peeling became the largest (200 mm) according to the following criteria. A and B are qualified.
此外,於表1中表示為「剝離性」。 In addition, it shows as "peelability" in Table 1.
(評價基準) (Evaluation criteria)
A:20N/200mm以下 A: 20N / 200mm or less
B:超過20N/200mm且為50N/200mm以下 B: More than 20N / 200mm and less than 50N / 200mm
C:超過50N/200mm C: more than 50N / 200mm
(6)糊劑殘留評價 (6) Evaluation of paste residue
針對剝離性評價中使用之實施例1之附表面保護帶之晶圓(凸塊高度:50μm)5片,使用光學顯微鏡(奧林巴斯)進行糊劑殘留觀察。將評價基準示於以下。 With respect to 5 wafers (bump height: 50 μm) with a surface protective tape used in the peelability evaluation of Example 1, paste residue observation was performed using an optical microscope (Olympus). The evaluation criteria are shown below.
(評價基準) (Evaluation criteria)
合格:全部附表面保護帶之晶圓均未產生糊劑殘留。 Pass: None of the wafers with surface protection tape produced paste residue.
不合格:至少1片附表面保護帶之晶圓產生糊劑殘留。 Failure: At least 1 wafer with surface protection tape has paste residue.
<試驗例3>耐熱性試驗 <Test Example 3> Heat resistance test
對鏡面晶圓進行實施例1之表面保護帶之貼合。貼合條件係與試驗例2中於矽晶圓貼合表面保護帶之條件相同。然後,於加熱至90℃之加熱板上,使帶面朝下而使表面保護帶之基材膜與加熱板相接,靜置3分鐘後,目視觀察帶表面。 The mirror wafer was bonded to the surface protective tape of Example 1. The bonding conditions are the same as those for bonding a surface protective tape to a silicon wafer in Test Example 2. Then, on a heating plate heated to 90 ° C., with the tape side facing downward, the base film of the surface protection tape was contacted with the heating plate. After standing for 3 minutes, the surface of the tape was visually observed.
(評價基準) (Evaluation criteria)
合格:基材膜未熔化。 Pass: The substrate film is not melted.
不合格:基材膜熔化。 Failure: The substrate film is melted.
<物性之測定> <Measurement of physical properties>
(熔點、菲卡軟化點、MFR) (Melting point, Fica softening point, MFR)
針對構成中間樹脂層之樹脂的熔點及菲卡軟化點,基於JIS K 7206進行測定。針對構成中間樹脂層之樹脂的熔體質量流率(MFR),基於JIS K 7210進行測定。基材膜之構成材料的熔點係基於JIS K 6977-2進行測定。 The melting point and the softening point of the resin constituting the intermediate resin layer were measured based on JIS K 7206. The melt mass flow rate (MFR) of the resin constituting the intermediate resin layer was measured based on JIS K 7210. The melting point of the constituent material of the base film is measured based on JIS K 6977-2.
(黏著力) (Adhesion)
藉由上述方法進行測定。 The measurement was performed by the above method.
<表之註釋> <Notes of the table>
黏著力之行之括弧標註表示形成黏著劑層所使用之黏著劑組成物之種類。 The brackets on the line of the adhesive force indicate the type of the adhesive composition used to form the adhesive layer.
由表1清楚可知,滿足本發明規定之實施例1~4的表面保護帶的密接性優異,能夠抑制灰塵侵入、搬送錯誤、晶圓破損。進而,實施例1~4之表面保護帶能夠抑制貼合於半導體晶圓表面之狀態下的翹曲,且剝離性、糊劑殘留及耐熱性優異。 It is clear from Table 1 that the surface protective tapes of Examples 1 to 4 satisfying the requirements of the present invention are excellent in adhesion, and can suppress dust intrusion, transfer errors, and wafer damage. Furthermore, the surface protective tapes of Examples 1 to 4 can suppress warpage in a state of being bonded to the surface of a semiconductor wafer, and are excellent in peelability, paste residue, and heat resistance.
相對於此,比較例1~3之表面保護帶則至少2個評價項目不合格。 In contrast, the surface protective tapes of Comparative Examples 1 to 3 failed at least two evaluation items.
以上,對本發明及其實施態樣進行了說明,但只要本發明未作特別指定,則無論於說明之任一細節中均非欲限定本發明,應該於不違反附加之申請專利範圍所示的發明精神與範圍下,作廣泛地解釋。 The invention and its embodiments have been described above, but as long as the invention is not specifically specified, it is not intended to limit the invention in any detail of the description, and it should be shown in the scope of the attached patent application without violating. Explained broadly within the spirit and scope of the invention.
本申請案主張基於2017年3月31日於日本提出專利申請之特願2017-71346的優先權,在此將其作為參照,將其內容作為本說明書之記載的一部分而併入本文中。 This application claims priority based on Japanese Patent Application No. 2017-71346, filed in Japan on March 31, 2017, which is hereby incorporated by reference, and the contents of which are incorporated herein as part of the description of this specification.
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US20220148905A1 (en) * | 2019-02-26 | 2022-05-12 | Disco Corporation | Back grinding adhesive sheet, and method for manufacturing semiconductor wafer |
JP7289688B2 (en) * | 2019-03-26 | 2023-06-12 | 日東電工株式会社 | Dicing tape with adhesive film |
JP6678795B1 (en) * | 2019-04-08 | 2020-04-08 | 古河電気工業株式会社 | Electronic component tape and electronic component processing method |
JP6678796B1 (en) * | 2019-04-08 | 2020-04-08 | 古河電気工業株式会社 | Electronic component tape and electronic component processing method |
KR102411362B1 (en) * | 2021-07-09 | 2022-06-22 | 구동필 | Adhesion film for wafer back grinding and its manufacturing method |
CN118077037A (en) * | 2021-10-20 | 2024-05-24 | 电化株式会社 | Substrate for adhesive sheet for processing semiconductor wafer having convex portion |
WO2023083248A1 (en) * | 2021-11-11 | 2023-05-19 | Ddp Specialty Electronic Materials Us, Llc | Adhesive system |
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JP4369584B2 (en) | 2000-01-21 | 2009-11-25 | 日東電工株式会社 | Adhesive sheet for semiconductor wafer holding protection |
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