CN111356789A - 锡或锡合金电镀液 - Google Patents
锡或锡合金电镀液 Download PDFInfo
- Publication number
- CN111356789A CN111356789A CN201880068858.8A CN201880068858A CN111356789A CN 111356789 A CN111356789 A CN 111356789A CN 201880068858 A CN201880068858 A CN 201880068858A CN 111356789 A CN111356789 A CN 111356789A
- Authority
- CN
- China
- Prior art keywords
- tin
- acid
- bump
- plating
- surfactant
- 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.)
- Granted
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910001128 Sn alloy Inorganic materials 0.000 title claims abstract description 49
- 238000009713 electroplating Methods 0.000 title claims description 11
- 238000007747 plating Methods 0.000 claims abstract description 120
- 239000004094 surface-active agent Substances 0.000 claims abstract description 50
- 150000003839 salts Chemical class 0.000 claims abstract description 46
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 35
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims abstract description 35
- -1 polyoxypropylene Polymers 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 15
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 25
- 239000011800 void material Substances 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 20
- 230000008021 deposition Effects 0.000 description 17
- 239000010949 copper Substances 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 10
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 235000006708 antioxidants Nutrition 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 3
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- 150000008365 aromatic ketones Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- 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
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 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
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 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
- 229920001577 copolymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 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 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-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
- 238000012360 testing method Methods 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 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
- 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
- MBIXGEBUUSDULP-UHFFFAOYSA-N 1-(2,4,6-trimethylphenyl)propan-2-one Chemical compound CC(=O)CC1=C(C)C=C(C)C=C1C MBIXGEBUUSDULP-UHFFFAOYSA-N 0.000 description 1
- XMCRWEBERCXJCH-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1Cl XMCRWEBERCXJCH-UHFFFAOYSA-N 0.000 description 1
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-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
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-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
- 238000005160 1H NMR spectroscopy Methods 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
- TWFSYIOOAAYYAL-UHFFFAOYSA-N 2,4,6-trichlorobenzaldehyde Chemical compound ClC1=CC(Cl)=C(C=O)C(Cl)=C1 TWFSYIOOAAYYAL-UHFFFAOYSA-N 0.000 description 1
- YSFBEAASFUWWHU-UHFFFAOYSA-N 2,4-dichlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C(Cl)=C1 YSFBEAASFUWWHU-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
- DMIYKWPEFRFTPY-UHFFFAOYSA-N 2,6-dichlorobenzaldehyde Chemical compound ClC1=CC=CC(Cl)=C1C=O DMIYKWPEFRFTPY-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-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
- 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
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 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
- ZWLIPWXABAEXNY-UHFFFAOYSA-N 2-hydroxydecane-1-sulfonic acid Chemical compound CCCCCCCCC(O)CS(O)(=O)=O ZWLIPWXABAEXNY-UHFFFAOYSA-N 0.000 description 1
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- CZFRHHAIWDBFCI-UHFFFAOYSA-N 2-hydroxyhexane-1-sulfonic acid Chemical compound CCCCC(O)CS(O)(=O)=O CZFRHHAIWDBFCI-UHFFFAOYSA-N 0.000 description 1
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- XWIJIXWOZCRYEL-UHFFFAOYSA-M potassium;methanesulfonate Chemical compound [K+].CS([O-])(=O)=O XWIJIXWOZCRYEL-UHFFFAOYSA-M 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
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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
- IAAKNVCARVEIFS-UHFFFAOYSA-M sodium;4-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(O)=CC=C(S([O-])(=O)=O)C2=C1 IAAKNVCARVEIFS-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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
- 239000000126 substance Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 1
- MHMUCYJKZUZMNJ-OWOJBTEDSA-N trans-3-chloroacrylic acid Chemical compound OC(=O)\C=C\Cl MHMUCYJKZUZMNJ-OWOJBTEDSA-N 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 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
- 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
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Abstract
本发明的锡或锡合金电镀液含有:(A)至少含有亚锡盐的可溶性盐;(B)选自有机酸及无机酸中的酸或其盐;(C)表面活性剂;及(D)流平剂。并且,表面活性剂含有聚氧乙烯聚氧丙烯烷基胺,聚氧乙烯聚氧丙烯烷基胺的烷基为CaH2a+1,其中,a=12~18。而且,当将聚氧乙烯聚氧丙烯烷基胺的聚氧丙烯设为p,将聚氧乙烯设为q时,p与q之和(p+q)为8~21,p与q之比(p/q)为0.1~1.6。
Description
技术领域
本发明涉及一种在电路基板上搭载半导体集成电路芯片时用于在基板上制造成为锡或锡合金的突起电极的凸点的锡或锡合金的电镀液。更详细而言,涉及一种即使在凸点直径不同的图案中,对基板上的导通孔的导通孔填充性也优异,且所形成的凸点的高度变得均匀的锡或锡合金电镀液。
本申请主张基于2017年10月24日于日本申请的专利申请2017-205201号及2018年10月19日于日本申请的专利申请2018-197081号的优先权,并将其内容援用于此。
背景技术
在搭载半导体集成电路芯片(以下,称为半导体芯片。)的电路基板中,为了对应轻薄短小,目前主要制造将封装基板面积小型化至与搭载于基板的半导体芯片大致相等的程度的CSP(Chip Size/scale Package,芯片尺寸/尺度封装)型半导体装置。为了连接该电路基板和半导体芯片,利用锡或锡合金填充基板侧的作为导通孔主体部的导通孔开口部而形成突起状的作为金属端子的突起电极的凸点,并将半导体芯片装填到该凸点。
以往,为了通过填充该锡或锡合金材料来形成凸点,将锡系焊膏等导电膏或锡系焊球填充到导通孔主体部,或者使用锡或锡合金的电镀液并利用电镀法在导通孔内形成锡电镀沉积层之后,通过热处理使导电膏、焊球或锡电镀沉积层熔融。
参考图1对利用电镀法形成凸点的通常的方法进行说明。如图1的(a)所示,在设置有配线等的基板1的表面上形成具有开口部的阻焊剂图案。接着,在阻焊层2的表面上进行化学镀,形成用于供电的铜晶种层3。接着,在铜晶种层3的表面上形成干膜抗蚀剂层4,并以与阻焊层2的开口部接合的方式形成具有开口部的干膜抗蚀剂图案。接着,通过经由上述铜晶种层3供电,在干膜抗蚀剂图案的导通孔6的内部进行电镀锡,且在铜晶种层3上的导通孔6内形成锡电镀沉积层7(镀锡皮膜)。接着,依次去除干膜抗蚀剂层和铜晶种层之后,通过回流处理将残留的锡电镀沉积层熔融,从而如图1的(b)所示,形成锡凸点8。
到目前为止,当使用电镀法形成锡或锡合金凸点时,通过改变锡或锡合金电镀液的含有成分,进行了与对基板上的导通孔的导通孔填充性或凸点内的空隙的抑制有关的改善(例如,参考专利文献1、2、3、4。)。
专利文献1中公开有一种含有特定的α,β-不饱和醛或特定的α,β-不饱和酮的化合物的锡或锡合金电镀液。该专利文献1中记载有:该电镀液的导通孔填充效果高,且当使用该电镀液时,镀锡选择性地沉积在凹部,因此可以获得实质上不具有空隙的镀锡沉积物;及在所形成的镀锡皮膜表面上不产生烧焦或异常析出,因此可以获得焊接性或耐变色性等优异的实用且具有良好的外观的镀锡皮膜。
并且,专利文献2中公开有一种锡或锡合金电镀液,其含有(a)含羧基化合物和(b)含羰基化合物,且成分(a)为1.3g/L以上及成分(b)为0.3g/L以上。该专利文献2中记载有:关于该电镀液,通过对具有盲孔或通孔的被镀物进行电镀,能够在短时间内可靠性高地填充盲孔或通孔;及能够利用于半导体的三维安装、印刷电路板上的盲孔或通孔的填充工序及硅贯通电极的形成。
并且,专利文献3中公开有一种锡或锡合金电镀液,其含有无机酸及有机酸以及其水溶性盐、表面活性剂及流平剂。其中,表面活性剂为选自聚氧化烯苯基醚或其盐及聚氧化烯多环苯基醚或其盐中的至少一种非离子表面活性剂,构成聚氧化烯苯基醚的苯基及构成聚氧化烯多环苯基醚的多环苯基可以被碳原子数1~24的烷基或羟基取代,流平剂为选自脂肪族醛、芳香族醛、脂肪族酮及芳香族酮中的至少一种;及α,β-不饱和羧酸或者其酰胺或它们的盐。该专利文献3中记载有:由于含有特定的非离子表面活性剂和特定的两种类的流平剂,因此凹槽填充性(导通孔填充性)优异,且能够抑制空隙的产生,由此,若使用该电镀液,则能够提供一种没有凹槽(凹部)而平滑,而且也不会产生回流后的空隙的良好的凸点。
而且,专利文献4中公开有一种突起电极形成用的锡或锡合金电镀液,该锡或锡合金电镀液含有:(A)由亚锡盐和亚锡盐与选自银、铜、铋、镍、铟、金中的金属的盐的混合物中的任一种组成的可溶性盐;(B)酸或其盐;(C)选自芳香族及脂肪族醛、芳香族及脂肪族酮、不饱和羧酸类、芳香族羧酸类中的填充用有机化合物;及(D)非离子系表面活性剂。该专利文献4中记载有:关于该电镀液,由于组合使用抑制锡系材料的析出的特定的化合物(C)和成分(D),因此有效地抑制导通孔上部的析出,能够使锡系材料的析出优先从导通孔底部朝向导通孔上方进行,从而能够防止空隙的产生的同时平滑地进行导通孔填充,其结果,回流或者不回流而能够良好地形成突起电极,且接合强度或电特性优异。
专利文献1:日本专利特开2014-125662号公报(权利要求2、第[0020]段)
专利文献2:日本专利特开2015-007276号公报(权利要求1、第[0011]、[0012]段)
专利文献3:日本专利特开2015-193916号公报(权利要求1、第[0019]段)
专利文献4:日本专利特开2016-074963号公报(权利要求1、第[0019]段)
近年来,在一个电路基板上混合存在有凸点直径或凸点间距不同的配线图案。在这种复杂的配线图案中,即使在凸点直径或凸点间距不同的情况下也要求将所有的凸点以均匀的高度形成。根据上述专利文献1~4的锡或锡合金电镀液,具有如下特点:凸点内的空隙的产生得到抑制,能够在短时间内可靠性高地对基板上的导通孔进行填充,导通孔填充性或外观优异。然而,这些文献中的基板用电镀液并非以实现凸点的高度均匀性为其课题。
具体而言,如图2所示,在凸点直径不同的图案的情况下,若使用以往的锡或锡合金电镀液进行电镀,则能够改善小径或者大径中的任一个的导通孔填充性,但另一个的导通孔填充性降低。即,当在同时存在小径及大径的导通孔的基板上,对两个导通孔同时进行电镀时,难以导通孔填充性良好地对两个导通孔进行电镀。如此,当存在导通孔填充性不同的导通孔时(图2的(b)),回流后的凸点高度偏差变大,无法实现凸点的高度均匀性(图2的(d))。因此,为了实现凸点的高度均匀性(图2的(c)),如图2的(a)所示,需要改善对小径及大径的两个导通孔的导通孔填充性。
发明内容
本发明的目的在于提供一种即使在凸点直径不同的图案中,对基板上的导通孔的导通孔填充性也优异,且所形成的凸点的高度变得均匀的锡或锡合金电镀液。
本发明的第一观点是一种锡或锡合金电镀液,其含有:(A)至少含有亚锡盐的可溶性盐;(B)选自有机酸及无机酸中的酸或其盐;(C)表面活性剂;及(D)流平剂,所述锡或锡合金电镀液的特征在于,表面活性剂含有聚氧乙烯聚氧丙烯烷基胺,聚氧乙烯聚氧丙烯烷基胺的烷基为CaH2a+1(其中,a=12~18),当将聚氧乙烯聚氧丙烯烷基胺的聚氧丙烯设为p,将聚氧乙烯聚氧丙烯烷基胺的聚氧乙烯设为q时,p与q之和(p+q)为8~21,p与q之比(p/q)为0.1~1.6。
本发明的第二观点是一种基于第一观点的发明,其特征在于,其还含有与上述表面活性剂不同的表面活性剂、抗氧化剂及碳原子数为1~3的醇中的两个以上。
本发明的第三观点是一种凸点的形成方法,其使用第一或第二观点中所述的锡或锡合金电镀液在基板上形成锡或锡合金电镀沉积层之后,进行回流处理来形成凸点。
本发明的第四观点是一种电路基板的制造方法,其使用通过第3观点中所述的方法形成的凸点来制造电路基板。
本发明的第一观点的锡或锡合金电镀液中,通过具有特定的胺结构,即表面活性剂含有聚氧乙烯聚氧丙烯烷基胺,聚氧乙烯聚氧丙烯烷基胺的烷基为CaH2a+1(其中,a=12~18),当将聚氧乙烯聚氧丙烯烷基胺的聚氧丙烯设为p,将聚氧乙烯聚氧丙烯烷基胺的聚氧乙烯设为q时,p与q之和(p+q)为8~21,p与q之比(p/q)为0.1~1.6,在电镀时,能够抑制Sn离子的析出,并能够在电镀对象表面上良好地进行电镀。尤其根据该电镀液,在凸点直径不同的图案的情况下,即使凸点直径大或者小,极化电阻也大,因此对基板上的导通孔的导通孔填充性优异,且所形成的凸点的高度变得均匀。
本发明的第二观点的锡或锡合金电镀液中,通过进一步含有与含有上述聚氧乙烯聚氧丙烯烷基胺的表面活性剂不同的表面活性剂、抗氧化剂及碳原子数为1~3的醇中的两个以上,可发挥以下效果。与上述含有聚氧乙烯聚氧丙烯烷基胺的表面活性剂不同的表面活性剂发挥电镀液的稳定化、溶解性的提高等效果。并且,抗氧化剂防止可溶性亚锡盐氧化成锡盐。而且,醇对提高表面活性剂的溶解性发挥效果。
本发明的第三观点的凸点的形成方法中,通过使用上述锡或锡合金电镀液在基板上形成锡或锡合金电镀沉积层之后,进行回流处理来形成凸点,即使在凸点直径不同的图案中,也能够形成高度均匀的凸点。
本发明的第四观点的电路基板的制造方法中,通过使用通过第三观点的方法形成的凸点来制造电路基板,能够制作无电连接不良的可靠性高的半导体装置。
附图说明
图1的(a)是在本发明的导通孔内形成电镀沉积层的截面结构图,(b)是剥离干膜及铜晶种层并加热电镀沉积层后的截面结构图。
图2的(a)是表示在凸点直径(导通孔直径)不同的图案中均匀地形成电镀沉积层的例子的截面结构图,(b)是表示在凸点直径(导通孔直径)不同的图案中不均匀地形成电镀沉积层的例子的截面结构图,(c)是表示在(a)中剥离干膜及铜晶种层并加热电镀沉积层之后,所形成的凸点的高度变得均匀的例子的截面结构图,(d)是表示在(b)中剥离干膜及铜晶种层并加热电镀沉积层之后,所形成的凸点的高度存在偏差的例子的截面结构图。
具体实施方式
接着,对用于实施本发明的方式进行说明。
本发明的锡或锡合金电镀液含有:(A)至少含有亚锡盐的可溶性盐;(B)选自有机酸及无机酸中的酸或其盐;(C)表面活性剂;及(D)流平剂。该表面活性剂含有聚氧乙烯聚氧丙烯烷基胺。
上述可溶性盐由亚锡盐和该亚锡盐与选自银、铜、铋、镍、锑、铟、锌中的金属的盐的混合物中的任一个组成。
本发明的锡合金为锡与选自银、铜、铋、镍、锑、铟、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、锡-铜-银合金等的三元合金。
因此,本发明的可溶性盐(A)是指在电镀液中生成Sn2+、Ag+、Cu+、Cu2+、Bi3+、Ni2+、Sb3 +、In3+、Zn2+等的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、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、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、2-羟基丙磺酸铋等。
本发明的酸或其盐(B)选自有机酸及无机酸或者其盐。上述有机酸可举出链烷磺酸、链烷醇磺酸、芳香族磺酸等有机磺酸或者脂肪族羧酸等,无机酸可举出氟硼酸、氟硅酸、氨基磺酸、盐酸、硫酸、硝酸、高氯酸等。其盐为碱金属盐、碱土金属盐、铵盐、胺盐、磺酸盐等。从金属盐的溶解性和排水处理的容易性的观点考虑,该成分(B)优选为有机磺酸。
作为上述链烷磺酸,能够使用由化学式CrH2r+1SO3H(例如,r=1~5,优选为1~3)所示的链烷磺酸,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、戊磺酸等以外,可举出己磺酸、癸烷磺酸、十二烷磺酸等。
作为上述链烷醇磺酸,能够使用由化学式CsH2s+1-CH(OH)-CtH2t-SO3H(例如,s=0~6、t=1~5)所示的链烷醇磺酸,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、2-羟基戊烷-1-磺酸等以外,可举出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、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、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、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、三氟乙酸等。
本发明的聚氧乙烯聚氧丙烯烷基胺的烷基为CaH2a+1(其中,a=12~18)。并且,当将聚氧乙烯聚氧丙烯烷基胺的聚氧丙烯设为p,将聚氧乙烯聚氧丙烯烷基胺的聚氧乙烯设为q时,p与q之和(p+q)为8~21,p与q之比(p/q)为0.1~1.6。具体而言,本发明的聚氧乙烯聚氧丙烯烷基胺由选自由以下通式(1)~(4)组成的组中的一个或两个以上的式表示。在此,不仅包括以下通式(1)~(4)中的任一式,还包括两个以上的式,这是因为由通式(1)~(4)表示的多种胺有时混合存在。
[化学式1]
其中,通式(1)~(4)中,R1为CaH2a+1(a=12~18),p及q分别为1以上,(p+q)为8~21,p/q为0.1~1.6。在此,若a小于12,则存在导通孔填充性差的不良情况,若a大于19,则存在难以溶解于聚氧乙烯聚氧丙烯烷基胺的电镀液中或发生电镀的外观异常的不良情况。并且,若(p+q)小于8,则存在难以溶解于聚氧乙烯聚氧丙烯烷基胺的电镀液中或发生电镀的外观异常的不良情况,若大于21,则存在难以溶解于聚氧乙烯聚氧丙烯烷基胺的电镀液中或导通孔填充性差,或者发生电镀的外观异常的不良。而且,若p/q小于0.1,则存在发生电镀的外观异常的不良情况,若p/q大于1.6,则存在难以溶解于聚氧乙烯聚氧丙烯烷基胺的电镀液中或发生电镀的外观异常的不良情况。
另外,上述聚氧乙烯聚氧丙烯烷基胺由聚氧乙烯(EO)与聚氧丙烯(PO)的交替共聚物、周期共聚物、嵌段共聚物或无规聚合物组成。将交替共聚物、周期共聚物、嵌段共聚物的分子式的例子分别示于下述式(5)及式(6)。此时,EO/PO比=(q+q)/(p+p)=q/p。
R1-N-(EO)q+q-(PO)p+p-H (5)
R1-N-(PO)p+p-(EO)q+q-H (6)
添加本发明的流平剂(D)是为了均匀且致密地形成电镀皮膜,并且使电镀皮膜平滑。而且,为了提高导通孔填充性并抑制空隙的产生,使用第一流平剂(D-1)及第二流平剂(D-2)这两种。作为第一流平剂(D-1),可举出选自由脂肪族醛、芳香族醛、脂肪族酮及芳香族酮组成的组中的一种或两种以上,作为第二流平剂(D-2),可举出α,β-不饱和羧酸或其酰胺或者它们的盐。
第一流平剂(D-1)为含有醛或酮的羰基化合物,且不含有第二流平剂(D-2)的α,β-不饱和羧酸。具体而言,例示以下。作为脂肪族醛,可举出甲醛、乙醛、烯丙醛等。并且,作为芳香族醛,可举出苯甲醛、2-氯苯甲醛、3-氯苯甲醛、4-氯苯甲醛、2,4-二氯苯甲醛、2,6-二氯苯甲醛、2,4,6-三氯苯甲醛、1-萘醛、2-萘醛、2-羟基苯甲醛、3-羟基苯甲醛、4-羟基苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-甲基苯甲醛、间茴香醛、邻茴香醛、对茴香醛等。并且,作为脂肪族酮,可举出乙酰丙酮等。而且,作为芳香族酮,可举出亚苄基丙酮(与苯甲丙酮同义)、2-氯苯乙酮、3-氯苯乙酮、4-氯苯乙酮、2,4-二氯苯乙酮、2,4,6-三氯苯乙酮等。它们可以单独使用,也可以使用两种以上。第一流平剂(D-1)在电镀浴中所占的优选含量(单独含有时为单独的量,含有两种以上时为它们的总量)为0.001g/L~0.3g/L,更优选为0.01g/L~0.25g/L。若上述成分的含量少,则其添加效果不充分,另一方面,若上述成分的含量过多,则有可能阻碍电镀皮膜的平滑化。
作为第二流平剂(D-2),可举出丙烯酸、甲基丙烯酸、吡啶甲酸、巴豆酸、3-氯丙烯酸、3,3-二甲基丙烯酸、2,3-二甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸2-乙基己酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸2-羟乙酯、甲基丙烯酸2-羟丙酯、甲基丙烯酸2-二甲基氨基乙酯、甲基丙烯酸酐、甲基丙烯酸甲酯等。并且,第二流平剂(D-2)中也包括α,β-不饱和羧酸的酰胺(例如,丙烯酰胺等)和α,β-不饱和羧酸的盐(例如,钾、钠、铵等的盐)。第二流平剂(D-2)在电镀浴中所占的优选含量(单独含有时为单独的量,含有两种以上时为它们的总量)为0.01g/L~50g/L,更优选为0.05g/L~30g/L,进一步优选为0.05g/L~10g/L。若上述成分的含量少,则其添加效果不充分,另一方面,若上述成分的含量过多,则有可能阻碍电镀皮膜的平滑化。
优选本发明的锡或锡合金电镀液中还含有与含有上述聚氧乙烯聚氧丙烯烷基胺的表面活性剂不同的表面活性剂(E)、抗氧化剂(F)及碳原子数为1~3的醇(G)中的两个以上。
作为此时的其他表面活性剂(E),可举出通常的阴离子系表面活性剂、阳离子系表面活性剂、非离子系表面活性剂及两性表面活性剂。
作为阴离子系表面活性剂,可举出聚氧乙烯(含有环氧乙烷:12摩尔)壬基醚硫酸钠等聚氧化烯烷基醚硫酸盐、聚氧乙烯(含有环氧乙烷: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、油基硫酸钠等烷基硫酸盐等。
作为阳离子系表面活性剂,可举出单至三烷基胺盐、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、十二烷基二甲基苄基铵盐、十六烷基二甲基苄基铵盐、十八烷基二甲基苄基铵盐、三甲基苄基铵盐、三乙基苄基铵盐、十六烷基吡啶鎓盐、十二烷基吡啶鎓盐、十二烷基甲吡啶鎓盐、十二烷基咪唑啉鎓盐、油基咪唑啉鎓盐、十八烷基胺乙酸酯、十二烷基胺乙酸酯等。
作为非离子系表面活性剂,可举出糖酯、脂肪酸酯、C1~C25烷氧基磷酸(盐)、山梨糖醇酐酯、C1~C22脂肪族酰胺等与2~300摩尔环氧乙烷(EO)和/或环氧丙烷(PO)加成缩合而成的物质、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产物的硫酸化或者磺化加成物等。
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、氨基羧酸等。
上述抗氧化剂(F)用于防止可溶性亚锡盐氧化成锡盐。作为抗氧化剂,以次磷酸类为首可举出抗坏血酸或其盐、苯酚磺酸(Na)、甲酚磺酸(Na)、对苯二酚磺酸(Na)、对苯二酚、α-萘酚或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、萘酚磺酸或者它们的盐等。
上述碳原子数为1~3的醇(G)用于提高上述表面活性剂的溶解性。作为醇,可举出甲醇、乙醇、1-丙醇、2-丙醇等。醇能够单独使用一种或组合两种以上使用。
表面活性剂(C)在电镀液中的含量为0.5g/L~50g/L,优选为1g/L~5g/L。若含量小于下限值,则由于Sn离子的过量供给而发生枝晶等电镀不良。并且,若含量大于上限值,则存在Sn离子不易到达电镀对象表面而导通孔填充性差(降低)的不良情况。
并且,上述规定可溶性金属盐(A)能够单用或并用,在电镀液中的含量为30g/L~100g/L,优选为40g/L~60g/L。若含量少于适当范围,则生产率降低,若含量多于适当范围,则导致电镀液的成本上升。
无机酸、有机酸或其盐(B)能够单用或并用,在电镀液中的含量为80g/L~300g/L,优选为100g/L~200g/L。若含量少于适当范围,则导电率低且电压上升,若含量多于适当范围,则电镀液的粘度上升而导致电镀液的搅拌速度降低。
另一方面,本发明的电镀液的液温通常为70℃以下,优选为10~40℃。基于电镀的电镀膜形成时的电流密度在0.1A/dm2以上且100A/dm2以下的范围,优选在0.5A/dm2以上且20A/dm2以下的范围。若电流密度过低,则生产率降低,若过高,则导致凸点的高度均匀性降低。
将含有本发明的表面活性剂(C)的锡或锡合金的电镀液应用于作为被镀物的电路基板上,从而能够在该电路基板上形成规定金属皮膜。作为电路基板,可举出印刷电路基板、柔性印刷电路基板、半导体集成电路基板等。
实施例
接着,结合比较例对本发明的实施例进行详细说明。
(实施例及比较例中使用的表面活性剂(C))
将在实施例1~10及比较例1~6中使用的作为表面活性剂(C)的聚氧乙烯聚氧丙烯烷基胺的各结构式和在比较例7中使用的作为表面活性剂(C)的聚氧乙烯聚氧丙烯-乙二胺的结构式示于表1~表4。并且,将表面活性剂(C)的通式(1)或(2)中的a、p、q、(p+q)及(p/q)的值示于表5。
另外,通过1H-NMR,根据p及q的重复中的C-H键的1H的信号强度计算p、q、(p+q)及(p/q)的值。并且,在本发明中,表面活性剂(C)并不仅由单一的聚氧乙烯聚氧丙烯烷基胺构成,有时也含有多种聚氧乙烯聚氧丙烯烷基胺。即,例如,在p=1、q=10的聚氧乙烯聚氧丙烯烷基胺的情况下,有时也含有p=2、q=9或q=11等的聚氧乙烯聚氧丙烯烷基胺。
[表1]
[表2]
[表3]
[表4]
[表5]
化合物No. | 应用的通式 | a | p | q | p+q | p/q |
C-1 | 式(1) | 14 | 1 | 10 | 11 | 0.10 |
C-2 | 式(3) | 18 | 4 | 7 | 11 | 0.57 |
C-3 | 式(1) | 12 | 4 | 4 | 8 | 0.90 |
C-4 | 式(1) | 12 | 5 | 4 | 9 | 1.56 |
C-5 | 式(2) | 18 | 2 | 8 | 10 | 0.13 |
C-6 | 式(2) | 15 | 4 | 17 | 21 | 0.33 |
C-7 | 式(2) | 12 | 5 | 15 | 20 | 0.35 |
C-8 | 式(4) | 16 | 7 | 9 | 16 | 0.76 |
C-9 | 式(2) | 13 | 8 | 6 | 14 | 1.51 |
C-10 | 式(1) | 12 | 1 | 15 | 16 | 0.07 |
C-11 | 式(3) | 15 | 13 | 7 | 20 | 1.92 |
C-12 | 式(1) | 20 | 5 | 5 | 10 | 1.10 |
C-13 | 式(1) | 10 | 4 | 10 | 14 | 0.51 |
C-14 | 式(1) | 9 | 13 | 7 | 20 | 1.92 |
C-15 | 式(1) | 12 | 6 | 16 | 22 | 0.38 |
C-16 | 式(1) | 18 | 0 | 5 | 5 | 0.00 |
C-17 | - | - | - | - | - | - |
适当的范围 | - | 12~18 | 1≤ | 1≤ | 8~21 | 0.1~1.6 |
<实施例1>
(Sn电镀液的建浴)
向甲磺酸Sn水溶液中混合作为游离酸的甲磺酸、作为抗氧化剂的对苯二酚、作为第一流平剂的1-萘醛、作为第二流平剂的甲基丙烯酸,成为均匀的溶液之后,作为表面活性剂进一步添加了上述(C-1)的聚氧乙烯聚氧丙烯烷基胺(质量平均分子量:1300)。然后,最后添加离子交换水,制成了下述组成的Sn电镀液。另外,通过使金属Sn板在甲磺酸水溶液中电解来制备了甲磺酸Sn水溶液。
(Sn电镀液的组成)
甲磺酸Sn(作为Sn2+):50g/L
甲磺酸钾(作为游离酸):100g/L
表面活性剂(C-1):2g/L
对苯二酚(作为抗氧化剂(F)):1g/L
1-萘醛(作为第一流平剂(D-1)):0.1g/L
甲基丙烯酸(作为第二流平剂(D-2)):2g/L
离子交换水:剩余部分
<实施例2~10、比较例1~7>
在实施例2~10及比较例1~7中,作为表面活性剂(C)使用了表1~表4中所示的结构式的聚氧乙烯聚氧丙烯烷基胺((C-2)~(C-16))。除此以外,以与实施例1相同的方式,制成了实施例2~10及比较例1~7的Sn电镀液。另外,在实施例4及比较例4中,作为除了Sn以外的金属含有Ag(作为Ag+,1.0g/L),在实施例6及比较例1中,作为除了Sn以外的金属含有Cu(作为Cu2+,0.5g/L)。
<比较例8>
在比较例8中,作为表面活性剂(C)使用了表4中所示的结构式的聚氧乙烯聚氧丙烯-乙二胺(C-17)。除此以外,以与实施例1相同的方式,制成了比较例8的Sn电镀液。另外,在比较例8中,作为除了Sn以外的金属含有Ag(作为Ag+,1.0g/L)。
<比较试验1及评价>
使用实施例1~10及比较例1~8的18种所制成的电镀液,在电流密度2ASD的条件下在具有凸点直径不同的图案的基板上进行电镀,并在导通孔内形成了锡或锡合金电镀沉积层。然后,使用回流装置加热至280℃,使电镀沉积层熔融而形成了凸点。
另外,关于后述的“导通孔内的锡或锡合金电镀沉积层的导通孔填充性”及“导通孔内的锡或锡合金电镀沉积层的外观”对回流前的电镀沉积层进行了测定,关于“凸点高度偏差”及“空隙产生容易性”对电镀沉积层的回流后所形成的凸点进行了测定。将其结果示于表6。
(1)导通孔内的锡或锡合金电镀沉积层的导通孔填充性
使用激光显微镜,观察导通孔内的锡或锡合金电镀沉积层,并测定了从电镀沉积层的最高点到最低点为止的高度差。将高度差大于5μm的情况判断为“不良”,将高度差为5μm以下的情况判断为“良好”,并示于表6的“导通孔填充性”栏。
(2)导通孔内的锡或锡合金电镀的沉积层的外观
使用激光显微镜,观察导通孔内的锡或锡合金电镀沉积层,并测定了表面粗糙度Ra。将电镀沉积层的表面粗糙度Ra大于2μm的情况判断为“不良”,将2μm以下的情况判断为“良好”,并示于表6的“电镀沉积层的外观”栏。
(3)凸点高度偏差
使用自动外观检查装置测定了基板的凸点的高度。根据所测定的凸点高度计算出高度偏差σ(标准偏差)。将高度偏差σ为3以下的情况判断为“均匀”,将高度偏差σ大于3的情况判断为“不均匀”,并将其结果示于表6的“凸点高度偏差σ”栏。
(4)空隙产生容易性
对以180μm、250μm、360μm的各间距间隔排列且直径为70μm、90μm、120μm的凸点(共2000个)拍摄了透射X射线图像。目视观察所拍摄的图像,将相对于凸点的大小观察到一个以上的1%以上的大小的空隙的情况判断为“NG”,将未观察到空隙的情况判断为“OK”,并将其结果示于表6的“空隙产生容易性”栏。
[表6]
从表6明确可知,在作为表面活性剂使用了化合物No.C-10的比较例1中,通式(1)中的p/q过小,为0.07,因此导通孔填充性为良好,但电镀沉积层的外观为不良,凸点高度偏差σ也大,为3.4,且凸点中观察到空隙而空隙产生容易性也为NG。并且,在作为表面活性剂使用了化合物No.C-11的比较例2中,通式(3)中的p/q过大,为1.92,因此导通孔填充性为良好,凸点中未观察到空隙而空隙产生容易性为OK,但电镀沉积层的外观为不良,凸点高度偏差σ也大,为2.8。相对于这些,在作为表面活性剂使用了化合物No.C-1~C-9的实施例1~9中,通式(1)~(4)中的p/q在适当范围内(0.1~1.6),为0.10~1.56,因此导通孔填充性及电镀沉积层的外观均为良好,凸点高度偏差σ也小,为1.4~2.0,且凸点中未观察到空隙而空隙产生容易性为OK。
另一方面,在作为表面活性剂使用了化合物No.C-12的比较例3中,通式(1)中的a过大,为21,因此导通孔填充性及电镀沉积层的外观为不良,凸点高度偏差σ也大,为3.6,且凸点中观察到空隙而空隙产生容易性也为NG。并且,在作为表面活性剂使用了化合物No.C-13的比较例4中,通式(1)中的a过小,为10,因此导通孔填充性及电镀沉积层的外观为不良,凸点高度偏差σ也大,为5.2,且凸点中观察到空隙而空隙产生容易性也为NG。相对于此,在作为表面活性剂使用了化合物No.C-1~C-9的实施例1~9中,通式(1)~(4)中的a在适当的范围内(12~18),为12~18,因此导通孔填充性及电镀沉积层的外观均为良好,凸点高度偏差σ也小,为1.4~2.0,且凸点中未观察到空隙而空隙产生容易性为OK。
另一方面,在作为表面活性剂使用了化合物No.C-14的比较例5中,通式(1)中的p/q过大,为1.92,且a过小,为9,因此凸点中未观察到空隙而空隙产生容易性为OK,但导通孔填充性及电镀沉积层的外观为不良,凸点高度偏差σ也大,为4.9。相对于此,在作为表面活性剂使用了化合物No.C-1~C-9的实施例1~9中,通式(1)~(4)中的p/q在适当的范围内(0.1~1.6),为0.10~1.56,且a在适当的范围内(12~18),为12~18,因此导通孔填充性及电镀沉积层的外观均为良好,凸点高度偏差σ也小,为1.4~2.0,且凸点中未观察到空隙而空隙产生容易性为OK。
另一方面,在作为表面活性剂使用了化合物No.C-15的比较例6中,(p+q)过大,为22,因此导通孔填充性及电镀沉积层的外观为不良,凸点中观察到空隙而空隙产生容易性也为NG,凸点高度偏差σ也大,为4.3。相对于此,在作为表面活性剂使用了化合物No.C-1~C-9的实施例1~9中,通式(1)~(4)中的p在适当的范围内(1以上),为1~8,且(p+q)在适当的范围内(8~21),为8~21,因此导通孔填充性及电镀沉积层的外观均为良好,凸点高度偏差σ也小,为1.4~2.0,且凸点中未观察到空隙而空隙产生容易性为OK。
另一方面,在作为表面活性剂使用了化合物No.C-16的比较例7中,通式(1)中的p过小,为0,且(p+q)过小,为5,因此凸点高度偏差σ小,为1.5,但导通孔填充性及电镀沉积层的外观为不良,凸点中观察到空隙而空隙产生容易性也为NG。相对于此,在作为表面活性剂使用了化合物No.C-1~C-9的实施例1~9中,通式(1)~(4)中的p在适当的范围内(1以上),为1~8,且(p+q)在适当的范围内(8~21),为8~21,因此导通孔填充性及电镀沉积层的外观均为良好,凸点高度偏差σ也小,为1.4~2.0,且凸点中未观察到空隙而空隙产生容易性为OK。
另外,在比较例8中,作为表面活性剂使用了化合物No.C-17的聚氧乙烯聚氧丙烯-乙二胺,因此导通孔填充性及电镀沉积层的外观为不良,凸点高度偏差σ也大,为8.0,且凸点中观察到空隙而空隙产生容易性也为NG。并且,在实施例10中,作为表面活性剂使用了将应用通式(1)的化合物No.C-1和应用通式(2)的化合物No.C-5进行混合而成的物质,但导通孔填充性及电镀沉积层的外观均为良好,凸点高度偏差σ也小,为1.8,且凸点中未观察到空隙而空隙产生容易性为OK。
<实施例11~20>
在实施例11~20中,将第一流平剂(D-1)、第二流平剂(D-2)或除了Sn以外的金属中的任一个和表面活性剂的质量平均分子量变更为如表7所示那样,除此以外,以与实施例1相同的方式,制成了Sn电镀液。另外,在表7的第一流平剂(D-1)中,D1A为苯甲醛,D1B为4-氯苯甲醛,D1C为1-萘醛。并且,在表7的第二流平剂(D-2)中,D2A为甲基丙烯酸,D2B为丙烯酸,D2C为丙烯酰胺。
<比较试验2及评价>
使用实施例11~20的10种所制成的电镀液,以与比较试验1相同的方式,在电流密度2ASD的条件下在具有凸点直径不同的图案的基板上进行电镀,并在导通孔内形成了锡或锡合金电镀沉积层。然后,使用回流装置加热至280℃,使电镀沉积层熔融而形成凸点,并对“导通孔内的锡或锡合金电镀沉积层的导通孔填充性”、“导通孔内的锡或锡合金电镀沉积层的外观”、“凸点高度偏差”及“空隙产生容易性”进行了评价。将其结果示于表7。
[表7]
从表7明确可知,在将第一流平剂(D-1)变更为苯甲醛、4-氯苯甲醛或1-萘醛中的任一个,将第二流平剂(D-2)变更为甲基丙烯酸、丙烯酸或丙烯酰胺中的任一个的实施例11~14中,导通孔填充性及电镀沉积层的外观均为良好,凸点高度偏差σ也为均匀,为1.9~2.3,且凸点中未观察到空隙而空隙产生容易性为OK。
并且,在将第一流平剂(D-1)变更为苯甲醛或1-萘醛,将第二流平剂(D-2)变更为甲基丙烯酸或丙烯酰胺,作为除了Sn以外的金属而进一步添加了Cu或Ag的实施例15~16中,导通孔填充性及电镀沉积层的外观均为良好,凸点高度偏差σ也为均匀,为1.8,且凸点中未观察到空隙而空隙产生容易性为OK。
而且,在将第一流平剂(D-1)的浓度分别变更为0.001g/L及0.3g/L的实施例17~18和将第二流平剂(D-2)的浓度分别变更为0.05g/L及30g/L的实施例19~20中,导通孔填充性及电镀沉积层的外观均为良好,凸点高度偏差σ也为均匀,为1.7~2.4,且凸点中未观察到空隙而空隙产生容易性为OK。
产业上的可利用性
本发明的锡或锡合金电镀液能够利用于印刷电路基板、柔性印刷电路基板、半导体集成电路等的电路基板。
符号说明
1-基板,2-阻焊层,3-铜晶种层,4-干膜抗蚀剂层,6-导通孔,7-锡电镀沉积层(镀锡皮膜),8-锡凸点。
Claims (4)
1.一种锡或锡合金电镀液,其含有:
(A)至少含有亚锡盐的可溶性盐;
(B)选自有机酸及无机酸中的酸或其盐;
(C)表面活性剂;及
(D)流平剂,所述锡或锡合金电镀液的特征在于,
所述表面活性剂含有聚氧乙烯聚氧丙烯烷基胺,
所述聚氧乙烯聚氧丙烯烷基胺的烷基为CaH2a+1,其中,a=12~18,
当将所述聚氧乙烯聚氧丙烯烷基胺的聚氧丙烯设为p,将聚氧乙烯聚氧丙烯烷基胺的聚氧乙烯设为q时,p与q之和p+q为8~21,
p与q之比p/q为0.1~1.6。
2.根据权利要求1所述的锡或锡合金电镀液,其还含有:
与所述表面活性剂不同的表面活性剂、抗氧化剂及碳原子数为1~3的醇中的两个以上。
3.一种凸点的形成方法,其使用权利要求1或2所述的锡或锡合金电镀液在基板上形成锡或锡合金电镀沉积层之后,进行回流处理来形成凸点。
4.一种电路基板的制造方法,其使用通过权利要求3所述的方法形成的凸点来制造电路基板。
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- 2018-10-23 KR KR1020207011533A patent/KR102221567B1/ko active IP Right Grant
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KR20200047736A (ko) | 2020-05-07 |
TWI707066B (zh) | 2020-10-11 |
JP2019077948A (ja) | 2019-05-23 |
EP3715508A4 (en) | 2021-10-27 |
TW201925538A (zh) | 2019-07-01 |
CN111356789B (zh) | 2021-04-16 |
EP3715508A1 (en) | 2020-09-30 |
KR102221567B1 (ko) | 2021-02-26 |
JP6620858B2 (ja) | 2019-12-18 |
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