WO2020110785A1 - Agent adhésif de type film pour semi-conducteur, dispositif à semi-conducteur et son procédé de fabrication - Google Patents
Agent adhésif de type film pour semi-conducteur, dispositif à semi-conducteur et son procédé de fabrication Download PDFInfo
- Publication number
- WO2020110785A1 WO2020110785A1 PCT/JP2019/044953 JP2019044953W WO2020110785A1 WO 2020110785 A1 WO2020110785 A1 WO 2020110785A1 JP 2019044953 W JP2019044953 W JP 2019044953W WO 2020110785 A1 WO2020110785 A1 WO 2020110785A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- adhesive
- film
- semiconductor
- semiconductor chip
- resin
- Prior art date
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 280
- 239000000853 adhesive Substances 0.000 title claims abstract description 247
- 238000000034 method Methods 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 103
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 69
- 230000001070 adhesive effect Effects 0.000 claims description 239
- 239000003795 chemical substances by application Substances 0.000 claims description 62
- 239000012790 adhesive layer Substances 0.000 claims description 41
- 239000000523 sample Substances 0.000 claims description 39
- 239000003822 epoxy resin Substances 0.000 claims description 37
- 229920000647 polyepoxide Polymers 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 32
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 27
- 239000004925 Acrylic resin Substances 0.000 claims description 11
- 229920000178 Acrylic resin Polymers 0.000 claims description 11
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 8
- 229920006287 phenoxy resin Polymers 0.000 claims description 7
- 239000013034 phenoxy resin Substances 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 117
- 150000001875 compounds Chemical class 0.000 description 54
- 230000004907 flux Effects 0.000 description 44
- 239000000945 filler Substances 0.000 description 38
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- 229910000679 solder Inorganic materials 0.000 description 21
- 238000002844 melting Methods 0.000 description 20
- 230000008018 melting Effects 0.000 description 20
- 230000008569 process Effects 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 12
- 238000011109 contamination Methods 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 239000005011 phenolic resin Substances 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- 239000002356 single layer Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- -1 tetraphenylphosphonium tetraphenylborate Chemical compound 0.000 description 10
- 239000002966 varnish Substances 0.000 description 10
- 150000008065 acid anhydrides Chemical class 0.000 description 9
- 239000011324 bead Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 238000012536 packaging technology Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004697 Polyetherimide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- RJIQELZAIWFNTQ-UHFFFAOYSA-N 2-phenyl-1h-imidazole;1,3,5-triazinane-2,4,6-trione Chemical compound O=C1NC(=O)NC(=O)N1.C1=CNC(C=2C=CC=CC=2)=N1 RJIQELZAIWFNTQ-UHFFFAOYSA-N 0.000 description 2
- UCCGHLMDDOUWAF-UHFFFAOYSA-N 2-phenylimidazole-1-carbonitrile Chemical compound N#CN1C=CN=C1C1=CC=CC=C1 UCCGHLMDDOUWAF-UHFFFAOYSA-N 0.000 description 2
- SPBDXSGPUHCETR-JFUDTMANSA-N 8883yp2r6d Chemical compound O1[C@@H](C)[C@H](O)[C@@H](OC)C[C@@H]1O[C@@H]1[C@@H](OC)C[C@H](O[C@@H]2C(=C/C[C@@H]3C[C@@H](C[C@@]4(O[C@@H]([C@@H](C)CC4)C(C)C)O3)OC(=O)[C@@H]3C=C(C)[C@@H](O)[C@H]4OC\C([C@@]34O)=C/C=C/[C@@H]2C)/C)O[C@H]1C.C1C[C@H](C)[C@@H]([C@@H](C)CC)O[C@@]21O[C@H](C\C=C(C)\[C@@H](O[C@@H]1O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C1)[C@@H](C)\C=C\C=C/1[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\1)O)C[C@H]4C2 SPBDXSGPUHCETR-JFUDTMANSA-N 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 2
- PQIJHIWFHSVPMH-UHFFFAOYSA-N [Cu].[Ag].[Sn] Chemical compound [Cu].[Ag].[Sn] PQIJHIWFHSVPMH-UHFFFAOYSA-N 0.000 description 2
- 239000011354 acetal resin Substances 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000004643 cyanate ester Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 229910000969 tin-silver-copper Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- MGENSHRLAKPCSM-UHFFFAOYSA-N 3-methylcyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound CC1CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O MGENSHRLAKPCSM-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 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
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 235000019692 hotdogs Nutrition 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RQAGEUFKLGHJPA-UHFFFAOYSA-N prop-2-enoylsilicon Chemical compound [Si]C(=O)C=C RQAGEUFKLGHJPA-UHFFFAOYSA-N 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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
- C09J7/30—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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
-
- 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
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- 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
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
- H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
- H01L2224/13001—Core members of the bump connector
- H01L2224/1302—Disposition
- H01L2224/13025—Disposition the bump connector being disposed on a via connection of the semiconductor or solid-state body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16135—Disposition the bump connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
- H01L2224/16145—Disposition the bump connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
- H01L2224/8119—Arrangement of the bump connectors prior to mounting
- H01L2224/81191—Arrangement of the bump connectors prior to mounting wherein the bump connectors are disposed only on the semiconductor or solid-state body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/8319—Arrangement of the layer connectors prior to mounting
- H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
Definitions
- the present invention relates to a film adhesive for semiconductors, a semiconductor device and a method for manufacturing the same.
- connection method FC connection method
- the COB (Chip On Board) type connection method that is actively used in BGA (Ball Grid Array), CSP (Chip Size Package), etc. also corresponds to the FC connection method.
- the FC connection method is also widely used in a COC (Chip On Chip) type connection method in which a connection portion (for example, a bump and a wiring) is formed on a semiconductor chip to connect the semiconductor chips.
- chip stack type packages POP (Package On Package), TSV (Throughh), in which chips are stacked using the connection method described above to form multiple stages. -Silicon Via) etc. are beginning to spread widely. Since such a stacking/multi-stage technology arranges semiconductor chips and the like in three dimensions, the package can be made smaller than the method of arranging in two dimensions. Further, since it is effective in improving the performance of semiconductors, reducing noise, reducing the mounting area, and saving power, it is drawing attention as a next-generation semiconductor wiring technology.
- connection portion for example, solder, tin, gold, silver, copper, nickel and the like can be mentioned, and a conductive material containing plural kinds of these is also used. ..
- the surface of the metal used for the connection portion may be oxidized to form an oxide film, and impurities such as oxides may be attached. If such an oxide film and impurities remain, the connectivity and insulation reliability between the semiconductor chip and the substrate or between the two semiconductor chips may deteriorate, and the merit of adopting the above-described connection method may be impaired. It
- this anti-oxidation film may cause a decrease in solder wettability during the connection process, a decrease in connection property, and the like.
- Patent Document 1 As a method for removing the above oxide film and impurities, a method using an adhesive film containing a flux agent has been proposed (see, for example, Patent Document 1).
- a semiconductor chip mounting substrate for example, a semiconductor chip, a semiconductor wafer, a printed circuit board, etc.
- the adhesive cures and shrinks. Due to the influence of heat history during the reflow process, stress may be applied to the base body and the semiconductor chip, causing warpage. The occurrence of warpage leads to cracking of the substrate and the semiconductor chip, improper fixing of the substrate in the sealing process, and the like, so it is required to reduce the amount of warpage.
- the inventors of the present invention include a thermoplastic resin having a Tg of less than 35° C. in a film adhesive for semiconductors made of a thermosetting adhesive to reduce the elastic modulus after curing, thereby reducing the amount of warpage. It has been found that can reduce.
- the semiconductor film adhesive may remain on the pick-up tool when picking up a semiconductor chip in the mounting process, thus contaminating the pick-up tool. It became clear. Contamination of the pick-up tool leads to deterioration of production efficiency due to process stop for cleaning the pick-up tool and quality abnormality due to spread of pollution from the pick-up tool to the bonding tool. It is required to reduce the warp.
- an object of the present invention is to provide a film-like adhesive for semiconductors, which can suppress the occurrence of warpage of the substrate and the semiconductor chip in the mounting process and the contamination of the pickup tool.
- Another object of the present invention is to provide a semiconductor device using the above film adhesive for semiconductors and a method for manufacturing the same.
- the film adhesive for semiconductors comprises a first thermosetting adhesive layer and a second thermosetting adhesive layer provided on the first thermosetting adhesive layer.
- the first thermosetting adhesive layer includes a first thermoplastic resin having a Tg of less than 35° C.
- the second thermosetting adhesive layer has a second Tg of 35° C. or more. Containing a thermoplastic resin.
- the conductive adhesive layer contains a thermoplastic resin (first thermoplastic resin) having a Tg of less than 35° C., warpage of the base and the semiconductor chip can be reduced.
- the above film-like adhesive for semiconductors is particularly suitable for use in producing a flip chip package (semiconductor device) by the wafer level packaging technology.
- the wafer-level packaging technology is a technology for efficiently manufacturing a plurality of packages by mounting a plurality of semiconductor chips on a semiconductor wafer, encapsulating them all at once, and dicing them into individual pieces.
- the wafer level packaging technology is useful as a technology for improving productivity because it can shorten the assembly time of the flip chip package.
- the wafer level packaging technology as the number of mounted semiconductor chips increases, the stress on the semiconductor wafer tends to increase, and the amount of warpage tends to increase.
- the above film adhesive for semiconductors it is possible to suppress the warp of the semiconductor wafer and the contamination of the pickup tool even when the semiconductor device is manufactured by the wafer level packaging technique.
- the film-like adhesive for semiconductors preferably has an elastic modulus at 35° C. of 5 MPa or less after curing. In this case, the amount of warp can be further reduced.
- the Tg of the second thermoplastic resin is preferably 60° C. or higher. In this case, contamination of the pickup tool can be further reduced.
- the second thermoplastic resin preferably contains a phenoxy resin. In this case, the contamination of the pickup tool can be further reduced, and the amount of warpage can be further reduced.
- At least one of the first thermosetting adhesive layer and the second thermosetting adhesive layer preferably contains a flux compound.
- the oxide film on the metal surface is sufficiently reduced and removed so that the metal can be easily melted, the molten metal is not hindered from spreading, and the state where a metal joint is formed ( Flux activity) is obtained. Therefore, excellent connectivity can be obtained.
- the flux compound preferably has a carboxyl group, and more preferably has two or more carboxyl groups. In this case, more excellent connection reliability (for example, connectability and insulation reliability) is likely to be obtained.
- the flux compound is preferably a compound represented by the following formula (2).
- R 1 and R 2 each independently represent a hydrogen atom or an electron-donating group, and n represents 0 or an integer of 1 or more.
- the melting point of the flux compound is preferably 150°C or lower.
- the flux is melted before the adhesive is hardened during thermocompression bonding, and the oxide film of solder or the like is reduced and removed, so that more excellent connection reliability is likely to be obtained.
- the first thermoplastic resin preferably contains a (meth)acrylic resin or a urethane resin. In this case, the amount of warp can be further reduced.
- At least one of the first thermosetting adhesive layer and the second thermosetting adhesive layer preferably contains a thermosetting resin and a curing agent, and an epoxy resin and an imidazole curing agent. It is more preferable to contain
- a film adhesive for semiconductors is a first thermosetting adhesive layer and a second thermosetting adhesive layer provided on the first thermosetting adhesive layer.
- the elastic modulus at 35° C. after curing is 5 MPa or less
- the probe tack value of the second thermosetting adhesive layer at a probe temperature of 50° C. and a stage temperature of 25° C. is 60 N/cm 2 or less. Is.
- the second thermosetting adhesive layer may come into contact with the pickup tool. Can be used to suppress the contamination of the pickup tool.
- the elastic modulus at 35° C. after curing is 5 MPa or less, it is possible to reduce the warpage of the substrate and the semiconductor chip.
- a method of manufacturing a semiconductor device includes a semiconductor wafer having a connecting portion on one main surface, and the above-mentioned film adhesive for semiconductors provided on the main surface of the semiconductor wafer.
- a laminate including a semiconductor wafer, a first thermosetting adhesive layer, and a second thermosetting adhesive layer, which are laminated in this order;
- connection of a semiconductor chip with a film adhesive by arranging from the film adhesive side on the main surface where the connection part of the semiconductor chip mounting substrate having a connection part on the main surface is provided and heating. And a step of electrically connecting the portion and the connecting portion of the semiconductor chip mounting substrate. According to this manufacturing method, it is possible to suppress the warp of the base body and the semiconductor chip and the contamination of the pickup tool.
- a semiconductor device is a semiconductor device in which respective connecting portions of a semiconductor chip and a semiconductor chip mounting substrate are electrically connected to each other, and at least a part of the connecting portion is the above-mentioned semiconductor. It is sealed with a cured product of a film-type adhesive for use. The warp amount of this semiconductor device is reduced.
- the present invention it is possible to provide a film adhesive for semiconductors, which can suppress the occurrence of warpage of the substrate and the semiconductor chip in the mounting process and the contamination of the pickup tool. Further, according to the present invention, it is possible to provide a semiconductor device using the film adhesive for semiconductors and a method for manufacturing the same.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of the film adhesive for semiconductors of the present invention.
- 2A to 2D are process sectional views schematically showing an embodiment of the method for manufacturing a semiconductor device of the present invention.
- 3A to 3D are process cross-sectional views schematically showing an embodiment of the method for manufacturing a semiconductor device of the present invention.
- 4A to 4D are process cross-sectional views schematically showing an embodiment of the method for manufacturing a semiconductor device of the present invention.
- FIG. 5 is a process sectional view schematically showing an embodiment of the method for manufacturing a semiconductor device of the present invention.
- 6A to 6D are process cross-sectional views schematically showing an embodiment of the method for manufacturing a semiconductor device of the present invention.
- FIG. 7 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present invention.
- FIG. 8 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.
- FIG. 1 is a schematic cross-sectional view showing a film-like adhesive for semiconductors of one embodiment.
- the film adhesive 1 for a semiconductor includes a first thermosetting adhesive layer 2 (hereinafter, also simply referred to as “first layer”) and a second thermosetting adhesive layer 2 provided on the first layer 2.
- Thermosetting adhesive layer 3 (hereinafter, also simply referred to as “second layer”).
- the first layer 2 is a layer made of a first thermosetting adhesive (hereinafter, also simply referred to as “first adhesive”)
- the second layer 3 is a second thermosetting adhesive. (Hereinafter, also simply referred to as “second adhesive”).
- the film adhesive 1 for a semiconductor is used, for example, in a semiconductor device in which respective connecting portions of a semiconductor chip and a semiconductor chip mounting substrate (for example, a semiconductor chip, a semiconductor wafer, a wiring circuit board, etc.) are electrically connected to each other. It is used to seal at least a part of the connection portion. Specifically, it can be used to manufacture a semiconductor device by the method described below.
- the first layer 2 contains a first thermoplastic resin having a Tg of less than 35° C. (hereinafter, also simply referred to as “first thermoplastic resin”), and the second layer 3 Contains a second thermoplastic resin having a Tg of 35° C. or higher (hereinafter, also simply referred to as “second thermoplastic resin”). That is, the first adhesive contains the first thermoplastic resin and the second adhesive contains the second thermoplastic resin. According to the film adhesive 1 for a semiconductor as described above, by using the second layer 3 so as to be in contact with the pickup tool, the pickup tool can be prevented from being contaminated, and the first layer 2 is Since it contains a thermoplastic resin having a Tg of less than 35° C. (first thermoplastic resin), it is possible to reduce the warpage of the semiconductor chip mounting base and the semiconductor chip.
- first thermoplastic resin a thermoplastic resin having a Tg of less than 35° C.
- the first adhesive is, for example, a composition containing a thermosetting resin and a curing agent as thermosetting components, and a first thermoplastic resin.
- a radically polymerizable compound and a thermal polymerization initiator may be used as the thermosetting component.
- thermosetting resin examples include epoxy resin, phenol resin (excluding cases where it is contained as a curing agent), polyimide resin, bismaleimide resin, and the like.
- the thermosetting resin is preferably an epoxy resin from the viewpoint that more excellent heat resistance and adhesiveness are easily obtained.
- the epoxy resin can be used without particular limitation as long as it has two or more epoxy groups in the molecule.
- the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane.
- Type epoxy resin, dicyclopentadiene type epoxy resin and various polyfunctional epoxy resins can be used. These can be used alone or as a mixture of two or more kinds.
- the epoxy resin it is preferable to use an epoxy resin having a thermal weight loss rate of 5% or less at the temperature at the time of connection, from the viewpoint of suppressing decomposition of volatile components at the time of connection at a high temperature.
- the connecting temperature is 250° C.
- the connecting temperature is 300° C.
- the thermogravimetric weight at 300° C. It is preferable to use an epoxy resin with a reduction rate of 5% or less.
- the content of the thermosetting resin is, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more, based on the total mass of the first adhesive.
- the content of the thermosetting resin is, for example, 75% by mass or less, preferably 50% by mass or less, and more preferably 45% by mass or less, based on the total mass of the first adhesive.
- the content of the thermosetting resin may be, for example, 5 to 75% by mass, 10 to 50% by mass or 15 to 45% by mass based on the total mass of the first adhesive.
- the thermosetting resin contains an epoxy resin
- the content of the epoxy resin is preferably within the above range.
- the “total mass of the first adhesive” in the present specification does not include the mass of the organic solvent.
- the curing agent can be appropriately selected according to the thermosetting resin used.
- a phenol resin-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, an imidazole-based curing agent, a phosphine-based curing agent, etc. may be used as the curing agent. it can. Since the phenol resin-based curing agent and the acid anhydride-based curing agent exhibit flux activity, the connection reliability can be further improved by using these curing agents as the curing agent.
- each curing agent will be described.
- Phenolic resin-based curing agent is not particularly limited as long as it has two or more phenolic hydroxyl groups in the molecule, and examples thereof include phenol novolac resin, cresol novolac resin, and phenol aralkyl resin. , Cresol naphthol formaldehyde polycondensate, triphenylmethane type polyfunctional phenol resin and various polyfunctional phenol resins can be used. These can be used alone or as a mixture of two or more kinds.
- the equivalent ratio of the phenolic resin-based curing agent to the epoxy resin is good curability, adhesiveness and storage stability. From the viewpoint, 0.3 to 1.5 is preferable, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is further preferable.
- the equivalent ratio is 0.3 or more, the curability and the adhesive strength tend to be improved, and when it is 1.5 or less, the unreacted phenolic hydroxyl group does not remain excessively and the water absorption is It tends to be kept low and the insulation reliability tends to be improved.
- Acid Anhydride Curing Agent examples include methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, and ethylene glycol bis.
- Anhydrotrimellitate can be used. These can be used alone or as a mixture of two or more kinds.
- the equivalent ratio of the acid anhydride-based curing agent to the epoxy resin is good curability, adhesiveness and storage. From the viewpoint of stability, 0.3 to 1.5 is preferable, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is further preferable. If the equivalent ratio is 0.3 or more, the curability and the adhesive strength tend to be improved, and if it is 1.5 or less, the unreacted acid anhydride does not remain excessively and the water absorption is It tends to be kept low and the insulation reliability tends to be improved.
- (Iii) Amine-Based Curing Agent As the amine-based curing agent, for example, dicyandiamide can be used.
- the equivalent ratio of the amine-based curing agent to the epoxy resin is from the viewpoint of good curability, adhesiveness and storage stability. 0.3 to 1.5 is preferable, 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is further preferable.
- the equivalent ratio is 0.3 or more, the curability and the adhesive strength tend to be improved, and when it is 1.5 or less, unreacted amine does not remain excessively and the insulation reliability is improved. Tend to do.
- Imidazole type curing agent examples include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[2'-Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-diamino-6-[2'-ethyl-4'-methylimidazole, 1-benzyl-2-methylimid
- 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitic acid from the viewpoint of excellent curability, storage stability and connection reliability.
- Tate 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6- [2′-Ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine Isocyanuric acid adducts, 2-phenylimidazole isocyanuric acid adducts, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferred. These can be used alone or in combination of two or more. Further, these may be microencapsulated latent curing agents.
- the content of the imidazole-based curing agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the epoxy resin.
- the content of the imidazole-based curing agent is 0.1 part by mass or more, the curability tends to be improved.
- the content of the imidazole-based curing agent is 20 parts by mass or less, the fluidity of the first adhesive at the time of pressure bonding can be ensured, and the first adhesive between the connecting portions can be sufficiently removed. be able to. As a result, the first adhesive is suppressed from being hardened in the state where it intervenes between the solder and the connection portion, so that poor connection is less likely to occur.
- phosphine-based curing agents include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra(4-methylphenyl)borate and tetraphenylphosphonium(4-fluorophenyl)borate. Be raised.
- the content of the phosphine-based curing agent is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin.
- the content of the phosphine-based curing agent is 0.1 part by mass or more, the curability tends to be improved, and when it is 10 parts by mass or less, the first adhesive is cured before the metal bond is formed. There is no problem, and poor connection is less likely to occur.
- Each of the phenol resin-based curing agent, the acid anhydride-based curing agent and the amine-based curing agent may be used alone or as a mixture of two or more kinds.
- the imidazole-based curing agent and the phosphine-based curing agent may be used alone, or may be used together with a phenol resin-based curing agent, an acid anhydride-based curing agent or an amine-based curing agent.
- the first thermoplastic resin has the function of reducing the elastic modulus of the film adhesive for semiconductors after curing, and contributes to the reduction of the amount of warpage.
- the Tg (glass transition temperature) of the first thermoplastic resin is less than 35° C., and from the viewpoint of being able to further reduce the amount of warpage, it is preferably 25° C. or less, more preferably 10° C. or less, and further preferably 0. It is below °C.
- the Tg of the first thermoplastic resin is preferably ⁇ 70° C. or higher, more preferably ⁇ 50° C. or higher, and further preferably ⁇ 30° C., from the viewpoint that the tack value of the first layer does not become too high. That is all.
- the Tg of the first thermoplastic resin may be, for example, ⁇ 70° C. or higher and lower than 35° C., ⁇ 50 to 25° C., ⁇ 30 to 10° C., or ⁇ 30 to 0° C.
- the first adhesive may include, as the first thermoplastic resin, a plurality of thermoplastic resins having different Tgs.
- the Tg of the first thermoplastic resin mainly contained is preferably within the above range, and the Tg of all the first thermoplastic resins is more preferably within the above range.
- Tg is a value obtained by, for example, DMA measurement.
- thermoplastic resin examples include phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, (meth)acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, Examples thereof include polyvinyl acetal resin and urethane resin.
- the first thermoplastic resin is a (meth)acrylic resin, a urethane resin, a polyamideimide resin, or a polyimide resin from the viewpoint of excellent heat resistance and film-forming property, and the effect of reducing elastic modulus.
- the (meth)acrylic resin is preferably an acrylic rubber from the viewpoint of excellent heat resistance and film forming property, and also from the viewpoint of excellent effect of reducing elastic modulus. That is, it is particularly preferable that the first thermoplastic resin contains at least one selected from the group consisting of acrylic rubber and urethane resin.
- the (meth)acrylic resin is a polymer compound obtained by polymerizing one or both of an acrylic ester and a methacrylic ester as a raw material. These thermoplastic resins may be used alone or as a mixture or copolymer of two or more kinds.
- the weight average molecular weight of the first thermoplastic resin is, for example, 10,000 or more, preferably 20,000 or more, and more preferably 30,000 or more. With such a thermoplastic resin, the heat resistance and the film forming property of the first adhesive can be improved.
- the weight average molecular weight of the first thermoplastic resin is preferably 1,000,000 or less, and more preferably 500000 or less. From these viewpoints, the weight average molecular weight of the first thermoplastic resin may be, for example, 10,000 to 1,000,000, 20,000 to 500,000, or 30,000 to 500,000. With such a thermoplastic resin, the heat resistance of the first adhesive can be improved.
- the weight average molecular weight means the weight average molecular weight measured by polystyrene conversion using high performance liquid chromatography (manufactured by Shimadzu Corporation, trade name: C-R4A).
- Detector LV4000 UV Detector (Hitachi, Ltd., trade name)
- Pump L6000 Pump (Hitachi, Ltd., trade name)
- Eluent: THF/DMF 1/1 (volume ratio)+LiBr (0.03 mol/L)+H3PO4 (0.06 mol/L) Flow rate: 1 mL/min
- the content of the first thermoplastic resin is, for example, 1% by mass or more, preferably 2% by mass or more, and more preferably 5% by mass or more, based on the total mass of the first adhesive.
- the content of the first thermoplastic resin is, for example, 30 mass% or less, preferably 20 mass% or less, and more preferably 15 mass% or less, based on the total mass of the first adhesive.
- the content of the first thermoplastic resin may be, for example, 1 to 30% by mass, 2 to 20% by mass or 5 to 15% by mass based on the total mass of the first adhesive.
- the ratio (mass ratio) of the content of the thermosetting resin to the content of the first thermoplastic resin in the first adhesive is preferably 0.01 to 5, and 0.05 to 3. It is more preferable, and 0.1 to 2 is even more preferable.
- the first adhesive may further contain a flux compound, if necessary.
- the flux compound is a compound having a flux activity and functions as a flux agent.
- any known flux compound can be used without particular limitation as long as it reduces and removes an oxide film on the surface of solder or the like to facilitate metal bonding.
- As the flux compound one kind may be used alone, or two or more kinds may be used in combination. However, the flux compound does not include the above-mentioned curing agent.
- the flux compound preferably has a carboxyl group, and more preferably has two or more carboxyl groups, from the viewpoint of obtaining sufficient flux activity and more excellent connection reliability.
- compounds having two carboxyl groups are preferable.
- the compound having two carboxyl groups is less likely to volatilize even at a high temperature at the time of connection as compared with the compound having one carboxyl group (monocarboxylic acid), and the generation of voids can be further suppressed.
- the increase in the viscosity of the film adhesive for semiconductors during storage and connection work is further suppressed, as compared with the case where a compound having three or more carboxyl groups is used. Therefore, the connection reliability of the semiconductor device can be further improved.
- the flux compound having a carboxyl group a compound having a group represented by the following formula (1) is preferably used.
- R 1 represents a hydrogen atom or an electron donating group.
- Examples of the flux compound include dicarboxylic acids selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid, and dicarboxylic acids thereof.
- a compound having an electron donating group substituted at the position can be used.
- the melting point of the flux compound is preferably 150°C or lower, more preferably 140°C or lower, and further preferably 130°C or lower. Such a flux compound is likely to exhibit sufficient flux activity before the curing reaction between the epoxy resin and the curing agent occurs. Therefore, according to the film-like adhesive for semiconductors using the first adhesive containing such a flux compound, a semiconductor device having further excellent connection reliability can be realized.
- the melting point of the flux compound is preferably 25°C or higher, more preferably 50°C or higher.
- the melting point of the flux compound may be, for example, 25-150°C, 50-140°C or 50-130°C.
- the flux compound is preferably solid at room temperature (25°C).
- the melting point of the flux compound can be measured using a general melting point measuring device.
- the sample whose melting point is to be measured is pulverized into fine powder and it is required to reduce the temperature deviation in the sample by using a trace amount.
- a capillary tube with one end closed is often used, but depending on the measuring device, there is also one that is sandwiched between two microscope cover glasses to form a container. Further, when the temperature is rapidly raised, a temperature gradient is generated between the sample and the thermometer, which causes a measurement error. Therefore, the heating at the time of measuring the melting point can be measured at an increase rate of 1° C. or less per minute. desirable.
- the sample whose melting point is measured is prepared as a fine powder, so the sample before melting is opaque due to diffuse reflection on the surface. It is usual to set the temperature at which the appearance of the sample begins to become transparent as the lower limit point of the melting point and the temperature at which the sample has completely melted as the upper limit point.
- the most classical device is a device in which a capillary tube filled with a sample is attached to a double-tube thermometer and heating is performed in a warm bath. A highly viscous liquid is used as the liquid for the hot bath for the purpose of attaching a capillary tube to the double-tube thermometer, and concentrated sulfuric acid or silicone oil is often used, so that the sample comes near the reservoir at the tip of the thermometer. Install.
- the melting point measuring device it is possible to use a device that heats using a metal heat block and automatically determines the melting point while adjusting the heating while measuring the light transmittance.
- the melting point of 150° C. or lower means that the upper limit of the melting point is 150° C. or lower
- the melting point of 25° C. or higher means that the lower limit of the melting point is 25° C. or higher. means.
- the content of the flux compound is, based on the total mass of the first adhesive, preferably 0.5 mass% or more.
- the content of the flux compound is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the first adhesive.
- the content of the flux compound may be, for example, 0.5 to 10 mass% or 0.5 to 5 mass% based on the total mass of the first adhesive.
- the first adhesive may further contain a filler, if necessary.
- the filler is preferably used for controlling the viscosity of the adhesive and the physical properties of the cured product of the adhesive. Specifically, by containing the filler, for example, it is possible to suppress the generation of voids at the time of connection, reduce the moisture absorption rate of the cured product of the adhesive, and the like.
- the filler examples include inorganic filler (inorganic particles) and organic filler (organic particles).
- the inorganic filler include glass, silica, alumina, titanium oxide, mica, insulating inorganic fillers such as boron nitride, and among them, at least one selected from the group consisting of silica, alumina, titanium oxide and boron nitride. At least one selected from the group consisting of silica, alumina and boron nitride is more preferable.
- the insulating inorganic filler may be whiskers. Examples of the whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, boron nitride and the like.
- organic filler examples include resin fillers (resin particles).
- resin filler examples include polyurethane and polyimide. Compared with inorganic fillers, resin fillers can impart flexibility at high temperatures such as 260° C., and thus are suitable for improving reflow resistance and, at the same time, can impart flexibility, thereby improving film formability. effective.
- the filler is preferably insulative (is an insulative filler) from the viewpoint of further excellent insulation reliability. It is preferable that the first adhesive does not contain a conductive metal filler (metal particles) such as a silver filler or a solder filler, and a conductive inorganic filler such as carbon black.
- a conductive metal filler metal particles
- carbon black a conductive inorganic filler
- the content of the insulating filler is such that the elastic modulus can be easily adjusted to a desired range, and the occurrence of voids can be more sufficiently reduced while suppressing warpage, and further excellent connection reliability can be obtained.
- the amount may be 50% by mass or more, 70% by mass or more, or 90% by mass or more based on the total mass of the filler.
- the filler may consist essentially of insulating filler. That is, the filler may be substantially free of conductive filler. "Substantially free" means that the content of the conductive filler in the filler is less than 0.5% by mass based on the total mass of the filler.
- the physical properties of the filler may be appropriately adjusted by surface treatment.
- the filler is preferably a surface-treated filler.
- the surface treatment agent include glycidyl (epoxy), amine, phenyl, phenylamino, (meth)acrylic, and vinyl compounds.
- silane treatment with a silane compound such as epoxysilane type, aminosilane type, acrylsilane type, etc. is preferable because of the ease of surface treatment.
- a silane compound such as epoxysilane type, aminosilane type, acrylsilane type, etc.
- the surface treatment agent at least one selected from the group consisting of glycidyl compounds, phenylamino compounds, and (meth)acrylic compounds is preferable from the viewpoint of excellent dispersibility, fluidity and adhesive strength. .. From the viewpoint of excellent storage stability, the surface treatment agent is preferably at least one selected from the group consisting of phenyl compounds and (meth)acrylic compounds.
- the average particle size of the filler is preferably 1.5 ⁇ m or less from the viewpoint of preventing biting during flip chip connection, and more preferably 1.0 ⁇ m or less from the viewpoint of excellent visibility (transparency).
- the content of the filler is determined from the viewpoint that the heat dissipation is suppressed to be low, and that the generation of voids and the tendency to increase the moisture absorption rate are likely to be suppressed, with respect to the total mass of the first adhesive.
- 30% by mass or more is preferable, and 40% by mass or more is more preferable.
- the content of the filler it is easy to suppress that the fluidity of the first adhesive decreases due to the increase in viscosity and the trapping of the filler into the connection portion (trapping) is easily suppressed, and the connection reliability decreases.
- the content of the filler is preferably 30 to 90% by mass, and more preferably 40 to 80% by mass, based on the total mass of the first adhesive.
- the first adhesive may further contain additives such as an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent and an ion trap agent, if necessary. These may be used alone or in combination of two or more. The blending amount of these may be appropriately adjusted so that the effect of each additive is exhibited.
- additives such as an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent and an ion trap agent, if necessary. These may be used alone or in combination of two or more. The blending amount of these may be appropriately adjusted so that the effect of each additive is exhibited.
- the first adhesive may contain a thermoplastic resin having Tg of 35° C. or higher (hereinafter referred to as “high Tg thermoplastic resin”), but a thermoplastic resin having Tg of less than 35° C. (hereinafter, It is preferable to mainly contain "a low Tg thermoplastic resin” (for example, to contain more than 50% by mass based on the total mass of the thermoplastic resin contained in the first adhesive), and to have a high Tg heat. It is further preferable that no plastic resin is contained.
- the content of the low Tg thermoplastic resin (first thermoplastic resin) in the first adhesive is 75 mass% or more and 85 mass% or more based on the total mass of the thermoplastic resin contained in the first adhesive. % Or 95% by mass may be used.
- the content of the high Tg thermoplastic resin in the first adhesive is, for example, 5% by mass or less, preferably 1% by mass or less, and more preferably 0% by mass, based on the total mass of the first adhesive. Is.
- the second adhesive contains, for example, a thermosetting resin and a curing agent as thermosetting components, and a second thermoplastic resin.
- a radically polymerizable compound and a thermal polymerization initiator may be used as the thermosetting component.
- the second adhesive may further contain a flux compound, a filler and other additives, if necessary.
- the thermosetting component, the flux compound, the filler and other additives in the second adhesive the components described above as the components contained in the first adhesive can be used, and the type and content of each component The same applies to preferred examples such as.
- the second thermoplastic resin contributes to the reduction of tack on the surface of the second layer.
- the Tg of the second thermoplastic resin is 35° C. or higher. That is, the second thermoplastic resin is a high Tg thermoplastic resin.
- the Tg of the second thermoplastic resin is preferably 50° C. or higher, and more preferably 60° C. or higher, from the viewpoint that the tack of the second layer can be further reduced and the contamination of the pickup tool can be further suppressed. is there.
- the Tg of the second thermoplastic resin is preferably 250° C. or lower, more preferably 200° C. or lower, still more preferably 160° C. or lower, from the viewpoint of further reducing the amount of warpage. From these viewpoints, the Tg of the second thermoplastic resin may be, for example, 35 to 250°C, 50 to 200°C or 60 to 160°C.
- the second adhesive may include, as the second thermoplastic resin, a plurality of thermoplastic resins having different Tg's. In this case, the Tg of the second thermoplastic resin mainly contained is preferably in the above range, and the Tg of all the second thermoplastic resins is more preferably in the above range.
- thermoplastic resin examples include phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, (meth)acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, Examples thereof include polyvinyl acetal resin and urethane resin.
- the second thermoplastic resin preferably contains at least one selected from the group consisting of a phenoxy resin, a (meth)acrylic resin and a polyimide resin, from the viewpoint of excellent heat resistance and film-forming property, and phenoxy It is more preferable to include a resin.
- thermoplastic resins may be used alone or as a mixture or copolymer of two or more kinds.
- the weight average molecular weight of the second thermoplastic resin is, for example, 10,000 or more, preferably 20,000 or more, and more preferably 30,000 or more. With such a thermoplastic resin, the heat resistance and the film forming property of the second adhesive can be improved.
- the weight average molecular weight of the second thermoplastic resin is preferably 1,000,000 or less, and more preferably 500000 or less. With such a thermoplastic resin, the heat resistance of the second adhesive can be improved. From these viewpoints, the weight average molecular weight of the second thermoplastic resin may be, for example, 10,000 to 1,000,000, 20,000 to 500,000, or 30,000 to 500,000.
- the content of the second thermoplastic resin is, for example, 4% by mass or more, preferably 7% by mass or more, and more preferably 10% by mass or more, based on the total mass of the second adhesive.
- the content of the second thermoplastic resin is, for example, 40% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less, based on the total mass of the second adhesive.
- the content of the second thermoplastic resin may be, for example, 4 to 40% by mass, 7 to 30% by mass or 10 to 20% by mass based on the total mass of the second adhesive.
- the “total mass of the second adhesive” in the present specification does not include the mass of the organic solvent.
- the content of the thermoplastic resin having Tg of 50° C. or higher is preferably in the above range based on the total mass of the second adhesive, and the content of the thermoplastic resin having Tg of 60° C. or higher is More preferably, the above range is based on the total mass of the second adhesive.
- the content of the thermoplastic resin having Tg of 250° C. or lower is more preferably in the above range based on the total mass of the second adhesive, and the content of the thermoplastic resin having Tg of 200° C. or lower is It is more preferable that the content is in the above range based on the total mass of the second adhesive, and the content of the thermoplastic resin having Tg of 160° C. or less is further within the range based on the total mass of the second adhesive. preferable.
- the ratio (mass ratio) of the content of the thermosetting resin to the content of the second thermoplastic resin in the second adhesive is preferably 0.01 to 5, and 0.05 to 3. It is more preferable, and 0.1 to 2 is even more preferable.
- the second adhesive preferably contains mainly a high Tg thermoplastic resin (for example, contains more than 50% by mass based on the total mass of the thermoplastic resin contained in the second adhesive), and has a low content. It is preferable not to contain Tg thermoplastic resin.
- the content of the high Tg thermoplastic resin (second thermoplastic resin) in the second adhesive is 75 mass% or more and 85 mass% or more based on the total mass of the thermoplastic resin contained in the second adhesive. % Or 95% by mass may be used.
- the content of the low Tg thermoplastic resin in the second adhesive is, for example, 5% by mass or less, preferably 1% by mass or less, and more preferably 0% by mass, based on the total mass of the second adhesive. Is.
- the thickness of the layer containing the flux compound may be appropriately adjusted so that the flux compound functions.
- the thickness of the first layer 2 may be adjusted to be equal to or higher than the height of the connecting portion of the semiconductor chip.
- connection surface At least a part (for example, a portion containing solder) of the surface connected to the connection portion of the semiconductor chip mounting base comes into contact with the first adhesive forming the first layer, and impurities on the contact surface are contacted. Is eliminated and the connection reliability is improved.
- the thickness of the film adhesive for semiconductors when the sum of the heights of the connection portions is x and the total thickness of the film adhesive for semiconductors is y, the relationship between x and y is as follows. From the viewpoints of connectivity and filling of the adhesive, it is preferable to satisfy 0.70x ⁇ y ⁇ 1.3x, and it is more preferable to satisfy 0.80x ⁇ y ⁇ 1.2x.
- the total thickness of the film adhesive for semiconductors may be, for example, 10 to 100 ⁇ m, 10 to 80 ⁇ m, or 10 to 50 ⁇ m.
- the first layer 2 it is preferable to thicken the first layer 2 from the viewpoint that the elastic modulus of the film adhesive for semiconductor 1 after curing can be further reduced and the effect of reducing warpage can be further obtained.
- the thickness of the first layer 2 may be, for example, 1 to 50 ⁇ m, 3 to 50 ⁇ m, 4 to 30 ⁇ m, or 5 to 20 ⁇ m.
- the thickness of the second layer 3 may be, for example, 7 to 50 ⁇ m, 8 to 45 ⁇ m, or 10 to 40 ⁇ m.
- the ratio of the thickness of the second layer 3 to the thickness of the first layer 2 is, for example, 0.1 to 10.0. May be from 0.5 to 6.0, from 1.0 to 4.0, from 0.1 to 1.5, from 0.1 to 1.2 Well, it may be 0.1 to 1.0.
- the probe tack value of the second layer can be made smaller than the probe tack value of the first layer 2, and contamination of the pickup tool can be prevented.
- Probe tack value of the first layer 2 is, for example, 70N / cm 2 or more and 150 N / cm 2 or less, is 70 ⁇ 150N / cm 2.
- the probe tack value of the second layer 3 is preferably 60 N/cm 2 or less, more preferably 50 N/cm 2 or less, and further preferably 30 N/cm 2 or less.
- the probe tack value of the second layer 3 may be 5 N/cm 2 or more.
- Probe tack value of the second layer 3 may be, for example, 5 ⁇ 60N / cm 2, 5 ⁇ 50N / cm 2 or 5 ⁇ 30N / cm 2.
- the probe tack value is a probe tack value at a probe temperature of 50° C. and a stage temperature of 25° C. Specifically, it is measured by the method described in Examples.
- the elastic modulus of the film adhesive 1 for a semiconductor after curing is, for example, 5 MPa or less, and is preferably 4.5 MPa or less, and more preferably 3.5 MPa or less from the viewpoint of further obtaining the effect of reducing warpage. is there.
- the elastic modulus of the film adhesive 1 for a semiconductor after curing may be 1 MPa or more.
- the elastic modulus of the film adhesive for semiconductor 1 after curing may be 1 to 5 MPa, 1 to 4.5 MPa, or 1 to 3.5 MPa.
- the above elastic modulus can be measured by the method described in Examples. That is, the elastic modulus of the film adhesive for semiconductor 1 after curing is the elastic modulus of a cured product of the film adhesive for semiconductor 1 obtained by heating the film adhesive for semiconductor 1 at 240° C. for 1 hour. You can call it back.
- the film adhesive for semiconductors of the present embodiment may further include layers other than the first layer and the second layer, and may be composed of only the first layer and the second layer.
- the film adhesive for semiconductors preferably does not include another layer on the side of the second layer opposite to the first layer. Further, the film adhesive for semiconductors of the present embodiment is on the surface of the second layer opposite to the first layer and/or the surface of the first layer opposite to the second layer.
- a base film and/or a protective film may be provided on the top.
- the film adhesive 1 for a semiconductor has an elastic modulus at curing of 35° C. of 5 MPa or less (for example, 1 to 5 MPa), and the probe tack value of the second layer 3 (probe temperature 50° C.).
- the probe tack value at a stage temperature of 25° C. is 60 N/cm 2 or less (for example, 5 to 60 N/cm 2 ).
- Examples of the elastic modulus at 35° C. after curing of the film adhesive 1 for a semiconductor, the range of the probe tack value of the first layer 2 and the probe tack value of the second layer 3, and examples of these measuring methods are: This is the same as in the first embodiment.
- examples of the type and content of each component in the first layer 2 and the second layer 3 and the layer configuration (layer thickness of the first layer 2 and the second layer 3) are as follows. It is the same as the example of the type and content of each component and the layer thickness illustrated in the embodiment, and the same is true of the preferable example.
- the film adhesive for semiconductors according to the second embodiment includes, for example, the first thermoplastic resin described above in the first layer 2 and the second thermoplastic resin described above in the second layer 3. It can be easily obtained. That is, typically, as the adhesive contains a thermoplastic resin having a lower Tg, the elastic modulus after curing of the adhesive can be decreased, while the tack value of the adhesive tends to increase. By including the first thermoplastic resin in the first layer 2, the elastic modulus at 35° C. after curing can be easily set to 5 MPa or less, and the second layer 3 can include the second thermoplastic resin. By including the above, the probe tack value of the second layer (probe tack value at a probe temperature of 50° C. and a stage temperature of 25° C.) can be set to 60 N/cm 2 or less.
- a first film adhesive having a first layer and a second film adhesive having a second layer are prepared, and a first film adhesive is prepared. It can be obtained by laminating a first film adhesive having a layer and a second film adhesive having a second layer.
- thermosetting resin and a curing agent as thermosetting components, a first thermoplastic resin, and a flux compound added as necessary
- a resin varnish is prepared by adding other components such as a filler to an organic solvent and dissolving or dispersing the mixture by stirring, mixing, kneading and the like. Then, on the base film or protective film that has been subjected to a release treatment, after coating the resin varnish using a knife coater, roll coater, applicator, etc., reduce the organic solvent by heating, the base film or protective film A first layer of a first adhesive can be formed on top.
- the organic solvent used for preparing the resin varnish is preferably one having the property of uniformly dissolving or dispersing each component.
- the organic solvent include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, And ethyl acetate.
- These organic solvents can be used alone or in combination of two or more kinds.
- Stirring and mixing and kneading at the time of preparing the resin varnish can be performed using, for example, a stirrer, a raker, a three-roll, a ball mill, a bead mill or a homodisper.
- the substrate film and the protective film are not particularly limited as long as they have heat resistance that can withstand the heating conditions when volatilizing the organic solvent, polypropylene film, polyolefin film such as polymethylpentene film, polyethylene terephthalate film, Examples thereof include polyester films such as polyethylene naphthalate film, polyimide films and polyetherimide films.
- the base film and the protective film are not limited to single-layer films made of these films, and may be multilayer films made of two or more materials. Moreover, the above-mentioned base film and protective film may be provided with an adhesive layer on one surface thereof.
- Drying conditions for volatilizing the organic solvent from the resin varnish applied to the base film are preferably conditions under which the organic solvent is sufficiently volatilized, specifically, 50 to 200° C. and 0.1 to 90 minutes. Is preferably heated.
- the organic solvent is preferably removed up to 1.5% by mass or less with respect to the total mass of the first film adhesive, as long as the voids or the viscosity adjustment after mounting are not affected.
- the second layer made of the second adhesive can be formed on the base film or the protective film by the same method as the first layer.
- a protective film may be used to form the second layer
- a substrate film may be used for formation.
- Lamination may be performed under heating conditions of, for example, 30 to 120°C.
- the film adhesive for semiconductors of the present embodiment for example, after forming one of the first layer or the second layer on the substrate film, on the obtained first layer or the second layer, It may be obtained by forming the other of the first layer and the second layer.
- the first layer and the second layer may be formed by the same method as the method for forming the first layer and the second layer in the production of the film adhesive described above.
- the film adhesive for semiconductors of the present embodiment may be obtained, for example, by forming the first layer and the second layer substantially simultaneously on the base film.
- Examples of the method for simultaneously applying and manufacturing the first adhesive and the second adhesive include a coating method such as a sequential coating method or a multilayer coating method.
- the semiconductor device manufacturing method of the present embodiment is (A) A semiconductor wafer A having a connecting portion 5 on one main surface, and a semiconductor wafer A provided on the main surface of the semiconductor wafer A such that the surface on the first layer 2 side is the semiconductor wafer A side.
- a step of preparing a laminate 6 including the film adhesive 1 (see FIG. 2 )
- B) The side of the laminated body 6 opposite to the side where the film adhesive 1 for semiconductor is provided (the side opposite to the side where the connecting portion 5 of the semiconductor wafer A is provided) is ground to perform the semiconductor wafer A.
- the step of thinning see FIG.
- step (C) a step of dividing the laminated body 6 after the step (b) into individual pieces to obtain a semiconductor chip 8 having a film-like adhesive and having a connecting portion 5 (see FIG. 4 ).
- step D) a step of picking up the semiconductor chip 8 with the film adhesive from the film adhesive 1a side (see FIG. 5)
- step E) The film-shaped adhesive 1a is provided on the main surface of the semiconductor chip mounting substrate 9 having the connection portion 10 on one main surface thereof.
- the step (b) may not be performed.
- the step (a) may be a step of preparing the laminated body 6 prepared in advance, or a step of manufacturing the laminated body 6.
- the laminated body 6 may be produced by the following method, for example.
- a substrate-attached film adhesive for semiconductor in which a substrate 4 is provided on the second layer 3 side of the film adhesive for semiconductor 1 is prepared and placed in a predetermined device (FIG. 2(a )reference).
- a semiconductor wafer A having a connection portion 5 (wiring, bump, etc.) on one main surface is prepared, and a semiconductor film-like adhesive is applied onto the main surface of the semiconductor wafer A (the surface on which the connection portion 5 is provided).
- Apply Agent 1 As a result, a laminated body with a substrate is obtained, which includes the laminated body 6 in which the semiconductor wafer A, the first layer 2, and the second layer 3 are laminated in this order (see FIG. 2B).
- the sticking of the film adhesive 1 for semiconductors can be performed by hot pressing, roll laminating, vacuum laminating, or the like.
- the supply area and thickness of the film adhesive 1 for a semiconductor are appropriately set depending on the sizes of the semiconductor wafer and the semiconductor chip mounting base, the height of the connecting portion, and the like.
- the semiconductor wafer A of the laminated body 6 is ground by using, for example, a grinder G (see FIGS. 3A and 3B).
- the thickness of the semiconductor wafer after grinding may be, for example, 10 ⁇ m to 300 ⁇ m. From the viewpoint of miniaturization and thinning of the semiconductor device, the thickness of the semiconductor wafer is preferably 20 ⁇ m to 100 ⁇ m.
- the dicing tape 7 is attached to the semiconductor wafer A side of the laminated body 6, the dicing tape 7 is placed in a predetermined device, and the base material 4 is peeled off (see FIG. 4A).
- the base material 4 may be peeled off before the laminated body 6 is attached to the dicing tape 7.
- the laminated body 6 is diced by the dicing saw D. In this way, the laminated body 6 is divided into individual pieces, and the semiconductor chip 8 with the film adhesive, which is provided with the film adhesive 1a on the semiconductor chip A′, is obtained (see FIG. 4B).
- a connection portion 5 is provided on the surface of the semiconductor chip A′ on the film adhesive 1a side.
- the film adhesive 1a has a layer 2a made of a first adhesive and a layer 3a made of a second adhesive.
- step (d) for example, by expanding (expanding) the dicing tape 7, the film-like adhesive semiconductor chips 8 obtained by the dicing are separated from each other and pushed up from the dicing tape 7 side by the needle N.
- the semiconductor chip 8 with the film adhesive is picked up from the film adhesive 1a side by the pickup tool P (see FIG. 5).
- step (e) for example, after the semiconductor chip 8 with the film adhesive is delivered to the bonding tool, the semiconductor chip 8 with the film adhesive is mounted from the side of the film adhesive 1a using the bonding tool.
- the substrate 9 is placed on the main surface provided with the connecting portions 10 (wiring, bumps, etc.) and heated (see FIGS. 6A and 6B).
- the semiconductor chip 8 with the film adhesive and the semiconductor chip mounting base 9 are aligned.
- the connecting portion 5 of the semiconductor chip 8 with the film adhesive and the connecting portion 10 of the semiconductor chip mounting base 9 are electrically connected, and the semiconductor chip A′ and the semiconductor chip mounting base 9 are connected to each other.
- a sealing portion 1a′ made of a cured product of the film adhesive 1a is formed on the substrate 1 and the connecting portion 5 and the connecting portion 10 are sealed to obtain the semiconductor device 11.
- the sealing portion 1a' has an upper portion 2a' containing a cured product of the first adhesive and a lower portion 3a' containing a cured product of the second adhesive.
- connection portion 5 or the connection portion 10 when a solder bump is used for one of the connection portion 5 or the connection portion 10 (for example, when the connection portion 5 or the connection portion 10 is a wiring provided with the solder bump), the connection portion 5 and the connection portion 10 are connected to each other. Are connected to each other electrically and mechanically.
- the heating in step (e) may be performed while arranging the semiconductor chip, or may be performed after arranging the semiconductor chip.
- the heating and placement in step (e) may be thermocompression bonding.
- the bumps (for example, solder bumps) provided in the connection part are temporarily fixed after alignment (in a state where a film adhesive for semiconductors is used) and heat-treated in a reflow furnace to remove bumps (for example, solder bumps) provided in the connection part.
- the semiconductor chip A′ and the semiconductor chip mounting substrate 9 may be melted and connected to each other.
- the heating temperature is preferably a temperature at which the film adhesive is cured, and more preferably a temperature at which the film adhesive is completely cured.
- the heating temperature and the heating time are set appropriately.
- connection load is set in consideration of variations in the number and height of the connection parts, the amount of deformation of the connection parts due to pressure, and the like.
- the connection temperature is preferably such that the temperature of the connection portion is equal to or higher than the melting point of the connection portion (for example, the melting point of the bump), but may be a temperature at which a metal bond of each connection portion is formed.
- solder bumps are used for the connecting portion, it is preferably about 240° C. or higher.
- connection time at the time of connection varies depending on the constituent metal of the connection part, but from the viewpoint of improving productivity, the shorter the connection time, the better.
- the connection time is preferably 20 seconds or less, more preferably 10 seconds or less, and further preferably 5 seconds or less.
- the connection time is preferably 60 seconds or less.
- a wafer composed of an elemental semiconductor composed of the same kind of element such as silicon or germanium, a wafer composed of a compound semiconductor such as gallium arsenide or indium phosphide can be used. Details of the semiconductor chip mounting base body and the connecting portion will be described later.
- FIG. 7 is a schematic cross-sectional view showing an embodiment of a semiconductor device.
- the semiconductor device 100 shown in FIG. 7A includes a semiconductor chip 20 and a semiconductor chip mounting base 25 facing each other, and wirings 15 arranged on the surfaces of the semiconductor chip 20 and the semiconductor chip mounting base 25 facing each other.
- the semiconductor chip 20 and the semiconductor chip mounting base 25 are flip-chip connected by the wiring 15 and the connection bumps 30.
- the wiring 15 and the connection bumps 30 are sealed with a cured product of an adhesive and are shielded from the external environment.
- the sealing portion 40 has an upper portion 40a containing a cured product of the first adhesive and a lower portion 40b containing a cured product of the second adhesive.
- a semiconductor device 200 shown in FIG. 7B includes a semiconductor chip 20 and a semiconductor chip mounting base 25 that face each other, and bumps 32 that are respectively arranged on surfaces of the semiconductor chip 20 and the semiconductor chip mounting base 25 that face each other. And a sealing portion 40 made of a cured product of an adhesive (first adhesive and second adhesive) filled in a space between the semiconductor chip 20 and the semiconductor chip mounting base 25 without any gap. ..
- the semiconductor chip 20 and the semiconductor chip mounting base 25 are flip-chip connected by connecting opposite bumps 32 to each other.
- the bump 32 is sealed with a cured product of an adhesive and is shielded from the external environment.
- the sealing portion 40 has an upper portion 40a containing a cured product of the first adhesive and a lower portion 40b containing a cured product of the second adhesive.
- the semiconductor chip 20 is not particularly limited, and a semiconductor chip composed of an elemental semiconductor composed of the same kind of element such as silicon or germanium, or a semiconductor chip composed of a compound semiconductor such as gallium arsenide or indium phosphide is used. be able to.
- the semiconductor chip mounting base 25 is not particularly limited as long as it can be used for mounting the semiconductor chip 20, and examples thereof include a semiconductor chip, a semiconductor wafer, and a printed circuit board.
- the example of the semiconductor chip that can be used as the semiconductor chip mounting base 25 is the same as the example of the semiconductor chip 20 described above, and the same semiconductor chip as the semiconductor chip 20 may be used as the semiconductor chip mounting base 25.
- the semiconductor wafer that can be used as the semiconductor chip mounting base 25 is not particularly limited, and may have a configuration in which a plurality of semiconductor chips exemplified as the semiconductor chip 20 are connected.
- the wired circuit board that can be used as the semiconductor chip mounting substrate 25 is not particularly limited, and a metal such as glass epoxy, polyimide, polyester, ceramic, epoxy, or bismaleimide triazine may be used on the surface of the insulating board.
- a circuit board or the like in which a wiring 15 is formed by printing a conductive substance can be used.
- connection parts such as the wiring 15 and the bumps 32 are mainly composed of gold, silver, copper, and solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper, etc.). ), nickel, tin, lead, etc., and may contain a plurality of metals.
- gold, silver, and copper are preferable, and silver and copper are more preferable, from the viewpoint of forming a package having excellent electrical and thermal conductivity of the connection portion.
- silver, copper, and solder which are inexpensive materials, are preferable, copper and solder are more preferable, and solder is still more preferable.
- gold, silver, copper and solder are preferable from the viewpoint of suppressing the formation of the oxide film, and gold and silver.
- Solder is more preferable, and gold and silver are more preferable.
- Gold, silver, copper, solder main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, etc.), tin, nickel, etc. are mainly formed on the surfaces of the wiring 15 and the bumps 32.
- the metal layer as a component may be formed by plating, for example. This metal layer may be composed of only a single component or may be composed of a plurality of components. Further, the metal layer may have a structure in which a single layer or a plurality of metal layers are laminated.
- the above semiconductor devices 100 and 200 can be obtained by the method for manufacturing a semiconductor device described above.
- the semiconductor device of this embodiment may have a structure in which a plurality of structures (packages) as shown in the semiconductor devices 100 and 200 are stacked.
- the semiconductor devices 100 and 200 include gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper, etc.), tin, nickel. They may be electrically connected to each other by bumps, wires, etc.
- FIG. 8 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention, which is a semiconductor device using the TSV technique.
- the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 20 via the connection bumps 30, so that the semiconductor chip 20 and the interposer 50 are flip-chip connected.
- the void between the semiconductor chip 20 and the interposer 50 is filled with a cured product of an adhesive (first adhesive and second adhesive) without any gap, and constitutes the sealing portion 40.
- the semiconductor chip 20 On the surface of the semiconductor chip 20 opposite to the interposer 50, the semiconductor chip 20 is repeatedly laminated via the wiring 15, the connection bump 30, and the sealing portion 40.
- the wirings 15 on the pattern surfaces on the front and back of the semiconductor chip 20 are connected to each other by the through electrodes 34 filled in the holes penetrating the inside of the semiconductor chip 20.
- the material of the through electrode 34 may be copper, aluminum or the like.
- the penetrating electrode 34 is vertically passed through the semiconductor chip 20, the distance between the semiconductor chips 20 facing each other and the distance between the semiconductor chip 20 and the interposer 50 can be shortened to enable flexible connection.
- the film adhesive for semiconductors of this embodiment can be applied as a film adhesive for semiconductors between the semiconductor chips 20 facing each other and between the semiconductor chips 20 and the interposer 50 in such a TSV technique.
- the semiconductor chip can be directly mounted on the motherboard without the interposer.
- the film-shaped adhesive for semiconductors of this embodiment can be applied to the case where such a semiconductor chip is directly mounted on a mother board.
- the film adhesive for semiconductors of the present embodiment can be applied when sealing the gap between the substrates when the two printed circuit boards are laminated.
- EP1032 polyfunctional solid epoxy containing triphenol methane skeleton, manufactured by Mitsubishi Chemical Corporation, trade name "jER1032H60", “jER” is a registered trademark (the same applies below)
- ⁇ YL983U bisphenol F type liquid epoxy, manufactured by Mitsubishi Chemical Corporation, trade name "jERYL983U"
- Thermoplastic resin LA2140 (acrylic resin, manufactured by Kuraray Co., Ltd., trade name "Clarity LA2140", "Clarity” is a registered trademark, Tg: about -24°C, Mw: about 60000) -D-21 (acrylic resin, manufactured by Hitachi Chemical Co., Ltd., trade name "CT-D21", Tg: about -11°C, Mw: about 550000) -T-8175N (urethane resin, manufactured by DIC Covestro Polymer Co., Ltd., trade name "Pandex T-8175N", "Pandex” is a registered trademark, Tg: -23°C, Mw: 120,000)
- [Filler] ⁇ SE2050 sica filler, manufactured by Admatechs Co., Ltd., trade name, average particle size: 0.5 ⁇ m
- SE2050-SEJ epoxysilane surface-treated filler, manufactured by Admatechs Co., Ltd., trade name, average particle size: 0.5 ⁇ m
- ⁇ YA050C-HGF methacryl surface treated nano silica filler, Admatechs Co., Ltd., trade name, average particle size: about 50 nm
- EXL-2655 organic filler, manufactured by Rohm and Haas Japan Co., Ltd., trade name "Paraloid EXL-2655", "Paraloid” is a registered trademark, core-shell type organic fine particles
- the epoxy resin, the curing agent, the flux compound, the thermoplastic resin, and the filler having the blending amounts (unit: parts by mass) shown in Table 1 were measured by NV value ([mass of paint after drying]/[mass of paint before drying] ⁇ 100) was added to the organic solvent (cyclohexanone) so that it would be 50%. After that, ⁇ 1.0 mm beads and ⁇ 2.0 mm beads were added in the same mass as the solid content (epoxy resin, curing agent, flux compound, thermoplastic resin and filler), and a bead mill (Fritsch Japan Co., Ltd. The mixture was stirred for 30 minutes with a pulverizer P-7). After stirring, the beads were removed by filtration to prepare coating varnishes a1 to a3 containing the first adhesive.
- the obtained coating varnishes a1 to a3 are coated on a base film (manufactured by Teijin DuPont Films Ltd., trade name "Purex A54”) with a small precision coating device (manufactured by Rensai Seiki Co., Ltd.). Then, it was dried (100° C./5 min) in a clean oven (manufactured by ESPEC Co., Ltd.) to obtain a single layer film A including layers (thermosetting adhesive layers) having the thickness shown in Table 2.
- the epoxy value, the curing agent, the flux compound, the thermoplastic resin and the filler of the compounding amounts (units: parts by mass) shown in Table 3 were measured by NV value ([mass of paint after drying]/[mass of paint before drying] ⁇ 100) was added to the organic solvent (cyclohexanone) so that it would be 50%. After that, ⁇ 1.0 mm beads and ⁇ 2.0 mm beads were added in the same mass as the solid content (epoxy resin, curing agent, flux compound, thermoplastic resin and filler), and a bead mill (Fritsch Japan Co., Ltd. The mixture was stirred for 30 minutes with a pulverizer P-7). After stirring, the beads were removed by filtration to prepare coating varnishes b1 and b2 containing the second adhesive.
- the obtained coating varnishes b1 and b2 are coated on a base film (manufactured by Teijin DuPont Films Ltd., trade name "Purex A54”) with a small precision coating device (manufactured by Renui Seiki Co., Ltd.). Then, it was dried (100° C./5 min) in a clean oven (manufactured by ESPEC Co., Ltd.) to obtain a monolayer film B including layers (thermosetting adhesive layers) having the thickness shown in Table 4.
- Examples 1 to 7 and Comparative Examples 1 to 8 Two of the single-layer films prepared above were prepared as a first film and a second film, and the first film and the second film were laminated at 50° C. to form a film having a total thickness of 40 ⁇ m. An adhesive was prepared.
- the combinations of single-layer films were as shown in Tables 5 and 6.
- the layer (thermosetting adhesive layer) formed on the first film is referred to as a first layer
- the layer (thermosetting adhesive layer) formed on the second film is referred to as a second layer. Of layers.
- the elastic modulus at 35° C. of the test sample was measured using a dynamic viscoelasticity measuring device. Details of the method for measuring the elastic modulus are as follows.
- Device name Dynamic viscoelasticity measurement device (UBM Co., Ltd., Rheogel-E4000) Measurement temperature range: 30-270°C Temperature rising rate: 5°C/min Frequency: 10Hz Distortion: 0.05%
- the film adhesive is cut into a predetermined size (length 76 mm x width 26 mm), the base film on the second layer side is peeled off, and the glass plate (size: length 76 mm x width 26 mm x thickness) is peeled off from the base film peeled side. 1.2 to 1.5 mm) was attached. Then, the base film on the first layer side was peeled off, and the tack value (probe tack value) of the first layer was measured using a tacking tester with the surface of the first layer facing upward. ..
- the film adhesive is cut into a predetermined size (length 76 mm x width 26 mm), the base film on the first layer side is peeled off, and a glass plate (size: length 76 mm x width 26 mm x thickness) 1.2 to 1.5 mm) was attached. Then, the base film on the second layer side was peeled off, and the tack value (probe tack value) of the second layer was measured using a tacking tester with the surface of the second layer facing upward. ..
- Tacking tester (Resc Co., Ltd., trade name: TAC-1000) Pressing speed 2.0mm/s Pressing load 200gf Pressing time 1.00s Lifting speed 10.0 mm/s Stage temperature 25°C Probe temperature 50°C
- the film-shaped adhesive is a silicon chip whose surface is covered with an oxide film from the first layer side by using a vacuum laminator (LM-50X50-S manufactured by NPC Co., Ltd.) (vertical 10 mm ⁇ horizontal). It was laminated on the oxide film of 10 mm ⁇ thickness of 0.05 mm). Next, the silicon chip laminated with the film adhesive was cured (240° C., 1 h) in a clean oven (manufactured by ESPEC). Thereby, a test sample was obtained.
- a vacuum laminator LM-50X50-S manufactured by NPC Co., Ltd.
- the amount of chip warpage of the test sample was measured. Specifically, in a state where the test sample is arranged so that the silicon chip is on the lower side (the cured product of the film-like adhesive is on the upper side), the surface shape measuring device is used to measure the cured product side of the film-shaped adhesive. The maximum value of the height difference on the surface was measured, and this was taken as the amount of warpage.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Die Bonding (AREA)
- Adhesive Tapes (AREA)
- Wire Bonding (AREA)
Abstract
L'invention concerne un agent adhésif 1 de type film pour semi-conducteur, l'agent adhésif 1 comprenant une première couche 2 d'agent adhésif thermodurcissable et une seconde couche 3 d'agent adhésif thermodurcissable déposée sur la première couche 2 d'agent adhésif thermodurcissable, la première couche 2 d'agent adhésif thermodurcissable contenant une première résine thermoplastique dans laquelle la Tg est inférieure à 35 °C, et la seconde couche 3 d'agent adhésif thermodurcissable contenant une seconde résine thermoplastique dans laquelle la Tg est supérieure ou égale à 35 °C.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020558357A JP7384171B2 (ja) | 2018-11-29 | 2019-11-15 | 半導体用フィルム状接着剤、半導体装置及びその製造方法 |
KR1020217007145A KR102652707B1 (ko) | 2018-11-29 | 2019-11-15 | 반도체용 필름상 접착제, 반도체 장치 및 그 제조 방법 |
CN201980070535.7A CN113169141A (zh) | 2018-11-29 | 2019-11-15 | 半导体用膜状黏合剂、半导体装置及其制造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018223726 | 2018-11-29 | ||
JP2018-223726 | 2018-11-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020110785A1 true WO2020110785A1 (fr) | 2020-06-04 |
Family
ID=70852012
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/044953 WO2020110785A1 (fr) | 2018-11-29 | 2019-11-15 | Agent adhésif de type film pour semi-conducteur, dispositif à semi-conducteur et son procédé de fabrication |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP7384171B2 (fr) |
KR (1) | KR102652707B1 (fr) |
CN (1) | CN113169141A (fr) |
TW (1) | TWI807135B (fr) |
WO (1) | WO2020110785A1 (fr) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009044732A1 (fr) * | 2007-10-05 | 2009-04-09 | Hitachi Chemical Company, Ltd. | Composition adhésive, matière de connexion de circuit l'utilisant, procédé de connexion d'éléments de circuit et structure de connexion de circuit |
JP2011018879A (ja) * | 2009-06-10 | 2011-01-27 | Sony Chemical & Information Device Corp | 絶縁性樹脂フィルム、並びにこれを用いた接合体及びその製造方法 |
JP2011515839A (ja) * | 2008-03-14 | 2011-05-19 | チェイル インダストリーズ インコーポレイテッド | 半導体パッケージ用複合機能テープ及びこれを用いた半導体素子の製造方法 |
WO2012014562A1 (fr) * | 2010-07-26 | 2012-02-02 | 日立化成工業株式会社 | Composition adhésive, structure de connexion, procédé de fabrication d'une structure de connexion et application de la composition adhésive |
JP2014210880A (ja) * | 2013-04-19 | 2014-11-13 | 日東電工株式会社 | 熱硬化性樹脂組成物及び半導体装置の製造方法 |
JP2017214528A (ja) * | 2016-06-02 | 2017-12-07 | 日東電工株式会社 | 真空プロセス用粘着テープ |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100248582B1 (ko) * | 1996-07-30 | 2000-03-15 | 이사오 우치가사키 | 서로 마주보는 전극들을 상호 접속하기 위한 접속시트, 및 이 접속시트를 사용하는 전극접속구조 및 접속방법 |
JP5539073B2 (ja) | 2010-07-02 | 2014-07-02 | キヤノン株式会社 | 認証システム、認証サービスの制御方法、プログラム |
CN110556344A (zh) | 2012-02-24 | 2019-12-10 | 日立化成株式会社 | 半导体用粘接剂、半导体装置的制造方法以及半导体装置 |
JP5738456B2 (ja) | 2014-05-22 | 2015-06-24 | リンテック株式会社 | 接着シートおよび半導体装置の製造方法 |
-
2019
- 2019-11-15 CN CN201980070535.7A patent/CN113169141A/zh active Pending
- 2019-11-15 KR KR1020217007145A patent/KR102652707B1/ko active IP Right Grant
- 2019-11-15 JP JP2020558357A patent/JP7384171B2/ja active Active
- 2019-11-15 WO PCT/JP2019/044953 patent/WO2020110785A1/fr active Application Filing
- 2019-11-22 TW TW108142613A patent/TWI807135B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009044732A1 (fr) * | 2007-10-05 | 2009-04-09 | Hitachi Chemical Company, Ltd. | Composition adhésive, matière de connexion de circuit l'utilisant, procédé de connexion d'éléments de circuit et structure de connexion de circuit |
JP2011515839A (ja) * | 2008-03-14 | 2011-05-19 | チェイル インダストリーズ インコーポレイテッド | 半導体パッケージ用複合機能テープ及びこれを用いた半導体素子の製造方法 |
JP2011018879A (ja) * | 2009-06-10 | 2011-01-27 | Sony Chemical & Information Device Corp | 絶縁性樹脂フィルム、並びにこれを用いた接合体及びその製造方法 |
WO2012014562A1 (fr) * | 2010-07-26 | 2012-02-02 | 日立化成工業株式会社 | Composition adhésive, structure de connexion, procédé de fabrication d'une structure de connexion et application de la composition adhésive |
JP2014210880A (ja) * | 2013-04-19 | 2014-11-13 | 日東電工株式会社 | 熱硬化性樹脂組成物及び半導体装置の製造方法 |
JP2017214528A (ja) * | 2016-06-02 | 2017-12-07 | 日東電工株式会社 | 真空プロセス用粘着テープ |
Also Published As
Publication number | Publication date |
---|---|
KR20210096591A (ko) | 2021-08-05 |
JP7384171B2 (ja) | 2023-11-21 |
KR102652707B1 (ko) | 2024-03-29 |
TWI807135B (zh) | 2023-07-01 |
TW202028391A (zh) | 2020-08-01 |
CN113169141A (zh) | 2021-07-23 |
JPWO2020110785A1 (ja) | 2021-10-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5900602B2 (ja) | 半導体用接着剤、フラックス剤、半導体装置の製造方法及び半導体装置 | |
JP5958529B2 (ja) | 半導体装置及びその製造方法 | |
JP5915727B2 (ja) | 半導体装置及びその製造方法 | |
JP7380926B2 (ja) | 半導体用フィルム状接着剤、半導体装置の製造方法及び半導体装置 | |
JP5867584B2 (ja) | 半導体用接着剤及び半導体装置の製造方法 | |
JP7363798B2 (ja) | 半導体用接着剤、半導体装置の製造方法及び半導体装置 | |
JP7183702B2 (ja) | 半導体用フィルム状接着剤、半導体用フィルム状接着剤の製造方法、半導体装置の製造方法及び半導体装置 | |
WO2020110785A1 (fr) | Agent adhésif de type film pour semi-conducteur, dispositif à semi-conducteur et son procédé de fabrication | |
JP7248007B2 (ja) | 半導体用接着剤及びそれを用いた半導体装置の製造方法 | |
JP2021061276A (ja) | 半導体装置の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19889265 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2020558357 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19889265 Country of ref document: EP Kind code of ref document: A1 |