JP2008019468A - Tin plating film - Google Patents
Tin plating film Download PDFInfo
- Publication number
- JP2008019468A JP2008019468A JP2006191093A JP2006191093A JP2008019468A JP 2008019468 A JP2008019468 A JP 2008019468A JP 2006191093 A JP2006191093 A JP 2006191093A JP 2006191093 A JP2006191093 A JP 2006191093A JP 2008019468 A JP2008019468 A JP 2008019468A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- plating film
- layer
- tin plating
- acid
- 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.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 169
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000010410 layer Substances 0.000 claims abstract description 110
- 230000004888 barrier function Effects 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 239000002344 surface layer Substances 0.000 claims abstract description 39
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 28
- 238000009713 electroplating Methods 0.000 claims abstract description 24
- 229910000679 solder Inorganic materials 0.000 claims description 21
- 230000000694 effects Effects 0.000 abstract description 12
- 229910001174 tin-lead alloy Inorganic materials 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 97
- -1 aromatic carboxylic acids Chemical class 0.000 description 25
- 238000005406 washing Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000013078 crystal Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 238000004453 electron probe microanalysis Methods 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 238000005554 pickling Methods 0.000 description 9
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 7
- 229910001128 Sn alloy Inorganic materials 0.000 description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 6
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 6
- 229910000906 Bronze Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000010974 bronze Substances 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 description 4
- 229960003237 betaine Drugs 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- YCELPWGPXSJYMB-OWOJBTEDSA-N (e)-2-sulfobut-2-enedioic acid Chemical compound OC(=O)\C=C(/C(O)=O)S(O)(=O)=O YCELPWGPXSJYMB-OWOJBTEDSA-N 0.000 description 1
- YCELPWGPXSJYMB-UPHRSURJSA-N (z)-2-sulfobut-2-enedioic acid Chemical compound OC(=O)\C=C(\C(O)=O)S(O)(=O)=O YCELPWGPXSJYMB-UPHRSURJSA-N 0.000 description 1
- MCXZBEZHTYZNRE-UHFFFAOYSA-N 1-chloropropane-1-sulfonic acid Chemical compound CCC(Cl)S(O)(=O)=O MCXZBEZHTYZNRE-UHFFFAOYSA-N 0.000 description 1
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 description 1
- OMPLFUALYIEKNF-UHFFFAOYSA-N 1-dodecyl-2-methylpyridin-1-ium Chemical class CCCCCCCCCCCC[N+]1=CC=CC=C1C OMPLFUALYIEKNF-UHFFFAOYSA-N 0.000 description 1
- NCBISIFFSNXYQJ-UHFFFAOYSA-N 1-dodecyl-4,5-dihydroimidazole Chemical class CCCCCCCCCCCCN1CCN=C1 NCBISIFFSNXYQJ-UHFFFAOYSA-N 0.000 description 1
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical class CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 1
- KDKIWFRRJZZYRP-UHFFFAOYSA-N 1-hydroxypropane-2-sulfonic acid Chemical compound OCC(C)S(O)(=O)=O KDKIWFRRJZZYRP-UHFFFAOYSA-N 0.000 description 1
- KAFOVUJOVUDROI-UHFFFAOYSA-N 1-nonoxynonane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCOCCCCCCCCC KAFOVUJOVUDROI-UHFFFAOYSA-N 0.000 description 1
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 description 1
- NSRGOAGKXKNHQX-UHFFFAOYSA-N 2-hydroxybutane-1-sulfonic acid Chemical compound CCC(O)CS(O)(=O)=O NSRGOAGKXKNHQX-UHFFFAOYSA-N 0.000 description 1
- RIYJUQDMHMUBMK-UHFFFAOYSA-N 2-hydroxypentane-1-sulfonic acid Chemical compound CCCC(O)CS(O)(=O)=O RIYJUQDMHMUBMK-UHFFFAOYSA-N 0.000 description 1
- OQXQWBAPFLMGSZ-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;tin(2+) Chemical compound [Sn+2].[Sn+2].[Sn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OQXQWBAPFLMGSZ-UHFFFAOYSA-H 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- SKEZDZQGPKHHSH-UHFFFAOYSA-J 2-hydroxypropanoate;tin(4+) Chemical compound [Sn+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O SKEZDZQGPKHHSH-UHFFFAOYSA-J 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- WBGKAOURNYRYBT-UHFFFAOYSA-N 2-sulfopropanoic acid Chemical compound OC(=O)C(C)S(O)(=O)=O WBGKAOURNYRYBT-UHFFFAOYSA-N 0.000 description 1
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 description 1
- OURSFPZPOXNNKX-UHFFFAOYSA-N 3-sulfopropanoic acid Chemical compound OC(=O)CCS(O)(=O)=O OURSFPZPOXNNKX-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
- YXTDAZMTQFUZHK-UHFFFAOYSA-L 5,6-dihydroxy-1,3,2$l^{2}-dioxastannepane-4,7-dione Chemical compound [Sn+2].[O-]C(=O)C(O)C(O)C([O-])=O YXTDAZMTQFUZHK-UHFFFAOYSA-L 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
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- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- MWZFQMUXPSUDJQ-KVVVOXFISA-M sodium;[(z)-octadec-9-enyl] sulfate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCCOS([O-])(=O)=O MWZFQMUXPSUDJQ-KVVVOXFISA-M 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- CSQOEEDPEGAXNJ-UHFFFAOYSA-L tin(2+);diformate Chemical compound [Sn+2].[O-]C=O.[O-]C=O CSQOEEDPEGAXNJ-UHFFFAOYSA-L 0.000 description 1
- FSBZGYYPMXSIEE-UHFFFAOYSA-H tin(2+);diphosphate Chemical compound [Sn+2].[Sn+2].[Sn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O FSBZGYYPMXSIEE-UHFFFAOYSA-H 0.000 description 1
- ZPRVNEJJMJMSCN-UHFFFAOYSA-L tin(2+);disulfamate Chemical compound [Sn+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZPRVNEJJMJMSCN-UHFFFAOYSA-L 0.000 description 1
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
【解決手段】基体上に形成された錫めっき皮膜であって、該錫めっき皮膜が２層以上の多層で構成され、上記多層のうちの１層が、上記基体に接して設けられた厚さ０．１〜２０μｍのバリア層であり、かつ他の１層が、基体から離間する側の表面部に設けられた厚さ０．１〜２０μｍの表面層であり、上記バリア層と基体との界面に形成される金属間化合物の均一性の変動係数ＣＶ値が４０％以下である錫めっき皮膜。
【効果】本発明の錫めっき皮膜は、錫−鉛合金めっきの代替として有用であり、錫皮膜において問題となるウィスカの発生を効果的に抑制したものである。そして、本発明の錫めっき皮膜は、一般的な錫めっき皮膜の作製工程とほとんど差がない簡便な、効率的な錫電気めっきで形成することができる。
【選択図】図１A tin plating film formed on a substrate, wherein the tin plating film is composed of two or more layers, and one of the multilayers is provided in contact with the substrate. A barrier layer having a thickness of 0.1 to 20 μm, and the other layer is a surface layer having a thickness of 0.1 to 20 μm provided on the surface portion on the side away from the substrate. A tin plating film having a coefficient of variation CV of uniformity of 40% or less for uniformity of intermetallic compounds formed at the interface.
[Effects] The tin plating film of the present invention is useful as an alternative to tin-lead alloy plating, and effectively suppresses the occurrence of whiskers which are a problem in the tin film. And the tin plating film of this invention can be formed by the simple and efficient tin electroplating which has almost no difference with the preparation process of a general tin plating film.
[Selection] Figure 1
Description
本発明は、被はんだ接合部などに形成され、ウィスカの発生が効果的に抑制された錫めっき皮膜に関する。 The present invention relates to a tin plating film that is formed at a soldered joint or the like and in which the generation of whiskers is effectively suppressed.
錫、錫−銅、錫−銀、錫−ビスマス等の錫又は錫合金めっき皮膜は、はんだ濡れ性に優れていることから電子部品等に広く利用されているが、これらのめっき皮膜に内部応力があるとウィスカと呼ばれるひげ状の結晶が発生しやすいことが知られており、このウィスカによって回路がショートするなどの問題が発生する。錫合金めっき皮膜は錫めっき皮膜に比べウィスカの発生の抑制効果が見られるものの十分ではない。 Tin or tin alloy plating films such as tin, tin-copper, tin-silver, tin-bismuth, etc. are widely used for electronic parts because of their excellent solder wettability. Is known to be easy to generate whisker-like crystals called whiskers, and this whisker causes problems such as short circuit. The tin alloy plating film is not sufficient, although the effect of suppressing whisker generation is seen compared to the tin plating film.
従来、ウィスカ発生を抑制するために、以下のような方法が用いられている。（三菱電機技報，ｖｏｌ．５３，Ｎｏ．１１，１９７９（非特許文献１））
・錫および錫合金めっきの下地にＮｉめっきを実施する。
基材の銅とめっきの錫との金属間化合物形成のバリアとなり、ウィスカの発生を抑える。ただし、必要な特性によりＮｉめっきができない部品が多数ある。
・錫および錫合金めっきの膜厚を厚くする（１０〜２０μｍ以上）。
膜厚を厚くすると、金属間化合物の形成により生じた内部応力の影響が、めっき表層まで及ばないためウィスカの発生が抑制される。ただし、電子部品によっては膜厚を厚くできない部品もある。
・錫および錫合金めっき後の熱処理、リフローの実施。
熱処理、リフローを実施することで金属間化合物の形成により生じためっき皮膜の内部応力を緩和し、ウィスカの発生を抑制することができる。ただし、熱処理、リフローにより錫皮膜上に酸化皮膜が形成され、はんだ濡れ性の低下が生じる。また、リフローの場合には溶融した錫皮膜が流動し、膜厚にばらつきが生じる。
Conventionally, the following methods are used to suppress whisker generation. (Mitsubishi Electric Technical Report, vol. 53, No. 11, 1979 (Non-Patent Document 1))
-Ni plating is performed on the base of tin and tin alloy plating.
It serves as a barrier for forming an intermetallic compound between the copper of the base material and the tin of the plating, and suppresses the generation of whiskers. However, there are many parts that cannot be Ni-plated due to the required characteristics.
-Increase the film thickness of tin and tin alloy plating (10 to 20 μm or more).
When the film thickness is increased, the influence of internal stress generated by the formation of the intermetallic compound does not reach the plating surface layer, so that the generation of whiskers is suppressed. However, some electronic components cannot be thickened.
-Heat treatment and reflow after tin and tin alloy plating.
By performing the heat treatment and reflow, the internal stress of the plating film generated by the formation of the intermetallic compound can be relaxed, and the generation of whiskers can be suppressed. However, an oxide film is formed on the tin film by heat treatment and reflow, and solder wettability is reduced. In the case of reflow, the molten tin film flows and the film thickness varies.
また、錫合金めっき皮膜は錫めっき皮膜に比べウィスカの抑制効果がみられるが、皮膜中の合金比率やめっき浴中の合金比率を管理することが非常に難しく、品質が安定しないという問題点がある。 In addition, the tin alloy plating film has a whisker suppression effect compared to the tin plating film, but it is very difficult to control the alloy ratio in the film and the alloy ratio in the plating bath, and the quality is not stable. is there.
本発明は、上記事情に鑑みなされたもので、電子部品等の被はんだ接合部などに形成される錫めっき皮膜として、ウィスカの発生を効果的に抑制した錫めっき皮膜を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a tin plating film in which generation of whiskers is effectively suppressed as a tin plating film formed on a soldered joint portion of an electronic component or the like. To do.
錫皮膜、特に錫めっき皮膜におけるウィスカは、皮膜を構成する粒界が、基材から表面まで被めっき面に対して垂直に成長した繊維様組織となることで、錫皮膜と基材との界面で形成された金属間化合物が粒界に沿って成長して皮膜に内部応力が発生し、これが駆動力となって発生すると考えられている。更に、形成される金属間化合物が、不均一であることも、内部応力を増大させ、ウィスカ発生を助長する原因となっている。 A whisker in a tin film, particularly a tin-plated film, has an interface between the tin film and the base material because the grain boundaries constituting the film become a fibrous structure that grows perpendicularly to the surface to be plated from the base material to the surface. It is considered that the intermetallic compound formed in (1) grows along the grain boundary and internal stress is generated in the film, which is generated as a driving force. Furthermore, the non-uniformity of the intermetallic compound formed also increases internal stress and promotes the generation of whiskers.
一方、ウィスカの発生が少ない錫−鉛合金の場合、錫皮膜の結晶粒界とは異なり、粒界が被めっき面に対して垂直に伸びた繊維様組織をとっておらず、結晶粒界が基材から表面に向かって被めっき面に対して垂直に伸びていない塊状（ランダム組織）となっている。 On the other hand, in the case of a tin-lead alloy with less whisker generation, unlike the crystal grain boundary of the tin coating, the grain boundary does not take a fiber-like structure extending perpendicular to the surface to be plated, and the crystal grain boundary is not It is a lump (random structure) that does not extend perpendicularly to the surface to be plated from the substrate toward the surface.
そこで、この錫−鉛合金皮膜のような結晶粒界（即ち、ランダム組織）を形成すること、繊維様組織をとっている粒界を途中で遮断して金属間化合物が皮膜表面まで延びないような層でブロックすること、又はこれら双方によりウィスカの発生を抑制することができると考えた。 Therefore, the formation of crystal grain boundaries (that is, random structures) such as this tin-lead alloy film, the grain boundaries taking the fiber-like structure are interrupted in the middle, and the intermetallic compound does not extend to the film surface. It was thought that generation of whiskers can be suppressed by blocking with a simple layer or both.
本発明者は、上記目的を達成するため鋭意検討を重ねた結果、高い陰極電流密度下でめっきすることにより、粒界が基体から表面まで被めっき面に対して垂直に成長していないランダム組織となり、この針状または角状の粗い粒界組織を有するバリア層が、基材との界面に形成された金属間化合物によって生じた内部応力を分散して、ウィスカの発生が抑制されることを見出した。 As a result of intensive studies in order to achieve the above object, the present inventor has obtained a random structure in which grain boundaries do not grow perpendicularly to the surface to be plated from the substrate to the surface by plating under a high cathode current density. This barrier layer having a needle-like or square-like grain boundary structure disperses the internal stress generated by the intermetallic compound formed at the interface with the base material, and suppresses the generation of whiskers. I found it.
しかしながら、このバリア層は、被はんだ接合部として要求される例えばはんだ濡れ性等の諸特性に劣ることがわかった。そこで、錫めっき皮膜を、成膜条件を変えて形成した結晶形態が異なる２層を含むように構成し、上層（即ち、錫めっき皮膜の表面側の層）を、めっき濡れ性等の被はんだ接合部としての諸特性に優れた通常の成膜条件で形成した表面層として基体から離間する側の表面部に設け、下層（即ち、上記上層以外の層のうちの１層）を、結晶形態が上述したランダム組織となっている針状または角状の粗いバリア層として基体に接して設け、バリア層を臨界電流密度の上限値の７０〜１００％の陰極電流密度でめっき形成すれば、このバリア層がウィスカの発生を助長する金属間化合物の粒界に沿った成長をブロックすることができると共に、特に、この下層（バリヤ層）を基体（被めっき物）と接するように設ければ、下層と基体との界面に形成される金属間化合物が、特に、均一性の指標である変動係数ＣＶ値が４０％以下という均一な状態で形成され、これらの相乗効果により、ウィスカの発生を抑制することができることを見出し、本発明をなすに至った。 However, it has been found that this barrier layer is inferior in various characteristics such as solder wettability required as a soldered joint. Therefore, the tin plating film is configured to include two layers having different crystal forms formed by changing the film forming conditions, and the upper layer (that is, the layer on the surface side of the tin plating film) is to be soldered such as plating wettability. Provided on the surface portion on the side away from the substrate as a surface layer formed under normal film forming conditions excellent in various properties as a bonding portion, and a lower layer (that is, one of the layers other than the upper layer) is in a crystalline form Is provided in contact with the substrate as a needle-like or square-like rough barrier layer having a random structure described above, and the barrier layer is formed by plating at a cathode current density of 70 to 100% of the upper limit value of the critical current density. The barrier layer can block the growth along the grain boundary of the intermetallic compound that promotes the generation of whiskers, and in particular, if this lower layer (barrier layer) is provided in contact with the substrate (substrate), Formed at the interface between the lower layer and the substrate It is found that the intermetallic compound is formed in a uniform state with a coefficient of variation CV value of 40% or less, which is an index of uniformity, and the occurrence of whiskers can be suppressed by these synergistic effects. Invented the invention.
即ち、本発明は、以下の錫めっき皮膜を提供する。
［１］ 基体上に形成された錫めっき皮膜であって、該錫めっき皮膜が２層以上の多層で構成され、上記多層のうちの１層が、上記基体に接して設けられた厚さ０．１〜２０μｍのバリア層であり、かつ他の１層が、基体から離間する側の表面部に設けられた厚さ０．１〜２０μｍの表面層であり、上記バリア層と基体との界面に形成される金属間化合物の均一性の変動係数ＣＶ値が４０％以下であることを特徴とする錫めっき皮膜。
［２］ 基体上に形成された錫めっき皮膜であって、該錫めっき皮膜が２層以上の多層で構成され、上記多層のうちの１層が、上記基体に接して設けられた厚さ０．１〜２０μｍのバリア層であり、かつ他の１層が、基体から離間する側の表面部に設けられた厚さ０．１〜２０μｍの表面層であり、上記バリア層を形成する際の陰極電流密度が臨界電流密度の上限値の７０〜１００％であることを特徴とする錫めっき皮膜。
［３］ 基体上に形成された錫めっき皮膜であって、該錫めっき皮膜が２層以上の多層で構成され、上記多層のうちの１層が、上記基体に接して設けられた厚さ０．１〜２０μｍのバリア層であり、かつ他の１層が、基体から離間する側の表面部に設けられた厚さ０．１〜２０μｍの表面層であり、上記バリア層を形成する際の陰極電流密度が臨界電流密度の上限値の７０〜１００％であり、上記バリア層と基体との界面に形成される金属間化合物の均一性の変動係数ＣＶ値が４０％以下であることを特徴とする錫めっき皮膜。
［４］ 上記バリア層を、光沢剤を含まない錫電気めっき浴にて形成したことを特徴とする［１］乃至［３］のいずれかに記載の錫めっき皮膜。
［５］ 上記表面層が、良好なはんだ接合特性を有することを特徴とする［１］乃至［４］のいずれかに記載の錫めっき皮膜。
［６］ 上記バリア層をめっきする際の陰極電流密度を１〜１００Ａ／ｄｍ2、上記表面層をめっきする際の陰極電流密度を０．０１〜５０Ａ／ｄｍ2として各々形成したことを特徴とする［１］乃至［５］のいずれかに記載の錫めっき皮膜。
That is, the present invention provides the following tin plating film.
[1] A tin plating film formed on a substrate, wherein the tin plating film is composed of two or more multilayers, and one of the multilayers is provided in contact with the substrate. A barrier layer having a thickness of 0.1 to 20 μm, and the other layer is a surface layer having a thickness of 0.1 to 20 μm provided on the surface portion on the side away from the substrate, and the interface between the barrier layer and the substrate A tin plating film having a coefficient of variation CV of uniformity of an intermetallic compound formed on the surface of 40% or less.
[2] A tin plating film formed on a substrate, wherein the tin plating film is composed of two or more multilayers, and one of the multilayers is provided in contact with the substrate. .1-20 μm barrier layer, and the other layer is a surface layer having a thickness of 0.1-20 μm provided on the surface portion on the side away from the substrate. A tin plating film, wherein the cathode current density is 70 to 100% of the upper limit value of the critical current density.
[3] A tin plating film formed on a substrate, wherein the tin plating film is composed of two or more multilayers, and one of the multilayers is provided in contact with the substrate. .1-20 μm barrier layer, and the other layer is a surface layer having a thickness of 0.1-20 μm provided on the surface portion on the side away from the substrate. The cathode current density is 70 to 100% of the upper limit value of the critical current density, and the coefficient of variation CV of uniformity of the intermetallic compound formed at the interface between the barrier layer and the substrate is 40% or less. A tin plating film.
[4] The tin plating film according to any one of [1] to [3], wherein the barrier layer is formed in a tin electroplating bath not containing a brightener.
[5] The tin plating film according to any one of [1] to [4], wherein the surface layer has good solder joint characteristics.
[6] The cathode current density when plating the barrier layer is 1 to 100 A / dm 2 , and the cathode current density when plating the surface layer is 0.01 to 50 A / dm 2. The tin plating film according to any one of [1] to [5].
本発明の錫めっき皮膜は、錫−鉛合金めっきの代替として有用であり、錫皮膜において問題となるウィスカの発生を効果的に抑制したものである。そして、本発明の錫めっき皮膜は、一般的な錫めっき皮膜の作製工程とほとんど差がない簡便な、効率的な錫電気めっきで形成することができる。 The tin plating film of the present invention is useful as an alternative to tin-lead alloy plating, and effectively suppresses the occurrence of whiskers that cause problems in the tin film. And the tin plating film of this invention can be formed by the simple and efficient tin electroplating which has almost no difference with the preparation process of a general tin plating film.
以下、本発明につき、更に詳しく説明する。
本発明の錫めっき皮膜は、基体（被めっき物：例えば、銅、銅合金等の基材）上に２層以上の多層として形成され、この多層のうちの１層は、基体から離間する側の表面部に設けられた厚さ０．１〜２０μｍの表面層として形成され、他の１層が、上記基体に接して設けられた厚さ０．１〜２０μｍのバリア層として形成されている。
Hereinafter, the present invention will be described in more detail.
The tin plating film of the present invention is formed as a multilayer of two or more layers on a substrate (substrate to be plated: for example, a base material such as copper or copper alloy), and one of the multilayers is a side away from the substrate. The surface layer is formed as a surface layer having a thickness of 0.1 to 20 μm, and the other layer is formed as a barrier layer having a thickness of 0.1 to 20 μm provided in contact with the substrate. .
バリア層は、針状又は角状の粗い（例えば、結晶粒径が１〜１０μｍ程度）塊状の結晶形態を有するものであり、また、結晶粒界が基体から表面まで被めっき面に対して垂直に成長していないランダム組織を有しており、これによりこの層と基材との界面に形成された金属間化合物によって生じた内部応力が分散され、ウィスカの発生が抑制される。また、このようなバリア層は、基材と接して形成された場合、銅等の基材との界面に形成される金属間化合物が均一に形成されるため、内部応力が高くならず、ウィスカの発生が更に抑制される。 The barrier layer has an acicular or horny rough crystal shape (for example, a crystal grain size of about 1 to 10 μm) and a crystal grain boundary is perpendicular to the surface to be plated from the substrate to the surface. Thus, the internal stress generated by the intermetallic compound formed at the interface between the layer and the substrate is dispersed, and the generation of whiskers is suppressed. In addition, when such a barrier layer is formed in contact with the base material, the intermetallic compound formed at the interface with the base material such as copper is uniformly formed. Is further suppressed.
一方、表面層は、基体から離間する側の表面部に設けられる。これは、上記バリア層はウィスカの発生を抑制する効果が優れているが、はんだ濡れ性などのはんだ接合部に要求される諸特性が十分でないため、これをカバーするため、はんだ接合部となる錫めっき皮膜の表面側の層をはんだ濡れ性等の特性に優れた表面層として形成するものである。 On the other hand, the surface layer is provided on the surface portion on the side away from the substrate. This is because the barrier layer has an excellent effect of suppressing the generation of whiskers, but since various properties required for the solder joint such as solder wettability are not sufficient, it becomes a solder joint to cover this. The layer on the surface side of the tin plating film is formed as a surface layer excellent in characteristics such as solder wettability.
このようなバリア層と表面層とを備える多層で構成された錫めっき皮膜としては、図１に示されるようなものを例示できる。図１（Ａ）は、バリア層と表面層との２層で構成された錫めっき皮膜を示し、これは基体１上に、バリア層２１と表面層２２とが順に積層されて錫めっき皮膜２をなしている。また、図１（Ｂ）は、バリア層と表面層とを含む３層で構成された錫めっき皮膜を示し、この場合は、基体１上に、バリア層２１と第３の層２３と表面層２２とが順に積層されて錫めっき皮膜２をなしている。 An example of the tin plating film composed of a multilayer having such a barrier layer and a surface layer is as shown in FIG. FIG. 1A shows a tin plating film composed of two layers, a barrier layer and a surface layer, which is formed by sequentially laminating a barrier layer 21 and a surface layer 22 on a substrate 1. I am doing. FIG. 1B shows a tin plating film composed of three layers including a barrier layer and a surface layer. In this case, a barrier layer 21, a third layer 23, and a surface layer are formed on the substrate 1. 22 are sequentially laminated to form a tin plating film 2.
上記第３の層は、バリア層と表面層との密着性を向上させるための層などとして形成され、例えば、バリア層と表面層との中間的な性質を有する錫めっき層を形成することができる。 The third layer is formed as a layer for improving the adhesion between the barrier layer and the surface layer. For example, a tin plating layer having intermediate properties between the barrier layer and the surface layer may be formed. it can.
バリア層の厚さは０．１〜２０μｍであり、好ましくは０．５〜１０μｍ、より好ましくは１〜５μｍである。バリア層の厚さが０．１μｍ未満では、金属間化合物の成長をブロックする効果や金属間化合物による内部応力を緩和する効果が得られず、ウィスカの発生を効果的に抑制できない。一方、バリア層の厚さを２０μｍを超えるように形成しても、ウィスカ発生の抑制効果はこれ以上厚くても同等であり、錫めっき皮膜全体の厚さが厚くなりすぎるため不利である。 The thickness of the barrier layer is 0.1 to 20 μm, preferably 0.5 to 10 μm, more preferably 1 to 5 μm. If the thickness of the barrier layer is less than 0.1 μm, the effect of blocking the growth of the intermetallic compound and the effect of relaxing the internal stress due to the intermetallic compound cannot be obtained, and the generation of whiskers cannot be effectively suppressed. On the other hand, even if the thickness of the barrier layer exceeds 20 μm, the effect of suppressing whisker generation is the same even if it is thicker than this, and it is disadvantageous because the thickness of the entire tin plating film becomes too thick.
一方、表面層の厚さは０．１〜２０μｍであり、好ましくは０．５〜５μｍである。表面層の厚さが０．１μｍ未満では、十分なめっき接合特性が得られない。一方、表面層の厚さを２０μｍを超えるように形成しても、はんだ接合特性はこれ以上厚くても同等であり、錫めっき皮膜全体の厚さが厚くなりすぎるため不利である。 On the other hand, the thickness of the surface layer is 0.1 to 20 μm, preferably 0.5 to 5 μm. If the thickness of the surface layer is less than 0.1 μm, sufficient plating bonding characteristics cannot be obtained. On the other hand, even if the surface layer is formed to have a thickness exceeding 20 μm, the solder bonding characteristics are the same even if it is thicker than this, and it is disadvantageous because the thickness of the entire tin plating film becomes too thick.
なお、錫めっき皮膜全体の厚さは、特に制限されるものではないが、例えば１〜３０μｍ、特に２〜２０μｍとすることができる。 In addition, although the thickness of the whole tin plating film is not specifically limited, For example, it can be set to 1-30 micrometers, especially 2-20 micrometers.
バリア層、表面層及び第３の層は、従来公知の錫電気めっき浴を用いて形成することができ、錫めっき皮膜は錫電気めっきにより形成することができる。上述したバリア層、表面層の結晶形態は、めっき液中の金属成分組成、遊離酸成分組成、めっき温度等を適宜選定することにより調整することが可能である。錫電気めっき浴としては、例えば、水溶性錫塩と、無機酸もしくは有機酸又はその水溶性塩と、界面活性剤とを含有するものを用いることが出来る。 The barrier layer, the surface layer, and the third layer can be formed using a conventionally known tin electroplating bath, and the tin plating film can be formed by tin electroplating. The crystal form of the barrier layer and the surface layer described above can be adjusted by appropriately selecting the metal component composition, free acid component composition, plating temperature, etc. in the plating solution. As the tin electroplating bath, for example, a bath containing a water-soluble tin salt, an inorganic acid or an organic acid or a water-soluble salt thereof, and a surfactant can be used.
ここで、錫塩としては第１錫塩と第２錫塩があり、第１錫塩（錫塩（ＩＩ））としては、イセチオン酸錫（ＩＩ）等のアルカノールスルホン酸錫（ＩＩ）、メタンスルホン酸錫（ＩＩ）等のアルカンスルホン酸錫（ＩＩ）などの有機スルホン酸錫（ＩＩ）、硫酸錫（ＩＩ）、塩化錫（ＩＩ）、臭化錫（ＩＩ）、ヨウ化錫（ＩＩ）、酸化錫（ＩＩ）、リン酸錫（ＩＩ）、ピロリン酸錫（ＩＩ）、酢酸錫（ＩＩ）、クエン酸錫（ＩＩ）、グルコン酸錫（ＩＩ）、酒石酸錫（ＩＩ）、乳酸錫（ＩＩ）、コハク酸錫（ＩＩ）、スルファミン酸錫（ＩＩ）、ホウフッ化錫（ＩＩ）、ギ酸錫（ＩＩ）、ケイフッ化錫（ＩＩ）等が挙げられ、第２錫塩（錫塩（ＩＶ））としては、錫酸ナトリウム、錫酸カリウム等が挙げられるが、特にイセチオン酸錫（ＩＩ）等のアルカノールスルホン酸錫（ＩＩ）、メタンスルホン酸錫（ＩＩ）等のアルカンスルホン酸錫（ＩＩ）などの有機スルホン酸錫（ＩＩ）が好ましく挙げられる。 Here, the tin salt includes a stannous salt and a second tin salt, and the first tin salt (tin salt (II)) includes tin (II) alkanol sulfonate such as tin (II) isethionate, methane. Organosulfonate tin (II) such as tin (II) alkane sulfonate such as tin (II) sulfonate, tin (II) sulfate, tin (II) chloride, tin (II) bromide, tin (II) iodide , Tin (II) oxide, tin (II) phosphate, tin (II) pyrophosphate, tin (II) acetate, tin (II) citrate, tin (II) gluconate, tin (II) tartrate, tin lactate ( II), tin (II) succinate, tin (II) sulfamate, tin (II) borofluoride, tin (II) formate, tin (II) silicofluoride and the like. )) Include sodium stannate, potassium stannate and the like, and in particular, tin isethionate (II Alkanol sulfonic tin etc. (II), organic sulfonic tin, such as alkanesulfonic tin such as methanesulfonate, tin (II) (II) (II) may be preferably mentioned.
この場合、上記水溶性錫塩のめっき浴中での含有量は、錫として５〜１００ｇ／Ｌ、特に１０〜７０ｇ／Ｌであることが好ましい。 In this case, the content of the water-soluble tin salt in the plating bath is preferably 5 to 100 g / L, particularly 10 to 70 g / L as tin.
次に、無機酸もしくは有機酸又はその水溶性塩としては、硫酸、塩酸、硝酸、フッ化水素酸、リン酸、ピロリン酸、縮合リン酸、スルファミン酸、有機スルホン酸（脂肪族スルホン酸、芳香族スルホン酸）、カルボン酸（脂肪族飽和カルボン酸、芳香族カルボン酸、アミノカルボン酸等）、ホスホン酸から選ばれる酸又はそれらの塩又はラクトン化合物が挙げられる。 Next, inorganic acids or organic acids or water-soluble salts thereof include sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, phosphoric acid, pyrophosphoric acid, condensed phosphoric acid, sulfamic acid, organic sulfonic acid (aliphatic sulfonic acid, aromatic Group sulfonic acids), carboxylic acids (aliphatic saturated carboxylic acids, aromatic carboxylic acids, aminocarboxylic acids, etc.), acids selected from phosphonic acids, or salts or lactone compounds thereof.
ここで、脂肪族スルホン酸又は芳香族スルホン酸としては、置換又は未置換のアルカンスルホン酸、ヒドロキシアルカンスルホン酸、ベンゼンスルホン酸、ナフタレンスルホン酸などが挙げられる。未置換アルカンスルホン酸は、ＣnＨ2n+1ＳＯ3Ｈ（但し、ｎは１〜５の整数、好ましくは１又は２である。）で示されるものが使用できる。 Here, examples of the aliphatic sulfonic acid or the aromatic sulfonic acid include substituted or unsubstituted alkane sulfonic acid, hydroxyalkane sulfonic acid, benzene sulfonic acid, and naphthalene sulfonic acid. As the unsubstituted alkanesulfonic acid, one represented by C n H 2n + 1 SO 3 H (where n is an integer of 1 to 5, preferably 1 or 2) can be used.
未置換のヒドロキシアルカンスルホン酸は、下記式で示されるものが使用できる。 As the unsubstituted hydroxyalkanesulfonic acid, those represented by the following formula can be used.
置換のアルカンスルホン酸、ヒドロキシアルカンスルホン酸は、そのアルキル基の水素原子の一部がハロゲン原子、アリール基、アルキルアリール基、カルボキシル基、スルホン酸基などで置換されたものが使用できる。 As the substituted alkanesulfonic acid and hydroxyalkanesulfonic acid, those in which some of the hydrogen atoms of the alkyl group are substituted with halogen atoms, aryl groups, alkylaryl groups, carboxyl groups, sulfonic acid groups, and the like can be used.
一方、ベンゼンスルホン酸、ナフタレンスルホン酸は、下記式で示されるものである。 On the other hand, benzenesulfonic acid and naphthalenesulfonic acid are those represented by the following formula.
置換ベンゼンスルホン酸、ナフタレンスルホン酸は、ベンゼン環、ナフタレン環の水素原子の一部が水酸基、ハロゲン原子、アルキル基、カルボキシル基、ニトロ基、メルカプト基、アミノ基、スルホン酸基などで置換されたものが使用できる。 In substituted benzene sulfonic acid and naphthalene sulfonic acid, part of hydrogen atoms of benzene ring and naphthalene ring are substituted with hydroxyl group, halogen atom, alkyl group, carboxyl group, nitro group, mercapto group, amino group, sulfonic acid group, etc. Things can be used.
具体的には、メタンスルホン酸、エタンスルホン酸、イセチオン酸、１−プロパンスルホン酸、２−プロパンスルホン酸、１−ブタンスルホン酸、２−ブタンスルホン酸、ペンタンスルホン酸、クロルプロパンスルホン酸、２−ヒドロキシエタン−１−スルホン酸、２−ヒドロキシプロパンスルホン酸、３−ヒドロキシプロパンスルホン酸、１−ヒドロキシ−２−プロパンスルホン酸、２−ヒドロキシブタン−１−スルホン酸、２−ヒドロキシペンタンスルホン酸、アリルスルホン酸、２−スルホ酢酸、２−スルホプロピオン酸、３−スルホプロピオン酸、スルホコハク酸、スルホマレイン酸、スルホフマル酸、ベンゼンスルホン酸、トルエンスルホン酸、キシレンスルホン酸、ニトロベンゼンスルホン酸、スルホ安息香酸、スルホサリチル酸、ベンズアルデヒドスルホン酸、ｐ−フェノールスルホン酸などが例示される。 Specifically, methanesulfonic acid, ethanesulfonic acid, isethionic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, chloropropanesulfonic acid, 2 -Hydroxyethane-1-sulfonic acid, 2-hydroxypropanesulfonic acid, 3-hydroxypropanesulfonic acid, 1-hydroxy-2-propanesulfonic acid, 2-hydroxybutane-1-sulfonic acid, 2-hydroxypentanesulfonic acid, Allylsulfonic acid, 2-sulfoacetic acid, 2-sulfopropionic acid, 3-sulfopropionic acid, sulfosuccinic acid, sulfomaleic acid, sulfofumaric acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, nitrobenzenesulfonic acid, sulfobenzoic acid , Sulfosalicyl , Benzaldehyde sulfonic acid, such as p- phenolsulfonic acid.
一方、カルボン酸は、具体的に脂肪族飽和カルボン酸としては、ギ酸、酢酸、乳酸、プロピオン酸、酪酸、グルコン酸等のモノカルボン酸、シュウ酸、マロン酸、コハク酸、酒石酸、リンゴ酸等のジカルボン酸、クエン酸、トリカルバリル酸等のトリカルボン酸などを挙げることができ、芳香族カルボン酸としては、フェニル酢酸、安息香酸、アニス酸などが挙げられる。また、アミノカルボン酸としては、イミノ二酢酸、ニトリロ三酢酸（ＮＴＡ）、エチレンジアミン四酢酸（ＥＤＴＡ）、ジエチレントリアミン五酢酸などが挙げられる。 On the other hand, the carboxylic acid specifically includes aliphatic carboxylic acids such as formic acid, acetic acid, lactic acid, propionic acid, butyric acid, gluconic acid and other monocarboxylic acids, oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, etc. And tricarboxylic acids such as dicarboxylic acid, citric acid, and tricarballylic acid. Examples of aromatic carboxylic acids include phenylacetic acid, benzoic acid, and anisic acid. Examples of aminocarboxylic acids include iminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid.
縮合リン酸としては、ピロリン酸、トリポリリン酸、テトラポリリン酸、ポリリン酸（重合度５以上）、ヘキサメタリン酸などが挙げられ、ホスホン酸としては、アミノトリメチレンホスホン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、エチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸などが挙げられる。 Examples of the condensed phosphoric acid include pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, polyphosphoric acid (polymerization degree of 5 or more), hexametaphosphoric acid, and the like. Examples of the phosphonic acid include aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1, Examples thereof include 1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid.
塩としては、上記酸のアルカリ金属塩（ナトリウム、カリウム、リチウム塩等）、アルカリ土類金属塩（マグネシウム、カルシウム、バリウム塩等）、２価の錫塩、４価の錫塩、アンモニウム塩、有機アミン塩（モノメチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、イソプロピルアミン、エチレンジアミン、ジエチレントリアミン等）などが挙げられる。また、ラクトン化合物としては、グルコノラクトン、グルコノヘプトラクトンなどが挙げられる。 Examples of the salt include alkali metal salts (sodium, potassium, lithium salts, etc.), alkaline earth metal salts (magnesium, calcium, barium salts, etc.), divalent tin salts, tetravalent tin salts, ammonium salts, And organic amine salts (monomethylamine, dimethylamine, trimethylamine, ethylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.). Examples of the lactone compound include gluconolactone and gluconoheptlactone.
これらの無機酸、有機酸及びその水溶性塩のめっき浴中の含有量は１０〜４００ｇ／Ｌ、特に１００〜２００ｇ／Ｌが好ましい。少なすぎるとめっき浴の安定性が悪くなり、多すぎると効果のない過剰量となる傾向となる。 The content of these inorganic acids, organic acids and water-soluble salts thereof in the plating bath is preferably 10 to 400 g / L, particularly preferably 100 to 200 g / L. When the amount is too small, the stability of the plating bath is deteriorated, and when the amount is too large, the amount tends to be ineffective.
また、めっき浴には非イオン性界面活性剤、陽イオン界面活性剤、陰イオン界面活性剤、両性界面活性剤の１種又は２種以上を配合することができる。特に発泡性が低い非イオン界面活性剤を配合することにより、めっき処理の作業性が向上する。 Moreover, 1 type, or 2 or more types of a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can be mix | blended with a plating bath. In particular, the workability of the plating treatment is improved by adding a nonionic surfactant having a low foaming property.
非イオン界面活性剤としては、アルキレンオキサイド系のものが好適であり、ポリオキシエチレンアルキルフェニルエーテル、エチレンオキサイドプロピレンオキサイドブロックコポリマー、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン多価アルコールエーテル、ポリエチレングリコールなどを使用することができるが、特にポリオキシエチレンアルキルフェニルエーテルが好ましく用いられる。 As the nonionic surfactant, those based on alkylene oxide are suitable, such as polyoxyethylene alkylphenyl ether, ethylene oxide propylene oxide block copolymer, polyoxyethylene alkyl ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid ester, Polyoxyethylene polyhydric alcohol ether, polyethylene glycol and the like can be used, and polyoxyethylene alkylphenyl ether is particularly preferably used.
陽イオン界面活性剤としては、ドデシルトリメチルアンモニウム塩、ヘキサデシルトリメチルアンモニウム塩、オクタデシルトリメチルアンモニウム塩、ドデシルジメチルアンモニウム塩、オクタデセニルジメチルエチルアンモニウム塩、ドデシルジメチルエチルアンモニウムベタイン、オクタデシルジメチルアンモニウムベタイン、ジメチルベンジルドデシルアンモニウム塩、ヘキサデシルジメチルベンジルアンモニウム塩、トリメチルベンジルアンモニウム塩、トリエチルベンジルアンモニウム塩、ヘキサデシルピリジニウム塩、ドデシルピリジニウム塩、ドデシルピコリニウム塩、ドデシルイミダゾリニウム塩、オレイルイミダゾリニウム塩、オクタデシルアミンアセテート、ドデシルアミンアセテートなどが挙げられる。 Cationic surfactants include dodecyl trimethyl ammonium salt, hexadecyl trimethyl ammonium salt, octadecyl trimethyl ammonium salt, dodecyl dimethyl ammonium salt, octadecenyl dimethyl ethyl ammonium salt, dodecyl dimethyl ethyl ammonium betaine, octadecyl dimethyl ammonium betaine, dimethyl Benzyldodecylammonium salt, hexadecyldimethylbenzylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, hexadecylpyridinium salt, dodecylpyridinium salt, dodecylpicolinium salt, dodecylimidazolinium salt, oleylimidazolinium salt, octadecylamine Examples include acetate and dodecylamine acetate.
陰イオン界面活性剤としては、アルキル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルベンゼンスルホン酸、（ポリ）アルキルナフタレンスルホン酸塩等が挙げられる。アルキル硫酸塩としては、ドデシル硫酸ナトリウム、オレイル硫酸ナトリウムなどが挙げられる。ポリオキシエチレン（ＥＯ１２）ノニルエーテル硫酸ナトリウム、ポリオキシエチレン（ＥＯ１５）ドデシルエーテル硫酸ナトリウムが挙げられる。 Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonic acids, (poly) alkyl naphthalene sulfonates, and the like. Examples of the alkyl sulfate include sodium dodecyl sulfate and sodium oleyl sulfate. Examples thereof include sodium polyoxyethylene (EO12) nonyl ether sulfate and sodium polyoxyethylene (EO15) dodecyl ether sulfate.
両性界面活性剤としては、ベタイン、スルホベタイン、アミノカルボン酸、イミダゾリニウムベタイン等が挙げられる。また、エチレンオキサイド及び／又はプロピレンオキサイドとアルキルアミン又はジアミンとの縮合生成物の硫酸化あるいはスルホン化付加物も使用できる。 Examples of the amphoteric surfactant include betaine, sulfobetaine, aminocarboxylic acid, imidazolinium betaine and the like. Further, sulfated or sulfonated adducts of condensation products of ethylene oxide and / or propylene oxide and alkylamines or diamines can also be used.
これらの界面活性剤の配合量は０．０１〜１００ｇ／Ｌ、特に５〜５０ｇ／Ｌが好ましく、少なすぎると高電流密度でヤケやコゲが発生する場合があり、多すぎるとめっき皮膜が黒っぽくなったり、色むらが発生するなどの不良を生じる場合がある。 The blending amount of these surfactants is preferably 0.01 to 100 g / L, and particularly preferably 5 to 50 g / L. If the amount is too small, burns and burns may occur at a high current density. If the amount is too large, the plating film becomes dark. There may be a case where a defect occurs such as color irregularity.
めっき浴は酸性であることが好ましく、特にｐＨが１未満であることが好ましい。 The plating bath is preferably acidic, and particularly preferably has a pH of less than 1.
バリア層は、粉状めっき、樹枝上めっきといわれるいわゆるヤケ状態となる直前の条件で形成され、この条件は、通常の錫めっき皮膜を形成するときの陰極電流密度より高い陰極電流密度が適用される。具体的には、バリア層をめっきする際の陰極電流密度は、用いるめっき浴及び適応される陰極電流密度以外のめっき条件によって異なるが、そのめっき浴及び陰極電流密度以外のめっき条件において決定される臨界電流密度の上限値の７０〜１００％、特に７０〜９０％の陰極電流密度で形成するとよい。この場合、臨界電流密度は、ＪＩＳ Ｈ ０４００において規定され、電気めっきにおいて正常な皮膜を生成する電流密度の上限値及び下限値である。 The barrier layer is formed under conditions immediately before the so-called burnt state called powder plating and dendrite plating, and this condition applies a cathode current density higher than the cathode current density when a normal tin plating film is formed. The Specifically, the cathode current density at the time of plating the barrier layer varies depending on the plating bath used and plating conditions other than the applicable cathode current density, but is determined in the plating conditions other than the plating bath and cathode current density. The cathode current density may be 70 to 100%, particularly 70 to 90% of the upper limit of the critical current density. In this case, the critical current density is defined in JIS H 0400, and is an upper limit value and a lower limit value of a current density that generates a normal film in electroplating.
この陰極電流密度条件は、ハルセル試験により決定することができ、具体的には、めっき処理したハルセル試験板と、ハルセルスケール（ハルセルテストを実施した電流値で試験板上の各ポイントの陰極電流密度が推定できる）とを合わせ、ヤケ状態が生じた範囲の下限の陰極電流密度（即ち、臨界電流密度の上限値）を決定する。そして実際に適用する陰極電流密度は、臨界電流密度の上限値の７０〜１００％、特に７０〜９０％の範囲内で設定する。臨界電流密度の上限値の７０％未満だと、結晶形態が針状又は角状の粗い皮膜とならずウィスカを抑制するバリア層の役目を果たさず、１００％を超えると、粉状めっき、樹枝状めっきといわれるヤケ状態となり、金属薄膜とならず素材との密着性も得られない。 This cathode current density condition can be determined by a hull cell test. Specifically, a hull cell test plate subjected to a plating process and a hull cell scale (a cathode current density at each point on the test plate at a current value obtained by performing the hull cell test). The lower limit cathode current density (that is, the upper limit value of the critical current density) in the range where the burnt state occurs is determined. The actually applied cathode current density is set within the range of 70 to 100%, particularly 70 to 90% of the upper limit value of the critical current density. If the critical current density is less than 70% of the upper limit of the critical current density, the crystal form does not become a needle-like or angular rough film and does not serve as a barrier layer for suppressing whiskers. It becomes a discolored state called a plate-like plating, and it does not become a metal thin film and also cannot be adhered to the material.
一方、表面層は、良好なはんだ接合性を与えるめっき条件が必要とされ、この場合は臨界電流密度の上限値の１〜７０％、特に５〜７０％の範囲で設定される。臨界電流密度の上限値の１％未満だと、析出速度が遅く効率的でなく、７０％を超えると析出形態が針状、角状となり良好なはんだ濡れ性が得られない。 On the other hand, the surface layer is required to have plating conditions that give good solderability. In this case, the surface layer is set in the range of 1 to 70%, particularly 5 to 70% of the upper limit value of the critical current density. If the critical current density is less than 1% of the upper limit of the critical current density, the deposition rate is slow and not efficient, and if it exceeds 70%, the form of precipitation becomes needle-like or square-like and good solder wettability cannot be obtained.
バリア層と表面層とを形成する際の陰極電流密度は、用いる錫めっき浴の種類によって異なるが、例えば、バリア層形成時の陰極電流密度は１〜１００Ａ／ｄｍ2、特に１〜５０Ａ／ｄｍ2とすることが好ましく、表面層形成時の陰極電流密度は０．１〜５０Ａ／ｄｍ2、特に０．２〜２０Ａ／ｄｍ2とすることが好ましい。 The cathode current density at the time of forming the barrier layer and the surface layer varies depending on the type of tin plating bath used. For example, the cathode current density at the time of forming the barrier layer is 1 to 100 A / dm 2 , particularly 1 to 50 A / dm. 2 and the cathode current density during the formation of the surface layer is preferably 0.1 to 50 A / dm 2 , particularly preferably 0.2 to 20 A / dm 2 .
なお、バリア層及び表面層を形成するために用いるめっき浴は、同じものでも異なるものでも良いが、バリア層を形成する場合は、光沢剤を含有しないめっき浴又は光沢剤を含有するものであれば少量、例えば０．０１〜０．５ｇ／Ｌで含有するめっき浴を用いることが好ましい。光沢剤に由来する層中の炭素含有量が０．０５質量％以下の場合、皮膜が粗くなりやすいことから、光沢剤を含有しないめっき浴を用いると、バリア層に要求される結晶形態を形成しやすく好適である。一方、表面層は光沢剤を含有しないめっき浴でも光沢剤を含有するめっき浴でも形成可能である。 The plating bath used to form the barrier layer and the surface layer may be the same or different. However, when the barrier layer is formed, any plating bath that does not contain a brightener or a brightener may be used. For example, it is preferable to use a plating bath containing a small amount, for example, 0.01 to 0.5 g / L. When the carbon content in the layer derived from the brightener is 0.05% by mass or less, the film tends to become rough, so if a plating bath that does not contain the brightener is used, the crystal form required for the barrier layer is formed. It is easy to do and is suitable. On the other hand, the surface layer can be formed by a plating bath containing no brightener or a plating bath containing a brightener.
また、バリア層を形成する際のめっき浴の錫イオン濃度を、表面層を形成するめっき浴より低く、例えば２０〜７５％程度低く設定することが好ましく、また、バリア層を形成する際のめっき浴の遊離酸濃度を、表面層を形成するめっき浴より高く、例えば１５０〜３００％程度高く設定することが好ましい。これは、このような濃度条件とすることにより、カソード近傍の錫イオン濃度が減少し、結晶形態の粗化が可能となるためである。 Moreover, it is preferable to set the tin ion concentration of the plating bath when forming the barrier layer to be lower than that of the plating bath that forms the surface layer, for example, about 20 to 75%, and plating when forming the barrier layer. It is preferable to set the free acid concentration of the bath higher than the plating bath for forming the surface layer, for example, about 150 to 300% higher. This is because such a concentration condition reduces the tin ion concentration in the vicinity of the cathode and makes it possible to roughen the crystal form.
本発明のめっき浴を用いて電気めっきする方法としては常法が採用し得、ラック法でもバレル法でもよく、ラックレスやリール・ツー・リール等の高速めっき法を採用することもできる。めっき温度は１０〜６０℃、特に２０〜５０℃とすることができるが、バリア層形成時の温度は、表面層形成時の温度より低く、例えば５〜２０℃程度低く設定することが好ましい。これは、温度を低く設定することにより、カソード近傍の錫イオン濃度が減少し、結晶形態の粗化が可能となるためである。 As a method of electroplating using the plating bath of the present invention, a conventional method can be adopted, a rack method or a barrel method may be used, and a high-speed plating method such as rackless or reel-to-reel can also be adopted. The plating temperature can be 10 to 60 ° C., particularly 20 to 50 ° C., but the temperature during the formation of the barrier layer is preferably set lower than the temperature during the formation of the surface layer, for example, about 5 to 20 ° C. This is because by setting the temperature low, the tin ion concentration in the vicinity of the cathode decreases, and the crystal form can be roughened.
撹拌は無撹拌でもよいが、カソードロッキング、スターラーによる撹拌、自動搬送装置による素材走行、ポンプによる液流動などの方法が採用し得る。陽極としては、可溶性陽極、即ち、通常錫を用いることが好ましいが、炭素、白金等の不溶性陽極でもよい。 Stirring may be performed without stirring, but methods such as cathode locking, stirring with a stirrer, material traveling with an automatic conveying device, and liquid flow with a pump may be employed. As the anode, a soluble anode, that is, usually tin is preferably used, but an insoluble anode such as carbon or platinum may be used.
また、各層を形成する間に水洗等の処理を行ってもよいが、水洗等の処理を行わずに、めっき浴に浸漬したまま、電流値の切り替えを行うことで結晶形態の異なる多層で構成された錫めっき皮膜を形成することも可能である。 In addition, it may be washed with water while forming each layer, but it is composed of multilayers with different crystal forms by switching the current value while immersed in the plating bath without performing washing or the like. It is also possible to form a tin plating film.
一方、基体（被めっき物）の種類は、特に制限されず、電気めっき可能な導電性部分を有するものであればよく、銅、銅合金等の金属等の導電性材料、又はこのような導電性材料とセラミック、鉛ガラス、プラスチック、フェライト等の絶縁性材料とが複合したものであってもよい。これら基体は、その材質に応じた適宜な前処理を施した後、めっきに供される。 On the other hand, the type of the substrate (to-be-plated object) is not particularly limited as long as it has a conductive portion that can be electroplated, and may be a conductive material such as a metal such as copper or copper alloy, or such a conductive material. A composite of an insulating material and an insulating material such as ceramic, lead glass, plastic, or ferrite may be used. These substrates are subjected to an appropriate pretreatment according to the material and then subjected to plating.
具体的には、基体として、チップ部品、水晶発振子、バンプ、コネクタ、リードフレーム、フープ材、半導体パッケージ、プリント基板の回路等のあらゆる電子機器構成部品やその他の製品のはんだ材料を必要とする部分にウィスカ抑制効果の高い錫めっき皮膜を形成し得る。 Specifically, as a base, it requires solder materials for all electronic device components such as chip parts, crystal oscillators, bumps, connectors, lead frames, hoop materials, semiconductor packages, printed circuit boards, and other products. A tin plating film having a high whisker suppressing effect can be formed on the portion.
上記のようにして形成された錫多層皮膜は、熱処理、リフロー処理を実施することなくウィスカ発生を効果的に抑制できることから、熱処理、リフロー処理によりはんだ濡れ性が劣化する懸念がない。 Since the tin multilayer coating formed as described above can effectively suppress whisker generation without performing heat treatment and reflow treatment, there is no concern that solder wettability deteriorates due to heat treatment and reflow treatment.
以下、実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
［実施例１〜６］
りん青銅材（Ｃ５１９１）に、下記処理工程に従い、錫電気めっき浴にて２層の錫めっき皮膜を形成した。各々の層を形成する際に用いためっき浴及びめっき条件、並びに各層及び錫めっき皮膜全体の厚さは表１に示すとおりである。
[Examples 1 to 6]
A two-layer tin plating film was formed on a phosphor bronze material (C5191) in a tin electroplating bath according to the following treatment steps. Table 1 shows the plating bath and plating conditions used when forming each layer, and the thickness of each layer and the entire tin plating film.
めっき処理工程
電解脱脂（２分）→水洗（１５秒）×３回→酸洗（２０秒）→水洗（１５秒）×３回→下層錫電気めっき（温度２５℃）→水洗（１５秒）×３回→酸洗（２０秒）→水洗（１５秒）×３回→上層錫電気めっき（温度２５℃）→水洗（１５秒）×３回→イオン交換水→乾燥
Plating treatment process Electrolytic degreasing (2 minutes) → Washing (15 seconds) × 3 times → Pickling (20 seconds) → Washing (15 seconds) × 3 times → Lower tin electroplating (temperature 25 ° C.) → Washing (15 seconds) × 3 times → pickling (20 seconds) → water washing (15 seconds) × 3 times → upper tin electroplating (temperature 25 ° C.) → water washing (15 seconds) × 3 times → ion exchange water → drying
次に、得られた錫めっき皮膜を評価試料として、以下の方法でウィスカ発生抑制効果を評価した。結果を表１に併記する。
ウィスカ発生抑制効果の評価
評価試料を、温度３０℃、相対湿度６０％ＲＨ下で１ヶ月放置した後、走査型電子顕微鏡（ＳＥＭ）によってウィスカを観察した。
Next, using the obtained tin plating film as an evaluation sample, the whisker generation suppressing effect was evaluated by the following method. The results are also shown in Table 1.
Evaluation Evaluation of Whisker Generation Suppression Effect The sample for evaluation was allowed to stand for 1 month at a temperature of 30 ° C. and a relative humidity of 60% RH, and then the whisker was observed with a scanning electron microscope (SEM).
１ヶ月放置した試料について、めっきと素材界面に形成された金属間化合物層を観察し、耐ウィスカ性との相関性を確認するため収束イオンビーム（ＦＩＢ：Ｆｏｃｕｓｅｄ Ｉｏｎ Ｂｅａｍ）で断面加工した箇所について走査イオン像（ＳＩＭ：Ｓｃａｎｎｉｎｇ Ｉｏｎ Ｍｉｃｒｏｓｃｏｐｅ）を観察した。実施例１のＳＩＭ像を図２に示す。観察したＳＩＭ像について以下の手順で金属間化合物層の厚さの均一性を評価するため変動係数（ＣＶ値）を算出した。 For a sample left for one month, observe the intermetallic compound layer formed at the interface between the plating and the material, and confirm the correlation with the whisker resistance in the section processed with a focused ion beam (FIB). Scanning Ion Microscope (SIM) was observed. A SIM image of Example 1 is shown in FIG. For the observed SIM image, the coefficient of variation (CV value) was calculated in order to evaluate the thickness uniformity of the intermetallic compound layer by the following procedure.
ＣＶ値の評価
断面写真（ＳＩＭ像）における１５μｍの任意の領域での金属間化合物層の膜厚を等間隔に９点、及び最大厚さ、最小厚さの計１１点の実測値により平均値、標準偏差を算出し、それを基にして変動係数を算出した。結果を表１に併記する。
変動係数（ＣＶ値）：サンプル値の標準偏差を平均値で割ることによって、実質的なデータのばらつきの大きさ（ばらつき度）を評価する尺度
ＣＶ値（％）＝標準偏差÷平均値×１００
ＣＶ値が４０％以下の場合 金属間化合物が均一に生成
ＣＶ値が４０％を超える場合 金属間化合物が不均一に生成
CV value evaluation cross-sectional photograph (SIM image) The average value of the film thickness of the intermetallic compound layer in an arbitrary region of 15 μm at an equal interval of 9 points and the measured values of 11 points in total, the maximum thickness and the minimum thickness. The standard deviation was calculated, and the coefficient of variation was calculated based on the standard deviation. The results are also shown in Table 1.
Coefficient of variation (CV value): A scale for evaluating the degree of substantial data dispersion (degree of dispersion) by dividing the standard deviation of sample values by the average value CV value (%) = standard deviation ÷ average value × 100
When the CV value is 40% or less, the intermetallic compound is generated uniformly. When the CV value is over 40%, the intermetallic compound is generated unevenly.
また、上記錫めっき皮膜と素材界面に形成された金属間化合物層の断面のＳＥＭ像を観察すると共に、金属間化合物層の均一性をさらに評価するためＥＰＭＡ分析で、評価試料断面の錫及び銅分布を観察した。実施例１の結果を図３に示す。なお、測定条件は以下のとおりである。 Moreover, while observing the SEM image of the cross section of the intermetallic compound layer formed at the interface between the tin plating film and the material, and further evaluating the uniformity of the intermetallic compound layer, the EPMA analysis was performed to evaluate tin and copper in the cross section of the evaluation sample. The distribution was observed. The results of Example 1 are shown in FIG. The measurement conditions are as follows.
ＥＰＭＡ測定条件
測定機器：分析走査電子顕微鏡ＪＸＡ−８６００ＭＸ（日本電子（株）製）−ＥＰＭＡ（波長分散型Ｘ線分析装置）
加速電圧：１５ｋＶ、照射電流：１．０×１０-8Ａ
EPMA measurement condition measuring instrument: analytical scanning electron microscope JXA-8600MX (manufactured by JEOL Ltd.)-EPMA (wavelength dispersive X-ray analyzer)
Acceleration voltage: 15 kV, irradiation current: 1.0 × 10 −8 A
一方、銅材（Ｃ１０２０）端子に、上記処理工程に従い、上記錫めっき浴にて２層の錫めっき皮膜を形成した。 On the other hand, a two-layered tin plating film was formed on a copper (C1020) terminal in the tin plating bath according to the above treatment process.
得られた錫めっき皮膜を評価試料として、以下の方法ではんだ濡れ性を評価した。結果を表１に併記する。
はんだ濡れ性の評価
加速劣化促進試験条件（ＰＣＴ）：温度１０５℃、相対湿度１００％ＲＨ、時間８時間
測定機器：タルチンケスター（株）製ＳＷＥＴ−２１００
はんだ：錫−３．０銀−０．５銅（千住金属工業（株）製Ｍ７０５）
フラックス：ＣＦ−１１０ＶＨ−２Ａ（タムラ化研（株）製）
はんだ温度：２５５℃
浸漬温度：２ｍｍ／ｓｅｃ
浸漬深さ：２ｍｍ
保持時間：１０ｓｅｃ
The obtained tin plating film was used as an evaluation sample, and the solder wettability was evaluated by the following method. The results are also shown in Table 1.
Evaluation of solder wettability Accelerated deterioration test condition (PCT): temperature 105 ° C., relative humidity 100% RH, time 8 hours Measuring instrument: SWET-2100 manufactured by Tarchin Kester Co., Ltd.
Solder: Tin-3.0 silver-0.5 copper (M705 manufactured by Senju Metal Industry Co., Ltd.)
Flux: CF-110VH-2A (Tamura Kaken Co., Ltd.)
Solder temperature: 255 ° C
Immersion temperature: 2mm / sec
Immersion depth: 2mm
Holding time: 10 sec
［実施例７］
りん青銅材（Ｃ５１９１）に、下記処理工程に従い、錫電気めっき浴にて３層の錫めっき皮膜を形成した。各々の層を形成する際に用いためっき浴及びめっき条件、並びに各層及び錫めっき皮膜全体の厚さは表１に示すとおりである。
[Example 7]
A three-layer tin plating film was formed on a phosphor bronze material (C5191) in a tin electroplating bath according to the following treatment steps. Table 1 shows the plating bath and plating conditions used when forming each layer, and the thickness of each layer and the entire tin plating film.
めっき処理工程
電解脱脂（２分）→水洗（１５秒）×３回→酸洗（２０秒）→水洗（１５秒）×３回→下層錫電気めっき（温度２５℃）→水洗（１５秒）×３回→酸洗（２０秒）→水洗（１５秒）×３回→中間層錫電気めっき（温度２５℃）→水洗（１５秒）×３回→酸洗（２０秒）→水洗（１５秒）×３回→上層錫電気めっき（温度２５℃）→水洗（１５秒）×３回→イオン交換水→乾燥
Plating treatment process Electrolytic degreasing (2 minutes) → Washing (15 seconds) × 3 times → Pickling (20 seconds) → Washing (15 seconds) × 3 times → Lower tin electroplating (temperature 25 ° C.) → Washing (15 seconds) × 3 times → pickling (20 seconds) → water washing (15 seconds) × 3 times → intermediate tin electroplating (temperature 25 ° C.) → water washing (15 seconds) × 3 times → pickling (20 seconds) → water washing (15 Sec) x 3 times → Upper tin electroplating (temperature 25 ° C) → Washing with water (15 sec) x 3 times → Ion exchange water → Drying
次に、得られた錫めっき皮膜を評価試料として、実施例１と同様の方法でウィスカ発生抑制効果を評価した。結果を表１に併記する。 Next, using the obtained tin plating film as an evaluation sample, the whisker generation suppressing effect was evaluated in the same manner as in Example 1. The results are also shown in Table 1.
１ヶ月放置した試料について、実施例１と同様の方法でＳＩＭ像を観察し、変動係数（ＣＶ値）を算出した。 For the sample left for one month, a SIM image was observed in the same manner as in Example 1, and the coefficient of variation (CV value) was calculated.
一方、銅材（Ｃ１０２０）端子に、上記処理工程に従い、上記錫めっき浴にて３層の錫めっき皮膜を形成した。 On the other hand, a three-layer tin plating film was formed on the copper material (C1020) terminal in the tin plating bath according to the above treatment process.
得られた錫めっき皮膜を評価試料として、実施例１と同様の方法ではんだ濡れ性を評価した。結果を表１に併記する。 The obtained tin plating film was used as an evaluation sample, and the solder wettability was evaluated in the same manner as in Example 1. The results are also shown in Table 1.
［比較例１、６、７］
りん青銅材（Ｃ５１９１）に、下記処理工程に従い、錫電気めっき浴にて２層の錫めっき皮膜を形成した。各々の層を形成する際に用いためっき浴及びめっき条件、並びに各層及び錫めっき皮膜全体の厚さは表２に示すとおりである。
[Comparative Examples 1, 6, and 7]
A two-layer tin plating film was formed on a phosphor bronze material (C5191) in a tin electroplating bath according to the following treatment steps. Table 2 shows the plating bath and plating conditions used when forming each layer, and the thickness of each layer and the entire tin plating film.
めっき処理工程
電解脱脂（２分）→水洗（１５秒）×３回→酸洗（２０秒）→水洗（１５秒）×３回→下層錫電気めっき（温度２５℃）→水洗（１５秒）×３回→酸洗（２０秒）→水洗（１５秒）×３→上層錫電気めっき（温度２５℃）→水洗（１５秒）×３回→イオン交換水→乾燥
Plating treatment process Electrolytic degreasing (2 minutes) → Washing (15 seconds) × 3 times → Pickling (20 seconds) → Washing (15 seconds) × 3 times → Lower tin electroplating (temperature 25 ° C.) → Washing (15 seconds) × 3 times → pickling (20 seconds) → water washing (15 seconds) × 3 → upper tin electroplating (temperature 25 ° C.) → water washing (15 seconds) × 3 times → ion exchange water → drying
次に、得られた錫めっき皮膜を評価試料として、実施例１と同様の方法でウィスカ発生抑制効果を評価した。結果を表２に併記する。 Next, using the obtained tin plating film as an evaluation sample, the whisker generation suppressing effect was evaluated in the same manner as in Example 1. The results are also shown in Table 2.
１ヶ月放置した試料について、実施例１と同様の方法でＳＩＭ像を観察し、変動係数（ＣＶ値）を算出した。 For the sample left for one month, a SIM image was observed in the same manner as in Example 1, and the coefficient of variation (CV value) was calculated.
一方、銅材（Ｃ１０２０）端子に、上記処理工程に従い、上記錫めっき浴にて２層の錫めっき皮膜を形成した。 On the other hand, a two-layered tin plating film was formed on a copper (C1020) terminal in the tin plating bath according to the above treatment process.
得られた錫めっき皮膜を評価試料として、実施例１と同様の方法ではんだ濡れ性を評価した。結果を表２に併記する。 The obtained tin plating film was used as an evaluation sample, and the solder wettability was evaluated in the same manner as in Example 1. The results are also shown in Table 2.
［比較例２、３］
りん青銅材（Ｃ５１９１）に、下記処理工程に従い、錫電気めっき浴にて１層の錫めっき皮膜を形成した。層を形成する際に用いためっき浴及びめっき条件、並びに層（錫めっき皮膜全体）の厚さは表２に示すとおりである。
[Comparative Examples 2 and 3]
One layer of tin plating film was formed on a phosphor bronze material (C5191) in a tin electroplating bath according to the following treatment steps. Table 2 shows the plating bath and plating conditions used when forming the layer, and the thickness of the layer (the entire tin plating film).
めっき処理工程
電解脱脂（２分）→水洗（１５秒）×３回→酸洗（２０秒）→水洗（１５秒）×３回→上層又は下層錫電気めっき（温度２５℃）→水洗（１５秒）×３回→イオン交換水→乾燥
Plating treatment step Electrolytic degreasing (2 minutes) → Washing (15 seconds) × 3 times → Pickling (20 seconds) → Washing (15 seconds) × 3 times → Upper or lower tin electroplating (temperature 25 ° C.) → Washing (15 Sec) x 3 times → ion exchange water → drying
次に、得られた錫めっき皮膜を評価試料として、実施例１と同様の方法でウィスカ発生抑制効果を評価した。結果を表２に併記する。 Next, using the obtained tin plating film as an evaluation sample, the whisker generation suppressing effect was evaluated in the same manner as in Example 1. The results are also shown in Table 2.
１ヶ月放置した試料について、実施例１と同様の方法でＳＩＭ像を観察した。比較例２のＳＩＭ像を図４、比較例３のＳＩＭ像を図６に示す。観察したＳＩＭ像について実施例１と同様の方法で金属間化合物層の厚さの均一性を評価するため変動係数（ＣＶ値）を算出した。 A SIM image was observed in the same manner as in Example 1 for the sample left for one month. The SIM image of Comparative Example 2 is shown in FIG. 4, and the SIM image of Comparative Example 3 is shown in FIG. For the observed SIM image, a coefficient of variation (CV value) was calculated by the same method as in Example 1 in order to evaluate the uniformity of the thickness of the intermetallic compound layer.
また、上記錫めっき皮膜と素材界面に形成された金属間化合物層の断面のＳＥＭ像を観察すると共に、金属間化合物層の均一性をさらに評価するため、ＥＰＭＡ分析で評価試料断面の錫及び銅分布を観察した。比較例２の結果を図５、比較例３の結果を図７に示す。なお、測定条件は実施例１と同様である。 In addition, in order to further observe the SEM image of the cross section of the intermetallic compound layer formed at the interface between the tin plating film and the material and to further evaluate the uniformity of the intermetallic compound layer, tin and copper in the cross section of the sample to be evaluated by EPMA analysis The distribution was observed. The result of Comparative Example 2 is shown in FIG. 5, and the result of Comparative Example 3 is shown in FIG. The measurement conditions are the same as in Example 1.
一方、銅材（Ｃ１０２０）端子に、上記処理工程に従い、上記錫めっき浴にて１層の錫めっき皮膜を形成した。 On the other hand, a single-layer tin plating film was formed on a copper (C1020) terminal in the tin plating bath according to the above treatment process.
得られた錫めっき皮膜を評価試料として、実施例１と同様の方法ではんだ濡れ性を評価した。結果を表２に併記する。 The obtained tin plating film was used as an evaluation sample, and the solder wettability was evaluated in the same manner as in Example 1. The results are also shown in Table 2.
［比較例４、５］
りん青銅材（Ｃ５１９１）に、下記処理工程に従い、錫電気めっき浴にて多層の錫めっき皮膜を形成した。各々の層を形成する際に用いためっき浴及びめっき条件、並びに錫めっき皮膜全体の厚さは表２に示すとおりである。
[Comparative Examples 4 and 5]
A multilayer tin plating film was formed on a phosphor bronze material (C5191) in a tin electroplating bath according to the following treatment process. Table 2 shows the plating bath and plating conditions used when forming each layer, and the thickness of the entire tin plating film.
めっき処理工程
電解脱脂（２分）→水洗（１５秒）×３回→酸洗（２０秒）→水洗（１５秒）×３回→錫電気めっき（温度２５℃）→水洗（１５秒）×３回→イオン交換水→乾燥
（但し、錫電気めっきは、電流値の切り替えにより、表２に示される下層めっき条件及び上層めっき条件を交互に適用し、比較例４は３１．５回（下層３２回、上層３１回）、比較例５は３１５回（下層３１５回、上層３１５回）繰り返した。
Plating treatment step Electrolytic degreasing (2 minutes) → water washing (15 seconds) x 3 times → pickling (20 seconds) → water washing (15 seconds) x 3 times → tin electroplating (temperature 25 ° C) → water washing (15 seconds) x 3 times-> ion exchange water-> drying (however, in the case of tin electroplating, the lower layer plating conditions and the upper layer plating conditions shown in Table 2 are applied alternately by switching the current value. Comparative Example 5 was repeated 315 times (lower layer 315 times, upper layer 315 times).
次に、得られた錫めっき皮膜を評価試料として、実施例１と同様の方法でウィスカ発生抑制効果を評価した。結果を表２に併記する。 Next, using the obtained tin plating film as an evaluation sample, the whisker generation suppressing effect was evaluated in the same manner as in Example 1. The results are also shown in Table 2.
１ヶ月放置した試料について、実施例１と同様の方法でＳＩＭ像を観察し、変動係数（ＣＶ値）を算出した。 For the sample left for one month, a SIM image was observed in the same manner as in Example 1, and the coefficient of variation (CV value) was calculated.
ウィスカ抑制効果
○：ウィスカ発生本数ゼロ
△：ウィスカが観察されたが、その長さが１０μｍ未満
×：ウィスカが観察され、その長さが１０μｍ以上
はんだ濡れ性
○：ゼロクロスタイム３秒未満
×：ゼロクロスタイム３秒以上
Whisker suppression effect ○: Number of whisker generation zero △: Whisker is observed but its length is less than 10 μm ×: Whisker is observed and its length is 10 μm or more Solder wettability ○: Zero cross time less than 3 seconds ×: Zero cross More than 3 seconds
１ 基体
２ 錫めっき皮膜
２１ バリア層
２２ 表面層
２３ 第３の層
DESCRIPTION OF SYMBOLS 1 Base | substrate 2 Tin plating film 21 Barrier layer 22 Surface layer 23 3rd layer
Claims (6)
The cathode current density when plating the barrier layer is 1 to 100 A / dm 2 , and the cathode current density when plating the surface layer is 0.01 to 50 A / dm 2 , respectively. The tin plating film according to any one of 1 to 5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012253292A (en) * | 2011-06-07 | 2012-12-20 | Murata Mfg Co Ltd | Electronic component |
| US9666547B2 (en) | 2002-10-08 | 2017-05-30 | Honeywell International Inc. | Method of refining solder materials |
| US11441231B2 (en) | 2019-09-19 | 2022-09-13 | Kunshan Yiding Industrial Technology Co., Ltd | Method for surface treatment of matte tinplated product |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01225781A (en) * | 1988-03-05 | 1989-09-08 | Kobe Steel Ltd | Tin or tin alloy-coated copper alloy material having excellent whisker resistance |
| JPH04247897A (en) * | 1991-01-24 | 1992-09-03 | Nippon Steel Corp | Production of surface treated steel sheet excellent in weldability and adhesion property with coating material |
| JP2002053981A (en) * | 2000-08-01 | 2002-02-19 | Fcm Kk | Electronic component material, method of connecting electronic component material, ball grid array type electronic component, and method of connecting ball grid array type electronic component |
| JP2003147580A (en) * | 2001-11-13 | 2003-05-21 | Murata Mfg Co Ltd | Metallic terminal, method of manufacturing metallic terminal and electronic parts |
| JP2005232484A (en) * | 2004-02-17 | 2005-09-02 | Fcm Kk | Terminal, parts and products having the same |
| JP2005344157A (en) * | 2004-06-02 | 2005-12-15 | Yuken Industry Co Ltd | Method for suppressing whisker formation from tin or tin alloy plating layer and contact member |
| WO2006006114A1 (en) * | 2004-07-07 | 2006-01-19 | Koninklijke Philips Electronics N.V. | Electronic component having tin rich deposit layer and the process for depositing the same |
-
2006
- 2006-07-12 JP JP2006191093A patent/JP2008019468A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01225781A (en) * | 1988-03-05 | 1989-09-08 | Kobe Steel Ltd | Tin or tin alloy-coated copper alloy material having excellent whisker resistance |
| JPH04247897A (en) * | 1991-01-24 | 1992-09-03 | Nippon Steel Corp | Production of surface treated steel sheet excellent in weldability and adhesion property with coating material |
| JP2002053981A (en) * | 2000-08-01 | 2002-02-19 | Fcm Kk | Electronic component material, method of connecting electronic component material, ball grid array type electronic component, and method of connecting ball grid array type electronic component |
| JP2003147580A (en) * | 2001-11-13 | 2003-05-21 | Murata Mfg Co Ltd | Metallic terminal, method of manufacturing metallic terminal and electronic parts |
| JP2005232484A (en) * | 2004-02-17 | 2005-09-02 | Fcm Kk | Terminal, parts and products having the same |
| JP2005344157A (en) * | 2004-06-02 | 2005-12-15 | Yuken Industry Co Ltd | Method for suppressing whisker formation from tin or tin alloy plating layer and contact member |
| WO2006006114A1 (en) * | 2004-07-07 | 2006-01-19 | Koninklijke Philips Electronics N.V. | Electronic component having tin rich deposit layer and the process for depositing the same |
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| US9666547B2 (en) | 2002-10-08 | 2017-05-30 | Honeywell International Inc. | Method of refining solder materials |
| JP2012253292A (en) * | 2011-06-07 | 2012-12-20 | Murata Mfg Co Ltd | Electronic component |
| US11441231B2 (en) | 2019-09-19 | 2022-09-13 | Kunshan Yiding Industrial Technology Co., Ltd | Method for surface treatment of matte tinplated product |
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