TWI534230B - A temporary adhesive composition, and a method for producing the thin wafers using the same - Google Patents
A temporary adhesive composition, and a method for producing the thin wafers using the same Download PDFInfo
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- TWI534230B TWI534230B TW101136500A TW101136500A TWI534230B TW I534230 B TWI534230 B TW I534230B TW 101136500 A TW101136500 A TW 101136500A TW 101136500 A TW101136500 A TW 101136500A TW I534230 B TWI534230 B TW I534230B
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- 239000000853 adhesive Substances 0.000 title claims description 54
- 230000001070 adhesive effect Effects 0.000 title claims description 54
- 239000000203 mixture Substances 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 235000012431 wafers Nutrition 0.000 title description 96
- 239000000758 substrate Substances 0.000 claims description 89
- 150000002430 hydrocarbons Chemical group 0.000 claims description 50
- -1 phenol compound Chemical class 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 41
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 36
- 230000015572 biosynthetic process Effects 0.000 claims description 34
- 125000003342 alkenyl group Chemical group 0.000 claims description 27
- 239000012790 adhesive layer Substances 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 24
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 20
- 125000000962 organic group Chemical group 0.000 claims description 19
- 238000005498 polishing Methods 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000002798 polar solvent Substances 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000002015 acyclic group Chemical group 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 6
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000004065 semiconductor Substances 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 16
- 229920002120 photoresistant polymer Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- 238000000227 grinding Methods 0.000 description 12
- 239000003495 polar organic solvent Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 230000005856 abnormality Effects 0.000 description 7
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical group CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 4
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 241000208340 Araliaceae Species 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 4
- 235000003140 Panax quinquefolius Nutrition 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 235000008434 ginseng Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 3
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XQFUVDNFWZHPEJ-UHFFFAOYSA-N 1,1,1-trichloroheptane Chemical compound CCCCCCC(Cl)(Cl)Cl XQFUVDNFWZHPEJ-UHFFFAOYSA-N 0.000 description 2
- NWHNXXMYEICZAT-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidin-4-ol Chemical compound CN1C(C)(C)CC(O)CC1(C)C NWHNXXMYEICZAT-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFUYDYUQFXMKFB-UHFFFAOYSA-N CC(C(Cl)(Cl)C)CCCCCCCC Chemical compound CC(C(Cl)(Cl)C)CCCCCCCC UFUYDYUQFXMKFB-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- 241001050985 Disco Species 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
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- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
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- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 2
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
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- 239000010421 standard material Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 2
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WABVQKPVNNPRHB-UHFFFAOYSA-N (1,1-dichloro-1-phenyldecan-2-yl)benzene Chemical compound C1(=CC=CC=C1)C(C(Cl)(Cl)C1=CC=CC=C1)CCCCCCCC WABVQKPVNNPRHB-UHFFFAOYSA-N 0.000 description 1
- LTBYTHUSUUWWBV-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-4-yl) but-3-enoate Chemical compound N1(C(CC(CC1(C)C)OC(=O)CC=C)(C)C)C LTBYTHUSUUWWBV-UHFFFAOYSA-N 0.000 description 1
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- GAJQCIFYLSXSEZ-UHFFFAOYSA-N tridecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCOP(O)(O)=O GAJQCIFYLSXSEZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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Description
本發明係關於臨時接著劑組成物、及使用其之薄型晶圓之製造方法。
三次元半導體安裝為實現更進一步之高積體化、大容量化所必須。三次元半導體安裝技術係使一個半導體晶片薄型化,接著以矽貫穿電極(TSV;through silicon via)使該等線連結同時經多層層合之半導體製作技術。為實現此技術,需要藉由背側研磨使形成半導體電路之基板薄型化,進而於背側形成含TSV之電極等之電極形成步驟。以往,電極形成步驟前之矽晶板之背面研磨步驟係於研磨面之相反側貼合保護膠帶,防止研磨時之晶圓破損。然而,該膠帶於基材係使用有機樹脂薄膜,具有柔軟性,但相對地強度或耐熱性不足,並不適於進行背面之配線層形成製程。
因此已提案透過接著劑將該半導體基板接合於矽、玻璃等支撐基板上,而可充分耐受背面研磨步驟、背面電極形成步驟之系統。此時重要的是接合二基板時之接著劑。該接著劑需要有可無間隙地接合基板之接著性、可耐受隨後製程之充分耐久性,進而需要最後可自支撐基板簡易地剝離薄型晶圓。因此,由於最後須剝離故將該接著劑稱為臨時接著劑。
迄今為止習知之臨時接著劑與其剝離方法,已提案有對含光吸收性物質之接著劑照射高強度之光,藉由使接著劑層分解而自支撐基板剝離接著劑層之技術(專利文獻1),及於接著劑中使用烴系之熱熔融性化合物,在加熱熔融狀態進行接合.剝離之技術(專利文獻2)。然而,前者需要雷射等之昂貴裝置,且有每一片基板之處理時間較長之問題。又後者由於僅藉加熱控制故較簡便,但相對地在超過200℃之高溫之熱安定性不足,製程之適用範圍狹窄。
[專利文獻1]特開2004-064040號公報
[專利文獻2]特開2006-328104號公報
[專利文獻3]美國專利第7541264號說明書
又,為實現三次元半導體之安裝技術,而提案於臨時接著劑層中使用聚矽氧黏著劑之技術(專利文獻3)。此係使用加成硬化型之聚矽氧黏著劑接合基板彼此,且在剝離時浸漬於藥劑中以使聚矽氧樹脂溶解或分解而使兩基板分離之技術。為此剝離須極長之時間,於實際之製造製程之應用較困難。
另一方面,該等臨時接著劑由於剝離後變得不需要,
故須以有機溶劑洗淨、去除殘存之接著劑,因此必須為容易溶解於洗淨用有機溶劑(非極性溶劑)中。然而,對於於接合基板之半導體側塗佈光阻劑並去除時使用之有機溶劑(極性溶劑)則要求為難溶。控制對該有機溶劑之溶解性為本用途中極為重要之特性。
以往之有機聚矽氧烷中使用之主要具有有機基即甲基、苯基者,大多對於丙酮或N-甲基吡咯烷酮等極性溶劑具有高的溶解性,在上述用途中須加以改良。
另一方面,藉由將非芳香族飽和烴基導入於有機聚矽氧烷中可提高對極性溶劑之耐溶劑性,但在高溫(例如270℃)加熱時由於烴基之分解而產生釋出氣體,進而產生孔洞而使熱安定性不足。
本發明係為解決上述課題而完成者,其目的係提供一種維持對極性溶劑之耐溶劑性,同時具有優異之熱安定性之臨時接著劑組成物及使用其之薄型晶圓之製造方法。
為解決上述課題,本發明提供一種臨時接著劑組成物,其特徵為含有(A)含有非芳香族飽和烴基之有機聚矽氧烷、(B)抗氧化劑、(C)有機溶劑;且前述(A)成分為100質量份、前述(B)成分為0.5~5質量份,前述(C)成分為10~1000質量份。
若為此臨時接著劑組成物,則其耐熱性(熱安定性)優異,且對於洗淨用之非極性有機溶劑為可溶,另一方面,對於將光阻劑塗佈於接合基板之半導體側並去除時等使用之極性有機溶劑可成為難溶。
又,前述(B)成分之抗氧化劑為由受阻酚系化合物、受阻胺系化合物、有機磷化合物、及有機硫化合物所組成群組中選出之至少一種以上之化合物。
若使用該種化合物作為抗氧化劑,則可更提高耐熱性。
又,前述(A)成分之含有非芳香族飽和烴基之有機聚矽氧烷較好為重量平均分子量為2,000~60,000,不溶於SP值大於9之極性溶劑中,且含有以下述(I)~(III)表示之單位之有機聚矽氧烷(A-1),或以該有機聚矽氧烷(A-1)作為原料經高分子量化之有機聚矽氧烷(A-2),
(I)以R1SiO3/2表示之矽氧烷單位(T單位):50~99莫耳%
(II)以R2R3SiO2/2表示之矽氧烷單位(D單位):0~49莫耳%
(III)以R4 3SiO1/2表示之矽氧烷單位(M單位):1~15莫耳%
(前述R1~R4為一價有機基,以R1~R3表示之全部有機基中之50~80莫耳%為相同或不同之含下述環狀構造之任一者之非芳香族飽和烴基:
且10~40莫耳%為相同或不同之碳數6~15之經取代或未經取代之一價非環狀飽和烴基,而且,前述以R1~R4所示之全部有機基中之環狀、非環狀飽和烴基以外為相同或不同之碳數1~7之經取代或未經取代之一價烴基)。
若(A)成分若為上述有機聚矽氧烷,則成為溶解性控制特別優異之臨時接著劑組成物。
又,前述有機聚矽氧烷(A-2)較好為使前述有機聚矽氧烷(A-1)中,以前述R1~R4表示之全部有機基中之2~10莫耳%為碳數2~7之烯基之含有烯基之有機聚矽氧烷(a1),與以下述通式(1)表示之一種以上之有機氫聚矽氧烷,
(式中,R5~R7可相同亦可不同,表示除烯基以外之碳數1~12之一價烴基,n為1~100之整數),且相對於前述含烯基之有機聚矽氧烷(a1)之總烯基,總SiH基成為0.4~1.0倍之量之前述有機氫聚矽氧烷(a2),在鉑族金屬系觸媒存在下經氫矽烷化反應而成者,重量平均分子量為30,000~200,000,且不溶於SP值大於9之極性溶劑中之有機聚矽氧烷。
(A-2)若為使上述有機聚矽氧烷(A-1)經高分子量化之有機聚矽氧烷,則成為接著性及耐熱性更為優異之臨時接著劑組成物。
另外,前述(C)成分之有機溶劑較好為沸點120~240℃、SP值為9以下之烴溶劑。
若為該有機溶劑,由於燃火點高故安全性高,且藉由塗佈有機溶劑後之加熱乾燥而容易揮發,不易留在膜內,故使臨時接著劑組成物於基板接合後之加熱製程中暴露於高溫時,可抑制接合面之氣泡形成。
又,本發明提供一種薄型晶圓之製造方法,其為使具有電路形成面及電路非形成面之晶圓與支撐基板接合並研磨以製造薄型晶圓之方法,其特徵為包含下列步驟:在前述電路形成面上及前述支撐基板表面上之至少一者上,以前述本發明之臨時接著劑組成物形成接著層,且介隔著該接著層,接合前述晶圓之電路形成面與前述支撐基板之接合步驟,研磨經接合前述支撐基板之晶圓之前述電路非形成面之研磨步驟,自前述支撐基板剝離前述研磨後之晶圓之剝離步驟,及去除殘存於前述剝離之晶圓之電路形成面上的前述接著層之去除步驟。
若為該薄型晶圓之製造方法,則在剝離.去除步驟中可以短時間內自支撐基板剝離晶圓,且,在薄型晶圓之製
造步驟中將光阻劑塗佈於接合基板之半導體側並去除亦不會使晶圓自支撐基板剝離,故而可高效率地生產薄型晶圓。
如以上說明,依據本發明之臨時接著劑組成物,為耐熱性優異,對非極性之有機溶劑為可溶,且可以短時間自支撐基板剝離。且另一方面,可提供對於將光阻劑塗佈於接合基板之半導體側並去除時等所使用之極性有機溶劑為難溶,且作為臨時接著劑時之接著性亦良好,將光阻劑塗佈於接合基板之半導體側且去除時不會剝離之臨時接著劑組成物。
進而,依據使用本發明之臨時接著劑組成物製造薄型晶圓之方法,可高效率地生產薄型晶圓。
以下,針對本發明加以詳細說明。
如上述,期望主要用以實現三次元半導體安裝技術之最適用之維持耐溶劑性同時具有優異熱安定性之臨時接著劑之開發。
本發明人等為達成上述課題而重複積極檢討之結果,發現後述組成之臨時接著劑組成物可維持對於將光阻劑在塗佈於接合基板之半導體側上並去除時等使用之極性有機溶劑為難溶、且對於非極性之有機溶劑維持可溶之耐溶劑
性,且具有優異之耐熱性(熱安定性),因而完成本發明。
以下,針對本發明之臨時接著劑組成物,使用其之薄型晶圓之製造方法加以詳細說明,但本發明並不限於該等。
本發明之臨時接著劑組成物之特徵為含有(A)含有非芳香族飽和烴基之有機聚矽氧烷、(B)抗氧化劑、(C)有機溶劑;
且前述(A)成分為100質量份、前述(B)成分為0.5~5質量份、前述(C)成分為10~1000質量份。
尤其,藉由含有(A)含有非芳香族飽和烴基之有機聚矽氧烷及(B)抗氧化劑,而成為顯示優異耐熱性及耐溶劑性者。
本發明之(A)成分為含有非芳香族飽和烴基之有機聚矽氧烷,臨時接著劑組成物中所含之有機聚矽氧烷可單獨使用一種,亦可併用兩種以上。至於可較好使用者,列舉大致區分為下述(A-1)、(A-2)兩種。以下依序加以說明。
有機聚矽氧烷(A-1)係重量平均分子量(Mw)[以
GPC(凝膠滲透層析儀)測定之聚苯乙烯換算值]為2,000~60,000,不溶於SP值[溶解度參數(cal/cm3)1/2]大於9之極性溶劑中且含有以下述(I)~(III)表示之單位之含非芳香族飽和烴基之有機聚矽氧烷。
(I)以R1SiO3/2表示之矽氧烷單位(T單位):50~99莫耳%
(II)以R2R3SiO2/2表示之矽氧烷單位(D單位):0~49莫耳%
(III)以R4 3SiO1/2表示之矽氧烷單位(M單位):1~15莫耳%
上述(I)~(III)所示之單位之R1~R4為一價有機基。
尤其就展現溶解性差之方面,含環狀構造之非芳香族飽和烴基(非芳香族環狀飽和烴基)之含量具重要性,前述R1~R3中之非芳香族環狀飽和烴基之含量較好為50~80莫耳%,若為50莫耳%以上,則在將光阻劑塗佈於接合基板之半導體側且去除時等使用之極性有機溶劑容易變成難溶。另一方面,若為80莫耳%以下,則存在溶解性差,且由於成為適度硬度故在塗佈於矽基板上後不會發生龜裂。
若為50~80莫耳%則於SP值[溶解度參數(cal/cm3)1/2]大於9之極性溶劑,例如丙酮(SP:10.0)、N-甲基吡咯烷酮(SP:11.2)中成為不溶,於烴系之非極性溶劑,例如正己烷(SP:7.3)、異十二烷(SP:7.7)中成為可溶。
作為此種非芳香族環狀飽和烴基列舉為包含下述環狀構造之任一者之非芳香族飽和烴基,
例如,環己基、降冰片基、降冰片基乙基等,其中以環己基、降冰片基較佳。
又,就溶解性差以及提高聚矽氧烷之接合性而言,非環狀飽和烴基之含量亦重要。前述R1~R3中之碳數6~15之經取代、未經取代之一價非環狀飽和烴基之含量較好為10~40莫耳%。若為10莫耳%以上,則可期待接合性之提高,若為40莫耳%以下,則高溫時黏度亦不會極度降低,可獲得充分之耐熱性。
至於該非環狀飽和烴基列舉為正己基、辛基、正癸基、正十二烷基等,更好為正己基、正十二烷基。
前述R1~R4所示之全部有機基中,上述環狀、非環狀飽和烴基以外之基較好為碳數1~7之經取代或未經取代之一價烴基,列舉為甲基、乙基、丙基、丁基、戊基等烷基;苯基、甲苯基等芳基;苄基等芳烷基;乙烯基、烯丙基、丁烯基、戊烯基、己烯基、庚烯基等之烯基等之不飽和烴基;氯甲基、3-氯丙基、3,3,3-三氟丙基等之鹵化烷基等,較好為甲基、苯基、烯基。
至於本發明之(A)成分之含非芳香族飽和烴基之有機聚矽氧烷之較佳之有機聚矽氧烷(A-1)係如上述,含50~99莫耳%之T單位、0~49莫耳%之D單位、1~15莫耳
%之M單位。
(A)成分之含非芳香族飽和烴基之有機聚矽氧烷在不超過40℃之溫度下具有固體形狀者在作業上較佳。
藉由含50~99莫耳%之T單位,(A)成分之含非芳香族飽和烴基之有機聚係氧烷在40℃以下容易成為固體,成為適於基板間之接合。
藉由含49莫耳%以下之D單位,(A)成分之含非芳香族飽和烴基之有機聚矽氧烷在40℃以下容易成為固體,且用於臨時接著劑組成物中時可使晶圓與支撐基板充分接合。
又,(A)成分之含有非芳香族飽和烴基之有機聚矽氧烷中,不殘留反應性之末端基亦即矽烷醇或水解性殘基,就後述之熱安定性之觀點而言較佳。據此較好為於末端導入M單位之構造,至於M單位之含量較好含1莫耳%以上。更好為1~15莫耳%。
藉由含1~15莫耳%之M單位,使(A)成分之含有非芳香族飽和烴基之有機聚矽氧烷成為反應性末端基充分減低之構造。若為1莫耳%以上,則可成為矽烷醇或水解性殘基等反應性末端基充分減低之構造。又若為15莫耳%以下,則有因末端基不會太多,而相對地並無使分子量變小之虞故較佳。
存在未以M單位封端之分子末端基即矽烷醇基、或烷氧基矽烷基等之水解性殘基時,該等反應性末端基之含量以儘可能少者較佳。若矽烷醇基及烷氧基矽烷基之末端殘
基在分子內為少量,則可抑制施加熱時因縮合反應而產生交聯,且可抑制基板剝離性之較大變化故較佳。且,矽烷醇基之OH基、及烷氧基矽烷基(Si-OR:R為作為原料使用之烷氧基矽烷之烷氧基殘基、甲氧基、乙氧基、正丙基、異丙基等)之OR基之總量,較好為全部樹脂固體成分中之5質量%以下,更好為3質量%以下。藉由M單位之導入,可將該反應性末端基減低至期望之量。
上述構造之有機聚矽氧烷可藉由邊控制作為原料之水解性矽烷之水解及縮合反應邊進行而製造。
可作為原料使用之水解性矽烷列舉為甲基三氯矽烷、苯基三氯矽烷、正丙基三氯矽烷、異丙基三氯矽烷、正丁基三氯矽烷、異丁基三氯矽烷、正戊基三氯矽烷、異戊基三氯矽烷、正己基三氯矽烷、環己基三氯矽烷、正辛基三氯矽烷、正癸基三氯矽烷、正十二烷基三氯矽烷、雙環[2.2.1]庚基三氯矽烷(以下稱為C1)、雙環[2.2.1]壬基三氯矽烷(以下稱為C2)、二甲基二氯矽烷、正丙基甲基二氯矽烷、異丙基甲基二氯矽烷、正丁基甲基二氯矽烷、異丁基甲基二氯矽烷、正己基甲基二氯矽烷、正辛基甲基二氯矽烷、正癸基甲基二氯矽烷、正十二烷基甲基二氯矽烷、環己基甲基二氯矽烷、二苯基二氯矽烷、雙環[2.2.1]庚基甲基二氯矽烷(以下稱為C3)、雙環[2.2.1]壬基甲基二氯矽烷(以下稱為C4)及該等之水解性基為甲氧基、乙氧基者。
尤其具有複數個環狀構造之下述(C1)~(C4)存在
橋(endo)、挂(exo)體之立體異構物,但該不管如何均可使用。
(A)成分之含有非芳香族飽和烴基之聚矽氧烷之分子量分布極為重要。亦即以GPC(凝膠滲透層析儀)測量,利用以聚苯乙烯標準物質製作之校正線獲得之重量平均分子量之值較好為2,000以上。若含有非芳香族飽和烴基之聚矽氧烷之重量平均分子量為2,000以上,則展現對極性、非極性溶劑之溶解性之差,若為60,000以下,則可使含有非芳香族飽和烴基之聚矽氧烷之分子量再現性良好地穩定合成。更佳之含有非芳香族飽和烴基之有機聚矽氧烷之重量平均分子量之範圍為3,000~50,000左右,又更好為5,000~30,000左右。
至於可進行該分析、解析之GPC裝置可使用TOSOH製造之HLC-8120GPC、HLC-8220GPC、HLC-8230GPC。
有機聚矽氧烷(A-2)為以前述有機聚矽氧烷(A-1)作為原料經高分子量化者。
較好以前述(A-1)表示之有機聚矽氧烷中,以前述
R1~R4表示之全部有機基中之2~10莫耳%為碳數2~7之烯基之含烯基之有機聚矽氧烷(a1),與以下述通式(1)表示之一種以上之有機氫聚矽氧烷:
(式中,R5~R7可相同亦可不同,表示除烯基以外之碳數1~12之一價烴基,n為1~100之整數),且相對於前述含烯基之有機聚矽氧烷(a1)之總烯基,總SiH基成為0.4~1.0倍之量之前述有機氫聚矽氧烷(a2),在鉑族金屬系觸媒存在下經氫矽烷化反應而成者,重量平均分子量為30,000~200,000(以GPC測定之聚苯乙烯換算值),且不溶於SP值[溶解度參數(cal/cm3)1/2]大於9之極性溶劑中之有機聚矽氧烷。
此時,烯基之含量至少為以R1~R4表示之全部有機基之2莫耳%~10莫耳%。若烯基之含量為2莫耳%以上,則藉由氫矽烷基化反應使分子量增加變大,而成為耐熱性等物性優異之有機聚矽氧烷故較佳。且若為10莫耳%以下,則對於將光阻劑塗佈於接合基板之半導體側且去除時等使用之極性有機溶劑之溶解性變得更低而較佳。
該烯基之例列舉為乙烯基、烯丙基、丁烯基、己烯基、環己烯基、降冰片烯基,但就反應性之觀點而言以乙烯基較佳。
相對於(a1)成分之總烯基的(a2)成分之總SiH量
較好為0.4~1.0。若為0.4以上,則分子量之增加充分,可獲得期望之耐熱性、接合性。又,若為1.0以下,則樹脂之交聯變適度而不易凝膠化,且亦可降低樹脂內殘存之SiH基,亦可抑制因接合後之耐熱試驗時殘存之SiH造成之發泡故較佳。
至於前述R5~R7之除烯基以外之碳數1~12之1價的烴基,具體例示為甲基、丙基、己基、環己基、苯基、癸基、十二烷基。最好為甲基、環己基、苯基。
以上述通式(1)表示之有機氫聚矽氧烷之聚合度n較好為0~100之整數,最好為0~60之整數。若n為100以下,則合成時不會有不易與含有烯基之有機聚矽氧烷(a1)之烯基進行氫矽烷基化反應之虞,可使反應充分進行,且經高分子量化之有機聚矽氧烷與矽基板之密著性亦良好。
另外,只要在上述範圍內則亦可使用不同之有機氫聚矽氧烷進行加成反應。
依據該經高分子量化之有機聚矽氧烷,對於非極性之有機溶劑為可溶,另一方面,對於將光阻劑塗佈於接合基板之半導體側並去除時等使用之極性有機溶劑為難溶,成為接合性、耐熱性更優異之有機聚矽氧烷。
含有烯基之有機聚矽氧烷(a1)與有機氫聚矽氧烷(a2)之反應可例如使含有烯基之有機聚矽氧烷(a1)溶
解於有機溶劑中,添加氫矽烷基化觸媒之鉑系金屬觸媒後,邊加熱至50~150℃,邊滴加有機氫聚矽氧烷(a2),而獲得經高分子量化之有機聚矽氧烷。
鉑觸媒為促進與SiH基之氫矽烷基化加成反應用之觸媒,至於該加成反應觸媒列舉為鉑黑、四氯化鉑、氯化鉑酸、氯化鉑酸與一元醇之反應物、氯化鉑酸與烯烴類之錯合物、雙乙醯基乙酸鉑等之鉑系觸媒、鈀系觸媒、銠系觸媒等之鉑族金屬觸媒。又,該加成反應觸媒之調配量可為觸媒量,但通常以鉑族金屬計相對於(a1)成分之重量較好調配1~800ppm,最好調配2~300ppm左右。
該等氫矽烷基化加成反應後之有機聚矽氧烷之分子量會影響臨時接著劑之特性,尤其是加熱時之熱變形、接著介面處孔洞發生等。
加成反應後之經高分子量化之聚有機矽氧烷之重量平均分子量Mw,依據使用GPC(凝膠滲透層析儀)以聚苯乙烯標準物質製作之校正線獲得之重量平均分子量之值較好為30,000~200,000。若為上述之重量平均分子量,則成為耐熱性優異且不會發生孔洞之有機聚矽氧烷。更佳之重量平均分子量範圍為35,000~170,000左右,又更好為40,000~150,000左右。
本發明之組成物中,(B)成分之抗氧化劑尤其係為了提高熱安定性而調配。
本發明中使用之(B)成分之抗氧化劑較好為由受阻酚系化合物、受阻胺系化合物、有機磷化合物及有機硫化合物所組成群組中選出之至少一種化合物。
受阻酚系化合物;本發明中使用之受阻酚系化合物並無特別限制,但較好為以下列舉之受阻酚系化合物。
1,3,5-三甲基-2,4,6-參(3,5-二第三丁基-4-羥基苄基)苯(商品名:IRGANOX 1330)、2,6-二第三丁基-4-甲基酚(商品名:Sumilizer BHT)、2,5-二第三丁基-氫醌(商品名:Nocrac NS-7)、2,6-二第三丁基-4-乙基酚(商品名:Nocrac M-17)、2,5-二第三戊基氫醌(商品名:Nocrac DAH)、2,2’-亞甲基雙(4-甲基-6-第三丁基酚)(商品名:Nocrac NS-6)、3,5-二第三丁基-4-羥基-苄基磷酸酯-二乙酯(商品名:IRGANOX 1222)、4,4’-硫基雙(3-甲基-6-第三丁基酚)(商品名:Nocrac 300)、2,2’-亞甲基雙(4-乙基-6-第三丁基酚)(商品名:Nocrac NS-5)、4,4’-亞丁基雙(3-甲基-6-第三丁基酚)(ADEKASTAB AO-40)、2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯(商品名:Sumilizer GM)、2-[1-(2-羥基-3,5-二第三戊基苯基)乙基]-4,6-二第三戊基苯基丙烯酸酯(商品名:Sumilizer GS)、2,2’-亞甲基雙[4-甲基-6-(α-甲基-環己基)酚]、4,4’-亞甲基雙(2,6-二第三丁基酚)(商品名:SHINOX 226M)、4,6-雙(辛硫基甲基)-鄰-甲酚(商品名:
IRGANOX 1520L)、2,2’-伸乙基雙(4,6-二第三丁基酚)、亞辛基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯(商品名:IRGANOX 1076)、1,1,3-參-(2-甲基-4-羥基-5-第三丁基苯基)丁烷(商品名:ADEKASTAB AO-30)、肆[亞甲基-(3,5-二第三丁基-4-羥基氫桂皮酸酯)]甲烷(商品名:ADEKASTAB AO-60)、三乙二醇雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯](商品名:IRGANOX 245)、2,4-雙-(正辛硫基)-6-(4-羥基-3,5-二第三丁基苯胺基)-1,3,5-三嗪(商品名:IRGANOX 565)、N,N’-六亞甲基雙(3,5-二第三丁基-4-羥基-氫桂皮醯胺)(商品名:IRGANOX 1098)、1,6-己二醇-雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯](商品名:IRGANOX 259)、2,2-硫基-二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯](商品名:IRGANOX 1035)、3,9-雙[2-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]1,1-二甲基乙基]2,4,8,10-四氧雜螺[5.5]十一烷(商品名:Sumilizer GA-80)、參-(3,5-二第三丁基-4-羥基苄基)異氰尿酸酯(商品名:IRGANOX 3114)、雙(3.5-二第三丁基-4-羥基苄基磺酸乙酯)鈣/聚乙烯蠟混合物(50:50)(商品名:IRGANOX 1425WL)、異辛基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯(商品名:IRGANOX 1135)、4,4’-硫基雙(6-第三丁基-3-甲基酚)(商品名:Sumilizer WX-R)、6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-第三丁基二苯并
[d,f][1,3,2]二氧雜磷環庚烷(商品名:Sumilizer GP)等。
受阻胺系化合物;本發明中使用之受阻胺系化合物並無特別限制,較好為以下列舉之受阻胺系化合物。
p,p’-二辛基二苯基胺(商品名:IRGANOX 5057)、苯基-α-萘基胺(Nocrac PA)、聚(2,2,4-三甲基-1,2-二氫醌)(商品名:Nocrac 224、224-S)、6-乙氧基-2,2,4-三甲基-1,2-二氫喹啉(商品名:Nocrac AW)、N,N’-二苯基-對-苯二胺(商品名:Nocrac DP)、N,N’-二-β-萘基-對-苯二胺(商品名:Nocrac White)、N-苯基-N’-異丙基-對-苯二胺(商品名:Nocrac 810NA)、N,N’-二烯丙基-對-苯二胺(商品名:Nonflex TP)、4,4’(α,α-二甲基苄基)二苯基胺(商品名:Nocrac CD)、p,p-甲苯磺醯基胺基二苯基胺(商品名:Nocrac TD)、N-苯基-N’-(3-甲基丙烯醯氧基-2-羥基丙基)-對-苯二胺(商品名:Nocrac G1)、N-(1-甲基庚基)-N’-苯基-對-苯二胺(商品名:Ozonon 35)、N,N’-二第二丁基-對-苯二胺(商品名:Sumilizer BPA)、N-苯基-N’-1,3-二甲基丁基-對-苯二胺(商品名:Antigene 6C)、烷基化二苯基胺(商品名:Sumilizer 9A)、琥珀酸二甲基-1-(2-羥基乙基)-4-羥基-2,2,6,6-四甲基哌啶聚縮合物(商品名:Tinuvin 622LD)、聚[[6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三嗪-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亞胺基]六亞甲基
[(2,2,6,6-四甲基-4-哌啶基)亞胺基]](商品名:CHIMASSORB 944)、N,N’-雙(3-胺基丙基)乙二胺-2,4-雙[N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基[-6-氯-1,3,5-三嗪縮合物(商品名:CHIMASSORB 119FL)、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯(商品名:TINUVIN 123)、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(商品名:TINUVIN 770)、2-(3,5-二第三丁基-4-羥基苄基)-2-正丁基丙二酸雙(1,2,2,6,6-五甲基-4-哌啶基)(商品名:TINUVIN 144)、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯(商品名:TINUVIN 765)、肆(1,2,2,6,6-五甲基-4-哌啶基)1,2,3,4-丁烷四羧酸酯(商品名:LA-57)、肆(2,2,6,6-四甲基-4-哌啶基)1,2,3,4-丁烷四羧酸酯(商品名:LA-52)、1,2,3,4-丁烷四羧酸與1,2,2,6,6-五甲基-4-哌啶醇及1-十三烷醇之混合酯化物(商品名:LA-62)、1,2,3,4-丁烷四羧酸與2,2,6,6-四甲基-4-哌啶醇及1-十三烷醇之混合酯化物(商品名:LA-67)、1,2,3,4-丁烷四羧酸與1,2,2,6,6-五甲基-4-哌啶醇及3,9-雙(2-羥基-1,1-二甲基乙基)-2,4,8,10-四氧雜螺[5.5]十一烷之混合酯化物(商品名:LA-63P)、1,2,3,4-丁烷四羧酸與2,2,6,6-四甲基-4-哌啶醇及3,9-雙(2-羥基-1,1-二甲基乙基)-2,4,8,10-四氧雜螺[5.5]十一烷之混合酯化物(商品名:LA-68LD)、(2,2,6,6-四亞甲基-4-哌啶基)-2-伸丙基羧酸酯(商品名:ADEKASTAB LA-82)、(1,2,2,6,6-五甲基-4-哌啶基)-2-伸丙基羧酸酯(商品
名:ADEKASTAB LA-87)等。
有機磷化合物;本發明中使用之有機磷化合物並無特別限制,但較好為以下所例舉之有機磷化合物。
雙(2,4-二第三丁基苯基)[1,1-聯苯]-4,4’-二基雙磷酸酯、9,10-二氫-9-氧雜-10-磷菲-10-氧化物(商品名:SANKO-HCA)、三乙基磷酸酯(商品名:JP302)、三正丁基磷酸酯(商品名:304)、三苯基磷酸酯(商品名:ADEKASTAB TPP)、二苯基單辛基磷酸酯(商品名:ADEKASTAB C)、三(對-甲苯基)磷酸酯(商品名:Chelex-PC)、二苯基單癸基磷酸酯(商品名:ADEKASTAB 135A)、二苯基單(十三烷基)磷酸酯(商品名:JPM313)、參(2-乙基己基)磷酸酯(商品名:JP308)、苯基二癸基磷酸酯(ADEKASTAB 517)、十三烷基磷酸酯(商品名:ADEKASTAB 3010)、四苯基二丙二醇二磷酸酯(商品名:JPP100)、雙(2,4-二第三丁基苯基)季戊四醇二磷酸酯(商品名:ADEKASTAB PEP-24G)、參(十三烷基)磷酸酯(商品名:JP333E)、雙(壬基苯基)季戊四醇二磷酸酯(商品名:ADEKASTAB PEP-4C)、雙(2,6-二第三丁基-4-甲基苯基)季戊四醇二磷酸酯(商品名:ADEKASTAB PEP-36)、雙[2,4-二(1-苯基異丙基)苯基]季戊四醇二磷酸酯(商品名:ADEKASTAB PEP-45)、三月桂基三硫代磷酸酯(商品名:JPS312)、參(2,4-二第三丁基苯基)磷酸酯
(IRGAFOS 168)、參(壬基苯基)磷酸酯(商品名:ADEKASTAB 1178)、二硬脂基季戊四醇二磷酸酯(商品名:ADEKASTAB PEP-8)、參(單、二壬基苯基)磷酸酯(商品名:ADEKASTAB 329K)、三油基磷酸酯(商品名:Chelex-OL)、三硬脂基磷酸酯(商品名:JP318E)、4,4’-亞丁基雙(3-甲基-6-第三丁基苯基二-十三烷基)磷酸酯(商品名:JPH1200)、四(C12-C15混合烷基)-4,4’-異亞丙基二苯基二磷酸酯(商品名:ADEKASTAB 1500)、四(十三烷基)-4,4’-亞丁基雙(3-甲基-6-第三丁基苯基)二磷酸酯(商品名:ADEKASTAB 260)、六(十三烷基)-1,1,3-參(2-甲基-5-第三丁基-4-羥基苯基)丁烷-三磷酸酯(商品名:ADEKASTAB 522A)、氫化雙酚A磷酸酯聚合物(HBP)、肆(2,4-二第三丁基苯氧基)4,4’-聯苯基-二膦(商品名:P-EPQ)、肆(2,4-二第三丁基-5-甲基苯氧基)4,4’-聯苯基-二膦(商品名:GSY-101P)、2-[[2,4,8,10-肆(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧雜磷環庚烷-6-基]氧基]-N,N-雙[2-[[2,4,8,10-肆(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧雜磷環庚烷-6-基]氧基]-乙基]乙胺(商品名:IRGAFOS 12)、2,2’-亞甲基雙(4,6-二第三丁基苯基)辛基磷酸酯(商品名:ADEKASTAB HP-10)等。
有機硫化合物;本發明中使用之有機硫化合物並無特別限制,較好為以下列舉之有機硫化合物。
二月桂基-3,3’-硫基二丙酸酯(商品名:Sumilizer TPL-R)、二肉荳蔻基-3,3’-硫基二丙酸酯(商品名:Sumilizer TPM)、二硬脂基-3,3’-硫基二丙酸酯(商品名:Sumilizer TPS)、季戊四醇肆(3-月桂基硫代丙酸酯)(商品名:Sumilizer TP-D)、二-十三烷基-3,3’-硫基二丙酸酯(商品名:Sumilizer TL)、2-巰基苯并咪唑(商品名:Sumilizer MB)、二-十三烷基-3,3’-硫基二丙酸酯(商品名:ADEKASTAB AO-503A)、1,3,5-參-β-硬脂基硫代丙醯氧基乙基異氰尿酸酯、3,3’-硫基雙丙酸二-十二烷酯(商品名:IRGANOX PS 800FL)、3,3’-硫基雙丙酸二-十八烷酯(商品名:IRGANOX PS 802FL)等。
上述抗氧化劑中,考慮(A)成分之含有非芳香族飽和烴基之有機聚矽氧烷及(C)成分之有機溶劑之相溶性時,最佳列舉為ADEKASTAB AO-60、IRGANOX 1076、IRGANOX 1135、IRGANOX 1520L(以上為商品名)等。
(B)成分之添加量,相對於(A)成分100質量份,為0.5~5質量份,較好為1~3質量份。比其少時無法獲得充分之耐熱效果,超過該等以上時,添加(C)成分之有機溶劑時無法獲得相溶性。
又,(B)成分並不限於一種,亦可併用複數種。
(C)成分之有機溶劑之SP值[溶解度參數(cal/cm3)1/2]宜為9以下,且較好為可使(A)成分之含
有非芳香族飽和烴基之有機聚矽氧烷及(B)成分之抗氧化劑溶解,可藉旋轉塗佈等習知塗膜形成方法形成膜厚1~200μm之薄膜者。此時,較好膜厚為5~180μm,更好為30~150μm。
據此,溶解(A)、(B)成分之(C)有機溶劑可使用酮類、酯類、醇類等之極性溶劑以外者,較好為非芳香族烴。
該等(C)有機溶劑之具體例並無特別限制,列舉為戊烷、己烷、環戊烷、環己烷、甲基環己烷、辛烷、異辛烷、癸烷、十一烷、異十二烷、檸檬烯(limonene)、蒎烯(pinene)等。
該等中,作為可獲得可旋轉塗佈且安全性亦高之臨時接著劑組成物之(C)有機溶劑較好為沸點120~240℃之烴溶劑。亦即,就該觀點而言較好為辛烷、異辛烷、癸烷、異癸烷、十二烷、異十二烷、檸檬烯。沸點若為120℃以上,則由於烴溶劑之燃火點亦高故較佳。且,沸點若為240℃以下,則烴溶劑藉塗佈後之加熱乾燥而易於揮發,不易留在膜內。因此,臨時接著劑組成物暴露於基板接合後之加熱製程之高溫時,可抑制於接合面之氣泡形成故較佳。
(C)成分之添加量相對於(A)成分100質量份為10~1000質量份,較好為20~200質量份。比其少時臨時接著劑組成物之黏度變得太高而無法塗佈於晶圓上,在其以上時塗佈後無法獲得充分膜厚。
又,(C)成分並不限於一種,亦可併用複數種。
除上述成分以外,本發明之臨時接著劑組成物在不妨礙本發明效果之範圍內,可進一步添加通常之臨時接著劑組成物中使用之成分。
例如,為提高塗佈性,本發明之臨時接著劑組成物中亦可添加習知界面活性劑。雖未特別限制,但具體列舉為聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯油基醚等之聚氧乙烯烷基醚類,聚氧乙烯辛基酚醚、聚氧乙烯壬基酚醚等之聚氧乙烯烷基芳基醚類,聚氧乙烯聚氧丙基嵌段共聚物類,山梨糖醇酐單月桂酸酯、山梨糖醇酐單棕櫚酸酯、山梨糖醇酐單硬脂酸酯等之山梨糖醇酐脂肪酸酯類,聚氧乙烯山梨糖醇酐單月桂酸酯、聚氧乙烯山梨糖醇酐單棕櫚酸酯、聚氧乙烯山梨糖醇酐單硬脂酸酯、聚氧乙烯山梨糖醇酐三油酸酯、聚氧乙烯山梨糖醇酐三硬脂酸酯等之聚氧乙烯山梨糖醇酐脂肪酸酯之非離子系界面活性劑、EF TOP EF301、EF303、EF352(TOKEMU PRODUCTS)、MEGAFAC F171、F172、DF173(大日本油墨化學工業)、FLUORAD FC430、FC431(住友3M)、ASAHI GUARD AG710、SURFLON S-382、S-382、SC101、SC102、SC103、SC104、SC105、SC106、SURFYNOL E1004、KH-10、KH-20、KH-30、KH-40(旭硝子)等之氟系界面活性劑,有機矽氧烷聚合物
KP-341、X-70-092、X-70-093(信越化學工業)、丙烯酸系或甲基丙烯酸系POLYFLOW No.75、No.95(共榮社油脂化學工業)。該等可單獨使用或以兩種以上之組合使用。
又,本發明提供一種薄型晶圓之製造方法,其係使具有電路形成面及電路非形成面之晶圓與支撐基板接合並研磨以製造薄型晶圓之方法,其特徵為包含下列步驟:在前述電路形成面上及前述支撐基板表面上之至少一者上,以前述之臨時接著劑組成物形成接著層,且介隔著該接著層,接合前述晶圓之電路形成面與前述支撐基板之接合步驟,研磨經接合前述支撐基板之晶圓之前述電路非形成面之研磨步驟,自前述支撐基板剝離前述研磨後之晶圓之剝離步驟,及去除殘存於前述剝離之晶圓之電路形成面上的前述接著層之去除步驟。
本發明之薄型晶圓之製造方法之特徵為使用前述臨時接著劑組成物作為具有半導體電路之晶圓與為使該晶圓之厚度變薄而使用之支撐基板之接著層。以本發明之製造方法獲得之薄型晶圓之厚度並無特別限制,典型上為300~5μm,更典型為100~10μm。
前述接合步驟係以上述本發明之臨時接著劑組成物,於電路形成面上及支撐基板表面上之至少一面形成接著層,且介隔著該接著層使晶圓之電路形成面與支撐基板接合之步驟。晶圓為其一面形成電路之電路形成面,另一面為電路非形成面之晶圓。
本發明可適用之晶圓並無特別限制,但通常為半導體晶圓。該晶圓之例不僅為矽晶圓,亦列舉為鍺晶圓、鎵-砷晶圓、鎵-磷晶圓、鎵-砷-鋁晶圓等。接合步驟中之晶圓為研磨步驟中經背面研磨前之晶圓,其厚度並無特別限制,典型為800~600μm,更典型為775~625μm。
至於支撐基板可使用矽晶圓、玻璃晶圓、石英晶圓等。本發明中,不需要通過支撐基板對接著層照射輻射能量線,故不要求支撐基板之光線透過性。
接著層係使用前述之本發明之臨時接著劑組成物,以例如旋轉塗佈等形成。接著層係形成於晶圓之電路形成面上及/或支撐基板上。藉由如此形成之接著層而接合晶圓與支撐基板。接著層形成於晶圓上時,係形成於該晶圓之電路形成面上。
以本發明之臨時接著劑組成物形成之接著層因加熱而軟化。使接著層中之樹脂軟化之溫度範圍為80~320℃,較好為100~300℃,更好為120~260℃,藉由於該溫度之減壓下,均勻壓著兩基板(亦即,晶圓與支撐基板),使晶圓
與支撐基板接合而形成接合基板。將設置兩基板之腔室內在減壓下加熱至上述溫度範圍,而使接著層中之樹脂一部份軟化或熔解後,藉由使兩基板接觸、加熱壓著,可於界面不夾帶氣泡地形成一樣的接合界面。經由接著層使晶圓與支撐基板接合時,支撐基板之溫度較好為上述溫度範圍。由於以該等接合溫度使接著層中之樹脂完全軟化,故可將晶圓之接合面上存在之凹凸無間隙地埋入。壓著時之荷重例如於8吋晶圓(直徑200mm)時於20kN以下,較好10kN以下,更好7kN以下可予以接合。
至於晶圓接合裝置列舉為市售之晶圓接合裝置,例如EVG公司之EVG520IS、850TB;SUSS公司製造之XBC300等。
研磨步驟為研磨經接合支撐基板之晶圓之電路非形成面之步驟。亦即,研磨接合步驟中經接合之層合基板之晶圓背面側,使該晶圓之厚度變薄之步驟。晶圓背面之研磨加工方式並無特別限制,可採用平面研磨盤等之習知研磨方式。研磨較好邊對晶圓與研磨石加水冷卻邊進行。研磨加工晶圓背面之裝置列舉為DISCO(股)製造之DAG-810(商品名)等。
本發明之薄型晶圓之製造方法於研磨步驟後剝離步驟
前可包含加工步驟。加工步驟為對研磨電路非形成面之晶圓,亦即對藉由背面研磨而薄型化之晶圓之電路非形成面側施以加工之步驟。該步驟包含以晶圓等級使用之各種製程,但舉例列舉為對電路非形成面之電極形成、金屬配線形成、保護膜形成等。更具體而言列舉為用以形成電極等之金屬濺鍍、蝕刻金屬濺鍍層之濕式蝕刻、欲成為金屬配線形成之遮罩之光阻劑塗佈、曝光及顯像之圖型形成、光阻劑之剝離、乾式蝕刻、金屬鍍敷之形成、TSV形成用之矽蝕刻、矽表面之氧化膜形成等以往習知之製程。
剝離步驟為於接著層自支撐基板剝離研磨後之晶圓之步驟。亦即,對薄型化之晶圓施以各種加工後,在晶片切割前自支撐基板剝離之步驟。剝離方法有主要使晶圓與支撐基板邊加熱邊朝水平相反方向滑動,而使兩基板分離之方法,將層合基板中之一基板水平固定,邊加熱邊使另一基板自水平方向以一定角度上拉之方法,及於經研磨晶圓之研磨面貼附保護膜,以撕離方式剝離晶圓與保護膜之方法等多種提案。
本發明中,可使用該等剝離方法之任一種,但以水平滑動剝離方式較佳。
由晶圓、接著層、支撐基板所成之層合體經加熱,使接著層熔解或軟化之狀態下施力,可使晶圓自支撐基板剝離。加熱溫度於本發明使用之接著層較好為50~300℃,更
好為60~230℃,又更好為70~220℃。
進行該等剝離之裝置列舉為EVG公司之EVG850DB、SUSS公司之XBC300等(均為商品名)。
去除步驟為將殘存於經剝離晶圓之電路形成面之接著層去除之步驟。殘存之接著層之去除可例如藉由洗淨晶圓進行。
去除步驟只要是使接著層中之樹脂,若是尤其使(A)成分之有機聚矽氧烷溶解之洗淨液則均可使用,具體而言可使用前述之(C)有機溶劑。該等溶劑可單獨使用一種亦可組合兩種以上使用。
又,不易去除殘存於電路形成面上之接著層時,亦可於上述溶劑中添加鹼類、酸類。鹼類之例可使用乙醇胺、二乙醇胺、三乙醇胺、三乙胺、氨等之胺類,氫氧化四甲基銨等之銨鹽類。酸類可使用乙酸、草酸、苯磺酸、十二烷基苯磺酸等之有機酸。該等鹼類、酸類之添加量為0.01~10質量%,較好為0.1~5質量%。
又,為提高殘存於電路形成面上之接著層之去除,亦可添加既有之界面活性劑。
洗淨方法可使用上述洗淨液,以溢液法進行洗淨之方法,以噴佈噴霧之洗淨方法、浸漬於洗淨槽中之方法。溫度宜為10~80℃,較好為15~65℃。
依據該薄型晶圓之製造方法,在剝離步驟中可於短時
間內自基板剝離晶圓,且,薄型晶圓之製造步驟中於接合基板之半導體側塗佈光阻劑並去除時亦不會使晶圓自支撐基板剝離,故可高效率地生產薄型晶圓。
以下顯示合成例、實施例及比較例更詳細說明本發明,但本發明並不受限於此。
於安裝攪拌裝置、冷卻裝置、溫度計之1L燒瓶中饋入水234g(13莫耳)、甲苯35g,以油浴加熱至85℃。於滴加漏斗中饋入環己基三氯矽烷108.8g(0.5莫耳)、正己基三氯矽烷65.9g(0.3莫耳)、二甲基二氯矽烷12.9g(0.1莫耳)、三甲基氯矽烷10.9g(0.1莫耳),邊攪拌邊於1小時內滴加於燒瓶內,滴加結束後,再於80℃進行攪拌熟成1小時。冷卻至室溫且靜置,去除分離之水相,接著混合10%硫酸鈉水溶液並攪拌10分鐘後,靜置30分鐘,重複去除分離之水相之水洗淨操作直到甲苯相成為中性為止,終止反應。安裝酯接收器,使含有機聚矽氧烷之甲苯相加熱回流,自甲苯相去除水,自內溫達110℃後再持續1小時後,冷卻至室溫。過濾所得有機聚矽氧烷溶液去除不溶物,接著藉減壓蒸餾去除甲苯,獲得固體之有機聚矽氧烷(A-I)119.1g。
所得有機聚矽氧烷(A-I)含T單位80莫耳%與D單位10莫耳%及M單位10莫耳%,末端每100g有機聚矽氧烷(A-I)含有0.06莫耳之矽烷醇基,且外觀為無色透明固體,重量平均分子量為44,000。全部有機基中之環己基含量為38莫耳%,正己基含量為23莫耳%。且,以R1~R3表示之全部有機基中之50莫耳%為環己基,30莫耳%為正己基。
以與合成例1相同之方法,於2L燒瓶中饋入水468g(26莫耳)、甲苯70g,以油浴加熱至80℃。除於滴加漏斗中讀入降冰片基三氯矽烷275.6g(1.2莫耳)、正己基三氯矽烷65.8g(0.3莫耳)、二甲基二氯矽烷25.8g(0.2莫耳)、甲基乙烯基二氯矽烷14.2g(0.1莫耳)、三甲基氯矽烷21.8g(0.2莫耳)以外,餘與合成例1同樣調製,獲得固體有機聚矽氧烷228.8g。
所得有機聚矽氧烷含T單位75莫耳%與D單位15莫耳%及M單位10莫耳%,每100g含有0.07莫耳之矽烷醇基,0.039莫耳之乙烯基。外觀為無色透明固體,重量平均分子量為9,300。全部有機基中之降冰片基含量為44莫耳%,正己基含量為11莫耳%,乙烯基含量為3.7莫耳%。又,以R1~R3表示之全部有機基中之57莫耳%為降冰片基,14莫耳%為正己基。
與合成例1同樣,於1L燒瓶中饋入水234g(13莫耳)、甲苯35g,以油浴加熱至80℃。除於滴加漏斗中饋入降冰片基三氯矽烷160.7g(0.7莫耳)、正十二烷基三氯矽烷45.6g(0.15莫耳)、甲基乙烯基二氯矽烷7.1g(0.05莫耳)、三甲基氯矽烷10.9g(0.1莫耳)以外,餘與合成例1同樣調製,獲得固體有機聚矽氧烷143.8g。
所得有機聚矽氧烷含T單位85莫耳%與D單位5莫耳%及M單位10莫耳%,每100g含有0.1莫耳之矽烷醇基,0.034莫耳之乙烯基。外觀為無色透明固體,重量平均分子量為6,100。全部有機基中之降冰片基含量為56莫耳%,正十二烷基含量為12莫耳%,乙烯基含量為4.0莫耳%。且,以R1~R3表示之全部有機基中之74莫耳%為降冰片基,16莫耳%為正十二烷基。
分別以表1所記載之組成調配作為(A)成分之上述合成例合成之有機聚矽氧烷A-I、A-II、A-III、(B)成分及(C)成分,隨後,經攪拌、混合、溶解後,以TEFLON(註冊商標)製之0.2微米過濾器進行精密過濾,獲得實施例1~3之本發明臨時接著劑組成物及比較例1~3之臨時接著劑組成物。
使用表1之實施例1~3及比較例1~3所示之組成物,在單面上形成電路之8吋矽晶圓(直徑:200mm,厚度:725μm)上,以旋轉塗佈形成表1計載之膜厚之接著層。以下述要領確認外觀,以8吋玻璃基板(玻璃晶圓)作為支撐基板,在真空接合裝置內以表1所示之接著溫度接合該支撐基板與具有接著層之矽晶圓,製作由晶圓、接著層及支撐基板構成之層合體。隨後,進行下述試驗。又,針對耐溶劑性另外製作實驗基板且進行評價。結果示於表1。
將旋轉塗佈後之塗膜在加熱板上以150℃進行乾燥2分鐘,使膜內之溶劑完全餾除後,以目視確認塗膜外觀、以指觸之觸黏感。無龜裂、觸黏者表示為良好(○),確認到龜裂、觸黏者表示為不良(×)。
8吋之晶圓接合係使用EVG公司之晶圓接合裝置520IS進行。接合溫度為表1所記載之值,接合時之腔室內壓力為10-3mbar以下,荷重以5kN進行。接合後,以目視確認冷卻至室溫後之界面之接著狀態,於界面未發生氣泡等異常之情況以○表示,發生異常之情況以×表示。
使用研磨機(DAG810 DISCO製造)進行矽基板之背面研磨。研磨至最終基板厚度為50μm後,以光學顯微鏡檢查有無龜裂、剝離等之異常。未發生異常之情況以○表示,發生異常之情況以×表示。
將矽基板經背面研磨後之層合體置於氮氣環境下之250℃烘箱中2小時後,於270℃之加熱板上加熱10分鐘後,調查有無外觀異常。未發生外觀異常之情況以○表示,發生外觀異常之情況以×表示。
使用EVG公司之EVG850DB,使進行耐熱性試驗後之層合基板再加熱至220℃,並使晶圓與支撐基板朝水平相反方向滑動予以分離。可分離之情況記為良好(○),無法分離之情況記為不良(×)。
以異十二烷藉溢液洗淨剝離性試驗後之晶圓之電路形成面300秒。洗淨後,觀察晶圓之電路形成面,未確認到殘留物者記為良好(○),確認到殘留物者記為不良(×)。
將實施例1~3、比較例1~3之組成物以旋轉塗佈,於6吋晶圓(直徑:150mm)上形成30μm厚度之塗膜,經150℃/2分鐘加熱乾燥後,於200℃/2分鐘加熱乾燥。隨後,將該塗膜浸漬於25℃之N-甲基吡咯烷酮(NMP)溶液中10分鐘,以目視檢視有無溶解。未確認到樹脂溶解者表示良好(○),確認到樹脂溶解者表示不良(×)。
如上述表1所示,未添加(B)成分之抗氧化劑之比
較例1~3在耐熱性試驗時出現孔洞,但實施例1~3因抗氧化劑之效果使耐熱性優異,亦即含有有機聚矽氧烷、抗氧化劑之本發明之臨時接著劑組成物顯示滿足上述要求特性。
由上述,若為本發明之臨時接著劑組成物,則成為顯示接著性優異,對非極性有機溶劑為可溶,另一方面對於在將光阻劑塗佈於接合基板之半導體側上並去除時等使用之極性有機溶劑為難溶,耐熱性亦優異之臨時接著劑組成物。再者,依據本發明之薄型晶圓之製造方法,在剝離步驟中可在短時間內自支撐基板剝離晶圓,且薄型晶圓之製造步驟中在將光阻劑塗佈於接合基板之半導體側上且去除實亦不會使晶圓自支撐基板剝離,故可高效率地生產薄型晶圓。
又,本發明並不限於上述實施形態。上述實施形態僅為例示,凡具有與本發明之申請專利範圍中所記載之技術想法實質上相同之構成,且發揮相同作用效果者,所有均包含於本發明之技術範圍內。
Claims (5)
- 一種臨時接著劑組成物,其特徵為含有(A)含有非芳香族飽和烴基之有機聚矽氧烷、(B)抗氧化劑、(C)有機溶劑,且前述(A)成分為100質量份、前述(B)成分為0.5~5質量份、前述(C)成分為10~1000質量份,前述(A)成分之含有非芳香族飽和烴基之有機聚矽氧烷為重量平均分子量2,000~60,000,不溶於SP值大於9之極性溶劑中,且含有以下述(I)~(III)表示之單位之有機聚矽氧烷(A-1),或以該有機聚矽氧烷(A-1)作為原料經高分子量化之有機聚矽氧烷(A-2);(I)以R1SiO3/2表示之矽氧烷單位(T單位):50~99莫耳%(II)以R2R3SiO2/2表示之矽氧烷單位(D單位):0~49莫耳%(III)以R4 3SiO1/2表示之矽氧烷單位(M單位):1~15莫耳%(前述R1~R4為一價有機基,以R1~R3表示之全部有機基中之50~80莫耳%為相同或不同之含下述環狀構造之任一者之非芳香族飽和烴基
- 如申請專利範圍第1項之臨時接著劑組成物,其中前述(B)成分之抗氧化劑為由受阻酚系化合物、受阻胺系化合物、有機磷化合物、及有機硫化合物所組成群組中選出之至少一種以上之化合物。
- 如申請專利範圍第1項之臨時接著劑組成物,其中前述有機聚矽氧烷(A-2),係使前述有機聚矽氧烷(A-1)中,以前述R1~R4表示之全部有機基中之2~10莫耳%為碳數2~7之烯基之含有烯基之有機聚矽氧烷(a1),與以下述通式(1)表示之一種以上之有機氫聚矽氧烷,
- 如申請專利範圍第1項之臨時接著劑組成物,其中 前述(C)成分之有機溶劑為沸點120~240℃,SP值為9以下之烴溶劑。
- 一種薄型晶圓之製造方法,其係使具有電路形成面及電路非形成面之晶圓與支撐基板接合並研磨以製造薄型晶圓之方法,其特徵為包含下列步驟:在前述電路形成面上及前述支撐基板表面上之至少一者上,以如申請專利範圍第1至4項中任一項之臨時接著劑組成物形成接著層,且介隔著該接著層,接合前述晶圓之電路形成面與前述支撐基板之接合步驟,研磨經接合前述支撐基板之晶圓之前述電路非形成面之研磨步驟,自前述支撐基板剝離前述研磨後之晶圓之剝離步驟,及去除殘存於前述經剝離之晶圓之電路形成面上的前述接著層之去除步驟。
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KR20130038157A (ko) | 2013-04-17 |
EP2578656A1 (en) | 2013-04-10 |
EP2578656B1 (en) | 2018-02-28 |
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