CN116710599A - Plating solution and method for producing metal-filled structure - Google Patents
Plating solution and method for producing metal-filled structure Download PDFInfo
- Publication number
- CN116710599A CN116710599A CN202180090962.9A CN202180090962A CN116710599A CN 116710599 A CN116710599 A CN 116710599A CN 202180090962 A CN202180090962 A CN 202180090962A CN 116710599 A CN116710599 A CN 116710599A
- Authority
- CN
- China
- Prior art keywords
- metal
- plating solution
- insulating film
- filled
- filling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 203
- 239000002184 metal Substances 0.000 title claims abstract description 203
- 238000007747 plating Methods 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 68
- 238000011049 filling Methods 0.000 claims abstract description 65
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- -1 mercapto compound Chemical class 0.000 claims description 13
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 96
- 229910052782 aluminium Inorganic materials 0.000 description 82
- 239000004020 conductor Substances 0.000 description 79
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 78
- 239000000758 substrate Substances 0.000 description 66
- 238000011282 treatment Methods 0.000 description 62
- 239000000243 solution Substances 0.000 description 61
- 239000011148 porous material Substances 0.000 description 41
- 230000004888 barrier function Effects 0.000 description 36
- 239000010949 copper Substances 0.000 description 36
- 239000011347 resin Substances 0.000 description 33
- 229920005989 resin Polymers 0.000 description 33
- 239000007864 aqueous solution Substances 0.000 description 31
- 229910052802 copper Inorganic materials 0.000 description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 24
- 239000010407 anodic oxide Substances 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- 238000007743 anodising Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- OBDVFOBWBHMJDG-UHFFFAOYSA-M 3-sulfanylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-M 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000010931 gold Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000005304 joining Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 9
- 238000005498 polishing Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009713 electroplating Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 4
- 238000005429 filling process Methods 0.000 description 4
- NPAWNPCNZAPTKA-UHFFFAOYSA-M sodium;propane-1-sulfonate Chemical compound [Na+].CCCS([O-])(=O)=O NPAWNPCNZAPTKA-UHFFFAOYSA-M 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- AMZPPWFHMNMIEI-UHFFFAOYSA-M sodium;2-sulfanylidene-1,3-dihydrobenzimidazole-5-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C2NC(=S)NC2=C1 AMZPPWFHMNMIEI-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000010897 surface acoustic wave method Methods 0.000 description 2
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 2
- 229940103494 thiosalicylic acid Drugs 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- AGWWTUWTOBEQFE-UHFFFAOYSA-N 4-methyl-1h-1,2,4-triazole-5-thione Chemical compound CN1C=NN=C1S AGWWTUWTOBEQFE-UHFFFAOYSA-N 0.000 description 1
- CWIYBOJLSWJGKV-UHFFFAOYSA-N 5-methyl-1,3-dihydrobenzimidazole-2-thione Chemical compound CC1=CC=C2NC(S)=NC2=C1 CWIYBOJLSWJGKV-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 239000011133 lead Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/08—Perforated or foraminous objects, e.g. sieves
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
The invention provides a plating solution capable of inhibiting the variation of filling height of metal filled in a through hole and a method for manufacturing a metal filling structure by using the plating solution. The plating solution of the present invention is a plating solution used when a metal is filled in a through hole of a structure having a plurality of through holes, and contains a salt of the metal filled in the through hole and a compound having a mercapto group, wherein the content of the compound having a mercapto group is more than 0.01mg/L and less than 2000mg/L.
Description
Technical Field
The present invention relates to a plating solution and a method for producing a metal-filled structure.
Background
A metal-filled microstructure (device) in which a metal is filled in micropores provided in an insulating substrate is one of fields in which nanotechnology has been attracting attention in recent years, and is expected to be used as an anisotropic conductive member, for example.
Since the anisotropic conductive member can be electrically connected to the circuit board by simply inserting the anisotropic conductive member between the electronic component such as a semiconductor element and the circuit board and pressing the anisotropic conductive member, the anisotropic conductive member is widely used as an electrical connection member for the electronic component such as a semiconductor element or as an inspection connector for performing a functional inspection.
As a method for producing such a metal-filled microstructure, for example, patent document 1 describes the following: a method for producing a metal-filled microstructure, comprising: an anodic oxidation treatment step of performing anodic oxidation treatment on a surface of one side of an aluminum substrate, and forming an anodic oxide film having micropores in a thickness direction and a barrier layer at the bottom of the micropores on the surface of one side of the aluminum substrate; a barrier layer removal step of removing the barrier layer of the anodized film using an alkaline aqueous solution containing a metal M1 having a hydrogen overvoltage higher than that of aluminum after the anodizing step; a metal filling step of filling the inside of the micropores with a metal M2 by performing an electrolytic plating treatment after the barrier layer removing step; and a substrate removal step of removing the aluminum substrate after the metal filling step to obtain a metal-filled microstructure. "([ claim 1 ]).
Technical literature of the prior art
Patent literature
Patent document 1: international publication No. 2017/057150
Disclosure of Invention
Technical problem to be solved by the invention
As a result of examining the method for producing a known metal-filled microstructure described in patent document 1 and the like, the inventors have found that there is a possibility that the height of the metal filled in the through holes such as micropores (hereinafter, also simply referred to as "filling height") may vary depending on the plating conditions, and that there is room for improvement in the plating conditions.
Accordingly, an object of the present invention is to provide a plating solution capable of suppressing variation in filling height of a metal filled in a through hole, and a method for producing a metal-filled structure using the plating solution.
Means for solving the technical problems
As a result of intensive studies to achieve the above object, the present inventors have found that, when a plating solution containing a salt of a metal filled in a through hole and a compound having a mercapto group is used, variations in the filling height of the metal filled in the through hole can be suppressed, and completed the present invention.
That is, it has been found that the above problems can be achieved by the following configuration.
[1] A plating solution for use in filling a metal into a through hole of a structure having a plurality of through holes, which contains a salt of the metal filled in the through hole and a compound having a mercapto group,
the content of the compound with mercapto group is more than 0.01mg/L and less than 2000mg/L.
[2] The plating solution according to [1], wherein,
the compound having a mercapto group contains a sulfonic acid or a salt thereof.
[3] The plating solution according to [1] or [2], wherein,
the content of the mercapto compound is 0.1-1000 mg/L.
[4] The plating solution according to any one of [1] to [3], wherein,
The mercapto-containing compound comprises sodium 3-mercapto-1-propanesulfonate.
[5] The plating solution according to any one of [1] to [4], wherein,
the ratio of the depth of the plurality of through holes to the opening diameter is 10 or more.
[6] A method for manufacturing a metal-filled structure, wherein a metal is filled in through holes of a structure having a plurality of through holes,
the plating solution according to any one of [1] to [5] is used when filling a metal into a through hole of a structure.
Effects of the invention
According to the present invention, it is possible to provide a plating solution capable of suppressing variation in the filling height of a metal filled in a through hole, and a method for producing a metal-filled structure using the plating solution.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a metal-filled structure.
Fig. 2 is a schematic plan view showing an example of the metal-filled structure.
Fig. 3 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a metal-filled structure according to an embodiment of the present invention.
Fig. 4 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a metal-filled structure according to an embodiment of the present invention.
Fig. 5 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a metal-filled structure according to an embodiment of the present invention.
Fig. 6 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a metal-filled structure according to an embodiment of the present invention.
Fig. 7 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a metal-filled structure according to an embodiment of the present invention.
Fig. 8 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a metal-filled structure according to an embodiment of the present invention.
Fig. 9 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a metal-filled structure according to an embodiment of the present invention.
Fig. 10 is a schematic view showing an example of a joined body according to an embodiment of the present invention.
Fig. 11 is a schematic view showing another example of the joined body according to the embodiment of the present invention.
Fig. 12 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a joined body according to an embodiment of the present invention.
Fig. 13 is a schematic cross-sectional view showing one step of an example of a method for producing a joined body according to an embodiment of the present invention.
Fig. 14 is a schematic view showing one step of an example of a method for manufacturing a laminated device using the structure according to the embodiment of the present invention.
Fig. 15 is a schematic view showing one step of an example of a method for manufacturing a laminated device using the structure according to the embodiment of the present invention.
Fig. 16 is a schematic view showing one step of an example of a method for manufacturing a laminated device using the structure according to the embodiment of the present invention.
Detailed Description
The present invention will be described in detail below.
The following description of the constituent elements has been made in accordance with the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range indicated by "to" means a range including the numerical values before and after "to" as the lower limit value and the upper limit value.
[ plating solution ]
The plating solution of the present invention is a plating solution used when a metal is filled in a through hole of a structure having a plurality of through holes, and contains a salt of the metal filled in the through hole and a compound having a mercapto group, wherein the content of the compound having a mercapto group is more than 0.01mg/L and less than 2000mg/L.
In the present invention, as described above, when a plating solution containing a salt of a metal filled in a through hole and a compound having a mercapto group is used, variation in the filling height of the metal filled in the through hole can be suppressed.
Although the details are not clear, it is assumed that the following is approximately.
That is, it is considered that when a compound having a mercapto group is used, a salt (metal ion) of a metal contained in the plating solution is precipitated as a refined crystal when precipitated as a metal by plating, and therefore, the salt is uniformly precipitated in the in-plane direction of the bottom surface of the through-hole in the initial stage, and the crystal growth rate becomes uniform easily later, so that variation in the filling height of the metal filled in the through-hole can be suppressed.
[ salt of metal ]
The metal salt contained in the plating solution of the present invention is a metal salt filled in the through-holes.
Examples of the metal include a metal having a resistivity of 10 3 Specific examples of the material having an ohm·cm or less include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and zinc (Zn).
Examples of the salts of the metals include salts of oxo acids of the metals, specifically, carboxylates (e.g., formic acid, acetic acid, and benzoate), phosphates, phosphonates, sulfonates, and sulfates.
In the present invention, the salt of the metal is preferably copper sulfate (CuSO 4 ) Nickel sulfate, silver nitrate, more preferably copper sulfate.
The concentration of the metal salt contained in the plating solution is not particularly limited, but is preferably 1 to 300g/L, more preferably 100 to 200g/L.
[ Compounds having mercapto groups ]
The compound having a mercapto group contained in the plating solution of the present invention is not particularly limited as long as it has 1 or more mercapto groups in the molecule, but from the viewpoint of operability, it has 1 or 2 mercapto groups and preferably has a molecular weight of 50 to 1000.
Specific examples of the compound having a mercapto group include sodium 3-mercapto-1-propane sulfonate (hereinafter, also simply referred to as "MPS"), 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-thiazoline-2-thiol, 2-mercaptoimidazole, 3-mercapto-4-methyl-4H-1, 2, 4-triazole, sodium 5-mercapto-1H-tetrazole methane sulfonate, thiosalicylic acid (Thiosalicylic acid), sodium 2-mercaptobenzothiazole, sodium 2-mercapto-5-benzimidazole sulfonate, sodium 3- (5-mercapto-1H-tetrazole-1-yl) benzenesulfonate monohydrate, 3-mercapto-1, 2-propanediol, and the like.
In the present invention, the mercapto group-containing compound preferably contains sulfonic acid or a salt thereof, more preferably contains sodium 3-mercapto-1-propane sulfonate, for the reason that variation in filling height can be further suppressed.
In the present invention, the content of the mercapto compound is preferably 0.1 to 1000mg/L, more preferably 1 to 500 mg/L, still more preferably 10 to 400mg/L, and most preferably 20 to 300mg/L, from the viewpoint that the variation in filling height can be further suppressed.
The molar ratio of the mercapto compound to the metal salt is preferably 0.0001 to 0.01, more preferably 0.001 to 0.005.
For reasons that the effect of using the plating solution of the present invention is remarkable, the ratio of the depth of the through-hole to the opening diameter (hereinafter, also simply referred to as "aspect ratio") of the metal filled with the plating solution of the present invention is preferably 10 or more, more preferably 500 to 5000.
The aspect ratio is calculated as a ratio of an average depth of the through holes to an average opening diameter.
The average opening diameter of the through-hole can be calculated as follows: a surface photograph (for example, 500 times magnification) was taken by a field emission scanning electron microscope (Field Emission Scanning Electron Microscope: FE-SEM), and the average opening diameter was calculated as an average value of 50 points.
The average depth of the through holes is the average thickness of the structure, and can be calculated as follows: the structure was cut in the thickness direction by a Focused Ion Beam (FIB), and a surface photograph (for example, 500 times magnification) was taken of a cross section of the structure by a field emission scanning electron microscope (Field Emission Scanning Electron Microscope: FE-SEM), and the average depth was calculated as an average value of 10 points.
[ acid ]
The plating solution of the present invention preferably contains an acid, more preferably an aqueous solution containing an acid.
Specific examples of such acids include hydrochloric acid, sulfuric acid, and phosphoric acid.
Among these, hydrochloric acid or sulfuric acid is preferable, and hydrochloric acid and sulfuric acid are more preferable in combination.
[ additives ]
In addition to the above components, the plating solution of the present invention may contain additives such as a sulfur-based saturated organic compound, a polymer component, and a surfactant, in addition to the above mercapto group-containing compound.
Specific examples of the sulfur-based saturated organic compound include 3,3' -dithiobis (sodium propane sulfonate).
In the present invention, the content in the case of containing 3,3' -dithiobis (sodium propane sulfonate) is preferably 15 to 500 parts by mass relative to 100 parts by mass of the above-mentioned mercapto group-containing compound, for the reason that the variation in filling height can be further suppressed.
Specific examples of the polymer component include polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymer.
As the surfactant, a surfactant whose hydrophilic portion is ionic (cationic, anionic, or amphoteric) or a surfactant whose nonionic (nonion) can be used, but a cationic surfactant is preferable in terms of avoiding occurrence of bubbles or the like on the surface of the plating object.
[ method for producing Metal-filled Structure ]
The method for producing a metal-filled structure of the present invention is a method for producing a metal-filled structure by filling a metal into a through hole of a structure having a plurality of through holes, and is a method for producing a metal-filled structure by using the plating solution of the present invention described above when filling a metal into a through hole of a structure.
The method for producing a metal-filled structure of the present invention can use a conventionally known method other than the above-described plating solution of the present invention when filling metal into the through-holes of the structure (metal filling step), and for example, a method described in japanese patent application laid-open publication No. 2008-270157, a method described in international publication No. 2017/057150, a method described in international publication No. 2018/155273, a method described in japanese patent application laid-open publication No. 2019-153415, and the like can be used.
Hereinafter, the structure of a metal-filled structure (hereinafter, also simply referred to as "structure") produced by the method for producing a metal-filled structure of the present invention will be specifically described.
The structure 10 shown in fig. 1 includes: an insulating film 12 having electrical insulation properties; and a plurality of conductors 14 penetrating the insulating film 12 in the thickness direction Dt and provided in an electrically insulated state from each other. The conductor 14 protrudes from at least one face of the insulating film 12 in the thickness direction Dt. In the case where the conductor 14 protrudes from at least one surface of the insulating film 12 in the thickness direction Dt, it is preferable that the conductor protrudes from the front surface 12a or the rear surface 12b in a structure protruding from one surface.
The structure 10 has a resin layer 20 partially covering the surface of the insulating film 12 from which the conductors 14 protrude. That is, the resin layer 20 is provided not on the entire surface 12a and the entire surface of the back surface 12b of the insulating film 12 but on the surface 12a of the insulating film 12 and on the back surface 12b of the insulating film 12. The insulating film 12 is constituted by, for example, an anodic oxide film 15.
The plurality of conductors 14 are arranged in the insulating film 12 in a state of being electrically insulated from each other. In this case, for example, the insulating film 12 has a plurality of pores 13 penetrating in the thickness direction Dt. A conductor 14 is provided in the plurality of pores 13. The conductor 14 protrudes from the surface 12a of the insulating film 12 in the thickness direction Dt.
The conductor 14 protrudes from the rear surface 12b of the insulating film 12 in the thickness direction Dt. A resin layer 20 having a surface partially covering the insulating film 12 on which the conductors 14 protrude.
The resin layer 20 has a resin layer portion 20a and a space 20b. The resin layer 20 has a resin layer portion 20a partially disposed on the surface 12a of the insulating film 12 with a space 20b left, and the resin layer portion 20a covers the protruding portion 14a of the conductor 14. The protruding portion 14a is buried in the resin layer portion 20 a.
A resin layer portion 20a is partially disposed on the rear surface 12b of the insulating film 12 so as to leave a space 20b, and the resin layer portion 20a covers the protruding portion 14b of the conductor 14. The protruding portion 14b is buried in the resin layer portion 20 a. The structure 10 is an anisotropic conductive structure having conductivity in the thickness direction Dt, but conductivity in a direction parallel to the surface 12a of the insulating film 12 is sufficiently low.
As shown in fig. 2, the structural body 10 has a rectangular outer shape, for example. The outer shape of the structure 10 is not limited to a rectangular shape, and may be, for example, a circular shape. The outer shape of the structure 10 may be a shape according to the application, ease of production, and the like.
By providing the structure 10 with the resin layer 20 (partially covering the surface of the insulating film 12 on which the conductors 14 protrude as described above), the space 20b is present in the resin layer 20, and thus the generated static electricity can be discharged, and electrification can be suppressed. This suppresses electrification during conveyance of the structure 10 and the like, and improves operability.
Further, the resin layer 20 is partially provided on the surface of the insulating film 12, and when the structural body 10 is inserted between an electronic component such as a semiconductor element and a circuit board and bonded by pressing, the resin layer 20 to be removed can be reduced, a large force is not required for pressing, and the force required for bonding can be reduced. Therefore, for example, the size of the bonding apparatus can be suppressed from increasing.
Hereinafter, the structure of the structure will be specifically described.
[ insulating film ]
The insulating film 12 is an insulating film that electrically insulates a plurality of conductors 14 made of an electric conductor from each other. The insulating film has electrical insulation. The insulating film 12 has a plurality of pores 13 in which conductors 14 are formed.
The insulating film is made of, for example, an inorganic material. For example, an insulating film having 10 can be used 14 An insulating film having a resistivity of about Ω·cm.
The term "formed of an inorganic material" refers to a specification for distinguishing from a polymer material, and is not limited to a specification of an insulating base material formed of only an inorganic material, but a specification of an inorganic material as a main component (50 mass% or more). As described above, the insulating film is constituted of, for example, an anodic oxide film.
The insulating film may be made of, for example, a ceramic such as a metal oxide, a metal nitride, glass, silicon carbide, or silicon nitride, a carbon substrate such as diamond-like carbon, polyimide, or a composite material thereof. In addition to this, for example, an insulating film formed of an inorganic material containing 50 mass% or more of a ceramic material or a carbon material may be formed on an organic material having a through hole.
The length of the insulating film 12 in the thickness direction Dt, that is, the thickness of the insulating film 12 is preferably in the range of 1 to 1000 μm, more preferably in the range of 5 to 500 μm, and even more preferably in the range of 10 to 300 μm. When the thickness of the insulating film 12 is within this range, the operability of the insulating film 12 becomes good.
From the viewpoint of ease of winding, the thickness ht of the insulating film 12 is preferably 30 μm or less, more preferably 5 to 20 μm.
The thickness of the anodized film was calculated as follows: the anodized film was cut in the thickness direction Dt by a Focused Ion Beam (FIB), and a surface photograph (5-ten thousand times magnification) was taken of a cross section of the anodized film by a field emission scanning electron microscope (FE-SEM), and the thickness of the anodized film was calculated as an average value of 10 points.
The interval between the conductors 14 in the insulating film 12 is preferably 5nm to 800nm, more preferably 10nm to 200nm, and even more preferably 20nm to 60nm. When the interval between the conductors 14 in the insulating film 12 is within the above range, the insulating film 12 sufficiently functions as a partition wall of electrical insulation of the conductors 14.
Here, the interval between the conductors is the width between the adjacent conductors, the cross section of the structure 10 is observed at 20 ten thousand times by a field emission scanning electron microscope, and the average value of the width between the adjacent conductors is measured at 10 points.
< average diameter of pores >
The average diameter of the fine pores is preferably 1 μm or less, more preferably 5 to 500nm, further preferably 20 to 400nm, still more preferably 40 to 200nm, and most preferably 50 to 100nm. If the average diameter d of the pores 13 is 1 μm or less and within the above range, a conductor 14 having the above average diameter can be obtained.
The average diameter of the pores 13 is measured by a scanning electron microscope at a magnification of 100 to 10000 times, and a photographic image is obtained by photographing the surface of the insulating film 12 from directly above. In the photographic image, at least 20 pores connected in a ring shape around the circumference are extracted, the diameter thereof is measured and used as an opening diameter, and the average value of the opening diameters is calculated as the average diameter of the pores.
The magnification can be appropriately selected in the above range to obtain a photographic image in which 20 or more micropores can be extracted. The maximum value of the distance between the end portions of the pore portion was measured for the opening diameter. That is, the shape of the opening of the pore is not limited to a substantially circular shape, and therefore, when the shape of the opening is non-circular, the maximum value of the distance between the end portions of the pore is defined as the opening diameter. Therefore, for example, even in the case of a pore having a shape in which 2 or more pores are integrated, it is regarded as 1 pore, and the maximum value of the distance between the end portions of the pore portions is regarded as the opening diameter.
[ alpha conductor ]
As described above, the plurality of conductors 14 are provided in the anodized film in a state of being electrically insulated from each other.
The plurality of conductors 14 have conductivity. The conductor is made of a conductive material. The conductive material is not particularly limited, and examples thereof include metals. Specific examples of the metal include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), and nickel (Ni) as appropriate. Copper, gold, aluminum, and nickel are preferable, copper and gold are more preferable, and copper is most preferable from the viewpoint of conductivity.
In addition to metals, oxide conductive substances may be mentioned. Examples of the oxide conductive substance include indium-doped tin oxide (ITO). However, since metals are excellent in ductility and are easily deformed as compared with oxide conductors, and are also easily deformed by compression at the time of joining, metals are preferable.
For example, the conductor may be made of a conductive resin containing nanoparticles of Cu, ag, or the like.
The height H of the conductor 14 in the thickness direction Dt is preferably 10 to 300 μm, more preferably 20 to 30 μm.
< shape of conductor >
The average diameter d of the conductor 14 is preferably 1 μm or less, more preferably 5 to 500nm, further preferably 20 to 400nm, still more preferably 40 to 200nm, and most preferably 50 to 100nm.
The density of conductors 14 is preferably 2 ten thousand/mm 2 The above, more preferably 200 ten thousand/mm 2 The above, more preferably 1000 ten thousand/mm 2 Above, particularly preferably 5000 ten thousand/mm 2 The above is most preferably 1 hundred million/mm 2 The above.
The center-to-center distance p between adjacent conductors 14 is preferably 20nm to 500nm, more preferably 40nm to 200nm, and even more preferably 50nm to 140nm.
As for the average diameter of the conductor, a scanning electron microscope was used to capture the surface of the anodized film from directly above at a magnification of 100 to 10000 times to obtain a captured image. In the photographic image, at least 20 conductors connected in a ring shape around the circumference are extracted, the diameters thereof are measured and used as opening diameters, and the average value of the opening diameters is calculated as the average diameter of the conductors.
The magnification can be appropriately selected in the above range to obtain a photographic image in which 20 or more conductors can be extracted. The opening diameter is measured as the maximum value of the distance between the ends of the conductor portions. That is, the shape of the opening of the conductor is not limited to a substantially circular shape, and when the shape of the opening is non-circular, the maximum value of the distance between the ends of the conductor portions is defined as the opening diameter. Therefore, for example, even in the case of a conductor having a shape in which 2 or more conductors are integrated, it is regarded as 1 conductor, and the maximum value of the distance between the ends of the conductor portions is regarded as the opening diameter.
[ example of a method for producing a Structure ]
Fig. 3 to 9 are schematic cross-sectional views showing an example of a method for manufacturing a structure according to an embodiment of the present invention in the order of steps. In fig. 3 to 9, the same components as those of the structures shown in fig. 1 and 2 are denoted by the same reference numerals, and detailed description thereof is omitted.
In an example of the method for manufacturing the structure, a case where the insulating film 12 in the structure 10 shown in fig. 1 is formed of an anodic oxide film of aluminum will be described as an example. An aluminum substrate is used for forming an anodic oxide film of aluminum. Accordingly, in an example of a method for manufacturing a structure, first, an aluminum substrate 30 is prepared as shown in fig. 3.
The aluminum substrate 30 is appropriately sized and has a thickness according to the thickness of the insulating film 12 of the structure 10 (see fig. 1) to be finally obtained, a processing apparatus, and the like. The aluminum substrate 30 is, for example, a rectangular plate material. The present invention is not limited to the aluminum substrate, and a metal substrate capable of forming the electrically insulating film 12 can be used.
Next, the surface 30a (see fig. 3) on one side of the aluminum substrate 30 is anodized. As a result, the surface 30a (see fig. 3) on one side of the aluminum substrate 30 is anodized, and as shown in fig. 4, an anodized film 15, which is an insulating film 12, is formed, and the insulating film 12 has a plurality of pores 13 extending in the thickness direction Dt of the aluminum substrate 30. At the bottom of each pore 13 there is a barrier layer 31. The step of performing the above-described anodic oxidation is referred to as an anodic oxidation treatment step.
In the insulating film 12 having the plurality of pores 13, as described above, the barrier layer 31 is present at the bottom of each pore 13, and the barrier layer 31 is removed as shown in fig. 4. Thereby, the insulating film 12 having the plurality of fine holes 13 without the barrier layer 31 is obtained (refer to fig. 5). The step of removing the barrier layer 31 is referred to as a barrier layer removal step.
In the barrier removal step, the barrier layer 31 of the insulating film 12 is removed by using an alkaline aqueous solution containing ions of the metal M1 having a higher hydrogen overvoltage than aluminum, and a metal layer 35a (see fig. 5) made of the metal (metal M1) is formed on the surface 32d (see fig. 5) of the bottom 32c (see fig. 5) of the pore 13. Thereby, the aluminum substrate 30 exposed to the fine holes 13 is covered with the metal layer 35 a. Thus, when the fine holes 13 are filled with metal by plating, plating is easy, and the metal is prevented from being insufficiently filled in the fine holes, and the metal is prevented from being not filled in the fine holes, so that formation defects of the conductor 14 are prevented.
The alkaline aqueous solution containing the ions of the metal M1 may further contain a compound containing aluminum ions (sodium aluminate, aluminum hydroxide, aluminum oxide, etc.). The content of the compound containing aluminum ions is preferably 0.1 to 20g/L, more preferably 0.3 to 12g/L, and still more preferably 0.5 to 6g/L in terms of the amount of aluminum ions.
Next, plating is performed from the surface 12a of the insulating film 12 having the plurality of fine holes 13 extending in the thickness direction Dt. In this case, the metal layer 35a can be used as an electrode for plating. The metal 35b is used for plating, and the plating is performed starting from the metal layer 35a formed on the surface 32d (see fig. 5) of the bottom 32c (see fig. 5) of the pore 13. As a result, as shown in fig. 6, the metal 35b constituting the conductor 14 is filled in the pores 13 of the insulating film 12. By filling the metal 35b in the pores 13, the conductive conductor 14 is formed. In addition, the metal layer 35a and the metal 35b are collectively referred to as the filled metal 35.
The step of filling the fine holes 13 of the insulating film 12 with the metal 35b is referred to as a metal filling step. As described above, the conductor 14 is not limited to being made of metal, and a conductive material can be used. Electroplating is used in the metal filling step, and the metal filling step will be described in detail later. The surface 12a of the insulating film 12 corresponds to one surface of the insulating film 12.
After the metal filling process, as shown in fig. 7, a part of the surface 12a of the insulating film 12 on the side where the aluminum substrate 30 is not provided is removed in the thickness direction Dt after the metal filling process so that the metal 35 filled in the metal filling process protrudes more than the surface 12a of the insulating film 12. That is, the conductor 14 is made more protruding than the surface 12a of the insulating film 12. Thereby, the protruding portion 14a can be obtained. The step of projecting the conductor 14 more than the surface 12a of the insulating film 12 is referred to as a surface metal projecting step.
After the surface metal protrusion process, the aluminum substrate 30 is removed as shown in fig. 8. The step of removing the aluminum substrate 30 is referred to as a substrate removal step.
Next, as shown in fig. 9, after the substrate removal step, the rear surface 12b, which is the surface of the insulating film 12 on the side where the aluminum substrate 30 is provided, is removed in the thickness direction Dt so that the metal 35, that is, the conductor 14, filled in the metal filling step protrudes more than the rear surface 12b of the insulating film 12. Thereby, the protruding portion 14b can be obtained.
The front metal projection step and the rear metal projection step may be two steps, but may be one step of the front metal projection step and the rear metal projection step. The front metal projecting step and the rear metal projecting step correspond to the "projecting step", and the front metal projecting step and the rear metal projecting step are both projecting steps.
As shown in fig. 9, conductors 14 each having a protruding portion 14a and a protruding portion 14b protrude from the front surface 12a and the rear surface 12b of the insulating film 12.
Next, a resin layer 20 is partially formed on the front surface 12a and the back surface 12b of the insulating film 12 on which the conductors 14 protrude (see fig. 1). This can obtain the structure 10 shown in fig. 1. The resin layer 20 may be, for example, a pattern shown in fig. 3 or 4. The process of forming the resin layer 20 will be described later.
In addition, in the case where the conductor 14 is not protruded from the rear surface 12b of the insulating film 12, the resin layer 20 is formed on the front surface 12a of the insulating film 12 in the state shown in fig. 8, whereby the structure 10 is obtained.
In the barrier layer removal step, the barrier layer is removed by using an alkaline aqueous solution containing ions of the metal M1 having a higher hydrogen overvoltage than aluminum, and not only the barrier layer 31 but also the metal layer 35a of the metal M1 which is less likely to generate hydrogen than aluminum is formed on the aluminum substrate 30 exposed at the bottom of the pores 13. As a result, the in-plane uniformity of the metal filling becomes good. This is thought to be because the generation of hydrogen gas by the plating solution is suppressed, and the metal filling is easily performed by the electrolytic plating.
In addition, a holding step is provided in the barrier layer removal step, in which the metal is held at a voltage (holding voltage) selected from the range of not less than 95% and not more than 105% of the voltage (voltage) less than 30% of the voltage in the anodizing step for a total of not less than 5 minutes, and by using an alkaline aqueous solution containing metal M1 ions in combination, it has been found that the uniformity of metal filling at the time of plating treatment is significantly improved. Therefore, the holding step is preferable.
The detailed mechanism is not clear, but it is considered that the reason for this is that, in the barrier layer removal step, the metal M1 layer is formed under the barrier layer by using an alkaline aqueous solution containing metal M1 ions, and thus, the interface between the aluminum substrate and the anodic oxide film is prevented from being damaged, and the uniformity of dissolution of the barrier layer is improved.
In the barrier removal step, the metal layer 35a made of metal (metal M1) is formed at the bottom of the pores 13, but the present invention is not limited thereto, and only the barrier layer 31 is removed to expose the aluminum substrate 30 at the bottom of the pores 13. In a state where the aluminum substrate 30 is exposed, the aluminum substrate 30 may be used as an electrode for electrolytic plating.
[ anodic oxide film ]
As described above, for the reason that pores having a desired average diameter are formed and a conductor is easily formed, for example, an anodic oxide film of aluminum is used for the anodic oxide film. However, the present invention is not limited to an anodic oxide film of aluminum, and an anodic oxide film of a valve metal can be used. Therefore, valve metal is used for the metal substrate.
Specifically, examples of the valve metal include tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, and antimony in addition to the aluminum. Among these, an anodized film of aluminum is preferable in terms of good dimensional stability and relatively low cost. Therefore, it is preferable to manufacture the structure using an aluminum substrate.
The thickness of the anodic oxide film is the same as the thickness ht of the insulating film 12.
[ Metal substrate ]
The metal substrate is used for manufacturing a structure, and is used for forming an anodic oxide film. For example, as described above, a metal substrate capable of forming an anodic oxide film can be used as the metal substrate, and a metal substrate composed of the valve metal can be used. For example, as described above, an aluminum substrate is used as the metal substrate for the reason that an anodic oxide film is easily formed.
[ aluminum substrate ]
The aluminum substrate used for forming the insulating film 12 is not particularly limited, and specific examples thereof include: a pure aluminum plate; an alloy sheet containing aluminum as a main component and a trace amount of a different element; a substrate on which high-purity aluminum is vapor-deposited on low-purity aluminum (for example, recycled material); a substrate made of high-purity aluminum coated on the surface of a silicon wafer, quartz, glass, or the like by vapor deposition, sputtering, or the like; an aluminum-laminated resin substrate; etc.
In the aluminum substrate, the purity of aluminum on the surface of the one side on which the anodized film is formed by the anodizing treatment is preferably 99.5 mass% or more, more preferably 99.9 mass% or more, and still more preferably 99.99 mass% or more. If the purity of aluminum is within the above range, the order of the micropore arrangement becomes sufficient.
The aluminum substrate is not particularly limited as long as it can form an anodized film, and for example, a material of 1050 in JIS (Japanese Industrial Standards japanese industrial standard) is used.
The surface of the anodized single side of the aluminum substrate is preferably subjected to a heat treatment, degreasing treatment, and mirror finishing treatment in advance.
Here, the heat treatment, degreasing treatment, and mirror finishing treatment can be performed in the same manner as the treatments described in paragraphs [0044] to [0054] of jp 2008-270158 a.
The mirror finishing treatment before the anodic oxidation treatment is, for example, electrolytic polishing, and electrolytic polishing is, for example, performed using an electrolytic polishing liquid containing phosphoric acid.
[ anodic oxidation treatment Process ]
The anodic oxidation treatment can be performed by a conventionally known method, and is preferably performed by a self-ordering method or a constant voltage treatment in order to improve the order of the micropores and to ensure anisotropic conductivity of the structure.
Here, the self-ordering method and the constant voltage treatment of the anodic oxidation treatment can be performed in the same manner as the treatments described in paragraphs [0056] to [0108] and [ fig. 3] of japanese patent application laid-open No. 2008-270158.
[ holding step ]
The method for manufacturing the structure may include a holding step. The holding step is as follows: after the anodizing step, the substrate is held at a voltage of 95% or more and 105% or less in a range selected from 1V or more and less than 30% of the voltage in the anodizing step for a total of 5 minutes or more. In other words, the holding step is the following step: after the anodizing step, an electrolytic treatment is performed for a total of 5 minutes or more at a voltage of 95% or more and 105% or less of a holding voltage selected from the range of 1V or more and less than 30% of the voltage in the anodizing step.
Here, the "voltage in the anodic oxidation treatment" means a voltage applied between aluminum and the counter electrode, and for example, when the electrolysis time by the anodic oxidation treatment is 30 minutes, the average value of the voltage held for 30 minutes is represented.
The voltage in the holding step is preferably 5% to 25% of the voltage in the anodic oxidation treatment, more preferably 5% to 20% from the viewpoint of controlling the thickness of the side wall of the anodic oxide film, that is, the thickness of the barrier layer to an appropriate thickness with respect to the depth of the pores.
Further, for the reason of further improving the in-plane uniformity, the total holding time in the holding step is preferably 5 minutes to 20 minutes, more preferably 5 minutes to 15 minutes, and still more preferably 5 minutes to 10 minutes.
The holding time in the holding step may be 5 minutes or more in total, and preferably 5 minutes or more in succession.
The voltage in the holding step may be set to be continuously or stepwise decreased from the voltage in the anodizing step to the voltage in the holding step, but is preferably set to be 95% to 105% of the holding voltage within 1 second after the end of the anodizing step for the reason of further improving the in-plane uniformity.
The holding step may be performed continuously with the anodizing step by, for example, lowering the electrolytic potential at the end of the anodizing step.
The holding step may use the same electrolytic solution and the same treatment conditions as those of the conventional known anodic oxidation treatment, except for the electrolytic potential.
In particular, when the holding step and the anodizing step are performed continuously, it is preferable to use the same electrolytic solution for the treatment.
In the anodic oxide film having a plurality of micropores, as described above, a barrier layer (not shown) is present at the bottom of the micropores. And a barrier layer removing step of removing the barrier layer.
[ Barrier removal Process ]
The barrier layer removal step is a step of removing the barrier layer of the anodized film using, for example, an alkaline aqueous solution containing metal M1 ions having a higher hydrogen overvoltage than aluminum.
The barrier layer is removed by the barrier layer removal step, and a conductive layer made of metal M1 is formed at the bottom of the micropores.
Here, the hydrogen overvoltage (hydrogen overvoltage) is a voltage required for generating hydrogen, and for example, the hydrogen overvoltage of aluminum (Al) is-1.66V (J.J.Chem.1982, (8), p 1305-1313). In addition, examples of the metal M1 having a higher hydrogen overvoltage than aluminum and hydrogen overvoltage values thereof are shown below.
<Metal M1 and hydrogen (1N H) 2 SO 4 ) Overvoltage device>
Platinum (Pt): 0.00V
Gold (Au): 0.02V
Silver (Ag): 0.08V
Nickel (Ni): 0.21V
Copper (Cu): 0.23V
Tin (Sn): 0.53V
Zinc (Zn): 0.70V
The micropores 13 can also be formed by expanding the micropores and removing the barrier layer. In this case, the Pore width (Pore width) treatment is used for expanding the micropores. The pore width treatment is a treatment of immersing the anodic oxide film in an acidic aqueous solution or an alkaline aqueous solution to dissolve the anodic oxide film and expand the pore diameter of the micropores. For the pore width treatment, an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or a mixture thereof, or an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide, or the like can be used.
In addition, the barrier layer at the bottom of the micropores can also be removed by a pore width treatment, and by using an aqueous sodium hydroxide solution in the pore width treatment, the micropores are expanded in diameter and the barrier layer is removed.
[ Metal filling procedure ]
< Metal for Metal filling procedure >
In the metal filling step, the metal filled as the conductor in the pores 13 and the metal constituting the metal layer preferably have a resistivity of 10 in order to form the conductor 3 Omega cm or less. Specific examples of the metal include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and zinc (Zn) as appropriate.
The conductor is preferably copper (Cu), gold (Au), aluminum (Al), or nickel (Ni), more preferably copper (Cu), or gold (Au), and even more preferably copper (Cu), from the viewpoints of conductivity and formation by plating.
< plating method >
The plating method for filling the metal into the pores is not particularly limited as long as the plating solution of the present invention is used, and for example, an electrolytic plating method or an electroless plating method can be used.
Here, in the conventionally known electrolytic plating method for coloring and the like, it is difficult to selectively deposit (grow) a metal in a hole with a high aspect ratio. This is thought to be because the precipitated metal is consumed in the pores and plating does not grow even when electrolysis is performed for a predetermined time or longer.
Therefore, in the case of filling metal by the electrolytic plating method, it is necessary to set an interruption time at the time of pulse electrolysis or constant potential electrolysis. The interruption time is preferably 30 to 60 seconds, which is 10 seconds or longer.
In order to promote stirring of the electrolyte, it is also preferable to apply ultrasonic waves.
The electrolysis voltage is usually 20V or less, preferably 10V or less, but the deposition potential of the target metal in the electrolyte to be used is measured in advance, and it is preferable to perform constant potential electrolysis within +1v of the potential. In addition, when constant potential electrolysis is performed, it is preferable to use cyclic voltammetry in combination, and Potentiostat (potential stat) devices such as Solartron corporation, BAS inc., HOKUTO DENKO corp., IVIUM corporation, etc. can be used.
[ substrate removal Process ]
The substrate removal step is a step of removing the aluminum substrate after the metal filling step. The method for removing the aluminum substrate is not particularly limited, and for example, a method for removing the aluminum substrate by dissolution is preferable.
< dissolution of aluminum substrate >
In the dissolution of the aluminum substrate, a treatment liquid which is not easily dissolved in the anodic oxide film and easily dissolves aluminum is preferably used.
The dissolution rate of the treatment liquid in aluminum is preferably 1 μm/min or more, more preferably 3 μm/min or more, and still more preferably 5 μm/min or more. Similarly, the dissolution rate of the anodic oxide film is preferably 0.1 nm/min or less, more preferably 0.05 nm/min or less, and still more preferably 0.01 nm/min or less.
Specifically, the treatment liquid contains at least 1 metal compound having a lower ionization tendency than aluminum and has a pH (hydrogen ion index) of preferably 4 or less or 8 or more, more preferably 3 or less or 9 or more, and still more preferably 2 or less or 10 or more.
The treatment liquid for dissolving aluminum is preferably an aqueous acid or alkali solution, and is prepared by mixing, for example, compounds of manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum, gold (for example, chloroplatinic acid), these fluorides, these chlorides, and the like.
Among these, an acidic aqueous solution base is preferable, and mixed chlorides are preferable.
In particular, from the viewpoint of the treatment range, a treatment solution in which mercury chloride is mixed in an aqueous hydrochloric acid solution (hydrochloric acid/mercury chloride) and a treatment solution in which copper chloride is mixed in an aqueous hydrochloric acid solution (hydrochloric acid/copper chloride) are preferable.
The composition of the treatment liquid for dissolving aluminum is not particularly limited, and for example, a bromine/methanol mixture, a bromine/ethanol mixture, aqua regia, and the like can be used.
The concentration of the acid or alkali in the treatment solution for dissolving aluminum is preferably 0.01 to 10mol/L, more preferably 0.05 to 5mol/L.
The treatment temperature using the treatment solution for dissolving aluminum is preferably-10 to 80 ℃, and more preferably 0 to 60 ℃.
The aluminum substrate is dissolved by bringing the aluminum substrate after the plating step into contact with the treatment liquid. The contact method is not particularly limited, and examples thereof include a dipping method and a spraying method. Among them, the impregnation method is preferable. The contact time in this case is preferably 10 seconds to 5 hours, more preferably 1 minute to 3 hours.
Further, a support may be provided on the insulating film 12, for example. The support body preferably has the same outer shape as the insulating film 12. By attaching the support body, operability is improved.
[ protruding procedure ]
When removing a part of the insulating film 12, for example, aluminum oxide (Al) which is an insulating film 12 is dissolved without dissolving the metal constituting the conductor 14 2 O 3 ) An acidic aqueous solution or a basic aqueous solution. By bringing the above-mentioned acidic aqueous solution or alkaline aqueous solution into contact with the insulating film 12 having the metal-filled fine holes 13, a part of the insulating film 12 is removed. The method of bringing the acidic aqueous solution or the alkaline aqueous solution into contact with the insulating film 12 is not particularly limited, and examples thereof include a dipping method and a spraying method. Among them, the impregnation method is preferable.
In the case of using an acidic aqueous solution, an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or a mixture thereof is preferably used. Among them, an aqueous solution containing no chromic acid is preferable in terms of excellent safety. The concentration of the acidic aqueous solution is preferably 1 to 10 mass%. The temperature of the acidic aqueous solution is preferably 25 to 60 ℃.
When an alkaline aqueous solution is used, at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide is preferably used. The concentration of the alkaline aqueous solution is preferably 0.1 to 5 mass%. The temperature of the alkaline aqueous solution is preferably 20 to 35 ℃.
Specifically, for example, 50g/L of an aqueous phosphoric acid solution at 40℃or 0.5g/L of an aqueous sodium hydroxide solution at 30℃or 0.5g/L of an aqueous potassium hydroxide solution at 30℃is preferably used.
The immersion time for the acidic aqueous solution or the alkaline aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, and even more preferably 15 to 60 minutes. Here, the dipping time refers to the total of the dipping times when the dipping treatment is repeated for a short period of time. In addition, a cleaning process may be performed during each dipping process.
Even if the metal 35 protrudes the conductor 14 from the front surface 12a or the rear surface 12b of the insulating film 12, the conductor 14 is preferably protruded from the front surface 12a or the rear surface 12b of the insulating film 12 by 10nm to 1000nm, and more preferably protruded from 50nm to 500nm. That is, the protruding amount of the protruding portion 14a from the front surface 12a and the protruding amount of the conductor 14 of the protruding portion 14b from the rear surface 12b are preferably 10nm to 1000nm, more preferably 50nm to 500nm, respectively.
The heights of the protruding portions 14a and 14b of the conductor 14 are average values of the heights of the protruding portions of the conductor measured at 10 points by observing the cross section of the structure 10 with a field emission scanning electron microscope at a magnification of 2 ten thousand times.
In the case of strictly controlling the height of the protruding portion of the conductor 14, it is preferable to fill the inside of the pore 13 with a conductive material such as a metal, then process the conductive material so that the insulating film 12 and the end of the conductive material such as a metal are flush with each other, and then selectively remove the anodized film.
After the metal is filled or after the protruding step, a heat treatment can be performed to relieve the strain in the conductor 14 caused by the metal filling.
From the viewpoint of suppressing oxidation of the metal, the heat treatment is preferably performed in a reducing atmosphere, specifically, preferably performed at an oxygen concentration of 20Pa or less, more preferably performed under vacuum. Here, vacuum refers to a space state in which at least one of the gas density and the gas pressure is lower than the atmosphere.
For correction purposes, it is preferable to apply stress to the insulating film 12 and perform heat treatment.
[ method for producing joined body ]
Another aspect of the present invention provides a method for manufacturing a joined body, wherein a joining step of joining a conductive member including a conductive portion having conductivity to the above-described structure by bringing a conductor of the structure into contact with the conductive portion is performed.
As a method for manufacturing the bonded body, a method for manufacturing the laminated device 40 having the anisotropic conductive member 45 shown in fig. 10 will be described.
Fig. 12 and 13 are schematic cross-sectional views showing an example of a method for manufacturing a joined body according to an embodiment of the present invention in the order of steps. In fig. 12 and 13, the same components as those of the stacked device 40 and the semiconductor elements 42 and 44 shown in fig. 10 and 11 are denoted by the same reference numerals, and detailed description thereof is omitted.
The method of manufacturing the stacked device 40 shown in fig. 12 and 13 relates to a chip-on-chip.
In manufacturing the laminated device 40 having the anisotropic conductive member 45, the semiconductor element 42, the semiconductor element 44, and the anisotropic conductive member 45 shown in fig. 12 are first prepared. The semiconductor element 42 includes, for example, a plurality of electrodes 52 for exchanging signals with the outside and for transmitting and receiving voltages or currents in the semiconductor element portion 50. Each electrode 52 is electrically insulated by an insulating layer 54. The electrode 52 protrudes, for example, more than the surface 54a of the insulating layer 54.
The semiconductor element 44 has the same structure as the semiconductor element 42. The semiconductor element 44 is provided with a plurality of electrodes 53 for exchanging signals with the outside and for transmitting and receiving voltages or currents, for example, on the interposer substrate 51. Each electrode 53 is electrically insulated by an insulating layer 55. The electrode 53 protrudes, for example, more than the surface 55a of the insulating layer 55. The interposer 51 has, for example, an extraction wiring layer, and the stacked device 40 is electrically connected to the outside through the electrode 53.
The anisotropic conductive member 45 includes a plurality of conductors 14, and the conductors 14 include protruding portions 14a protruding from the front surface 12a of the insulating film 12 and protruding portions 14b protruding from the rear surface 12b. Further, the resin layer 20 is partially provided on the front surface 12a and the back surface 12b of the insulating film 12, respectively. Since the anisotropic conductive member 45 has the same structure as the structure 10, a detailed description thereof is omitted.
As shown in fig. 12, the semiconductor element 42 and the semiconductor element 44 are arranged to face the electrode 53 and the electrode 52 with the anisotropic conductive member 45 interposed therebetween.
At this time, alignment is performed using alignment marks (not shown) provided on the semiconductor elements 42 and 44 and the anisotropic conductive member 45, respectively.
The alignment using the alignment mark is not particularly limited, and a known alignment method can be appropriately used, for example, an image or a reflection image of the alignment mark can be obtained, and positional information of the alignment mark can be obtained.
Next, the semiconductor element 42, the anisotropic conductive member 45, and the semiconductor element 44 are brought close to each other, and as shown in fig. 13, the semiconductor element 42, the anisotropic conductive member 45, and the semiconductor element 44 are stacked, and the semiconductor element 42, the anisotropic conductive member 45, and the semiconductor element 44 are bonded in a state where the semiconductor element 42, the anisotropic conductive member 45, and the semiconductor element 44 are aligned. Thereby, the semiconductor element 42, the anisotropic conductive member 45, and the semiconductor element 44 are bonded, and the stacked device 40 can be obtained.
In this way, the joined body can be obtained through the joining step of joining the conductive member including the conductive portion having conductivity to the structure by bringing the conductor of the structure into contact with the conductive portion.
In addition, in the anisotropic conductive member 45, the resin layer 20 is partially provided on the front surface 12a and the back surface 12b of the insulating film 12, respectively. Therefore, charging can be suppressed when the anisotropic conductive member 45 is conveyed, and processing becomes easy, so that the anisotropic conductive member 45 can be easily arranged between the semiconductor element 42 and the semiconductor element 44.
Also, at the time of joining, since the resin layer 20 is partially provided, the force required for joining can be reduced.
[ example of a method for manufacturing a laminate device ]
Next, an example of a method for manufacturing a device using a structure will be described with reference to the laminated device 40 shown in fig. 10.
An example of a method for manufacturing a stacked device using a structure is related to a chip on a wafer.
Fig. 14 to 16 are schematic views showing an example of a method for manufacturing a laminated device using the structure according to the embodiment of the present invention in order of steps.
In an example of a method for manufacturing a laminated device using a structure, a plurality of element regions (not shown) are provided on the surface 60a of the first semiconductor wafer 60, and an anisotropic conductive member 45 is provided for each element region.
Next, the semiconductor element 44 is disposed toward c of the first semiconductor wafer 60. The semiconductor element 44 has an electrode (not shown).
Next, alignment of the semiconductor element 44 with respect to the first semiconductor wafer 60 is performed using the alignment mark of the semiconductor element 44 and the alignment mark of the first semiconductor wafer 60.
In addition, the alignment is not particularly limited as long as digital image data can be obtained with respect to the image or reflection image of the alignment mark of the first semiconductor wafer 60 and the image or reflection image of the alignment mark of the semiconductor element 44, and a known image pickup device can be appropriately used.
Next, the semiconductor element 44 is placed on the anisotropic conductive member 45 provided in the element region of the first semiconductor wafer 60, and is temporarily bonded by applying a predetermined pressure thereto, heating to a predetermined temperature, and holding for a predetermined time. This operation is performed for all the semiconductor elements 44, and as shown in fig. 15, all the semiconductor elements 44 are temporarily bonded to the element region of the first semiconductor wafer 60.
Regarding the temporary bonding, for example, a partially provided resin layer 20 (refer to fig. 1) is utilized. However, the use of the resin layer 20 (refer to fig. 1) is not limited. For example, the semiconductor element 44 may be temporarily bonded to the element region of the first semiconductor wafer 60 by supplying a sealing resin or the like to the anisotropic conductive member 45 of the first semiconductor wafer 60 by a dispenser or the like, or the semiconductor element 44 may be temporarily bonded to the element region on the first semiconductor wafer 60 using an insulating resin Film (NCF (Non-conductive Film)) supplied in advance.
Next, in a state where all the semiconductor elements 44 are temporarily bonded to the element region of the first semiconductor wafer 60, the semiconductor elements 44 are heated to a predetermined temperature by applying a predetermined pressure thereto, and held for a predetermined time, whereby all the plurality of semiconductor elements 44 are collectively bonded to the element region of the first semiconductor wafer 60 via the anisotropic conductive member 45. This engagement is called formal engagement. Thus, the terminal (not shown) of the semiconductor element 44 is bonded to the anisotropic conductive member 45 of the first semiconductor wafer 60. At the time of the main joining, since the resin layer 20 (refer to fig. 1) is partially provided, the force required for the joining can be reduced. The main bonding corresponds to a bonding step of bonding the electrode of the semiconductor element 44 to the structure 10, which is the anisotropic conductive member 45, by bringing the conductor of the structure into contact with the electrode of the semiconductor element 44.
Next, as shown in fig. 16, the first semiconductor wafer 60 to which the semiconductor elements 44 are bonded is singulated by dicing, laser scribing, or the like for each element region. Thereby, the stacked device 40 in which the semiconductor element 42 and the semiconductor element 44 are bonded can be obtained.
Further, when the temporary joining is performed, if the temporary joining strength is weak, positional deviation occurs in the conveying process or the like and the process until the joining is performed, and therefore the temporary joining strength becomes important.
The temperature conditions and the pressurizing conditions in the temporary bonding step are not particularly limited, and the temperature conditions and the pressurizing conditions described below are exemplified.
The temperature conditions and the pressurizing conditions in the final bonding are not particularly limited. By performing the main bonding under appropriate conditions, the resin layer flows between the electrodes of the semiconductor element 44, and is less likely to remain in the bonding portion. As described above, in the main bonding, the bonding of the plurality of semiconductor elements 44 is performed at once, so that the tact time can be reduced and the productivity can be improved.
In addition, the stacked device 40 having the structure shown in fig. 11 can also be manufactured as described above. The stacked device 40 shown in fig. 10 and 11 can be manufactured by using a wafer-on-wafer manufacturing method.
The semiconductor element 42, the semiconductor element 44, and the semiconductor element 46 have element regions (not shown). As for the element region, as described above. As described above, the element constituting circuit and the like are formed in the element region, and a rewiring layer (not shown) is provided in the semiconductor element, for example.
The stacked device can be configured, for example, as a combination of a semiconductor element having a logic circuit and a semiconductor element having a memory circuit. The semiconductor elements may all have memory circuits, and may all have logic circuits. The combination of the semiconductor elements in the stacked device 40 may be a combination of a sensor, an actuator, an antenna, and the like, and a memory circuit and a logic circuit, and may be appropriately determined according to the purpose of the stacked device 40, and the like.
[ object to be bonded of Structure ]
As described above, the semiconductor element is exemplified as the bonding object of the structure, and has an electrode or an element region, for example. Examples of the element having an electrode include a semiconductor element which has a specific function as a single body, but a plurality of semiconductor elements are also included to have a specific function. Further, a wiring member or the like is included to transmit only an electric signal, and a printed circuit board or the like is also included in the member having the electrode.
The element region is a region in which various element constituent circuits and the like for functioning as electronic elements are formed. The element region includes, for example: a region in which a memory circuit such as a flash memory, a microprocessor, and a logic circuit such as an FPGA (field-programmable gate array: field programmable gate array) are formed; and a region where a communication module such as a wireless tag and wiring are formed. In addition to this, a MEMS (Micro Flectro Mechanical Systems: microelectromechanical system) may be formed in the element region. Examples of MEMS include sensors, actuators, and antennas. The sensor includes various sensors such as an acceleration sensor, a sound sensor, and a light sensor.
As described above, the element region is provided with an element constituting circuit or the like, and an electrode (not shown) for electrically connecting the semiconductor chip to the outside is provided. The element region has an electrode region where an electrode is formed. The electrode in the element region is, for example, a Cu pillar. The electrode region is a region including substantially all of the electrodes formed. However, if the electrodes are provided separately, the region where each electrode is provided is also referred to as an electrode region.
The structure may be singulated as a semiconductor chip, a semiconductor wafer, or a wiring layer.
The structure is bonded to the object to be bonded, but the object to be bonded is not particularly limited to the semiconductor element or the like, and may be, for example, a semiconductor element in a wafer state, a semiconductor element in a chip state, a printed circuit board, a heat sink, or the like.
[ semiconductor element ]
The semiconductor element 42, the semiconductor element 44, and the semiconductor element 46 are other than the above elements, and examples thereof include: logic LSI (Large Scale Integration: large-scale integrated circuits) (e.g., ASIC (Application Specific Integrated Circuit: application specific integrated circuit), FPGA (Field Programmable Gate Array: field programmable gate array), ASSP (Applic at ion Spec ific Standard Product: application specific standard product), etc.), microprocessor (e.g., CPU (Central Processing Unit: central processing unit), GPU (Graphics Processing Unit: graphic processing unit), etc.), memory (e.g., DRAM (Dynamic Random Access Memory: dynamic random access Memory), HMC (Hybrid Memory Cube: hybrid Memory cube), MRAM (magnetic RAM) AND PCM (Phase-Change Memory) Phase Change Memory), reRAM (Resistive RAM: resistive random access Memory), feRAM (Ferroelectric RAM: random access Memory), flash Memory (NAND (AND) flash Memory), etc.), LED (Light Emitting Diode: light emitting diode), (e.g., micro flash Memory of portable terminal, in-vehicle use, projector light source, LCD backlight, general lighting, etc.), power/device, analog IC (Integrated Circuit: integrated circuit), (e.g., DC (Direct Current n: direct Current) -DC (Direct Current acceleration) converter, insulated gate transistor), (MEMS (62: direct Current acceleration) transducer, etc.), bipolar sensor (IGBT), (MEMS (62, MEMS) voltage sensor, MEMS gyroscope, etc., transducer, etc. Radio (e.g., GPS (Global Positioning System: global positioning System), FM (Frequency Modulation: frequency modulation), NFC (Nearfield communication: near field communication), RFEM (RF Expansion Module: radio Frequency expansion Module), MMIC (Monolithic Microwave Integrated Circuit: monolithic microwave Integrated Circuit), WLAN (Wireless LocalAreaNetwork), etc.), discrete elements, BSI (Back Side Illumination: backside illumination), CIS (Contact Image Sensor: contact image sensor), camera module, CMOS (Complementary Metal Oxide Semiconductor: complementary metal oxide semiconductor), passive elements, SAW (Surface Acoustic Wave: surface Acoustic wave) filter, RF (Radio Frequency) filter, RFPD (Radio Frequency Integrated Passive Devices: radio Frequency Integrated Passive device), BB (Broadband: broadband), etc.
The semiconductor element is formed of one semiconductor element, for example, and the semiconductor element alone performs a specific function such as a circuit or a sensor. The semiconductor element may be a semiconductor element having an intermediate function. For example, a plurality of devices such as a logic chip and a memory chip having a logic circuit can be stacked on a device having an intermediate function. In this case, bonding can be performed even if the electrode sizes of the respective devices are different.
The stacked device is not limited to the 1-to-plurality method in which a plurality of semiconductor elements are bonded to 1 semiconductor element, and may be a plurality-to-plurality method in which a plurality of semiconductor elements are bonded to a plurality of semiconductor elements.
The present invention is constructed substantially as described above. While the plating solution, the structure, the method for producing the joined body, and the method for producing the device have been described in detail, the present invention is not limited to the above-described embodiments, and various modifications and alterations can be made without departing from the gist of the present invention.
Examples
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited thereto.
Example 1
< preparation of aluminum substrate >
The method comprises the following steps: 0.06 mass%, fe:0.30 mass%, cu:0.005 mass%, mn:0.001 mass%, mg:0.001 mass%, zn:0.001 mass%, ti:0.03 mass% of an aluminum alloy containing Al and unavoidable impurities as the remainder, and then, after molten metal treatment and filtration, an ingot having a thickness of 500mm and a width of 1200mm was produced by DC (Direct Chill) casting.
Next, after milling the surface with a face mill at an average thickness of 10mm, soaking was performed at 550 ℃ for about 5 hours, and when the temperature was lowered to 400 ℃, a rolled sheet having a thickness of 2.7mm was produced using a hot rolling mill.
Further, after heat treatment at 500℃using a continuous annealing machine, the aluminum substrate was finished to a thickness of 1.0mm by cold rolling, to obtain an aluminum substrate of JIS1050 material.
After the aluminum substrate was made 1030mm wide, the following treatments were performed.
< electrolytic polishing treatment >
The aluminum substrate was subjected to electrolytic polishing treatment using an electrolytic polishing liquid having the following composition under the conditions of a voltage of 25V, a liquid temperature of 65℃and a liquid flow rate of 3.0 m/min.
The cathode was a carbon electrode, and the power supply was GP0110-30R (manufactured by TAKASAGD LTD.). Also, the flow rate of the electrolyte was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE corporation).
(composition of electrolytic polishing liquid)
660mL of 85% by mass phosphoric acid (reagent manufactured by FUJIFILM Wako Pure Chemical corporation)
160mL of pure water
Sulfuric acid 150mL
Ethylene glycol 30mL
< anodizing Process >
Next, the aluminum substrate after the electrolytic polishing treatment is anodized by a self-ordering method in the order described in japanese patent application laid-open No. 2007-204802.
The aluminum substrate after the electrolytic polishing treatment was subjected to pre-anodic oxidation treatment with an electrolyte of 0.50mol/L oxalic acid at a voltage of 40V, a liquid temperature of 16℃and a liquid flow rate of 3.0 m/min for 5 hours.
Thereafter, the aluminum substrate after the pre-anodic oxidation treatment was subjected to a stripping treatment by immersing it in a mixed aqueous solution of 0.2mol/L chromic anhydride and 0.6mol/L phosphoric acid (liquid temperature: 50 ℃ C.) for 12 hours.
Thereafter, re-anodizing treatment was performed with an electrolyte of 0.50mol/L oxalic acid at a voltage of 40V at a liquid temperature of 16℃and a liquid flow rate of 3.0 m/min, to obtain an anodized film having a film thickness of 30. Mu.m.
In addition, the pre-anodic oxidation treatment and the re-anodic oxidation treatment were both performed using stainless steel electrodes as the cathode, and GP0110-30R (manufactured by TAKASAGD LTD.) was used as the power source. The cooling device was a NeoCool BD36 (Yamato Scientific CO., ltd.) and the stirring and heating device was a pair of stirrers PS-100 (EYELATOKYO RIKAKIKAI CO., ltd.). Further, the flow rate of the electrolyte was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE corporation).
< Barrier removal Process >
Next, after the anodic oxidation treatment step, an etching treatment was performed in which 2000ppm of zinc oxide was dissolved in an aqueous sodium hydroxide solution (50 g/l) and immersed at 30 ℃ for 150 seconds to remove the barrier layer located at the bottom of the micropores of the anodic oxide film, and at the same time, zinc was deposited on the surface of the exposed aluminum substrate.
The average thickness of the anodized film after the barrier removal step (i.e., the average depth of the through holes due to micropores) was 30 μm. Further, since the average opening diameter of the micropores was 60nm, the aspect ratio (average depth/average opening diameter) was 500.
< Metal filling Process >
Then, a plating process was performed using an aluminum substrate as a cathode and platinum as a positive electrode.
Specifically, a metal-filled structure in which copper is filled in micropores was produced by performing constant current electrolysis using a copper plating solution having the composition shown below.
Here, constant current electrolysis was performed using a plating apparatus manufactured by Yamamoto-ms co., ltd and a power supply (HZ-3000) manufactured by HOKUTO DENKO CORPORATION, and after a deposition potential was confirmed by cyclic voltammetry in a plating solution, a treatment was performed under the conditions shown below.
(copper plating solution composition and conditions)
Copper sulfate 100g/L
Sulfuric acid 50g/L
Hydrochloric acid 15g/L
Sodium 3-mercapto-1-propanesulfonate (MPS) 50mg/L
Temperature 25 DEG C
Current density 10A/dm 2
Example 2
In the metal filling step, a metal-filled structure was produced in the same manner as in example 1, except that the MPS content in the copper plating solution composition was set to 10 mg/L.
Example 3
In the metal filling step, a metal-filled structure was produced in the same manner as in example 1, except that the MPS content in the copper plating solution composition was 3 mg/L.
Example 4
A metal-filled structure was produced in the same manner as in example 1, except that MPS in the copper plating solution composition was changed to sodium 2-mercapto-5-benzimidazole sulfonate in the metal-filling step.
Example 5
A metal-filled structure was produced in the same manner as in example 1, except that MPS in the copper plating solution composition was changed to 3-mercapto-1, 2-propanediol in the metal-filling step.
Example 6
A metal-filled structure was produced in the same manner as in example 1, except that 50mg/L of 3,3' -dithiobis (sodium propane sulfonate) was added to the copper plating solution composition in the metal-filling step.
Example 7
In the metal filling step, a metal-filled structure was produced in the same manner as in example 1, except that the MPS content in the copper plating solution composition was 300 mg/L.
Example 8
In the metal filling step, a metal-filled structure was produced in the same manner as in example 1, except that the MPS content in the copper plating solution composition was 500 mg/L.
Example 9
In the metal filling step, a metal-filled structure was produced in the same manner as in example 1, except that the MPS content in the copper plating solution composition was 1000 mg/L.
Example 10
In the metal filling step, a metal-filled structure was produced in the same manner as in example 1, except that the content of MPS in the copper plating solution composition was set to 0.1 mg/L.
Examples 11 to 14
In the metal filling step, a metal-filled structure was produced in the same manner as in example 1, except that MPS and 3,3' -dithiobis (sodium propane sulfonate) contents in the copper plating solution composition were set to values shown in table 1 below.
Example 15
In the anodizing treatment step, a metal-filled structure was produced in the same manner as in example 1, except that the time for re-anodizing treatment was shortened and an anodized film having a film thickness of 10 μm was formed. In addition, as in example 1, the average opening diameter of the micropores was 60nm, and thus the aspect ratio (average depth/average opening diameter) was 167.
Example 16
A metal-filled structure was produced in the same manner as in example 1, except that the plating solution used in the metal-filling step was changed to the following composition and conditions.
(composition and conditions of Nickel plating solution)
300g/L of Nickel sulfate
60g/L of Nickel chloride
Boric acid 40g/L
Sodium 3-mercapto-1-propanesulfonate (MPS) 50mg/L
Temperature of 50 DEG C
Current density 10A/dm 2
Comparative example 1
In the metal filling step, a metal-filled structure was produced in the same manner as in example 1, except that MPS in the copper plating solution composition was not added.
Comparative example 2
In the metal filling step, a metal-filled structure was produced in the same manner as in example 1, except that the MPS content in the copper plating solution composition was set to 2000 mg/L.
Comparative example 3
In the metal filling step, a metal-filled structure was produced in the same manner as in example 1, except that the content of MPS in the copper plating solution composition was set to 0.01 mg/L.
[ evaluation ]
< filling height deviation >
The metal-filled structures produced in examples 1 to 16 and comparative examples 1 to 3 were cut in the thickness direction with F1B, and the heights of the highest filling height and the lowest filling height were measured by taking a section of the metal-filled structures with FE-SM, and the difference was calculated. The same measurement and calculation were performed on 5 sections, and the average value of the difference was used as the variation in filling height. The results are shown in table 1 below.
TABLE 1
As is clear from the results shown in table 1, in the case of using a plating solution containing no mercapto group-containing compound, the variation in filling height was more than 20 μm (comparative example 1).
Further, it was found that filling failure occurred when the content of the compound having a mercapto group was 2000mg/L (comparative example 2).
Further, it was found that when the content of the mercapto compound was 0.01mg/L, the variation in the filling height was more than 20. Mu.m (comparative example 3).
In contrast, it was found that when a plating solution containing a compound having a mercapto group was used, the variation in filling height was 20 μm or less (examples 1 to 16).
Further, as is clear from the comparison of examples 1, 4 and 5, when the compound having a mercapto group is a sulfonic acid or a salt thereof, variation in filling height can be further suppressed.
Further, as is clear from the comparison between example 1 and example 4, when the compound having a mercapto group is sodium 3-mercapto-1-propanesulfonate, variation in filling height can be further suppressed.
Further, as is clear from the comparison of examples 1 to 3 and examples 7 to 10, if the content of the mercapto compound is 0.1 to 1000mg/L, the variation in filling height can be further suppressed, and for the same reason, the content of the mercapto compound is more preferably 1 to 500mg/L, still more preferably 10 to 400mg/L, and most preferably 20 to 300mg/L.
Further, as is clear from the comparison between example 1 and example 15, when the aspect ratio (average depth/average opening diameter) of the metal-filled through-holes is 500 to 5000, the effect of suppressing the variation in the filling height of the metal filled through-holes is more remarkable.
Symbol description
10-structure, 12-insulating film, 12 a-surface, 12 b-back surface, 13-pore, 14-conductor, 14 a-protrusion, 14 b-protrusion, 15-anodized film, 20, 21, 22-resin layer, 20a, 22 a-resin layer portion, 20b, 22 b-space, 30-aluminum substrate, 30 a-surface, 31-barrier layer, 32 c-bottom, 32 d-face, 35-metal, 35 a-metal layer, 35 b-metal, 40-stacked device, 41-junction, 42, 44, 46-semiconductor element, 45-anisotropic conductive member, 50-semiconductor element portion, 51-interposer, 52, 53-electrode, 54, 55-insulating layer, 54a, 55a, 60 a-surface, 60-first semiconductor wafer, ds-stacking direction, dt-thickness direction, d-average diameter, H-height, hm-average thickness, hm-thickness, p-center spacing.
Claims (6)
1. A plating solution used when filling a metal into a through hole of a structure having a plurality of through holes,
the plating solution contains a salt of a metal filled in the through-hole and a compound having a mercapto group,
the content of the compound with sulfhydryl groups is more than 0.01mg/L and less than 2000mg/L.
2. The plating solution of claim 1, wherein,
the mercapto compound comprises a sulfonic acid or a salt thereof.
3. Plating solution according to claim 1 or 2, wherein,
the content of the compound with the sulfhydryl group is 0.1 mg/L-1000 mg/L.
4. The plating solution according to any one of claims 1 to 3, wherein,
the compound having a mercapto group comprises sodium 3-mercapto-1-propane sulfonate.
5. The plating solution according to any one of claims 1 to 4, wherein,
the ratio of the depth of the plurality of through holes to the opening diameter is 10 or more.
6. A method for manufacturing a metal-filled structure, wherein the metal-filled structure is manufactured by filling a metal into a through-hole of a structure having a plurality of through-holes,
the plating solution according to any one of claims 1 to 5 is used when filling a metal in the through hole of the structure.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2021-006991 | 2021-01-20 | ||
| JP2021006991 | 2021-01-20 | ||
| PCT/JP2021/048930 WO2022158277A1 (en) | 2021-01-20 | 2021-12-28 | Plating solution and method for producing metal-filled structure |
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| CN116710599A true CN116710599A (en) | 2023-09-05 |
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| KR (1) | KR20230121857A (en) |
| CN (1) | CN116710599A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220165619A1 (en) * | 2019-08-16 | 2022-05-26 | Fujifilm Corporation | Method for manufacturing structure |
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| JP2001073182A (en) * | 1999-07-15 | 2001-03-21 | Boc Group Inc:The | Improved acidic copper electroplating solution |
| KR100366631B1 (en) * | 2000-09-27 | 2003-01-09 | 삼성전자 주식회사 | Electrolyte for copper plating comprising polyvinylpyrrolidone and electroplating method for copper wiring of semiconductor devices using the same |
| CN103361694A (en) * | 2013-08-08 | 2013-10-23 | 上海新阳半导体材料股份有限公司 | Micro-pore electroplated copper filling method for three-dimensional (3D) copper interconnection high aspect ratio through-silicon-via technology |
| WO2017057150A1 (en) * | 2015-09-29 | 2017-04-06 | 富士フイルム株式会社 | Method for manufacturing metal-filled microstructure device |
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- 2021-12-28 CN CN202180090962.9A patent/CN116710599A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220165619A1 (en) * | 2019-08-16 | 2022-05-26 | Fujifilm Corporation | Method for manufacturing structure |
| US12002713B2 (en) * | 2019-08-16 | 2024-06-04 | Fujifilm Corporation | Method for manufacturing structure |
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| KR20230121857A (en) | 2023-08-21 |
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