TW202339948A - 用於高溫應用之銀塗層 - Google Patents
用於高溫應用之銀塗層 Download PDFInfo
- Publication number
- TW202339948A TW202339948A TW112112821A TW112112821A TW202339948A TW 202339948 A TW202339948 A TW 202339948A TW 112112821 A TW112112821 A TW 112112821A TW 112112821 A TW112112821 A TW 112112821A TW 202339948 A TW202339948 A TW 202339948A
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- TW
- Taiwan
- Prior art keywords
- silver
- layer
- nickel
- tin
- copper
- Prior art date
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 204
- 239000004332 silver Substances 0.000 title claims abstract description 204
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 195
- 238000000576 coating method Methods 0.000 title claims description 13
- 239000011248 coating agent Substances 0.000 title claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 216
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 107
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 70
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 21
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 241000212941 Glehnia Species 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 28
- 239000002184 metal Substances 0.000 abstract description 28
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 199
- 239000000203 mixture Substances 0.000 description 51
- 238000007747 plating Methods 0.000 description 45
- 239000002253 acid Substances 0.000 description 19
- 229910001369 Brass Inorganic materials 0.000 description 18
- 239000010951 brass Substances 0.000 description 18
- 229910052718 tin Inorganic materials 0.000 description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 15
- 230000004888 barrier function Effects 0.000 description 15
- 238000009713 electroplating Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- -1 phenol Sulfonic acids Chemical class 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 150000007513 acids Chemical class 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000000872 buffer Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000012776 electronic material Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000003878 thermal aging Methods 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- 150000002816 nickel compounds Chemical class 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000003623 enhancer Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 3
- 229910000367 silver sulfate Inorganic materials 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical class [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KYGZCKSPAKDVKC-UHFFFAOYSA-N Oxolinic acid Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC2=C1OCO2 KYGZCKSPAKDVKC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910002065 alloy metal Inorganic materials 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- NEMJXQHXQWLYDM-JJKGCWMISA-M silver;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ag+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O NEMJXQHXQWLYDM-JJKGCWMISA-M 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-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
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910005887 NiSn Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- ZWFRZGJUJSOHGL-UHFFFAOYSA-N [Bi].[Cu].[Sn] Chemical compound [Bi].[Cu].[Sn] ZWFRZGJUJSOHGL-UHFFFAOYSA-N 0.000 description 1
- PQIJHIWFHSVPMH-UHFFFAOYSA-N [Cu].[Ag].[Sn] Chemical compound [Cu].[Ag].[Sn] PQIJHIWFHSVPMH-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940053195 antiepileptics hydantoin derivative Drugs 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000007979 citrate buffer Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical class [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229940071575 silver citrate Drugs 0.000 description 1
- YPDPYLJJBBKICP-JIZZDEOASA-M silver;(2r)-2-amino-3-hydroxy-3-oxopropane-1-thiolate;nitric acid Chemical compound [Ag+].O[N+]([O-])=O.[S-]C[C@H](N)C(O)=O YPDPYLJJBBKICP-JIZZDEOASA-M 0.000 description 1
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 1
- MLKQJVFHEUORBO-UHFFFAOYSA-M silver;methanesulfonate Chemical compound [Ag+].CS([O-])(=O)=O MLKQJVFHEUORBO-UHFFFAOYSA-M 0.000 description 1
- KALHNGQSDVPNRB-UHFFFAOYSA-L silver;sodium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].[Ag+].[O-]S([O-])(=O)=S KALHNGQSDVPNRB-UHFFFAOYSA-L 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical class S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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- 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
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
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- 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
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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Abstract
揭露了一種製品和製造該製品之方法,其中該製品包括金屬層序列,該等金屬層被佈置來抑制金屬層間的黏附失效。該等金屬層包括銀頂塗層、銀中間層、銀-錫合金層和鎳層。該等層黏附至含有銅或銅合金的基材上。
Description
本發明關於用於高溫應用的耐高溫銀塗覆基材。更具體地,本發明關於用於高溫應用的耐高溫銀塗覆基材,其含有具有改善的黏附性的與銅或銅合金基材相鄰的銀、銀-錫、以及鎳或鎳合金層序列。
銀飾面因其高導電性、良好的可焊性和耐腐蝕性而廣泛用於電子部件。對於連接件應用,銅合金先用鎳塗覆然後用銀飾面層塗覆。鎳充當阻擋層以阻止銅擴散到銀中,並且保留了銀功能層的電學特性。多年來,這樣的組合在電子工業中應用,用於在約-10°C至約35°C的低溫和約36°C至約100°C的中等操作溫度。隨著技術進步,如在電動車輛中,某些電氣連接件的操作溫度已大幅增加。
近來,使用銀塗層用於高溫應用(典型地在150°C以上的溫度)受到不同工業越來越多的關注。在這樣的高溫下,必須使用鎳阻擋層,因為銅會快速擴散到銀層。此外,在這樣的高溫條件下,銀下面的鎳可能容易發生氧化,導致鎳與銀之間的黏附失效。
圖 1和
圖 2對此進行了說明。
圖 1係銅基材的截面,該銅基材具有約3 µm的電鍍鎳層,該電鍍鎳層塗覆有約4 µm的電鍍銀層。該鎳層塗覆有約10-20 nm的非常薄的金打底(strike)層,以試圖抑制氧向下擴散至鎳層,從而阻止鎳氧化。在200°C下暴露1000小時後,銀層和鎳層的介面處形成了相當大的縫隙,顯著損害了銀層與鎳層之間的黏附。
圖 2示出了長時間暴露於高溫的銀層與鎳層之間黏附失效的另一個實例。
圖 2係銅基材的截面,該銅基材具有約3 µm的電鍍鎳層,該電鍍鎳層塗覆有約4 µm的電鍍銀層。該鎳層塗覆有約10-20 nm的非常薄的鈀打底層,同樣試圖抑制鎳氧化。在約200°C下暴露約1000小時後,在銀層和鎳層的介面處形成了相當大的縫隙,顯著損害了銀層與鎳層之間的黏附。
銀下面的鎳在高溫下的加速氧化現象還沒有被完全理解。似乎係氧穿過銀晶粒晶界擴散導致的。對於金和鈀打底層,如
圖 1-2中所示,用於增強銀對鎳的黏附的常規方法(如金、鈀或銀打底層和鎳表面活化)還不能克服在高溫應用下的氧化和黏附問題。因此,需要用於高溫應用的具有銀層的改善的金屬製品。
一種製品,其包括含有銅或銅合金的基材、與該基材的銅或銅合金相鄰的鎳層或鎳合金層、與該鎳層或鎳合金層相鄰的銀底塗層,與該銀底塗層相鄰的銀-錫合金層、以及與該銀-錫合金層相鄰的銀頂塗層。
一種方法包括:
a) 提供包含銅或銅合金的基材;
b) 沈積與該基材的銅或銅合金相鄰的鎳層或鎳合金層;
c) 沈積與該鎳層或鎳合金層相鄰的銀底塗層;
d) 沈積與該銀底塗層相鄰的銀-錫合金層;以及
e) 沈積與該銀-錫合金層相鄰的銀頂塗層。
本發明之製品即使在高溫下也具有良好的金屬層間黏附特性並且具有良好的接觸電阻。
如本說明書通篇所使用的,術語「電鍍(electroplating)」、「沈積(depositing)」和「電鍍(plating)」可互換使用。在整個說明書中,術語「組成物」和「浴」可互換使用。術語「與……相鄰」意指鄰接、或緊挨著並且相鄰層具有共同介面的連接。術語「基於銅的基材」意指至少包含銅或銅合金並且可以包含其他材料如額外的金屬、塑膠、樹脂或其他有機和介電材料的基材。術語「接觸電阻」意指可能由電導線的介面接觸和連接導致的對系統電流的總電阻的增加。「牛頓」係力的SI單位,其等於給予1千克質量1米/秒/秒的加速度的力並且等於100,000達因。術語「歐姆」係電阻的SI單位,表示當受到1伏特的電位差時,傳導1安培電流的電路中的電阻。術語「試樣」意指較大的整體部分,尤其是取樣進行化學分析或其他處理的部分。術語「法向力」意指表面施加以阻止固體物質穿過彼此的力。不定冠詞「一個/種(a/an)」旨在包括單數和複數二者。
除非上下文另有明確指示,否則以下縮寫具有以下含義:°C = 攝氏度;g = 克;mL = 毫升;L = 升;ASD = A/dm
2= 安培/平方分米;PVD = 物理氣相沈積;CVD = 化學氣相沈積;PCB = 印刷電路板或印刷線路板;SEM = 掃描電子顯微照片;EDX = EDS = 能量色散X射線光譜法;ASTM = 美國標準測試方法;mN = 毫牛頓;mOhms = 毫歐姆;cm = 釐米;μm = 微米;nm = 奈米;Ag = 銀;Sn = 錫;Ni = 鎳;Cu = 銅;EX = 實例,並且NA = 不可用。
除非另有指示,否則所有百分比和比率均按重量計。所有範圍皆為包含的,並且可以按任何順序組合,除非該等數值範圍被限制為加起來最高100%係合乎邏輯的。
圖 3示出了本發明之製品,具有銀頂塗層
1、與銀頂塗層相鄰的銀-錫合金層
2、與銀-錫合金層相鄰的銀底塗層
3、與銀底塗層相鄰的含鎳阻擋層
4,含鎳阻擋層與基於銅的基材
5相鄰。視需要,銀頂塗層可以具有抗銹蝕層(未示出)。該製品可以用作各種電子器件中的部件,如可能將該製品暴露於150°C和更高(如200°C)的溫度並且仍保持金屬層之間的良好黏附的那些器件。
將一個或多個鎳或鎳合金層沈積在包含銅的基材上。鎳充當阻擋層來抑制銅擴散到銀頂層中。基材可以基本上全係銅或可以包含一種或多種銅合金,如但不限於銅-錫、銅-銀、銅-金、銅-鉍、銅-鋅、銅-鎳、銅-錫-銀和銅-錫-鉍。較佳的是,基材係銅、銅-鋅、或銅-鉍。基材可以是PCB或介電材料,如具有銅或銅合金層的塑膠或樹脂材料。沈積鎳或鎳合金,使得該等層與基材的銅或銅合金層的表面相鄰,從而形成與銅或銅合金表面的介面。較佳的是,鎳或鎳合金層係至少0.5 µm厚度,或如從0.5 µm至10 µm厚度,或如從1 µm至5 µm厚度。可以藉由本領域中使用的常規方法沈積一個或多個鎳或鎳合金層,以在基材上沈積鎳或鎳合金。最較佳的是,沈積與基材的銅或銅合金層相鄰的鎳層。這樣之方法包括但不限於PVD、CVD、電解和無電解金屬電鍍。這樣之方法係本領域和文獻中眾所周知的。較佳的是,使用電解金屬電鍍來沈積與基材的銅或銅合金相鄰的鎳或鎳合金。
較佳的是,鎳或鎳合金電鍍可以在至少0.01 ASD的電流密度下進行。更較佳的是,電流密度係從0.1 ASD至15 ASD,甚至更較佳的是從0.5 ASD至6 ASD。可以使用小實驗來定制特定基材的電流密度。所使用的電鍍方法可以是常規的。
電鍍組成物中的鎳離子可以藉由使用任何合適的溶液可溶性鎳化合物、較佳的是水溶性鎳鹽來提供。這樣的鎳化合物包括但不限於硫酸鎳、氯化鎳、胺基磺酸鎳和磷酸鎳。可以在電鍍組成物中使用鎳化合物的混合物。較佳的是,將鎳化合物以足夠的量添加到電鍍組成物中,以在電鍍組成物中提供0.1 g/L至150 g/L、或如0.5 g/L至100 g/L、或如1 g/L至70 g/L的鎳離子濃度。
多種電解質可以用於鎳電鍍組成物(包括酸和鹼)中。酸電解質包括但不限於烷烴磺酸,如甲磺酸、乙磺酸和丙磺酸;烷基醇磺酸(alkylol sulfonic acid);芳基磺酸,如甲苯磺酸、苯基磺酸和苯酚磺酸;含胺基的磺酸,如胺基磺酸;胺磺酸;無機酸;羧酸,如甲酸和鹵代乙酸;鹵化氫酸;以及焦磷酸鹽。酸和鹼的鹽也可以用作電解質。此外,電解質可以含有酸的混合物、鹼的混合物、或一種或多種酸與一種或多種鹼的混合物。此類電解質通常可商購於各種來源,如威斯康辛州密爾沃基的奧德里奇化學公司(Aldrich Chemical Company, Milwaukee, Wisconsin)。
視需要,在鎳電鍍組成物中可以使用多種表面活性劑。可以使用陰離子、陽離子、兩性和非離子表面活性劑中的任一種,只要其不干擾鎳電鍍的性能。表面活性劑可以以常規量包含在內,該等係本領域眾所周知的。
視需要,鎳電鍍組成物可以含有一種或多種額外的組分。這樣的額外的組分包括但不限於增亮劑、晶粒細化劑和延展增強劑。這樣的額外組分係本領域眾所周知的並且以常規量使用。
鎳電鍍組成物可以視需要含有緩衝劑。示例性的緩衝劑包括但不限於硼酸鹽緩衝劑(如硼砂)、磷酸鹽緩衝劑、檸檬酸鹽緩衝劑、碳酸鹽緩衝劑和氫氧化物緩衝劑。所使用的緩衝劑的量係足以使電鍍組成物的pH保持在希望水平的量,這樣的量係熟悉該項技術者眾所周知的。
一種或多種合金金屬可以包含在鎳電鍍組成物中。這樣的合金金屬包括但不限於錫、銅和鉍。鎳-磷係較佳的合金。這樣的金屬以其溶液可溶性鹽提供,係本領域中眾所周知的。可以以常規量包含在鎳電鍍組成物中以提供鎳合金沈積物。較佳的是,合金金屬不包括在鎳電鍍浴中。
合適的電解鎳電鍍浴係可商購的,並且很多揭露在文獻中。可商購的電解鎳浴的實例係NICKEL GLEAM™電解鎳產品和NIKAL™ SC電解鎳產品,這兩者皆為從美國麻塞諸塞州瑪律堡的羅門哈斯電子材料有限公司(Rohm and Haas Electronic Materials, LLC, Marlborough, MA, U.S.A)可獲得的。另外的電解鎳電鍍浴的實例係U.S. 3,041,255中揭露的Watts型浴。
無電解鎳電鍍組成物可以包含還原劑。較佳的是,無電解鎳電鍍組成物包含還原劑。此類還原劑包括但不限於次磷酸鈉、次磷酸鉀、硫脲和硫脲衍生物、乙內醯脲和乙內醯脲衍生物、氫醌和氫醌衍生物、間苯二酚、以及甲醛和甲醛衍生物、DEA(n-二乙基-胺硼烷)、硼氫化鈉和肼。此類還原劑可以以常規量、如0.1 g/L至40 g/L使用。可商購的無電解鎳組成物的實例包括DURAPOSIT™ SMT 88無電解鎳和NIPOSIT™ PM 980和PM 988無電解鎳。所有都從羅門哈斯電子材料有限公司可獲得。
鎳電鍍組成物可以具有1至14、較佳的是1至12、更較佳的是1至8範圍內的pH。電鍍期間鎳電鍍組成物的工作溫度可以是10°C至100°C、或如20°C至50°C。
沈積鎳或鎳合金之後,沈積與一個或多個鎳或鎳合金層相鄰的一個或多個銀底塗層。可以藉由本領域中使用的常規方法沈積銀,如電解銀電鍍、無電解銀電鍍或浸漬銀電鍍。較佳的是,電鍍或無電解電鍍與鎳或鎳合金相鄰的銀。更較佳的是,電鍍與鎳或鎳合金層相鄰的銀。銀底塗層較佳的是具有至少0.01 µm、或如0.05 µm至2 µm、或如0.1 µm至2 µm、或如0.1 µm至1 µm的厚度。
可以使用常規的電鍍銀組成物。銀組成物可以是含氰化物的銀組成物或不含氰化物的銀組成物。當使用含氰化物的銀組成物電鍍銀時,較佳的是,銀組成物係鹼性的。銀離子源包括但不限於:氰化鉀銀、硝酸銀、硫代硫酸鈉銀、葡糖酸銀;銀-胺基酸錯合物,如銀-半胱胺酸錯合物;烷基磺酸銀鹽,如甲磺酸銀。可以使用銀化合物的混合物。組成物中的銀離子濃度較佳的是2 g/L至60 g/L。此類銀化合物可商購於各種來源,如威斯康辛州密爾沃基的奧德里奇化學公司。可商購的銀電鍍組成物的實例係來自羅門哈斯電子材料有限公司的SILVER GLO™ 3K銀電鍍浴、SILVERJET™ 300銀電鍍浴、SILVER GLEAM™ 360銀電鍍浴、ENLIGHT™銀電鍍600和620。
多種常規表面活性劑可以用於銀電鍍組成物中,如陰離子、陽離子、兩性和非離子表面活性劑。表面活性劑可以以常規量包括在內。銀電鍍組成物可以含有一種或多種額外的常規組分。這樣的額外組分包括但不限於電解質、緩衝劑、增亮劑、晶粒細化劑、螯合劑、錯合劑、還原劑、流平劑和延展增強劑。這樣的額外組分係本領域眾所周知的並且以常規量使用。
銀電鍍組成物可以具有1至14、較佳的是1至12、並且還更較佳的是1至10範圍內的pH。銀電鍍期間銀電鍍組成物的工作溫度為10°C至100°C,或如20°C至60°C。較佳的電流密度為0.1 ASD至50 ASD,更較佳的是1 ASD至20 ASD。
較佳的是,銀底塗層在厚度上與隨後的銀-錫合金層相同或更大。銀底塗層抑制隨後的銀-錫合金層形成鎳和錫的金屬間化合物。此外,銀底塗層抑制在鎳介面處形成不希望的科肯德爾(Kirkendal)空隙,該等空隙可能在長時間使用期間導致製品黏附失效。較佳的是,銀底塗層與銀-錫合金層的厚度比在1 : 1至20 : 1或更高的範圍內,更較佳的是在1 : 1至40 : 1的範圍內。
沈積的與銀底塗層相鄰的銀-錫合金層銀含量豐富,具有至少60 wt%的銀,其餘係錫。銀-錫合金層係易延展的並且可以抑制氧擴散至鎳表面,從而防止或減少腐蝕。較佳的是,將銀-錫合金電鍍在銀底塗層上。可以使用常規的銀-錫合金電鍍浴。可商購的銀-錫合金電鍍浴的實例係從羅門哈斯電子材料有限公司可獲得的SILVERON™ GT-820銀-錫合金電鍍浴。
銀-錫合金電鍍浴包含一種或多種銀離子源。銀離子源包括但不限於水溶性銀鹽,如鹵化銀、葡糖酸銀、檸檬酸銀、乳酸銀、硝酸銀、硫酸銀、烷烴磺酸銀和烷醇磺酸銀。當使用鹵化銀時,較佳的是鹵化物係氯化物。較佳的是,銀鹽係硫酸銀、烷烴磺酸銀或其混合物,更較佳的是硫酸銀、甲烷磺酸銀或其混合物。銀鹽通常是可商購的或可藉由文獻中所述之方法製備。浴中使用的一種或多種銀鹽的量取決於例如待沈積的所希望的合金組成和操作條件。較佳的是,浴中的銀鹽為1 g/L至100 g/L、較佳的是10 g/L至80 g/L。
水溶性錫離子源包括但不限於鹵化錫、硫酸錫、烷烴磺酸錫、烷醇磺酸錫和酸。當使用鹵化錫時,較佳的是鹵化物係氯化物。較佳的是,錫離子源係硫酸錫、氯化錫或烷烴磺酸錫,更較佳的是,錫離子源係硫酸錫或甲烷磺酸錫。錫化合物通常是可商購的或可藉由文獻中已知之方法製備。浴中使用的錫鹽的量取決於待沈積的合金的所希望的組成和操作條件。較佳的是,錫鹽範圍為0.01 g/L至80 g/L、更較佳的是0.5 g/L至40 g/L。
銀-錫合金浴可以是酸性或鹼性的。較佳的是,銀-錫合金浴係酸性的。酸電解質包括但不限於烷烴磺酸,如甲磺酸、乙磺酸和丙磺酸,芳基磺酸,如苯基磺酸、苯酚磺酸和甲苯磺酸,硫酸,胺磺酸,鹽酸、氫溴酸、氟硼酸及其混合物。此類酸電解質可以以常規量包括在內。較佳的是,酸電解質以10 g/L至400 g/L、更較佳的是50 g/L至400 g/L的量被包括在內。這樣的銀-錫合金浴具有小於2、較佳的是小於1的pH。
常規的表面活性劑可以包含在銀-錫合金電鍍組成物中,如陰離子、陽離子、兩性和非離子表面活性劑。表面活性劑可以以常規量包括在內。銀-錫合金電鍍組成物可以含有一種或多種額外的常規組分。這樣的額外組分包括但不限於電解質、緩衝劑、增亮劑、晶粒細化劑、螯合劑、錯合劑、還原劑、流平劑和延展增強劑。這樣的額外組分係本領域眾所周知的並且以常規量使用。
較佳的是,沈積銀-錫合金的電流密度為0.05 ASD或更大,更較佳的是1 ASD至25 ASD。可以在室溫至55°C的溫度下、或者如室溫至40°C、或如室溫至30°C的溫度下電鍍銀-錫合金。
可以使用浴來沈積各種組成物的富含銀的銀-錫合金。較佳的是,銀-錫合金具有60 wt%至95 %的銀含量,其餘為錫;更較佳的是,銀含量的範圍為70 wt%至90 wt%,其餘為錫;最較佳的是,銀含量為75 wt%至85 wt%,其餘為錫。
然後沈積與銀-錫合金層相鄰的銀頂塗層。銀頂塗層較佳的是至少1 µm厚度、或如1 µm至20 µm厚度、或如1 µm至10 µm厚度、或如1 µm至5 µm厚度。銀頂塗層使得製品即使在200°C和更高的溫度下暴露長時間段(如1000小時或更長)後仍具有良好的導電性和低接觸電阻。
可以使用用於沈積銀底塗層的上述常規銀沈積組成物和方法沈積與銀-錫合金層相鄰的銀頂塗層。較佳的是,使用上述銀電鍍組成物藉由電鍍銀來沈積與銀-錫合金層相鄰的銀頂塗層。銀組成物可以是含氰化物的銀組成物或不含氰化物的銀組成物。銀電鍍在與如上文對於銀底塗層所述之溫度和電流密度相同的參數下進行。進行銀電鍍,直至達到頂塗層的所希望的銀厚度。較佳的是,進行銀電鍍,直至銀頂塗層與銀-錫合金層的厚度比在2 : 1至100 : 1的範圍內、更較佳的是在3 : 1至30 : 1的範圍內、甚至更較佳的是在6 : 1至12 : 1的範圍內。
視需要,可以在銀頂塗層上沈積抗銹蝕層。可以使用常規的抗銹蝕組成物。此類抗銹蝕材料的商業實例係NO-TARN™ PM 3抗銹蝕配製物、PORE BLOCKER™ 100抗銹蝕配製物、和PORE BLOCKER™ 200抗銹蝕配製物(從羅門哈斯電子材料有限公司可獲得)。
較佳的是,本發明之製品的銀頂塗層上沒有金、鈀或一個或多個其他金屬層,如一個或多個閃光層(flash layer)。銀頂塗層消除了對於一個或多個此類額外的金屬層或閃光層的需要。進一步較佳的是,本發明之製品由以下組成:與基於銅的基材相鄰的含鎳阻擋層、與含鎳阻擋層相鄰的銀底塗層、與銀底塗層相鄰的銀-錫合金層、與銀-錫合金層相鄰的銀頂塗層、以及視需要與銀頂塗層相鄰的抗銹蝕層。更較佳的是,本發明之製品由以下組成:與基於銅的基材相鄰的含鎳阻擋層、與含鎳阻擋層相鄰的銀底塗層、與銀底塗層相鄰的銀-錫合金層、與銀-錫合金層相鄰的銀頂塗層、以及視需要與銀頂塗層相鄰的抗銹蝕層,其中銀頂塗層比銀-錫層更厚,並且銀底塗層在厚度上等於銀-錫合金層或比銀-錫合金層的厚度更大。甚至更較佳的是,本發明之製品由以下組成:與基於銅的基材相鄰的含鎳阻擋層、與含鎳阻擋層相鄰的銀底塗層、與銀底塗層相鄰的銀-錫合金層、與銀-錫合金層相鄰的銀頂塗層、以及視需要與銀頂塗層相鄰的抗銹蝕層,其中銀頂塗層與銀-錫合金層的厚度的厚度比為2 : 1至100 : 1,並且銀底塗層與銀-錫合金層的厚度比較佳的是1 : 1至20 : 1或更大,更較佳的是1 : 1至40 : 1。
銀頂塗層與銀-錫層的厚度的厚度比為2 : 1至100 : 1使得製品具有低接觸電阻,從而改善了導電性,並且銀底塗層與銀-錫層的厚度的厚度比較佳的是1 : 1至20 : 1或更大、更較佳的是1 : 1至40 : 1,抑制了科肯德爾空隙和NiSn金屬間化合物的形成,改善了製品金屬層的黏附性。此外,據信具有0.05 µm和更大厚度的銀-錫合金層防止不希望的氧向鎳或鎳合金層的擴散。鎳或鎳合金層的氧化可以使用本領域眾所周知的標準EDS或EDX分析法測量。
本發明之製品可以用於低溫和高溫環境,極少有金屬層黏附失效的擔心。該等製品可以用作PCB、電氣連接件、發光二極體(LED)、電動車輛以及其他應用中的零件或元件,在該等應用中銀層可能暴露於150°C和更高的溫度。
包括以下實例來說明本發明,但並不旨在限制本發明之範圍。
實例1-7
使用從費希爾公司(Fischer)可獲得的Fisherscope型號XDV-SD X射線螢光計(XRF)測量電鍍的銀和銀-錫合金層的厚度。使用來自博曼公司(Bowman)的銀和錫的純元素厚度標準和藉由組合純元素標準與XRF說明手冊中的基本參數(FP)計算的銀和銀-錫合金組成和厚度來校準XRF。
根據ASTM D3359進行劃格黏附性測試,其係用膠帶測量黏附性的標準測試方法。該測試藉由藉由適當工具(如小刀或刀片)在膜製成的切片上施加並移除壓敏膠帶來評估膜塗層對金屬基材的黏附性。還使用非標準的銷釘彎曲法(經常應用於生產線)來評估金屬層的黏附性。該方法包括將銷釘彎曲至90°角度並且然後通過光學顯微鏡觀察彎曲的銷釘的外側(發生材料的擴展側)和內側(發生材料的壓縮側)從而確定層的任何剝離。
使用從德國WSK Mess-und Datentechnik GmbH公司可獲得的KOWI 3000商業接觸電阻測量裝置評估熱老化前後的接觸電阻。數位壓力計配備有具有2.5 mm直徑的半球形尖端的鍍金銅合金探針。藉由使用KOWI 3000集成電流源自動測量鍍金銅合金探針與電鍍有銀頂塗層/銀-錫合金/銀底塗層/鎳金屬層的多個黃銅板(從瑞典OSSIAN Lagerqvist AB公司可獲得)之間的接觸電阻作為接觸力的函數。測量10 mN、20 mN、30 mN、40 mN、50 mN、60 mN、70 mN和80 mN下的接觸電阻。在200°C下進行熱老化持續500小時,並且在200°C下進行1000小時。使用常規的對流爐進行熱老化。
取板的截面並且在配備有EDX的ZEISS SEM掃描電子顯微鏡下以10,000X或15,000X進行檢查。
每個黃銅板塗覆有2-3 µm的鎳。使用SILVERJET™ 300 SD銀電鍍浴電鍍銀底塗層和銀頂塗層。使用SILVERON™ GT-820銀-錫合金電鍍浴電鍍銀-錫合金層。
對比實例6電鍍有約20 nm的銀打底層,代替使用包含2 gm/L銀離子和100 g/L的游離氰化鉀的氰化銀鉀打底層浴的銀底塗層,並且對比實例7電鍍有約20 nm的銀打底層,同樣來代替使用SILVERON™ GT-101打底層浴(不含氰化物的銀電鍍浴)的銀底塗層。所有浴都從羅門哈斯電子材料有限公司可獲得。
將黃銅板連接至整流器並且對電極係鍍鉑的鈦電極。電鍍期間,銀和銀-錫合金浴的溫度為45°C。在電鍍期間使用常規攪拌裝置攪拌浴。電流密度範圍為約1-5 ASD。進行電鍍,直至達到所希望的銀和銀-錫合金厚度。表1揭露了在塗覆有鎳的黃銅板上電鍍的銀和銀-錫合金的厚度。將板從電鍍浴中移出並在室溫下用去離子水沖洗。
[表1]
實例 | 銀底塗層( µm ) | 銀 - 錫 ( µm ) | 銀頂塗層 ( µm ) |
1(本發明) | 1 | 1 | 3 |
2(本發明) | 1 | 0.5 | 3 |
3(本發明) | 1 | 0.1 | 3 |
4(本發明) | 0.5 | 0.25 | 3 |
5(對比) | 0 | 2 | 2 |
6(對比) | 約0.02 | 0 | 2 |
7(對比) | 約0.02 | 3 | 0 |
評估不同法向力下電鍍後的黃銅板以毫歐姆測量的室溫接觸電阻,如表2所示。
[表2]
實例 | 10 mN | 20 mN | 30 mN | 40 mN | 50 mN | 60 mN | 70 mN | 80 mN |
1 | 3 | 2.5 | 2 | 2 | 2 | 1.8 | 1.9 | 2 |
2 | 3 | 2.5 | 2.3 | 2 | 2 | 1.8 | 1.8 | 1.8 |
3 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
4 | 3 | 2.5 | 2.3 | 2 | 2 | 1.8 | 1.9 | 1.9 |
5 | 2.9 | 2.6 | 2.3 | 2.2 | 1.9 | 1.8 | 1.8 | 1.7 |
6 | 3.7 | 3.2 | 2.8 | 2.5 | 2.5 | 2.2 | 2.3 | 2.3 |
7 | 63 | 39.8 | 27 | 18.7 | 14.1 | 12.1 | 10.5 | 10.5 |
如表2中所示,實例1-4中的電鍍有本發明之金屬層並且在室溫下儲存了500小時或1000小時的黃銅板在施加的不同法向力下具有降低的接觸電阻。對比實例5和6的接觸電阻同樣與具有銀頂層的那些板的一樣低。相比之下,具有銀-錫合金作為頂層的對比實例7在室溫下儲存後具有高的接觸電阻,因為合金中存在的錫發生了氧化。
切割實例1-4中的電鍍後的黃銅板的試樣並嵌入環氧樹脂-胺成型聚合物中。使用本領域已知的常規拋光和蝕刻方法來拋光和蝕刻試樣的樣品,以得到所希望的截面。在ZEISS SEM掃描電子顯微鏡下檢查截面和金屬層。
圖 4係在室溫下的電鍍後的黃銅板中的一個的SEM。可以清楚地看到每個金屬層:銀頂塗層
( 1 )、與銀頂塗層相鄰的銀-錫合金層
( 2 )、與銀-錫合金層相鄰的銀底塗層
( 3 )、與銀底塗層相鄰的鎳阻擋層
( 4 )、與鎳阻擋層相鄰的含銅合金基材
( 5 )。在鎳介面處未觀察到金屬層的分離。在室溫下儲存了500小時的板的結果與在室溫下儲存了1000小時的那些板的結果相同。
在在室溫下儲存500小時或1000小時後的實例1-7的電鍍後的黃銅板試樣上進行劃格黏附性測試和彎曲測試。未觀察到試樣的金屬層的分離。
然後在200°C下將實例1和3-7的電鍍後的黃銅板試樣加熱500小時。500小時後,測量板的接觸電阻,結果在下表3中。
[表3]
實例 | 10 mN | 20 mN | 30 mN | 40 mN | 50 mN | 60 mN | 70 mN | 80 mN |
1 | 11.4 | 7.5 | 5.4 | 3.9 | 3.3 | 3.3 | 2.8 | 2.5 |
2 | NA | NA | NA | NA | NA | NA | NA | NA |
3 | 11.5 | 7.6 | 5.9 | 4.8 | 4.4 | 4.1 | 3.7 | 3.4 |
4 | 3.8 | 3 | 3 | 2.7 | 2.5 | 2.5 | 2.6 | 2.7 |
5 | 2090.7 | 1498.5 | 1080.9 | 830.7 | 452.9 | 452.9 | 356.1 | 337 |
6 | 7.4 | 4.9 | 4.4 | 4.1 | 3.4 | 3.4 | 3.1 | 3.4 |
7 | 1015.6 | 501.4 | 427.5 | 320 | 243.2 | 243.2 | 221.9 | 213.6 |
實例1、3和4中的電鍍有本發明之金屬層的黃銅板的接觸電阻在不同法向力下具有低接觸電阻。具有純銀飾面的對比實例6在退火後保持低接觸電阻。相比之下,包含厚銀-錫合金中間層的對比實例5和7在200°C下退火500小時後展現出高接觸電阻。實例1、3、4和對比實例5表明,銀頂層的厚度應該大於銀-錫合金中間層,以在退火後保持低接觸電阻。
在在200°C下熱老化500小時後的實例1-4和對比實例6的電鍍後的黃銅板試樣上進行劃格黏附性測試和彎曲測試。對比實例6的所有樣品都未藉由兩個測試,表明了熱老化後鎳上的銀層的較差黏附。
圖 5係實例6的試樣的電鍍板之一在807X下的SEM,顯示在劃格區域銀層與鎳層分離。來自實例1-4的試樣的所有電鍍板在劃格黏附性測試和彎曲測試兩者中都具有良好的黏附性。沒有在任何樣品中觀察到的黏附失效。
將如表1中的實例1-4和7中的具有2-3 µm鎳層厚度並且具有金屬電鍍層的多個電鍍黃銅板和銅銷釘(從瑞典的OSSIAN Lagerqvist AB公司可獲得)儲存在200°C下的常規對流爐中1,000小時。1000小時後,將黃銅板和銷釘從爐中取出並使其冷卻至室溫。在實例1至4的試樣上進行劃格黏附性測試和彎曲測試。黃銅板和銅銷釘沒有可見的層分離。
將銅銷釘的試樣交叉切開,並檢查金屬層的黏附性能和層中的空隙。沒有觀察到金屬層分離。
圖 6係實例1的電鍍後的銅銷釘之一在15000X下的SEM。所有的金屬層看起來連接在一起,沒有觀察到任何分離,並且沒有觀察到科肯德爾空隙。銀-錫合金層(在圖中無法分辨)與銀頂塗層
( 1 )和銀底塗層
( 3 )的一部分反應,使得不能清楚地分辨銀-錫層的邊界。鎳阻擋層
( 4 )和含銅合金層
( 5 )的邊界清晰可辨。
圖 6頂部的與銀頂塗層
( 1 )的介面處的黑色縫隙係特定位置處的銀上的環氧樹脂-胺成型聚合物的較差黏附。
來自銀-錫合金層的錫部分地與銀層
( 1 )和
( 3 )反應形成銀-錫金屬間化合物。因為銀-錫合金層的晶粒晶界沒有與銀層
( 1 )和
( 3 )的晶粒晶界對齊,所以據信銀-錫金屬間化合物阻擋了氧穿過銀層
( 1 )晶粒晶界的擴散途徑,防止氧移動到可能發生氧化的鎳表面。雖然不受理論的束縛,但是不存在穿過銀頂塗層到達下面的銀底層和鎳的直接通道或晶粒晶界。這係因為銀-錫合金的晶粒取向和晶粒尺寸與銀層的銀不同。缺少直接通路阻擋氧原子向下移動至鎳表面。
與實例1-4的試樣相比,在在銀-錫合金層和鎳層之間僅含有約20 nm的非常薄的銀層的比對實例7的截面中觀察到了科肯德爾空隙。科肯德爾空隙可能導致長期使用後的黏附失效。本發明增加了銀底層層的厚度以防止銀-錫合金層的錫與鎳層反應後形成這樣的空隙。
在來自在200°C下的常規爐中儲存1000小時後的對比實例6的試樣的黃銅板和銅銷釘上進行劃格黏附性測試和彎曲測試。所有樣品都沒有藉由兩個測試,表明在200°C下熱老化1000小時後鎳上的銀層的較差黏附。
圖 7係電鍍板之一在1040X下的SEM,顯示銀層與鎳層分離。
測量在200°C下加熱了1000小時的實例1-4和7的電鍍黃銅板的試樣的接觸電阻。結果在下表4中。
[表4]
實例 | 10 mN | 20 mN | 30 mN | 40 mN | 50 mN | 60 mN | 70 mN | 80 mN |
1 | 8.4 | 5.7 | 4.7 | 4.1 | 3.7 | 3.4 | 3.3 | 3.2 |
2 | 4.2 | 3.7 | 3.1 | 3.0 | 2.7 | 2.7 | 2.7 | 2.6 |
3 | 20.9 | 15.1 | 10.3 | 8.1 | 6.6 | 6.4 | 5.7 | 5.3 |
4 | 6.6 | 5.2 | 4.4 | 4.1 | 3.6 | 3.4 | 3.1 | 3.0 |
5 | NA | NA | NA | NA | NA | NA | NA | NA |
6 | NA | NA | NA | NA | NA | NA | NA | NA |
7 | 1086.5 | 1102.7 | 1047.7 | 994.9 | 953.6 | 925.8 | 906.3 | 896.0 |
與對比實例7相比,實例1-4中的電鍍有本發明之金屬層的黃銅板的接觸電阻在施加的不同法向力下具有減小的接觸電阻。對比實例7中的接觸電阻非常高,其包含與鎳相鄰的銀打底層和與銀打底層相鄰的銀-錫頂層但不包括銀頂塗層。高接觸電阻係由於銀-錫層中存在的錫的氧化。這還表明厚的純銀頂層係必須的,以在200°C的溫度下持續1000小時仍保持低接觸電阻。
無
[ 圖 1]係在金打底層上塗覆有銀層的鎳層之10,000X SEM截面,示出了在200°C下儲存1000小時後銀和鎳介面處的相當大的縫隙。
[
圖 2]係在鈀打底層上塗覆有銀層的鎳層之10,000X SEM截面,示出了在200°C下儲存1000小時後銀與鎳介面之間相當大的縫隙。
[
圖 3]示出了製品之截面,該製品具有銀頂塗層、與銀頂塗層相鄰的銀-錫合金層、與銀-錫合金層相鄰的銀底塗層,該銀底塗層與鎳阻擋層相鄰,並且鎳阻擋層與基於銅的基材相鄰。
[
圖 4]係以下項在室溫下之15,000X SEM截面:銀頂塗層、與銀頂塗層相鄰的銀-錫合金層、與銀-錫合金層相鄰的銀底塗層、與銀底塗層相鄰的鎳層,該鎳層與銅合金基材相鄰。
[
圖 5]係具有銀層的塗覆有鎳的銅基材之807X SEM,示出了在200°C下熱老化500小時後銀層與鎳的黏附失效。
[
圖 6]係在200°C下儲存1000小時後以下項之15,000X SEM截面:銀頂塗層、與銀頂塗層相鄰的銀-錫合金層、與銀-錫合金層相鄰的銀底塗層、與銀底塗層相鄰的鎳層,該鎳層與含銅合金的基材相鄰。
[
圖 7]係具有銀層的塗覆有鎳的銅基材之1040X SEM,示出了在200°C下熱老化1000小時後銀層與鎳的黏附失效。
無
Claims (13)
- 一種製品,其包括包含銅或銅合金的基材、與該基材的銅或銅合金相鄰的鎳或鎳合金層、與該鎳層相鄰的銀底塗層,與該銀底塗層相鄰的銀-錫合金層、以及與該銀-錫合金層相鄰的銀頂塗層。
- 如請求項1所述之製品,其中,該銀底塗層的厚度等於或大於該銀-錫合金層的厚度。
- 如請求項1所述之製品,其中,該銀頂塗層的厚度大於該銀-錫層的厚度。
- 如請求項1所述之製品,其中,該銀頂塗層與該銀-錫層的厚度比為2 : 1至100 : 1。
- 如請求項1所述之製品,其中,該銀底塗層與該銀-錫層的厚度比為1 : 1至40 : 1。
- 如請求項1所述之製品,其中,該銀底塗層的厚度等於或大於0.5 µm。
- 如請求項1所述之製品,其中,該銀-錫合金層的厚度等於或大於0.1 µm。
- 如請求項1所述之製品,其中,該銀頂塗層的厚度等於或大於1 µm。
- 一種方法,其包括: a) 提供包含銅或銅合金的基材; b) 沈積與該基材的銅或銅合金相鄰的鎳或鎳合金層; c) 沈積與該鎳或鎳合金層相鄰的銀底塗層; d) 沈積與該銀底塗層相鄰的銀-錫層;以及 e) 沈積與該銀-錫層相鄰的銀頂塗層。
- 如請求項9所述之方法,其中,該銀底塗層的厚度等於或大於該銀-錫合金層的厚度。
- 如請求項9所述之方法,其中,該銀頂塗層的厚度大於該銀-錫層的厚度。
- 如請求項9所述之方法,其中,該銀頂塗層與該銀-錫層的厚度比為2 : 1至100 : 1。
- 如請求項9所述之方法,其中,該銀底塗層與該銀-錫層的厚度比為1 : 1至40 : 1。
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