CN107429415B - 使用了磷盐的电镀液 - Google Patents
使用了磷盐的电镀液 Download PDFInfo
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- CN107429415B CN107429415B CN201680015498.6A CN201680015498A CN107429415B CN 107429415 B CN107429415 B CN 107429415B CN 201680015498 A CN201680015498 A CN 201680015498A CN 107429415 B CN107429415 B CN 107429415B
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- Prior art keywords
- acid
- salt
- electroplate liquid
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- tin
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- 239000007788 liquid Substances 0.000 title claims abstract description 63
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 title claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 31
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000007747 plating Methods 0.000 description 29
- -1 paraffin sulfonates Chemical class 0.000 description 27
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 210000000981 epithelium Anatomy 0.000 description 12
- 229910001128 Sn alloy Inorganic materials 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 10
- 238000009713 electroplating Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011469 building brick Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 6
- 229910001316 Ag alloy Inorganic materials 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 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
- 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 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 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
- 239000011148 porous material Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 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 2
- VDXUUGGONYMWFW-UHFFFAOYSA-N 1,10-phenanthroline-2,3-dione Chemical class C1=CN=C2C3=NC(=O)C(=O)C=C3C=CC2=C1 VDXUUGGONYMWFW-UHFFFAOYSA-N 0.000 description 2
- 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
- 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 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 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 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 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 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N alpha-naphthol Natural products C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
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- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
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- 229960003237 betaine Drugs 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- 238000004070 electrodeposition Methods 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
- 239000000174 gluconic acid Substances 0.000 description 2
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- 150000004820 halides Chemical class 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 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
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000010453 quartz Substances 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
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
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- 235000011150 stannous chloride Nutrition 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
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 2
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-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
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- 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
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- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
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- NSRGOAGKXKNHQX-UHFFFAOYSA-N 2-hydroxybutane-1-sulfonic acid Chemical compound CCC(O)CS(O)(=O)=O NSRGOAGKXKNHQX-UHFFFAOYSA-N 0.000 description 1
- ZWLIPWXABAEXNY-UHFFFAOYSA-N 2-hydroxydecane-1-sulfonic acid Chemical compound CCCCCCCCC(O)CS(O)(=O)=O ZWLIPWXABAEXNY-UHFFFAOYSA-N 0.000 description 1
- CZFRHHAIWDBFCI-UHFFFAOYSA-N 2-hydroxyhexane-1-sulfonic acid Chemical compound CCCCC(O)CS(O)(=O)=O CZFRHHAIWDBFCI-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
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
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- 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
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 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
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 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
- 150000003606 tin compounds Chemical class 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 125000005270 trialkylamine group Chemical group 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
- 239000008096 xylene Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种电镀液,该电镀液包含:(A)至少包含亚锡盐的可溶性盐;(B)选自有机酸及无机酸中的酸或其盐;及(C)添加剂,其包含磷盐,该磷盐包含两个以上的芳香族环。
Description
技术领域
本发明涉及一种均镀能力优异且抑制形成有凸点电极时孔隙的产生的锡或锡合金的电镀液。
本申请主张基于2015年3月26日于日本申请的专利申请2015-064067号及2016年3月22日于日本申请的专利申请2016-056773号的优先权,并将其内容援用于此。
背景技术
以往,公开有一种铅-锡合金焊镀液,所述铅-锡合金焊镀液由含有选自酸及其盐的至少一种、可溶性铅化合物、可溶性锡化合物、非离子表面活性剂及萘磺酸的甲醛缩合物或其盐的水溶液构成(例如,参考专利文献1)。该电镀液含有相对于铅离子为0.02~1.50质量%的萘磺酸的甲醛缩合物或其盐作为添加物。专利文献1中记载有如下内容:即使通过该电镀液以高电流密度进行电镀,也能够形成表面的高度偏差较小、平滑且铅/锡组成比的偏差较少的铅-锡合金突起电极。
并且,公开有一种锡或锡合金电镀液,所述锡或锡合金电镀液含有(A)由锡盐及银、铜、铋、铅等的规定金属盐的混合物以及锡盐中的任一种组成的可溶性盐;(B)酸或其盐;以及(C)特定的菲罗啉二酮化合物(例如,参考专利文献2)。专利文献2中记载有如下内容:该电镀液含有特定的菲罗啉二酮化合物作为添加物,因此通过该电镀液能够具备在宽范围的电流密度范围内优异的均镀能力及良好的皮膜外观,能够在宽范围的电流密度范围获得均匀的合成组成。
而且,公开有一种锡电镀液,所述锡电镀液含有锡离子源、至少一种非离子表面活性剂、作为添加物的咪唑啉双羧酸盐及1,10-菲罗啉(例如,参考专利文献3)。专利文献3中记载有如下内容:通过该锡电镀液,即使在高度复杂化的印刷电路板的电镀中也没有黄变,面内膜厚分布的均匀性优异,通孔电镀的均匀性也优异。
专利文献1:日本特开2005-290505号公报(A)(权利要求1,[0004]段)
专利文献2:日本特开2013-044001号公报(A)(摘要,[0010]段)
专利文献3:日本特开2012-087393号公报(A)(摘要,[0006]段)
通过以往的上述专利文献1~3中所记载的添加剂,锡或锡合金的电镀液的均镀能力得到了改善,但近年来,对电镀皮膜的质量要求提高,要求进一步提高均镀能力。并且在倒装芯片封装中为了连接半导体器件,通过电镀法形成设置于基板上的凸点电极时,有时会在回焊处理后的凸点的内部形成称为孔隙的空隙,从而要求不形成可能会产生接合不良的这种孔隙。然而,提高均镀能力与抑制孔隙的产生是对立关系。即,均镀能力可通过加大电极面的极化电阻来改善,另一方面,孔隙的产生可通过减小阴极的过电压来抑制。近年来,要求满足两者特性的电镀液的添加剂。
发明内容
本发明的目的在于提供一种均镀能力优异且抑制形成有凸点电极时的孔隙的产生的锡或锡合金的电镀液。
本发明的第1方式为包含(A)至少包含亚锡盐的可溶性盐、(B)选自有机酸及无机酸中的酸或其盐及(C)添加剂的电镀液。其特征在于,所述添加剂包含由以下通式(1)表示的包含两个以上的芳香族环的磷盐。
[化学式1]
其中,式(1)中,R1、R2可以相同或不同,表示苯基、氢原子、CH2-O-CnH2n+1、CnH2n+1(n=1~5),Ph表示苯基,X表示卤素。
本发明的第2方式为基于第1方式的发明,是所述添加剂还包含由以下通式(2)表示的非离子表面活性剂的电镀液。
[化学式2]
R3-Yl-Z-Y2-R4 (2)
其中,式(2)中,R3、R4为由下述式(A)表示的基团,Y1、Y2为选自单键、-O-、-COO-及-CONH-中的基团,Z表示苯环或2,2-二苯基丙烷。式(A)中,n表示2或3。m表示1~15的整数。
[化学式3]
-(CnH2n-O)m-H (A)
本发明的第3方式为基于第1或第2方式的发明,是所述添加剂还包含络合剂和/或抗氧剂的电镀液。
在本发明的第1方式的电镀液中,通过将磷盐用作添加剂,外观良好且能够在宽范围的电流密度范围内改善均镀能力,而且能够抑制形成有凸点电极时的孔隙的产生,从而能够形成可靠性高的电镀皮膜。其结果,能够制造出可以以高质量应对窄间距及复杂的布线图案的产品。
在本发明的第2方式的电镀液中,还包含由上述式(2)表示的非离子表面活性剂,由此能够抑制形成有凸点电极时孔隙的产生,并且能够进一步降低电镀皮膜的厚度偏差。
在本发明的第3方式的电镀液中,还包含络合剂和/或抗氧剂,由此发挥如下效果。络合剂在包含银等贵金属的电镀液中使贵金属离子等在液中稳定并且使析出合金组成均匀化。并且抗氧剂防止可溶性亚锡盐氧化为正锡盐。
具体实施方式
接着,对用于实施本发明的方式进行说明。
本发明的一方式即电镀液(以下,称为“本发明的电镀液”)为锡或锡合金的电镀液,包含(A)至少包含亚锡盐的可溶性盐、(B)选自有机酸及无机酸中的酸或其盐及(C)添加剂。该添加剂包含由以下通式(1)表示的包含两个以上的芳香族环的磷盐。上述可溶性盐由亚锡盐和该亚锡盐及选自银、铜、铋、镍、锑、铟、锌中的金属的盐的混合物中的任一种构成。
[化学式4]
其中,式(1)中,R1、R2可以相同或不同,表示苯基、氢原子、CH2-O-CnH2n+1、CnH2n+1(n=1~5),Ph表示苯基,X表示卤素。
本发明的电镀液中所包含的锡合金为锡与选自银、铜、铋、镍、锑、铟及锌中的规定金属的合金,例如可举出锡-银合金、锡-铜合金、锡-铋合金、锡-镍合金、锡-锑合金、锡-铟合金、锡-锌合金的二元合金、锡-铜-铋及锡-铜-银合金等三元合金。
因此,本发明的电镀液中所包含的可溶性盐(A)表示在电镀液中生成Sn2+、Ag+、Cu+、Cu2+、Bi3+、Ni2+、Sb3+、In3+及Zn2+等各种金属离子的任意的可溶性盐,例如可举出该金属的氧化物、卤化物、无机酸或有机酸的该金属盐等。
作为金属氧化物,可举出氧化亚锡、氧化铜、氧化镍、氧化铋、氧化锑、氧化铟及氧化锌等,作为金属的卤化物,可举出氯化亚锡、氯化铋、溴化铋、氯化亚铜、氯化铜、氯化镍、氯化锑、氯化铟及氯化锌等。
作为无机酸或有机酸的金属盐,可举出硫酸铜、硫酸亚锡、硫酸铋、硫酸镍、硫酸锑、硝酸铋、硝酸银、硝酸铜、硝酸锑、硝酸铟、硝酸镍、硝酸锌、乙酸铜、乙酸镍、碳酸镍、锡酸钠、氟硼酸亚锡、甲磺酸亚锡、甲磺酸银、甲磺酸铜、甲磺酸铋、甲磺酸镍、甲磺酸铟、二甲磺酸锌、乙磺酸亚锡及2-羟基丙磺酸铋等。
本发明的电镀液中所包含的酸或其盐(B)从有机酸及无机酸或其盐中选择。上述有机酸中,可举出链烷烃磺酸、链烷醇磺酸、芳香族磺酸等有机磺酸或脂肪族羧酸等,无机酸中,可举出氟硼酸、硅氟氢酸、氨基磺酸、盐酸、硫酸、硝酸及高氯酸等。其盐为碱金属的盐、碱土类金属的盐、铵盐、胺盐及磺酸盐等。从金属盐的溶解性及排水处理的简易性的观点考虑,该成分(B)优选有机磺酸。
作为上述链烷烃磺酸,能够使用由化学式CnH2n+1SO3H(例如,n=1~5,优选为1~3)表示的链烷烃磺酸,具体而言,除了甲磺酸、乙磺酸、1-丙磺酸、2-丙磺酸、1-丁磺酸、2-丁磺酸及戊烷磺酸等以外,还可以举出己烷磺酸、癸烷磺酸及十二烷基磺酸等。
作为上述链烷醇磺酸,能够使用由化学式CmH2m+1-CH(OH)-CpH2p-SO3H(例如,m=0~6,p=1~5)表示的链烷醇磺酸,具体而言,除了2-羟基乙烷-1-磺酸、2-羟基丙烷-1-磺酸、2-羟基丁烷-1-磺酸及2-羟基戊烷-1-磺酸等以外,还可以举出1-羟基丙烷-2-磺酸、3-羟基丙烷-1-磺酸、4-羟基丁烷-1-磺酸、2-羟基己烷-1-磺酸、2-羟基癸烷-1-磺酸及2-羟基十二烷-1-磺酸等。
上述芳香族磺酸基本上为苯磺酸、烷基苯磺酸、苯酚磺酸、萘磺酸及烷基萘磺酸等,具体而言,可举出1-萘磺酸、2-萘磺酸、甲苯磺酸、二甲苯磺酸、对苯酚磺酸、甲酚磺酸、磺基水杨酸、硝基苯磺酸、磺基苯甲酸及二苯胺-4-磺酸等。
作为上述脂肪族羧酸,例如可举出乙酸、丙酸、丁酸、柠檬酸、酒石酸、葡糖酸、磺基琥珀酸及三氟乙酸等。
如前述,本发明的电镀液中所包含的添加剂(C)中所包含的磷盐由以下通式(1)表示。
[化学式5]
式(1)中,R1、R2可以相同,也可以不同,这些取代基R1、R2从
(a)苯基、
(b)氢原子、
(c)CH2-O-CnH2n+1(n=1~5)、及
(d)CnH2n+1(n=1~5)
中选择。并且式(1)中,Ph表示苯基,X表示卤素。
本发明的电镀液中所包含的磷盐的具体例如下。
(i)磷盐1为四苯基氯化磷。上述式(1)中,取代基R1、R2均为苯基,X为氯,由下式表示。
[化学式6]
(ii)磷盐2为甲氧基甲基三苯基氯化磷。上述式(1)中,取代基R1为苯基,R2为CH2-O-CH3,X为氯,由下式表示。
[化学式7]
(iii)磷盐3为丁氧基甲基三苯基溴化磷。上述式(1)中,取代基R1为苯基,R2为CH2-O-C4H9,X为溴,由下式表示。
[化学式8]
(iv)磷盐4为丁基三苯基氯化磷。上述式(1)中,取代基R1为苯基,R2为C4H9,X为氯,由下式表示。
[化学式9]
(v)磷盐5为甲基戊基二苯基氯化磷。上述式(1)中,取代基R1为CH3,R2为C5H11,X为氯,由下式表示。
[化学式10]
(vi)磷盐6为三苯基氯化磷。上述式(1)中,取代基R1为H,R2为苯基,X为氯,由下式表示。
[化学式11]
(vii)磷盐7为癸基三苯基溴化磷。上述式(1)中,取代基R1为苯基,R2为C10H21,X为溴,由下式表示。
[化学式12]
本发明的电镀液中,作为其他添加剂,优选还含有由下述式(2)表示的非离子表面活性剂。
[化学式13]
R3-Yl-Z-Y2-R4 (2)
其中,式(2)中,R3、R4为由下述式(A)表示的基团,Y1、Y2为选自单键、-O-、-COO-及-CONH-中的基团,Z表示苯环或2,2-二苯基丙烷。式(A)中,n表示2或3。m表示1~15的整数。
[化学式14]
-(CnH2n-O)m-H (A)
本发明的电镀液中所包含的由式(2)表示的非离子表面活性剂的具体例如下。由式(2)表示的非离子表面活性剂1为双酚聚氧乙烯醚。上述式(2)中,取代基R3为H-(CH2-CH2-O)p(p为2~10的整数),Y1为-O-,Z为(C6H10)C3H4(C6H10),Y2为-O-,R4为H-(CH2-CH2-O)p(p为2~10的整数),由下式表示。
[化学式15]
由式(2)表示的非离子表面活性剂2为聚氧乙烯苯基醚。上述式(2)中,取代基R3为H-(CH2-CH2-O)q(q为2~15的整数),Y1为-O-,Z为C6H10,Y2为单键,R4为CH2-CH2-OH,由下式表示。
[化学式16]
本发明的电镀液中,作为其他添加剂,优选还包含上述以外的其他表面活性剂、络合剂和/或抗氧剂。
作为该情况下的其他表面活性剂,可举出常规的阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂及两性表面活性剂。
作为阴离子表面活性剂,可举出聚氧乙烯(环氧乙烷:含12摩尔)壬基醚硫酸钠等聚氧化烯烷基醚硫酸盐;聚氧乙烯(环氧乙烷:含12摩尔)十二烷基苯基醚硫酸钠等聚氧化烯烷基苯基醚硫酸盐;十二烷基苯磺酸钠等烷基苯磺酸盐;1-萘酚-4-磺酸钠、2-萘酚-3,6-二磺酸二钠等萘酚磺酸盐;二异丙基萘磺酸钠、二丁基萘磺酸钠等(聚)烷基萘磺酸盐;十二烷基硫酸钠、油烯基硫酸钠等烷基硫酸盐等。
作为阳离子表面活性剂,可举出单烷基~三烷基胺盐、二甲基二烷基铵盐、三甲基烷基铵盐、十二烷基三甲基铵盐、十六烷基三甲基铵盐、十八烷基三甲基铵盐、十二烷基二甲基铵盐、十八烯基二甲基乙基铵盐、十二烷基二甲基苯甲基铵盐、十六烷基二甲基苯甲基铵盐、十八烷基二甲基苯甲基铵盐、三甲基苯甲基铵盐、三乙基苯甲基铵盐、十六烷基吡啶盐、十二烷基吡啶盐、十二烷基甲基吡啶、十二烷基咪唑盐、油烯基咪唑盐、十八烷胺乙酸盐及月桂胺乙酸盐等。
作为非离子表面活性剂,可举出糖酯、脂肪酸酯、C1~C25烷氧基磷酸(盐)、脱水山梨糖醇酯、对C1~C22脂肪族酰胺等加成缩合2~300摩尔的环氧乙烷(EO)和/或环氧丙烷(PO)而成的生成物、硅系聚氧乙烯醚、硅系聚氧乙烯酯、氟系聚氧乙烯醚、氟系聚氧乙烯酯、环氧乙烷和/或环氧丙烷与烷基胺或二胺的缩合生成物的硫酸化或磺酸化加成物等。
作为两性表面活性剂,可举出甜菜碱、羧基甜菜碱、咪唑啉甜菜碱、磺基甜菜碱及氨基羧酸等。
上述络合剂是为了在包含银等贵金属的电镀液中使贵金属离子等在液中稳定并且使析出合金组成均匀化而使用。作为络合剂,可举出羟基羧酸、聚羧酸及单羧酸等。具体而言可举出,葡糖酸、柠檬酸、葡庚糖酸、葡糖酸内酯、葡庚糖酸内酯、甲酸、乙酸、丙酸、丁酸、抗坏血酸、草酸、丙二酸、琥珀酸、乙醇酸、苹果酸、酒石酸、二甘醇酸、巯基乙酸、亚硫基二乙酸、硫甘醇、硫二甘醇、巯基丁二酸、3,6-二硫杂-1,8-辛二醇、3,6,9-三硫代癸烷-1,11-二磺酸、硫代双(十二甘醇)、二(6-甲基苯并噻唑基)二硫三磺酸、二(6-氯苯并噻唑基)二硫三磺酸、二硫代二苯胺、二吡啶二硫醚、亚硫酸盐、硫代硫酸盐、乙二胺、乙二胺四乙酸(EDTA)、二乙基三胺五乙酸(DTPA)、次氮基三乙酸(NTA)、亚氨基二乙酸(IDA)、亚氨基二丙酸(IDP)、羟乙基乙二胺三乙酸(HEDTA)、三亚乙基四胺六乙酸(TTHA)、亚乙基二氧基双(乙胺)-N,N,N’,N’-四乙酸、甘氨酸类及次氮基三甲基膦酸或它们的盐等。并且,有硫脲类等含硫化合物及三(3-羟基丙基)膦等磷化合物。并且,作为导电盐,可举出硫酸、盐酸、磷酸、氨基磺酸、磺酸的钠盐、钾盐、镁盐、铵盐及胺盐等。
上述抗氧剂为了防止可溶性亚锡盐氧化为正锡盐而使用。作为抗氧剂,以次磷酸类为代表,可举出抗坏血酸或其盐、苯酚磺酸(钠)、甲酚磺酸(钠)、对苯二酚磺酸(钠)、对苯二酚、α或β-萘酚、邻苯二酚、间苯二酚、间苯三酚、肼、苯酚磺酸、邻苯二酚磺酸、羟基苯磺酸及萘酚磺酸或它们的盐等。
本发明的电镀液中所包含的磷盐(C)能够单独使用或同时使用,电镀液中的含量为0.1~10g/L,优选为0.5~5g/L。若含量少于适当范围则无法获得充分的均镀能力及皮膜外观的提高效果等,若过多则可能会发生黄变等。
并且,上述规定的可溶性金属盐(A)能够单独使用或同时使用,电镀液中的含量为30~100g/L,优选为40~60g/L。若含量少于适当范围则生产率下降,若含量变多则电镀液的成本将会上升。
无机酸、有机酸或其盐(B)能够单独使用或同时使用,电镀液中的含量为80~300g/L,优选为100~200g/L。若含量少于适当范围则导电率较低且电压上升,若含量变多则电镀液的粘度上升且电镀液的搅拌速度将会下降。
另外,上述(A)~(C)的各成分的添加浓度根据滚镀、挂镀、高速连续电镀、无机架电镀及凸点电镀等电镀方式任意调整、选择。
另一方面,本发明的电镀液的液体温度通常为70℃以下,优选为10~40℃。阴极电流密度通常为0.01~150A/dm2,优选为0.1~100A/dm2。若电流密度过低则生产率变差,若过高则均镀能力将会变差。
将包含本发明的电镀液中所包含的磷盐的锡或锡合金的电镀液应用于作为待镀对象的电子组件,而能够在电子组件上形成规定的金属皮膜。作为电子组件,可举出印刷电路板、挠性印刷电路板、膜载体、半导体集成电路、电阻、电容器、滤波器、电感器、热敏电阻、晶体振子、开关及导线等。并且,也能够在如晶圆的凸点电极等电子组件的一部分应用本发明的电镀液而形成皮膜。
实施例
<实施例1~8及比较例2中使用的磷盐>
实施例1~8中,实施例1为含有所述磷盐1的锡电镀液的例子,实施例2为含有所述磷盐1的锡-银合金电镀液的例子,实施例3为含有所述磷盐2的锡-银合金电镀液的例子,实施例4为含有所述磷盐3的锡电镀液的例子,实施例5为含有所述磷盐4的锡-铜合金电镀液的例子,实施例6为含有所述磷盐5的锡-银合金电镀液的例子。实施例7为含有所述磷盐6的锡-铋合金电镀液的例子,实施例8为含有所述磷盐5的锡-锌合金电镀液的例子。并且比较例1~2中,比较例1为不含所述磷盐的锡电镀液的例子,比较例2为含有所述磷盐7的锡-银合金电镀液的例子。实施例1、4及比较例1为酸性锡电镀液,实施例2~3、5~8及比较例2为酸性锡合金电镀液。
实施例1~8的磷盐1~6及比较例2的磷盐7能够从化工品厂商购入。将实施例1~8及比较例2中使用的磷盐的详细内容示于表1中。
[表1]
<实施例1~8及比较例1~2>
将对上述(A)~(C)的各成分及表面活性剂、络合剂、抗氧剂的配合进行了各种变更的实施例1~8及比较例1~2示于表2及表3中。在表3中,“表面活性剂1”表示双酚聚氧乙烯醚,“表面活性剂2”表示聚氧乙烯苯基醚。
[表2]
[表3]
<评价试验>
关于实施例1~8及比较例1~2中得到的电镀液,进行赫尔槽试验及电镀试验,对各电镀液的电沉积性进行了评价。将其结果示于表4中。
(a)赫尔槽试验
赫尔槽试验使用了市售的赫尔槽试验仪(YAMAMOTO-MS Co.,LTD.制),电镀对象的基材使用了铜制赫尔槽板(长70mm,宽100mm,厚0.3mm)。赫尔槽试验仪中加入电镀液,将液体温度设为25℃,将通电电流设为2A。电镀处理时间为5分钟,在电镀处理中未搅拌电镀液。通过经电镀处理的赫尔槽板有无黄变来进行了赫尔槽评价。
(b)电镀试验
(b-1)电镀膜厚的偏差
如下进行了第1电镀试验:将铜制基板(长10cm,宽10cm,厚0.3mm)浸渍于液体温度25℃的电镀液中,并以5A/dm2的电流密度通电1分钟。通过荧光X射线膜厚测试仪(SIINanoTechnology Inc制)测量了所得到的电镀皮膜的10处膜厚。计算出10处膜厚的标准偏差(3σ),由此对电镀膜厚的偏差进行评价即对是否均匀地进行了电沉积进行了评价。
(b-2)电镀皮膜的孔隙产生率
如下进行了第2电镀试验:将铜制基板(长10cm,宽7cm,厚0.3mm)浸渍于液体温度25℃的电镀液中,并以3A/dm2的电流密度通电13分钟,在基板上形成了膜厚20μm的电镀皮膜。将该带电镀皮膜基板的中央以长10mm、宽10mm的正方形的小片来切出,模仿回焊处理,在氮气氛中,用热板对这些小片进行升温直至基板的表面温度成为270℃,并以该温度保持10秒钟后,进行了快速冷却。通过透射X射线来观察回焊后的电镀皮膜,孔隙所占面积除以长10mm、宽10mm的小片的面积以计算出孔隙面积率,由此进行了孔隙的评价。关于是否产生了孔隙,当孔隙面积率为0.1%以上时规定为“产生孔隙”。
[表4]
<评价的结果>
由表4可知,用不含磷盐的锡电镀液进行了电镀的比较例1中,电镀膜厚的偏差较大,为1.93。并且用包含上述式(1)的R2为C10H21的磷盐的锡电镀液进行了电镀的比较例2中,CnH2n+1的n为10,因此孔隙面积率较大,为5.7%。相对于此,用包含上述式(1)的R1及R2满足规定的条件的磷盐的锡电镀液进行了电镀的实施例1~8中,电镀膜厚的偏差较小,为0.45~0.88。并且可知实施例1~8中,孔隙面积率也较小,为0.01~0.07,均镀能力良好,未产生孔隙,得到了良好的电镀皮膜。
产业上的可利用性
本发明的电镀液能够利用于印刷电路板、挠性印刷电路板、膜载体、半导体集成电路、电阻、电容器、滤波器、电感器、热敏电阻、晶体振子、开关、导线等电子组件及如晶圆的凸点电极等部分电子组件。
Claims (3)
1.一种电镀液,其包含:
(A)至少包含亚锡盐的可溶性盐;
(B)选自有机酸及无机酸中的酸或其盐;及
(C)添加剂,
所述电镀液的特征在于,
所述添加剂包含由以下通式(1)表示的包含两个以上的芳香族环的磷盐,
[化学式1]
其中,式(1)中,R1、R2可以相同或不同,表示苯基、氢原子、CH2-O-CnH2n+1、CnH2n+1,其中n=1~5,Ph表示苯基,X表示卤素,
所述可溶性盐在所述电镀液中的含量为30~100g/L,
所述酸或其盐在所述电镀液中的含量为80~300g/L,
所述磷盐在所述电镀液中的含量为0.1~10g/L。
2.根据权利要求1所述的电镀液,其中,
所述添加剂还包含由以下通式(2)表示的非离子表面活性剂,
[化学式2]
R3-Y1-Z-Y2-R4 (2)
其中,式(2)中,R3、R4为由下述式(A)表示的基团,Y1、Y2为选自单键、-O-、-COO-及-CONH-中的基团,Z表示苯环或2,2-二苯基丙烷,式(A)中,n表示2或3,m表示1~15的整数,
[化学式3]
-(CnH2n-O)m-H (A)。
3.根据权利要求1或2所述的电镀液,其中,
所述添加剂还包含络合剂和/或抗氧剂。
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US10174434B2 (en) | 2019-01-08 |
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JP6631348B2 (ja) | 2020-01-15 |
EP3276045A1 (en) | 2018-01-31 |
EP3276045B1 (en) | 2019-10-09 |
CN107429415A (zh) | 2017-12-01 |
JP2016183409A (ja) | 2016-10-20 |
EP3276045A4 (en) | 2018-11-21 |
KR20170131422A (ko) | 2017-11-29 |
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