TW201704545A - 使用鏻鹽之鍍敷液 - Google Patents
使用鏻鹽之鍍敷液 Download PDFInfo
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- TW201704545A TW201704545A TW105109518A TW105109518A TW201704545A TW 201704545 A TW201704545 A TW 201704545A TW 105109518 A TW105109518 A TW 105109518A TW 105109518 A TW105109518 A TW 105109518A TW 201704545 A TW201704545 A TW 201704545A
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- Prior art keywords
- acid
- salt
- plating solution
- formula
- tin
- Prior art date
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- 238000007747 plating Methods 0.000 title claims abstract description 98
- 150000004714 phosphonium salts Chemical class 0.000 title abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 63
- 239000002253 acid Substances 0.000 claims abstract description 30
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 16
- 239000002736 nonionic surfactant Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- MILSYCKGLDDVLM-UHFFFAOYSA-N 2-phenylpropan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 MILSYCKGLDDVLM-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 56
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 19
- -1 phenanthrolinedione compound Chemical class 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 229910001128 Sn alloy Inorganic materials 0.000 description 11
- 239000011800 void material Substances 0.000 description 11
- 238000004070 electrodeposition Methods 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 7
- 229910001316 Ag alloy Inorganic materials 0.000 description 6
- 150000000703 Cerium Chemical class 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 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 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 5
- 159000000009 barium salts Chemical class 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 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 4
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 3
- 229910001152 Bi alloy Inorganic materials 0.000 description 3
- 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 3
- 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 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 239000000174 gluconic acid Substances 0.000 description 3
- 235000012208 gluconic acid Nutrition 0.000 description 3
- 235000012209 glucono delta-lactone Nutrition 0.000 description 3
- 229960003681 gluconolactone Drugs 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- 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 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- 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 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 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
- 239000003945 anionic surfactant Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 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 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- KWMLJOLKUYYJFJ-GASJEMHNSA-N (2xi)-D-gluco-heptonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C(O)=O KWMLJOLKUYYJFJ-GASJEMHNSA-N 0.000 description 1
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-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
- DWANEFRJKWXRSG-UHFFFAOYSA-N 1,2-tetradecanediol Chemical compound CCCCCCCCCCCCC(O)CO DWANEFRJKWXRSG-UHFFFAOYSA-N 0.000 description 1
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical compound CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-UHFFFAOYSA-N 0.000 description 1
- WMCMCZTWKQMHBE-UHFFFAOYSA-N 1-decoxydecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCOCCCCCCCCCC WMCMCZTWKQMHBE-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-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
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-UHFFFAOYSA-N 0.000 description 1
- IKQCSJBQLWJEPU-UHFFFAOYSA-N 2,5-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(O)C(S(O)(=O)=O)=C1 IKQCSJBQLWJEPU-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
- PDHFSBXFZGYBIP-UHFFFAOYSA-N 2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethanol Chemical compound OCCSCCSCCO PDHFSBXFZGYBIP-UHFFFAOYSA-N 0.000 description 1
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- WSFYPFLCEFLXOZ-UHFFFAOYSA-N 2-decylbutanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)CC(O)=O WSFYPFLCEFLXOZ-UHFFFAOYSA-N 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 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
- 229940095574 propionic acid Drugs 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- RUQIYMSRQQCKIK-UHFFFAOYSA-M sodium;2,3-di(propan-2-yl)naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(C(C)C)C(C(C)C)=CC2=C1 RUQIYMSRQQCKIK-UHFFFAOYSA-M 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 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
- WEGDVNIPLOLRJC-UHFFFAOYSA-M sodium;naphthalene-1-carboxylate Chemical compound [Na+].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 WEGDVNIPLOLRJC-UHFFFAOYSA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- MKRZFOIRSLOYCE-UHFFFAOYSA-L zinc;methanesulfonate Chemical compound [Zn+2].CS([O-])(=O)=O.CS([O-])(=O)=O MKRZFOIRSLOYCE-UHFFFAOYSA-L 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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- C25D3/30—Electroplating: Baths therefor from solutions of tin
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/097—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds comprising two or more noble metals or noble metal alloys
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- C25D7/00—Electroplating characterised by the article coated
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- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
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Abstract
提供含有(A)至少含有亞錫鹽的可溶性鹽、與(B)選自有機酸及無機酸的酸或其鹽、與(C)含2個以上之芳香族環的鏻鹽之添加劑的鍍敷液。
Description
本發明係關於均勻電沈積性優異、且形成凸塊電極時抑制空洞產生之錫或錫合金的鍍敷液。
本發明基於2015年3月26日在日本申請的特願2015-064067號及2016年3月22日在日本申請的特願2016-056773號而主張優先權，其內容在此援用。
以往揭示由含有選自酸及其鹽之至少一種、可溶性鉛化合物、可溶性錫化合物、非離子系界面活性劑及萘磺酸的甲醛縮合物或其鹽之水溶液所構成的鉛-錫合金焊料鍍敷液(例如，專利文獻1作為參考。)。該鍍敷液，相對於鉛離子含有0.02~1.50質量%之萘磺酸的甲醛縮合物或其鹽作為添加物。專利文獻1中，記載因該鍍敷液而即使以高電流密度進行鍍敷，可形成表面高度不均小、平滑且鉛/錫組成比之不均少的鉛-錫合金突起電極。
又，揭示含有由(A)錫鹽與錫鹽及銀、銅、鉍、鉛等之指定的金屬鹽之混合物任一而成的可溶性鹽、
與(B)酸或其鹽、與(C)特定的菲繞啉二酮化合物之錫或錫合金鍍敷浴(例如，專利文獻2作為參考。)。專利文獻2中記載，該鍍敷浴因為含有特定的菲繞啉二酮化合物作為添加物，因該鍍敷浴而在廣範圍的電流密度區域可具備優異的均勻電沈積性與良好的皮膜外觀，在廣範圍的電流密度區域可得到均勻的合成組成。
進一步，揭示含有錫離子源、與至少1種的非離子系界面活性劑、與作為添加物的咪唑啉二羧酸酯及1,10-菲繞啉之錫鍍敷液(例如，專利文獻3作為參考。)。專利文獻3中，記載因該錫鍍敷液，即使在高度複雜化的印刷基板之鍍敷中，亦無灼燒，且面內膜厚分布之均勻性優異、貫穿孔鍍敷之均勻性亦優異。
〔專利文獻1〕日本特開2005-290505號公報(A)(請求項1、段落〔0004〕)
〔專利文獻2〕日本特開2013-044001號公報(A)(摘要、段落〔0010〕)
〔專利文獻3〕日本特開2012-087393號公報(A)(摘要、段落〔0006〕)
因以往上述專利文獻1~3記載之添加劑，而錫或錫合金的鍍敷液之均勻電沈積性被改善，但近年對鍍敷皮膜的品質要求增高、追求均勻電沈積性更提升。又在倒晶封裝實裝中，為了連接半導體裝置，將設置於基板的凸塊電極以鍍敷法形成時，有在回焊處理後的凸塊內部形成稱為空洞的空隙之情形，產生接合不良之虞，而追求不形成該空洞。然而，使均勻電沈積性提升與抑制空洞產生為相反之關係。即均勻電沈積性係藉由使電極面的分極電阻增大而被改善，另一方面，空洞之產生係藉由使陰極的過電壓變小而被抑制。近年追求著滿足兩者特性之鍍敷液的添加劑。
本發明之目的在於提供均勻電沈積性優異、且形成凸塊電極時抑制空洞產生之錫或錫合金的鍍敷液。
本發明之第1態樣為含有(A)至少含有亞錫鹽的可溶性鹽、(B)選自有機酸及無機酸的酸或其鹽、(C)添加劑之鍍敷液。其特徵在於前述添加劑含有下述一般式(1)所表示之含2個以上之芳香族環的鏻鹽。
但，式(1)中，R1、R2可為相同或相異，苯基、氫原子、CH2-O-CnH2n+1、CnH2n+1；(n=1~5)，Ph為苯基，X為鹵素。
本發明之第2態樣係基於第1觀點之發明，為前述添加劑再含有下述一般式(2)所表示之非離子系界面活性劑之鍍敷液。
【化2】R3-Y1-Z-Y2-R4 (2)
但，式(2)中，R3、R4為下述式(A)所表示之基，Y1、Y2為單鍵、-O-、-COO-及-CONH-所選出的基，Z為苯環或2,2-二苯基丙烷。式(A)中，n為2或3。m為1~15的整數。
【化3】-(CnH2n-O)m-H (A)
本發明之第3態樣為基於第1或第2觀點之發明，其為前述添加劑再含有錯化劑及/或抗氧化劑之鍍敷液。
在本發明之第1態樣的鍍敷液，藉由使用鏻鹽作為添加劑，外觀良好且可在廣範圍電流密度範圍改善均勻電沈積性，且可抑制形成凸塊電極時空洞之產生，可形成信賴性高的鍍敷皮膜。結果，可製造能以高品質對應狹窄間距或複雜配線圖型之製品。
在本發明之第2態樣的鍍敷液，藉由再含有上述式(2)所表示之非離子系界面活性劑，可抑制形成凸塊電極時空洞之產生，同時可更降低鍍敷皮膜的厚度不均。
在本發明之第3態樣的鍍敷液，藉由更含有錯化劑及/或抗氧化劑，達到下述效果。錯化劑為含有銀等之貴金屬之鍍敷液，使貴金屬離子等在浴中安定化同時使析出合金組成均勻化。又抗氧化劑防止可溶性亞錫鹽氧化為正錫鹽。
接著說明本實施發明之最佳形態。
本發明之一態樣的鍍敷液(以下、稱「本發明之鍍敷液」)為錫或錫合金的鍍敷液，且含有(A)至少含有亞錫鹽的可溶性鹽、(B)選自有機酸及無機酸的酸或其鹽、(C)添加劑。該添加劑包含下述一般式(1)所表示之含2個以上之芳香族環的鏻鹽。上述可溶性鹽係由亞錫鹽、與該亞錫鹽及銀、銅、鉍、鎳、銻、銦、鋅所構成的群選出的金屬之鹽的混合物之任一所構成。
但，式(1)中，R1、R2可為相同或相異，為苯基、氫原子、CH2-O-CnH2n+1、CnH2n+1；(n=1~5)，Ph為苯基，X為鹵素。
本發明之鍍敷液所含之錫合金為錫、與銀、銅、鉍、鎳、銻、銦、鋅所選出的指定金屬之合金，可舉例如，錫-銀合金、錫-銅合金、錫-鉍合金、錫-鎳合金、錫-銻合金、錫-銦合金、錫-鋅合金的2元合金、錫-銅-鉍、錫-銅-銀合金等之3元合金。
因此，本發明之鍍敷液所含之可溶性鹽(A)
係指在鍍敷液中，生成Sn2+、Ag+、Cu+、Cu2+、Bi3+、Ni2+、Sb3+、In3+、Zn2+等之各種金屬離子之任意可溶性鹽，可舉例如該金屬的氧化物、鹵素化物、無機酸或有機酸的該金屬鹽等。
作為金屬氧化物，可舉例如氧化亞錫、氧化銅、氧化鎳、氧化鉍、氧化銻、氧化銦、氧化鋅等，金屬的鹵素化物，可舉例如氯化亞錫、氯化鉍、溴化鉍、氯化亞銅、氯化銅、氯化鎳、氯化銻、氯化銦、氯化鋅等。
無機酸或有機酸的金屬鹽，可舉例如硫酸銅、硫酸亞錫、硫酸鉍、硫酸鎳、硫酸銻、硝酸鉍、硝酸銀、硝酸銅、硝酸銻、硝酸銦、硝酸鎳、硝酸鋅、乙酸銅、乙酸鎳、碳酸鎳、錫酸鈉、氟硼酸亞錫、甲磺酸亞錫、甲磺酸銀、甲磺酸銅、甲磺酸鉍、甲磺酸鎳、甲磺酸銦、雙甲磺酸鋅、乙烷磺酸亞錫、2-羥基丙烷磺酸鉍等。
本發明之鍍敷液所含之酸或其鹽(B)為由有機酸及無機酸、或者其鹽選出。上述有機酸中，可舉例如烷烴磺酸、烷醇磺酸、芳香族磺酸等之有機磺酸、或者脂肪族羧酸等，無機酸中，可舉例如氟硼酸、氟矽酸、氨基磺酸、鹽酸、硫酸、硝酸、過氯酸等。其鹽為鹼金屬的鹽、鹼土類金屬的鹽、銨鹽、胺鹽、磺酸鹽等。該成分(B)由金屬鹽的溶解性或排水處理之難易性觀點，以有機磺酸為佳。
上述烷烴磺酸，可使用化學式CnH2n+1SO3H(例如，n=1~5、較佳為1~3)所示者，具體上甲磺酸、
乙烷磺酸、1-丙烷磺酸、2-丙烷磺酸、1-丁烷磺酸、2-丁烷磺酸、戊烷磺酸等之外，可舉例如己烷磺酸、癸烷磺酸、十二烷磺酸等。
上述烷醇磺酸，可使用化學式CmH2m+1-CH(OH)-CpH2p-SO3H(例如，m=0~6、p=1~5)所表示者，具體上，可舉例如2-羥基乙烷-1-磺酸、2-羥基丙烷-1-磺酸、2-羥基丁烷-1-磺酸、2-羥基戊烷-1-磺酸等之外、1-羥基丙烷-2-磺酸、3-羥基丙烷-1-磺酸、4-羥基丁烷-1-磺酸、2-羥基己烷-1-磺酸、2-羥基癸烷-1-磺酸、2-羥基十二烷-1-磺酸等。
上述芳香族磺酸，基本上為苯磺酸、烷基苯磺酸、酚磺酸、萘磺酸、烷基萘磺酸等，具體上，可舉例如1-萘磺酸、2-萘磺酸、甲苯磺酸、二甲苯磺酸、p-酚磺酸、甲酚磺酸、磺基水楊酸、硝基苯磺酸、磺基安息香酸、二苯基胺-4-磺酸等。
上述脂肪族羧酸，可舉例如乙酸、丙酸、酪酸、檸檬酸、酒石酸、葡萄糖酸、磺基琥珀酸、三氟乙酸等。
本發明之鍍敷液所含之添加劑(C)所含之鏻鹽，如前述，以下述一般式(1)表示。
式(1)中，R1、R2可為相同或相異，此等之取代基R1、R2係由(a)苯基(b)氫原子(c)CH2-O-CnH2n+1；(n=1~5)(d)CnH2n+1；(n=1~5)中所選出。又式(1)中，Ph為苯基，X為鹵素。
本發明之鍍敷液所含之鏻鹽的具體例如下。
(i)鏻鹽1為四苯基鏻氯化物。上述式(1)中，取代基R1、R2皆為苯基，X為氯，且以下式表示。
(ii)鏻鹽2為甲氧基甲基三苯基鏻氯化物。上述式(1)中，取代基R1為苯基，R2為CH2-O-CH3，X為氯，且以下式表示。
(iii)鏻鹽3為丁氧基甲基三苯基溴化鏻。上述式(1)中，取代基R1為苯基，R2為CH2-O-C4H9，X為溴，且以下式表示。
(iv)鏻鹽4為丁基三苯基鏻氯化物。上述式(1)中，取代基R1為苯基，R2為C4H9，X為氯，且以下式表示。
(v)鏻鹽5為甲基戊基二苯基鏻氯化物。上述式(1)中，取代基R1為CH3，R2為C5H11，X為氯，且以下式表示。
(vi)鏻鹽6為三苯基鏻氯化物。上述式(1)中，取代基R1為H，R2為苯基，X為氯，且以下式表示。
(vii)鏻鹽7為癸基三苯基溴化鏻。上述式(1)中，取代基R1為苯基，R2為C10H21，X為溴，且以下式表示。
本發明之鍍敷液中，以再含有下述式(2)所表示之非離子系界面活性劑作為其他添加劑為佳。
【化13】R3-Y1-Z-Y2-R4 (2)
但，式(2)中，R3、R4為下述式(A)所表
示之基，Y1、Y2為單鍵、-O-、-COO-及-CONH-所選出的基，Z為苯環或2,2-二苯基丙烷。式(A)中，n為2或3。m為1~15的整數。
【化14】-(CnH2n-O)m-H (A)
本發明之鍍敷液所含之式(2)所表示之非離子系界面活性劑的具體例如下。式(2)所表示之非離子系界面活性劑1為聚氧化乙烯雙酚醚。上述式(2)中，取代基R3為H-(CH2-CH2-O)p(p為2~10的整數)、Y1為-O-，Z為(C6H10)C3H4(C6H10)、Y2為-O-、R4為H-(CH2-CH2-O)p(p為2~10的整數)，且以下式表示。
式(2)所表示之非離子系界面活性劑2為聚氧化乙烯苯基醚。上述式(2)中，取代基R3為H-(CH2-CH2-O)q(q為2~15的整數)，Y1為-O-，Z為C6H10，Y2為單鍵，R4為CH2-CH2-OH，且以下式表示。
本發明之鍍敷液中，以再含有上述以外其他的界面活性劑、錯化劑及/或抗氧化劑作為其他添加劑為佳。
此時，其他的界面活性劑方面，可舉例如一般的陰離子系界面活性劑、陽離子系界面活性劑、非離子系界面活性劑及兩性界面活性劑。
陰離子系界面活性劑，可舉例如聚氧化乙烯(環氧乙烷：含有12莫耳)壬基醚硫酸鈉等之聚氧化烯烷基醚硫酸鹽、聚氧化乙烯(環氧乙烷：含有12莫耳)十二烷基苯基醚硫酸鈉等之聚氧化烯烷基苯基醚硫酸鹽、十二烷基苯磺酸鈉等之烷基苯磺酸鹽、1-萘酚-4-磺酸鈉、2-萘酚-3,6-二磺酸二鈉等之萘酚磺酸鹽、二異丙基萘磺酸鈉、二丁基萘磺酸鈉等之(聚)烷基萘磺酸鹽、十二烷基硫酸鈉、油烯基硫酸鈉等之烷基硫酸鹽等。
陽離子系界面活性劑，可舉例如單~三烷基胺鹽、二甲基二烷基銨鹽、三甲基烷基銨鹽、十二烷基三甲基銨鹽、十六基三甲基銨鹽、十八基三甲基銨鹽、十二烷基二甲基銨鹽、十八碳烯基二甲基乙基銨鹽、十二烷基二甲基苄基銨鹽、十六基二甲基苄基銨鹽、十八基二甲基苄基銨鹽、三甲基苄基銨鹽、三乙基苄基銨鹽、十六基吡啶
鎓鹽、十二烷基吡啶鎓鹽、十二烷基甲基吡啶鎓鹽、十二烷基咪唑啉鎓鹽、油烯基咪唑啉鎓鹽、十八基胺乙酸酯、十二烷基胺乙酸酯等。
非離子系界面活性劑，可舉例如糖酯、脂肪酸酯、C1~C25烷氧基磷酸(鹽)、山梨糖醇酐酯、C1~C22脂肪族醯胺等與環氧乙烷(EO)及/或環氧丙烷(PO)以2~300莫耳加成縮合者，矽系聚氧化乙烯醚、矽系聚氧化乙烯酯、氟系聚氧化乙烯醚、氟系聚氧化乙烯酯、環氧乙烷及/或環氧丙烷與烷基胺或二胺之縮合生成物的硫酸化或者磺化加成物等。
兩性界面活性劑，可舉例如甜菜鹼、羧基甜菜鹼、咪唑啉鎓甜菜鹼、磺基甜菜鹼、胺基羧酸等。
上述錯化劑係用在含銀等之貴金屬之鍍敷液，使貴金屬離子等在浴中安定化同時使析出合金組成均勻化。錯化劑，可舉例如羥基羧酸、聚羧酸、單羧酸等。具體上，可舉例如葡萄糖酸、檸檬酸、葡萄庚酸、葡萄糖酸內酯、葡庚內酯、甲酸、乙酸、丙酸、酪酸、抗壞血酸、草酸、丙二酸、琥珀酸、乙醇酸、蘋果酸、酒石酸、二乙醇酸、乙硫醇酸、硫二乙醇酸、巰基乙醇、硫二甘醇、巰基琥珀酸、3,6-二硫雜-1,8-辛烷二醇、3,6,9-三硫雜癸烷-1,11-二磺酸、硫雙(十二乙二醇)、二(6-甲基苯並噻唑基)二硫化物三磺酸、二(6-氯苯並噻唑基)二硫化物二磺酸、葡萄糖酸、檸檬酸、葡萄庚酸、葡萄糖酸內酯、葡庚內酯、二硫二苯胺、二吡啶基二硫化物、巰基
琥珀酸、亞硫酸鹽、硫代硫酸鹽、乙二胺、乙二胺四乙酸(EDTA)、二二乙三胺五乙酸(DTPA)、氨三乙酸(NTA)、亞胺基二乙酸(IDA)、亞胺基二丙酸(IDP)、羥基乙基乙二胺三乙酸(HEDTA)、三乙烯四胺六乙酸(TTHA)、乙烯二氧雙(乙基胺)-N,N,N',N'-四乙酸、甘胺酸類、次氮基三甲基膦酸、或此等之鹽等。又，有硫尿素類等之含硫化合物、參(3-羥基丙基)膦等之磷化合物。又，導電性鹽，可舉例如硫酸、鹽酸、磷酸、氨基磺酸、磺酸的鈉鹽、鉀鹽、鎂鹽、銨鹽、胺鹽等。
上述抗氧化劑係用於防止可溶性亞錫鹽氧化為正錫鹽。抗氧化劑方面，以次亞磷酸類為首，可舉例如抗壞血酸或其鹽、酚磺酸(Na)、甲酚磺酸(Na)、氫醌磺酸(Na)、氫醌、α或β-萘酚、兒茶酚、間苯二酚、間苯三酚、肼、酚磺酸、兒茶酚磺酸、羥基苯磺酸、萘酚磺酸、或者此等之鹽等。
本發明之鍍敷液所含之鏻鹽(C)可單用或併用，在鍍敷液之含量為0.1~10g/L、較佳為0.5~5g/L。含量比適當範圍少，則有無法得到充分均勻電沈積性或皮膜外觀之提升效果等，過多則有產生灼燒等之虞。
又，上述指定的可溶性金屬鹽(A)可單用或併用，在鍍敷液中之含量為30~100g/L、較佳為40~60g/L。含量比適當範圍少，則生產性降低，含量過多，則鍍敷液的成本上昇。
無機酸、有機酸或其鹽(B)可單用或併用，在鍍敷液中之含量為80~300g/L、較佳為100~200g/L。含量比適當範圍少，則導電率低且電壓上昇，含量過多，則鍍敷液的黏度上昇且鍍敷液的攪拌速度降低。
又，上述(A)~(C)之各成分的添加濃度，因應滾鍍、掛鍍、高速連續鍍敷、Rack-less plating。凸塊鍍敷等之鍍敷方式而任意調整．選擇。
另一方面，本發明之電鍍敷液的液溫，一般為70℃以下、較佳為10~40℃。陰極電流密度，一般為0.01~150A/dm2、較佳為0.1~100A/dm2。電流密度過低則生產性惡化，過高則均勻電沈積性惡化。
將本發明之鍍敷液所含之含鏻鹽的錫或錫合金的鍍敷液用於被鍍敷物之電子零件，可於電子零件形成指定的金屬皮膜。電子零件方面，可舉例印刷基板、可撓性印刷基板、薄膜載體、半導體積體電路、電阻、電容器、過濾器、電感器、熱敏電阻、晶體振盪器、開關、導線等。又，亦可於晶圓之凸塊電極等電子零件之一部份使用本發明之鍍敷液形成皮膜。
實施例1~8中，實施例1為含有前述鏻鹽1之錫鍍敷
液的例、實施例2為含有前述鏻鹽1之錫-銀合金鍍敷液的例、實施例3為含有前述鏻鹽2之錫-銀合金鍍敷液的例、實施例4為含有前述鏻鹽3之錫鍍敷液的例、實施例5為含有前述鏻鹽4之錫-銅合金鍍敷液的例、實施例6為含有前述鏻鹽5之錫-銀合金鍍敷液的例。實施例7為含有前述鏻鹽6之錫-鉍合金鍍敷液的例、實施例8為含有前述鏻鹽5之錫-鋅合金鍍敷液的例。又比較例1~2中，比較例1為不含前述鏻鹽之錫鍍敷液的例、比較例2為含有前述鏻鹽7之錫-銀合金鍍敷液的例。實施例1、4與比較例1為酸性錫鍍敷液、實施例2~3、5~8與比較例2為酸性錫合金鍍敷液。
實施例1~8之鏻鹽1~6及比較例2之鏻鹽7可由化學藥品廠商購入。實施例1~8與比較例2使用之鏻鹽的詳細如表1。
將上述(A)~(C)之各成分與界面活性劑、錯化劑、抗氧化劑的搭配種種改變後的實施例1~8及比較例1~2如表2及表3。表3中，「界面活性劑1」為聚氧化乙烯雙酚醚，「界面活性劑2」為聚氧化乙烯苯基醚。
對實施例1~8及比較例1~2所得到的鍍敷液，進行赫爾槽試驗與鍍敷試驗，評估各鍍敷液的電沈積性。結果如表4。
赫爾槽試驗使用市售的赫爾槽試驗器(山本鍍金試驗器公司製)，鍍敷對象的基材，使用銅製赫爾槽板(長70mm、寬100mm、厚度0.3mm)。於赫爾槽試驗器放入
鍍敷液，液溫為25℃，通電電流為2A。鍍敷處理時間為5分鐘，鍍敷處理中不攪拌鍍敷液。赫爾槽評估係以經鍍敷處理的赫爾槽板之有無灼燒來進行。
第1鍍敷試驗，係使銅製基板(長10cm、寬10cm、厚度0.3mm)浸漬於液溫25℃的鍍敷液，以5A/dm2電流密度進行1分鐘。將得到的鍍敷皮膜的10處之膜厚以螢光X線膜厚測定器(SII納米科技(股)公司製)測定。算出10處之膜厚的標準偏差(3σ)，評估鍍敷膜厚的不均、即電沈積是否均勻地進行。
第2鍍敷試驗，係使銅製基板(長10cm、寬7cm、厚度0.3mm)浸漬於液溫25℃的鍍敷液，以3A/dm2電流密度通電13分鐘，於基板上形成膜厚20μm的鍍敷皮膜。將該附鍍敷皮膜的基板的中央切出長10mm、寬10mm的正方形小片，模擬回焊處理，將此等之小片在氮環境中，以加熱板昇溫至基板的表面溫度升溫至270℃，在該溫度維持10秒鐘後、急速冷卻。空洞評估係藉由以透過X線觀察回焊後的鍍敷皮膜，將空洞所佔有的面積除以長10mm、寬10mm的小片之面積，算出空洞面積率來進行。空洞產生與否，空洞面積率在0.1%以上時訂為
「產生空洞」。
由表4可明白，在以不含鏻鹽的錫鍍敷液進行鍍敷的比較例1，鍍敷膜厚的不均大到為1.93。又在含有以上述式(1)之R2為C10H21之鏻鹽的錫鍍敷液進行鍍敷之比較例2，因為CnH2n+1之n為10，空洞面積率大到為5.7%。相對於此，以含有上述式(1)之R1及R2符合指定的條件之鏻鹽的錫鍍敷液進行鍍敷之實施例1~8，鍍敷膜厚的不均小到為0.45~0.88。又在實施例1~8，空洞面積率亦小至0.01~0.07，均勻電沈積性佳、無空洞之產生、可得到良好的鍍敷皮膜。
本發明之鍍敷液，可利用於印刷基板、可撓性印刷基板、薄膜載體、半導體積體電路、電阻、電容器、過濾器、電感器、熱敏電阻、晶體振盪器、開關、導線等之電子零件、及晶圓之凸塊電極等電子零件的一部份。
Claims (3)
- 一種鍍敷液，其係含有(A)至少含有亞錫鹽的可溶性鹽、(B)選自有機酸及無機酸的酸或其鹽、(C)添加劑，其特徵係前述添加劑含有下述一般式(1)所表示之含2個以上之芳香族環的鏻鹽，
- 如請求項1記載之鍍敷液，其中，前述添加劑再含有下述一般式(2)所表示之非離子系界面活性劑，【化2】R3-Y1-Z-Y2-R4 (2)但，式(2)中，R3、R4為下述式(A)所表示之 基，Y1、Y2為單鍵、由-O-、-COO-及-CONH-所選出的基，Z為苯環或2,2-二苯基丙烷，式(A)中，n為2或3，m為1~15的整數，【化3】-(CnH2n-O)m-H (A)。
- 如請求項1或2記載之鍍敷液，其中，前述添加劑再含有錯化劑及/或抗氧化劑。
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| JP2001073153A (ja) | 1999-09-03 | 2001-03-21 | Nippon Chem Ind Co Ltd | 防腐された無電解めっき液及び無電解めっき液防腐方法 |
| US6818313B2 (en) | 2002-07-24 | 2004-11-16 | University Of Dayton | Corrosion-inhibiting coating |
| US6875260B2 (en) * | 2002-12-10 | 2005-04-05 | Enthone Inc. | Copper activator solution and method for semiconductor seed layer enhancement |
| JP4582294B2 (ja) | 2004-04-02 | 2010-11-17 | 三菱マテリアル株式会社 | 鉛−スズ合金ハンダめっき液 |
| GB0513804D0 (en) | 2005-07-06 | 2005-08-10 | Univ Leicester | New mixture |
| JP5574912B2 (ja) | 2010-10-22 | 2014-08-20 | ローム・アンド・ハース電子材料株式会社 | スズめっき液 |
| JP5412612B2 (ja) | 2011-08-22 | 2014-02-12 | 石原ケミカル株式会社 | スズ及びスズ合金メッキ浴、当該浴により電着皮膜を形成した電子部品 |
| JP6133056B2 (ja) | 2012-12-27 | 2017-05-24 | ローム・アンド・ハース電子材料株式会社 | スズまたはスズ合金めっき液 |
| US9243340B2 (en) | 2013-03-07 | 2016-01-26 | Nano And Advanced Materials Institute Limited | Non-vacuum method of manufacturing light-absorbing materials for solar cell application |
-
2016
- 2016-03-22 JP JP2016056773A patent/JP6631348B2/ja not_active Expired - Fee Related
- 2016-03-24 KR KR1020177026158A patent/KR20170131422A/ko not_active Application Discontinuation
- 2016-03-24 US US15/560,629 patent/US10174434B2/en active Active
- 2016-03-24 CN CN201680015498.6A patent/CN107429415B/zh not_active Expired - Fee Related
- 2016-03-24 EP EP16768886.0A patent/EP3276045B1/en active Active
- 2016-03-25 TW TW105109518A patent/TWI689629B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CN107429415A (zh) | 2017-12-01 |
| JP2016183409A (ja) | 2016-10-20 |
| EP3276045A4 (en) | 2018-11-21 |
| TWI689629B (zh) | 2020-04-01 |
| US10174434B2 (en) | 2019-01-08 |
| EP3276045B1 (en) | 2019-10-09 |
| JP6631348B2 (ja) | 2020-01-15 |
| US20180051383A1 (en) | 2018-02-22 |
| KR20170131422A (ko) | 2017-11-29 |
| CN107429415B (zh) | 2019-08-23 |
| EP3276045A1 (en) | 2018-01-31 |
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