TWI377268B - Method for coating substrates containing antimony compounds with tin and tin alloys - Google Patents
Method for coating substrates containing antimony compounds with tin and tin alloys Download PDFInfo
- Publication number
- TWI377268B TWI377268B TW094128797A TW94128797A TWI377268B TW I377268 B TWI377268 B TW I377268B TW 094128797 A TW094128797 A TW 094128797A TW 94128797 A TW94128797 A TW 94128797A TW I377268 B TWI377268 B TW I377268B
- Authority
- TW
- Taiwan
- Prior art keywords
- tin
- solution
- ruthenium
- metal
- metallization
- Prior art date
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000000758 substrate Substances 0.000 title claims abstract description 41
- 229910001128 Sn alloy Inorganic materials 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 title description 3
- 238000000576 coating method Methods 0.000 title description 3
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 title description 2
- 150000001463 antimony compounds Chemical class 0.000 title description 2
- 239000011135 tin Substances 0.000 claims description 92
- 229910052718 tin Inorganic materials 0.000 claims description 92
- 239000000243 solution Substances 0.000 claims description 87
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 238000001465 metallisation Methods 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 24
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 23
- 229910052707 ruthenium Inorganic materials 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- -1 tin methanesulfonate (yttrium) Chemical compound 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001622 bismuth compounds Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims 2
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 239000010955 niobium Substances 0.000 claims 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 229910052787 antimony Inorganic materials 0.000 abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 38
- 238000000151 deposition Methods 0.000 description 15
- 230000008021 deposition Effects 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000011188 CEM-1 Substances 0.000 description 8
- 101100257127 Caenorhabditis elegans sma-2 gene Proteins 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical class CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 238000005234 chemical deposition Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000005385 peroxodisulfate group Chemical group 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- GSJBKPNSLRKRNR-UHFFFAOYSA-N $l^{2}-stannanylidenetin Chemical compound [Sn].[Sn] GSJBKPNSLRKRNR-UHFFFAOYSA-N 0.000 description 1
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- RIKSBPAXKLQKOR-UHFFFAOYSA-M [O-2].O[Ta+4].[O-2] Chemical compound [O-2].O[Ta+4].[O-2] RIKSBPAXKLQKOR-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- XWIJIXWOZCRYEL-UHFFFAOYSA-M potassium;methanesulfonate Chemical compound [K+].CS([O-])(=O)=O XWIJIXWOZCRYEL-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000004381 surface treatment Methods 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
- 150000003585 thioureas Chemical class 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0392—Pretreatment of metal, e.g. before finish plating, etching
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- ing And Chemical Polishing (AREA)
Description
1377268 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於將錫與錫合金層無電沉積在含有銻化合 物(例如’三氧化二銻)之基板上的方法β此方法特別適 合用來於含銻化合物之印刷電路板上製造可接合錫與錫合 . 金最上層,該錫與錫合金最上層被施用於導線圖案的銅部 分,即,未被防焊劑覆蓋者。文中所用「可接合性」指表 φ面的可結合性或可焊接性。 本文中,銻化合物係作爲防焰劑以及用於改善製造通 孔的沖壓性。 【先前技術】 製造印刷電路板時,產生可接合性的最上層於最終製 造步驟中的一個步驟被施加於導線圖案的銅部分,即,未 被防焊劑覆蓋者。導線圖案中未被銅覆蓋的部分特別指不 φ爲導線構成的表面部分。這些部分的基材會與最終金屬化 (例如,錫)的溶液直接接觸。 爲達此目的,無電沉積的錫與錫合金層仍具有成長中 的市佔率。這是因爲此方法不敏感且可靠又具有廣泛的加 工範圍,也因爲在多次高溫曝曬後錫與錫合金仍具有優異 的可焊接性。所以,此層比簡單的有機保護層優異。再者 ,此法比例如,施加鎳金層,更具成本效益。 「無電沉積法」一詞指未使用外加電源(如電鍍法( galvanization method)所用者)之方法。於還原浴中沉積 -5- (2) 金屬所需的電子由電解質提供。此浴中包括還原劑,例如 ’次磷酸鈉、甲醛或硼烷,其可將金屬離子還原成對應金 屬。若爲交換浴(exchange baths),則不需還原劑,因 爲溶解的金屬離子能夠因電位差而直接與各自之表面反應 。此類典型例子爲鎳上的金以及銅上的錫或銀》 下面將詳細說明無電法。 已知有各種方法來施加可接合錫與錫合金最上層,這 些方法如此技藝現況所述者。 除了純錫層之外,亦可依該法施加錫合金,例如, 錫-銀、錫-鉍、錫-鉛、錫-鋅、錫-鎳。 長久以來,係以使工件表面覆以銅或銅合金而形成抗 腐蝕表面的無電法來施加錫最上層。這些無電法中,基材 金屬溶解補償所沉積錫離子。 錫覆層以某些置換型無電電鍍法施加於銅或銅合金表 面上,即,藉由浸入電鍍技術,如US 2,891,871,US 3,303,029,US 4,715,8 94所揭示的。於這些錫浸入電鍍技 術中,製造包括錫(11 )鹽與酸的水溶液,並以硫脲或硫 脲衍生物作爲實質成分。於該錫浸入電鍍法中,將具有銅 表面的物件(例如,鍍銅電路板)浸入電鍍浴中一段時間 ,於此期間表面上的金屬銅被氧化成銅(I)並被硫脲錯 合且其於表面的位置被金屬錫置換(該金屬錫由同時的錫 (Π )離子還原而得到)。當置換電鍍達到所需厚度後, 將物件自浴中移出並潤洗移除殘留的電鍍溶液。 無電置換電鍍用於製造印刷電路板(PCB )及’特別 -6- (3) 1377268 是,多層印刷電路板。印刷電路板包括不導電或介電板, 例如,玻璃纖維/環氧樹脂板,其單面或雙面上被鍍以導 電金屬層,例如,銅。加工前,PCB上的金屬層典型爲連 續銅層,可由連接板兩面的電鍍通孔或接點之圖案所中斷 。加工中,移除銅層的選定部份以形成PCB突起的銅線圖 案。多層印刷電路板由重疊圖案化導線層(例如,含銅層 )與介電黏著層(例如,部份固化之B階樹脂,即,預浸 B物)而形成多層夾心結構,此夾心結構後來用熱與壓力連 結。此類型印刷電路板的製造記載於"Printed Circuits Handbook” 第三版,C_ F. Coombs,Jr.編輯,McGraw Hill ,1988。因爲具有平滑銅表面的導電層並不適合與預浸物 結合,故發展出對銅表面的不同處理以增加其與多層PCB 夾心結構的結合強度。 此種銅表面的處理應用浸入錫與錫合金組成物作爲多 層電路的結合介質,如Holtzman等人於US 4,1 75,894所揭 (p示的。此方法揭示含有硫脲化合物與脲化合物二者之浸入 錫組成物,而用於以浸入法於層疊形成多層印刷電路板之 前置換掉錫而使PCB銅表面鍍敷。 US 5,435,838揭示於銅表面上無電沉積錫鉍合金的方 法。此法中,錫與鉍以其甲磺酸鹽形式使用。硫脲係作爲 錯合劑以與表面溶出的銅形成錯合物。 但是所述沉積錫與錫合金的方法並不適合塗覆含銻化 合物之基板。銻化合物廣泛用於業界且係用作爲防焰劑或 用於改善沖壓性’例如’於製造印刷電路板時。 (4) 1377268 此限制顯著縮限了施加錫之化學法的應用領域。所以 本案發明的目的即在於提出可以成功用在所述類別的基板 之方法。 此類含銻化合物之基板中,例如,稱爲CEM-1之印刷 電路板爲最具成本效益的基材。此材料的優點爲鑽孔可由 簡單的沖壓過程所取代,鑽孔過程爲製造印刷電路板時最 複雜且最昂貴的步驟之一》直至目前爲止,並無法以無電 φ錫法於CEM-1材料上進行塗覆。原因爲其使用銻化合物, 特別是,三氧化二銻,作爲防焰劑或用於改善基材沖壓性 。所以’例如,Isola公司(USA )揭示其基材65Μ62的三 氧化二銻含量爲5.74%。加工步驟中,三氧化二銻於基材 的邊緣及沖壓孔處溶出。所以,於錫與錫合金的沉積浴中 會有渾濁與暗色析出物出現。使得沉積的錫層具有暗色汙 點。所以,其作爲可接合最上層的性質不足。 再者,錫與錫合金的沉積浴無法用於製造已經塗覆有 φ數層印刷電路板的金屬化基板。所以,並無將錫塗覆至 CEM-1印刷電路板之商業化應用。 以〇 94/2 60 82有關於使印刷電路板穿通連接(11^〇1^11-connecting)的方法,即,藉著使用直接金屬化之導電塑 膠,其中將具有固有導電性之聚合物層施加固定至印刷電 路板的不導電部份。之後於其上施加金屬層。此方法未對 印刷電路板進行氧化預處理。除了其他基材,CEM被指爲 基材之一。基材可用某些方法預處理,包括機械清潔、潤 洗與蝕刻(見W0 94/26082第8頁第】-4行)。 (5) 1377268 最後,WO 94/26082陳述,特別是,錫爲適合 之金屬(見其第10頁第31行至第11頁第3行)。 EP 0 926 264 A2說明一種水性、強酸性交換浴 將錫無電沉積至銅上,其包括錫(II)鹽、硫脲或 物、硫乙內醯脲、錫之細粒添加劑、乳化劑及界面 〇 申請人之WO 9 9/ 13696有關於使具有不導電表 |之基板金屬化的方法,其中該基板以貴金屬膠體溶 ,然後以含氫離子(濃度不超過0.5 mol/kg溶液) 化氫的蝕刻溶液處理。於該不導電表面上以無電金 製得第一金屬層,然後以電解金屬沉積製得第二金 此方法包括以過氧化氫作爲氧化劑。 出人意料外地,可由預處理溶液簡單預處理含 物之基板將含銻化合物自表面移除而解決所述問題 φ【發明內容】 本發明所用預處理溶液不含任何氧化劑,例如 過程中常用的過氧化物(且通常再與硫酸倂用), 過氧化氫、過氧二硫酸鹽或過氧硫酸鹽。使用此類 造成金屬基板的金屬剝離,例如,印刷電路板的銅 ,表面變得粗糙。本發明所用預處理溶液含強酸溶 必要成分,其中可能含酸溶液製造方法中所產生的 所以可採用工業級的酸於本發明預處理溶液中。 應用本發明方法,基板所含銻化合物之干擾效 金屬化 ,用於 其衍生 活性劑 面部份 液處理 與過氧 屬沉積 屬層。 銻化合 ,蝕刻 例如, 氧化劑 。所以 液作爲 雜質。 應可被 -9- (6) 1377268 降低至避免不想要之析出的程度。當應用本發 所沉積的錫層具有在可接合性與耐用性上之優 錫浴的可用壽命得以延長,所以可以達成經濟 本發明的主題爲一種使含銻化合物之基材 金無電金屬化之方法,包括蝕刻、以錫鹽溶液 潤洗該基材,此方法特徵爲其還包括預處理步 基材於金屬化前與預處理溶液接觸,該預處理 I酸溶液但不含氧化劑,且將該銻化合物於金屬 表面移除。 可作爲預處理溶液的強酸溶液包括無機酸 酸、鹽酸)或強有機酸(如烷磺酸)。 如熟習此項技藝人士所知的,酸於水溶液 HX + H20 = H30+ + X_ (其中乂_代表酸的 應的平衡常數Ks ( =Ka )導出。 「強酸」一詞指酸性常數K s爲5 5 . 3 4 · 3 . 1 6 > φ於pKs爲-1.74至4.5)之酸。本發明使用具有戶/ 的酸。 根據本發明,預處理溶液中的硫酸濃度爲 的重量份/溶液的重量份),較好爲10-30%, 5 - 4 0 % ’較好爲5 - 2 5 % »例如,烷磺酸可爲甲磺 5-70%,較好爲10-40%。酸的鹽,例如,甲磺 鉀鹽,可用來代替該酸。本發明說明中「酸溶 酸或其鹽的水溶液。所以,亦可使用甲磺酸鈉 酸鉀溶液作爲本發明方法的酸溶液。 明方法時, 異性質,且 之應用。 以錫或錫合 金屬化,及 驟,其中該 溶液包括強 化前自基材 (硫酸、硝 中的強度由 陰離子)反 <1(Γ5 (相當 f述pKs範圍 ,5-6 0% (酸 硝酸濃度爲 酸,濃度爲 酸的鈉鹽或 液j 一詞指 溶液或甲磺 -10- (7) 1377268 本發明方法的一個特佳具體例中,欲塗覆的基板以鹽 酸預處理溶液處理。鹽酸含量爲5-38 % HC1,較好爲logo % H C1 , 最好爲 1 5 - 2 5 % H C1 。 本發明方法通常於15-80 °C的溫度進行,較好爲30·70 °C ·’最好爲5 0-65 °C。視所用預處理溶液,特別視其濃度 ,處理時間通常爲卜60分鐘,較好爲1-25分鐘,最好爲2-1 0分鐘。 | 本發明方法中,溶於預處理溶液的銻化合物可以銻形 式沉積於印刷電路板的銅表面上。這些沉積金屬層可任意 再以微蝕刻溶液移除。 此類微蝕刻溶液爲通常使銅於塗覆錫或其他最上層之 前用來清潔銅的溶液,且爲此項技藝所公知,一般係由鹼 金屬過氧二硫酸鹽或過氧化氫與硫酸組合之水溶液所組成 。一種銅表面處理的蝕刻溶液見於US 6,03 6,7 5 8,此蝕刻 溶液含有過氧化氫與芳族磺酸或其鹽。另外,此蝕刻溶液 φ含有,特別是,無機酸,較好爲硫酸。有一種蝕刻(抛光 )溶液見於EP 1 167 482,其包括N-雜環化合物,過氧化 氫與十二烷基苯磺酸鹽。 此類微蝕刻溶液尙可以爲含有硫酸與過氧二硫酸或其 鹽或者過氧單硫酸鹽。 以本發明方法預處理的印刷電路板接著可於錫浴中化 學地金屬化。並不會觀察到浴液的明顯暗色渾濁與汙點形 成。此錫最上層具有所需性質,例如,優異的可接合性與 耐用性。 -11 - (8) (8)1377268 當以商業規模進行含銻化合物之基材的預處理時,本 發明預處理溶液必須要連續更換,因爲溶於其中的銻濃度 增加,所以銻會沉積於欲塗覆錫的錫銅層上。此將不利地 影響連續的錫最上層的表面性質,如耐用性與可接合性。 事實上,可於微蝕刻步驟中延長蝕刻時間而自銅再次移除 銻。但是,若預處理溶液中的銻濃度很高,蝕刻步驟所需 時間變得太長,影響此方法的成本效益。 所以建議於本發明一具體例中將預處理溶液的銻移除 (藉由將銻沉積於另一金屬上)。 爲此目的,令含銻化合物之預處理溶液連續地或不連 續地通過含金屬的管柱,使其中溶解的銻物種自預處理溶 液以銻形式沉積出來。亦可將金屬直接加入預處理溶液中 。此類金屬的例子包括銅、鐵 '鎳、鈷、錫與鋅》金屬可 呈粒狀、桿狀、棒狀或球粒狀的形式,溶解的銻則沉積於 其表面上。 當該表面完全被銻覆蓋而使管柱的容量耗盡時,引入 微蝕刻溶液(如上所述)充分潤洗而使管柱再生。之後, 管柱便可再次用於再生預處理溶液。預處理溶液的服務壽 命可用此法顯著地延長。 仍沉積於基材上的少量銻殘留物,其會於金屬化時溶 於錫浴中,可用額外步驟自錫浴中移除。 爲此目的,令錫浴連續地或不連續地通過金屬錫或者 將金屬錫直接加入錫浴中。藉此便可將錫浴中所含銻沉積 於金屬錫上,然後自浴液的循環中移除。 -12- (9) 1377268 爲了避免錫浴中錫離子濃縮,可使用此項技藝公知的 再生法。較好以DE 1 0 1 32 47 8所揭示的再生單元來達到溶 液中錫離子的恆定濃度。 所述方法使含銻化合物之基材(如CEM-1 )被錫有效 的化學金屬化得以實現。錫與錫合金的沉積浴之服務壽命 可大大地延長,且所得層之性質在耐用性與可接合性受到 正面的影響。本發明方法所用預處理溶液可於另一加工步 I驟再生。所以,廢水問題大致獲得解決,使得此方法有額 外的好處。於錫浴中,由基材瀝濾出而溶解的銻殘留物則 如上述般由錫浴再生(利用金屬錫)來移除。 【.實施方式】 本發明以下述實施例進一步詳細說明。 實例I : φ 令—由CEM-1材料製成的印刷電路板(5x5cm )以含 18%鹽酸的水溶液於50 〇c處理5分鐘。然後以微蝕刻溶液 Micro Etch SF (得自Atotech,主要含有過氧二硫酸鹽的 硫酸溶液)於35°C處理1分鐘,接著使用Atotech的錫化學 沉積法(包括下述二步驟)以錫金屬化: 1. 以Stannadip F於室溫處理1分鐘,Stannadip f主要 包含甲磺酸錫(11 )與硫脲的酸性溶液; 2. 以 Stannatech F 於 6〇t 處理 5 分鐘,Stannatech F 主要 包含甲磺酸錫(Π)與硫脲的酸性溶液。 -13- (10) (10)1377268 上述處理後,印刷電路板以去離子水潤洗,於60 °C乾 燥。 所沉積的錫層厚度約爲〇.5μηι,並具有焊接所需的優 異耐用性與可接合性 重複上述步驟總共五次。印刷電路板的化學金屬化浴 液保持原始性質,未發生所述的錫浴渾濁與暗色析出。所 沉積的錫層並未有任何暗色汙點,且仍保有其表面特性。 實例2 : 令一由CEM-1材料製成的印刷電路板(5x5cm)以含 1 0%鹽酸的水溶液於60 °C處理5分鐘。然後以微蝕刻溶液 Micro Etch SF (得自Atotech)於35°C處理1分鐘,接著使 用Atotech的錫化學沉積法(包括下述二步驟)以錫金屬化 1. 以Stannadip F於室溫處理1分鐘, 2. 以 StannatechF於 60°C 處理 5分鐘。 上述處理後,印刷電路板以去離子水(VE-water)潤 洗,於60°C乾燥》 所沉積的錫層厚度約爲〇.5μηι,並具有焊接所需的優 異耐用性與可接合性 重複上述步驟總共五次。印刷電路板的化學金屬化浴 液保持原始性質,未發生所述的錫浴渾濁與暗色析出。所 沉積的錫層並未有任何暗色汙點,且仍保有其表面特性。 -14- (11) 1377268 實例3 : 如同實例1般使用含1 8%鹽酸的水溶液來預處理印刷電 路板。將一部分的溶液自浴液中連續地移出並通過塡有銅 顆粒的管柱。因而使銻沉積在顆粒表面上》當銅表面大部 分被金屬銻所覆蓋時,以Atotech的微蝕刻溶液"Micro Etch SF"處理使銻溶解,然後將此溶液移出管柱並送至廢 水處理。應用此方法可以用鹽酸溶液處理超過5 0片印刷電 路板而無須更換溶液。 預處理後的印刷電路板如實例1或2般加工。 實例4 : 將實例1中用於將基板錫金屬化之Stannatech F溶液之 一部分自浴液中連續地移出並通過塡有錫顆粒的管柱。因 而使銻沉積在顆粒表面上。當錫表面大部分被金屬銻所覆 蓋時,以Atotech的微蝕刻溶液"Micro Etch SF”處理使銻溶 φ解,然後將此溶液移出管柱並送至廢水處理。 銻於印刷電路板上的不想要的沉積可以用此處理大致 完全避免。 實例5 : 將50g錫顆粒加入實例1中用於將基板錫金屬化之 Stannatech F溶液中》因而使銻沉積在顆粒表面上。當錫 表面大部分被金屬銻所覆蓋時,將錫顆粒自金屬化溶液移 出並以Atotech的微蝕刻溶液"Micro Etch SF"處理該被覆蓋 •15- (12) (12)1377268 之顆粒使銻溶解,然後將此溶液送至廢水處理,不含銻之 錫顆粒則送回金屬化溶液。 銻於印刷電路板上的不想要的沉積可以用此處理大致 完全避免。 比較實施例 比較例1 : 令一由CEM-1材料製成的印刷電路板(5x5cm )以 Atotech的清潔劑"Pro Select SF"(其爲印刷電路板習用金 屬化之標準藥劑)於40°C處理5分鐘。然後以Atotech的微 蝕刻溶液Micro Etch SF於35°C處理1分鐘,接著以錫金屬 化。爲達此目的,使用Atotech的錫化學沉積法,此方法包 括下述二步驟: 1. 以StannadipF於室溫處理1分鐘, 2. 以 St anna tech F於 6 0 °C 處理 5分鐘。 上述處理後,印刷電路板以去離子水(VE-water )潤 洗,於60°C乾燥。 所沉積的錫層厚度約爲〇 . 5 μηι,且最初具有最低所需 的可接合性。 該Stann ate ch浴液於下個金屬化步驟便已失去其最初 性質。錫浴產生渾濁與形成暗色析出。所沉積的錫層具有 暗色汙點,且失去所需表面特性。錫浴的性質迅速被破壞 。第四次後,金屬化已不完全且浴液無法再使用。 -16- (13) (13)1377268 比較例2 : 令一由CEM-1材料製成的印刷電路板(5x5cm)未經 預處理即以Atotech的微蝕刻溶液Micro Etch SF於35°C處 理1分鐘’接著以錫金屬化。爲達此目的,使用A tote ch的 錫化學沉積法,此方法包括下述二步驟: 1. 以Stannadip F於室溫處理1分鐘, 2. 以 Stannatech F於 60°C處理 5分鐘》 上述處理後,印刷電路板以去離子水(VE-water)潤 洗,於60°C乾燥。 所沉積的錫層厚度約爲0.5 μηι,且最初具有最低所需 的可接合性。 但是,該St an n at ech浴液於下個金屬化步驟便已失去 其最初性質。錫浴產生渾濁與形成暗色析出。所沉積的錫 層具有暗色汙點,且失去所需表面特性。錫浴的性質迅速 被破壞。數次後,金屬化已不完全。浴液必須要丟棄。 -17-
Claims (1)
1377268 附件3A :第094128797號專利申請案中文申請專利範圍修正本 民國101年7月12 日修正 十、申請專利範圍 1. 一種使含銻化合物之基材以錫或錫合金無電金屬化 之方法’包括蝕刻、以錫鹽溶液金屬化,及潤洗該基材, 此方法特徵爲其還包括預處理步驟,其中該基材於金屬化 前與預處理溶液接觸,該預處理溶液包括強酸溶液但不含 Φ 氧化劑’且將該銻化合物於金屬化前自基材表面移除, 其中以選自鹽酸溶液'硫酸溶液、與硝酸溶液之無機 酸溶液作爲預處理溶液,以及其中溶於預處理溶液中的銻 化合物經由與金屬之化學交換反應而沉積,進而自該溶液 移除。 2 .如申請專利範圍第1項之方法,其中以濃度5 - 3 8 %之 鹽酸溶液作爲預處理溶液。 3 ·如申請專利範圍第2項之方法,其中以濃度1 〇 - 3 0 % φ 之鹽酸溶液作爲預處理溶液。 4.如申請專利範圍第3項之方法,其中以濃度1 5 - 2 5 % 之鹽酸溶液作爲預處理溶液。 5 ·如申請專利範圍第1項之方法,其中將該溶液連續 地或不連續地通過裝塡有金屬的管柱,使銻經由化學交換 反應而沉積出來。 6.如申請專利範圍第1項之方法,其中將金屬直接加 入預處理溶液中使銻經由化學交換反應而沉積出來。 7_如申請專利範圍第1項之方法,其中於化學交換反 1377268 應中用來沉積銻的金屬呈粒狀、桿狀、棒狀或球粒狀的形 式。 8.如申請專利範圍第1項之方法,其中於化學交換反 應中用來沉積銻的金屬係選自銅、鐵、鎳、鈷、錫與鋅。 9·如申請專利範圍第1項之方法,其中於化學交換反 應中形成在金屬上的銻層以微蝕刻溶液處理而再次移除。 10. 如申請專利範圍第1項之方法,其中含於錫或錫合 金之金屬化溶液中的銻化合物經由與金屬錫之化學交換反 應而沉積,進而自該溶液移除。 11. 如申請專利範圍第10項之方法,其中將該溶液連 續地或不連續地通過裝塡有金屬錫的管柱,使銻經由化學 交換反應而沉積出來。 12. 如申請專利範圍第10項之方法,其中於化學交換 反應中形成在錫上的銻層以微蝕刻溶液處理而再次移除。 13. 如申請專利範圍第1項之方法,其中由含甲磺酸錫 (Π)作爲錫來源的金屬化溶液進行錫或錫合金之塗覆。 14. 如申請專利範圍第1項之方法,其中由含硫脲的金 屬化溶液進行錫或錫合金之塗覆。 15. —種如申請專利範圍第1至14項中任一項之方法的 應用,係用來製造錫或錫合金可接合層。 16. —種如申請專利範圍第1至14項中任一項之方法的 應用,係用來製造電路的基板或用於半導體技術中垂直及 /或水平裝置中。 17. 如申請專利範圍第16項的應用,其中該電路的支 1377268 撐爲印刷電路板。 18.—種作爲電路之支撐(support),其特徵爲具有可由 如申請專利範圍第1至14項中任一項之方法得到的錫或錫 合金層。
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EP04090330A EP1630252A1 (de) | 2004-08-27 | 2004-08-27 | Verfahren zur beschichtung von Substraten enthaltend Antimonverbindungen mit Zinn und Zinnlegierungen |
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US (1) | US20090081370A1 (zh) |
EP (2) | EP1630252A1 (zh) |
JP (1) | JP4616886B2 (zh) |
KR (1) | KR101188435B1 (zh) |
CN (1) | CN101027427B (zh) |
AT (1) | ATE495279T1 (zh) |
DE (1) | DE602005025908D1 (zh) |
MY (1) | MY143782A (zh) |
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FR2933105B1 (fr) | 2008-06-27 | 2010-09-03 | Essilor Int | Procede de depot non-electrolytique |
EP2476779B1 (en) * | 2011-01-13 | 2013-03-20 | Atotech Deutschland GmbH | Immersion tin or tin alloy plating bath with improved removal of cupurous ions |
CN102548066A (zh) * | 2012-02-08 | 2012-07-04 | 惠州中京电子科技股份有限公司 | 一种pcb板表面处理工艺 |
CN102544131A (zh) * | 2012-03-12 | 2012-07-04 | 谢振华 | 一种改进的太阳能电池板的电极结构 |
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2005
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- 2005-08-25 US US11/661,237 patent/US20090081370A1/en not_active Abandoned
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EP1807549B1 (en) | 2011-01-12 |
DE602005025908D1 (de) | 2011-02-24 |
KR20070072858A (ko) | 2007-07-06 |
EP1630252A1 (de) | 2006-03-01 |
JP4616886B2 (ja) | 2011-01-19 |
MY143782A (en) | 2011-07-15 |
ATE495279T1 (de) | 2011-01-15 |
CN101027427B (zh) | 2011-01-12 |
KR101188435B1 (ko) | 2012-10-08 |
TW200622033A (en) | 2006-07-01 |
JP2008510885A (ja) | 2008-04-10 |
CN101027427A (zh) | 2007-08-29 |
US20090081370A1 (en) | 2009-03-26 |
EP1807549A1 (en) | 2007-07-18 |
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