TW201716636A - 含有胺與醌之反應產物的化合物的銅電鍍浴 - Google Patents
含有胺與醌之反應產物的化合物的銅電鍍浴 Download PDFInfo
- Publication number
- TW201716636A TW201716636A TW105131754A TW105131754A TW201716636A TW 201716636 A TW201716636 A TW 201716636A TW 105131754 A TW105131754 A TW 105131754A TW 105131754 A TW105131754 A TW 105131754A TW 201716636 A TW201716636 A TW 201716636A
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- TW
- Taiwan
- Prior art keywords
- copper
- branched
- hydrogen
- substrate
- alkyl
- Prior art date
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- 239000010949 copper Substances 0.000 title claims abstract description 58
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000009713 electroplating Methods 0.000 title claims abstract description 34
- 239000007795 chemical reaction product Substances 0.000 title claims abstract description 25
- 150000001412 amines Chemical class 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 title claims description 16
- 150000004053 quinones Chemical class 0.000 title 1
- 239000000758 substrate Substances 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- -1 hydroxy (C 1 -C 10 )alkyl halogen Chemical class 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 150000002923 oximes Chemical class 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 125000006569 (C5-C6) heterocyclic group Chemical group 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- KHBQMWCZKVMBLN-IDEBNGHGSA-N benzenesulfonamide Chemical group NS(=O)(=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 KHBQMWCZKVMBLN-IDEBNGHGSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 229910001432 tin ion Inorganic materials 0.000 claims 2
- 238000006845 Michael addition reaction Methods 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 abstract 4
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000007747 plating Methods 0.000 description 50
- 239000003795 chemical substances by application Substances 0.000 description 22
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 3
- 229940067157 phenylhydrazine Drugs 0.000 description 3
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- MHGUSQPDQPUNQD-UHFFFAOYSA-N 2-(2,2-disulfoethyldisulfanyl)ethane-1,1-disulfonic acid Chemical compound OS(=O)(=O)C(S(O)(=O)=O)CSSCC(S(O)(=O)=O)S(O)(=O)=O MHGUSQPDQPUNQD-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
- FULCXPQDMXUVSB-UHFFFAOYSA-N 3-(3-sulfanylpropylsulfonyloxy)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOS(=O)(=O)CCCS FULCXPQDMXUVSB-UHFFFAOYSA-N 0.000 description 1
- WRBSVISDQAINGQ-UHFFFAOYSA-N 3-(dimethylcarbamothioylsulfanyl)propane-1-sulfonic acid Chemical compound CN(C)C(=S)SCCCS(O)(=O)=O WRBSVISDQAINGQ-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- REEBJQTUIJTGAL-UHFFFAOYSA-N 3-pyridin-1-ium-1-ylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCC[N+]1=CC=CC=C1 REEBJQTUIJTGAL-UHFFFAOYSA-N 0.000 description 1
- FXNSVEQMUYPYJS-UHFFFAOYSA-N 4-(2-aminoethyl)benzenesulfonamide Chemical compound NCCC1=CC=C(S(N)(=O)=O)C=C1 FXNSVEQMUYPYJS-UHFFFAOYSA-N 0.000 description 1
- WCUFJNSMGXUEGL-UHFFFAOYSA-J 4-methylbenzenesulfonate tin(4+) Chemical compound [Sn+4].Cc1ccc(cc1)S([O-])(=O)=O.Cc1ccc(cc1)S([O-])(=O)=O.Cc1ccc(cc1)S([O-])(=O)=O.Cc1ccc(cc1)S([O-])(=O)=O WCUFJNSMGXUEGL-UHFFFAOYSA-J 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- KIAYKYHZRPLPLD-UHFFFAOYSA-J benzenesulfonate tin(4+) Chemical compound [Sn+4].[O-]S(=O)(=O)c1ccccc1.[O-]S(=O)(=O)c1ccccc1.[O-]S(=O)(=O)c1ccccc1.[O-]S(=O)(=O)c1ccccc1 KIAYKYHZRPLPLD-UHFFFAOYSA-J 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QXQGNOWHBCJPQH-UHFFFAOYSA-N butan-1-ol;ethene Chemical group C=C.CCCCO QXQGNOWHBCJPQH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229940108925 copper gluconate Drugs 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 1
- MRYMYQPDGZIGDM-UHFFFAOYSA-L copper;4-methylbenzenesulfonate Chemical compound [Cu+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 MRYMYQPDGZIGDM-UHFFFAOYSA-L 0.000 description 1
- RIOSFUBRIQHOMS-UHFFFAOYSA-L copper;benzenesulfonate Chemical compound [Cu+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 RIOSFUBRIQHOMS-UHFFFAOYSA-L 0.000 description 1
- SSOVMNXYUYFJBU-UHFFFAOYSA-L copper;ethanesulfonate Chemical compound [Cu+2].CCS([O-])(=O)=O.CCS([O-])(=O)=O SSOVMNXYUYFJBU-UHFFFAOYSA-L 0.000 description 1
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 1
- NPSDYIWFLLIHOT-UHFFFAOYSA-L copper;propane-1-sulfonate Chemical compound [Cu+2].CCCS([O-])(=O)=O.CCCS([O-])(=O)=O NPSDYIWFLLIHOT-UHFFFAOYSA-L 0.000 description 1
- WIYCQLLGDNXIBA-UHFFFAOYSA-L disodium;3-(3-sulfonatopropyldisulfanyl)propane-1-sulfonate Chemical group [Na+].[Na+].[O-]S(=O)(=O)CCCSSCCCS([O-])(=O)=O WIYCQLLGDNXIBA-UHFFFAOYSA-L 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- SOUPVZCONBCBGI-UHFFFAOYSA-M potassium;3-sulfanylpropane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)CCCS SOUPVZCONBCBGI-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- KQFAFFYKLIBKDE-UHFFFAOYSA-M sodium;ethanesulfonate Chemical compound [Na+].CCS([O-])(=O)=O KQFAFFYKLIBKDE-UHFFFAOYSA-M 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical class [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract
本發明係關於由胺與醌之反應產物構成的聚合物。所述醌為邁克爾加成受體。所述聚合物可為銅電鍍浴之添加劑。所述聚合物可充當調平劑且使銅電鍍浴能夠具有高均鍍能力並提供團塊減少之銅沈積物。
Description
本發明係關於含有胺與作為邁克爾加成(Michael addition)受體之醌之反應產物的化合物的銅電鍍浴。更特定言之,本發明係關於含有胺與作為邁克爾加成受體之醌之反應產物的化合物的銅電鍍浴,其具有高均鍍能力及團塊減少之銅沈積物。
用金屬塗料電鍍物品之方法一般涉及在鍍覆溶液中之兩個電極之間通電流,其中一個電極為待鍍覆物品。典型的酸性銅電鍍溶液包含經溶解之銅(通常為硫酸銅)、足以賦予浴液導電性之量的酸電解質(諸如硫酸)、鹵化物源及用以改良鍍覆均一性及金屬沈積物之品質的專用添加劑。此類添加劑尤其包含調平劑、促進劑及抑制劑。
電解銅鍍覆溶液用於多種工業應用(諸如裝飾及防腐蝕塗料)以及電子工業中,尤其用於製造印刷電路板及半導體。關於電路板製造,通常將銅電鍍於印刷電路板表面之所選部分上、盲通道及溝槽中以及穿過電路板基底材料表面之間的通孔之壁上。首先諸如藉由無電金屬化使盲通道、
溝槽及通孔之經暴露表面(亦即,壁及底層)導電,隨後將銅電鍍於此等孔口之表面上。經鍍覆通孔提供自一個板表面至另一板表面之導電路徑。通道及溝槽提供電路板內層之間的導電路徑。關於半導體製造,將銅電鍍於含有多種特徵(諸如通道、溝槽或其組合)之晶圓的表面上。將通道及溝槽金屬化,以提供半導體裝置之各個層之間的導電性。
眾所周知,在某些鍍覆領域中,諸如在印刷電路板(「PCB」)之電鍍中,在電鍍浴中使用調平劑在達成基板表面上之均一金屬沈積方面可為至關重要的。電鍍具有不規則表面形態之基板可造成困難。在電鍍期間,在表面中之孔口內通常發生電壓降,其可引起表面與孔口之間的金屬沈積不均勻。在電壓降相對極端之處,亦即,在孔口窄且高之處,電鍍不規則性加劇。因此,沈積具有實質上均一厚度之金屬層常常為電子裝置製造中具有挑戰性的步驟。常在銅鍍覆浴中使用調平劑以在電子裝置中提供實質上均一或齊平的銅層。
電子裝置之便攜性與增加之功能性組合的趨勢已驅使PCB小型化。具有通孔互連件之習知多層PCB並非總是實用的解決方案。已研發出高密度互連件之替代方法,諸如利用盲通道之依序累積技術。使用盲通道之方法的目標之一為使通道填充達到最大,同時使通道與基板表面之間的銅沈積之厚度變化減至最小。此舉在PCB含有通孔及盲通道時尤其具有挑戰性。
在銅鍍覆浴中使用調平劑以調平基板表面上之沈積且改良電鍍浴之均鍍能力。均鍍能力定義為通孔中心銅
沈積厚度與其在表面處之厚度的比率。製造出含有通孔及盲通道兩者之較新的PCB。當前的浴添加劑,特定言之當前的調平劑,並非總提供基板表面與經填充通孔及盲通道之間的齊平銅沈積。通道填充之特徵在於經填充通道與表面中之銅之間的高度差。因此,本領域中仍需要適用於製造PCB之金屬電鍍浴中之調平劑以提供齊平銅沈積,同時增強浴液之均鍍能力。
一種包含胺與醌之反應產物的化合物,其中所述胺具有下式:
其中R'選自氫或部分:-CH2-CH2-;R選自H2N-(CH2)m-、HO-(CH2)m-、-HN-CH2-CH2-、Q-(CH2)m-、具有以下結構之部分:
具有以下結構之部分:或具有以下結構之部分:
其中R1-R14獨立地選自氫及(C1-C3)烷基;m為2-12之整
數,n為2-10之整數,p為1-10之整數,q為2-10之整數且r、s及t為1至10之數目;Q為在環中具有一個或兩個氮原子之5-6員雜環或Q為苯磺醯胺部分;且限制條件為當R'為-CH2-CH2-時,R為-HN-CH2-CH2-且R之氮與R'之碳原子形成共價鍵以形成雜環。
一種電鍍浴,其包含一或多種銅離子源、一或多種促進劑、一或多種抑制劑、一或多種電解質及一或多種包括上文所揭示之反應產物的化合物。
一種電鍍方法包含提供基板;將所述基板浸沒於上文所揭示之電鍍浴中;施加電流至所述基板及所述電鍍浴;及將銅電鍍於所述基板上。
反應產物在基板上、甚至在具有小特徵之基板上及在具有多種特徵尺寸之基板上提供具有實質上齊平表面之銅層。電鍍方法有效地將銅沈積於基板上及沈積於盲通道及通孔中,使得銅鍍覆浴具有高均鍍能力。另外,銅沈積物的團塊減少。
除非上下文另外明確指示,否則如本說明書通篇所用,以下縮寫應具有以下含義:A=安培;A/dm2=安培/平方公寸;℃=攝氏度;g=公克;ppm=百萬分率=mg/L;L=公升;μm=微米;mm=毫米;cm=公分;DI=去離子;mL=毫升;mol=莫耳;mmol=毫莫耳;Mw=重量平均分子量;Mn=數目平均分子量;=
-CH2-CH2-;PCB=印刷電路板。所有數值範圍均為包含性的且可以任何順序組合,除非顯而易見此類數值範圍限於合計達100%。
如本說明書通篇所用,「特徵」係指基板上之幾何結構。「孔口」係指包含通孔及盲通道之凹陷特徵。如本說明書通篇所用,術語「鍍覆」係指電鍍。「沈積」及「鍍覆」在本說明書通篇可互換使用。「調平劑」係指能夠提供實質上齊平或平坦的金屬層之有機化合物或其鹽。術語「調平劑(leveler)」及「調平劑(leveling agent)」在本說明書通篇可互換使用。「促進劑」係指增加電鍍浴之鍍覆速率的有機添加劑。「抑制劑」係指在電鍍期間抑制金屬之鍍覆速率的有機添加劑。術語「印刷電路板」及「印刷線路板」在本說明書通篇可互換使用。術語「部分」意謂可包含整個官能基或官能基之一部分作為子結構的分子或聚合物的一部分。術語「部分」及「基團」在本說明書通篇可互換使用。冠詞「一(a/an)」係指單數及複數。
化合物包含胺與作為邁克爾加成受體之醌的反應產物。本發明之胺具有下式:
其中R'選自氫或部分-CH2-CH2-;R選自部分H2N-(CH2)m-、HO-(CH2)m-、-HN-CH2-CH2-、Q-(CH2)m-、具有以下結構之部分:
具有以下結構之部分:或具有以下結構之部分:
其中R1-R14獨立地選自氫及(C1-C3)烷基,較佳地,R1-R6獨立地選自氫及甲基,更佳地,R1-R6選自氫;較佳地,R7-R14獨立地選自氫及甲基;m為2-12、較佳地2-3之整數,n為2-10、較佳地2-5之整數,p為1-10、較佳地1-5、更佳地1-4之整數,q為2-10之整數且r、s及t獨立地為1至10之數目;Q為在環中具有一個或兩個氮原子之5-6員雜環,諸如咪唑或吡啶部分,或Q為具有下式(V)之苯磺醯胺部分;且限制條件為當R'為-CH2-CH2-時,R為-HN-CH2-CH2-且R之氮與R'之碳形成共價鍵以形成雜環,諸如哌嗪環。最佳地,R'為氫且R為部分(II)。
具有式(I)之胺包含(但不限於)乙二胺、胺基乙-1-醇、2,2'-(伸乙二氧基)雙(乙胺)、3,3'-(丁-1,4-二基雙(氧基))雙(丙-1-胺)、聚(1-(2-((3-(2-胺基丙氧基)丁-2-基)氧基)乙氧
基)丙-2-胺)及4-(2-胺基乙基)苯磺醯胺。
當n為2且p為5時,具有部分(II)之較佳化合物為6,8,11,15,17-五甲基-4,7,10,13,16,19-六氧雜二十二烷-2,21-二胺,其具有以下結構:
具有部分(IV)之較佳化合物具有以下結構:
其中變量r、s及t為上文所定義。較佳地,Mw範圍介於200g/mol至2000g/mol。
較佳地,醌包含具有下式之化合物:
其中R15、R16、R17及R18獨立地選自氫、羥基、直鏈或分支鏈羥基(C1-C10)烷基鹵素、直鏈或分支鏈(C1-C10)烷基及直鏈或分支鏈胺基(C1-C10)烷基,其中R15及R16之碳原子可連在一起形成稠合芳族環,以形成具有下式之結構:
其中R19及R20與上文所述之R17及R18相同且R21、R22、R23及R24獨立地選自氫、羥基、直鏈或分支鏈羥基(C1-C10)烷基鹵素、直鏈或分支鏈(C1-C10)烷基及直鏈或分支鏈胺基(C1-C10)烷基。較佳地,醌為式(VI),其中R15、R16、R17及R18獨立地選自氫、羥基及直鏈或分支鏈(C1-C5);或式(VII),其中R19、R20、R21、R22、R23及R24獨立地選自氫、羥基及直鏈或分支鏈(C1-C5)烷基。更佳地,醌係選自式(VI),其中R15、R16、R17及R18獨立地選自氫及羥基;及式(VII),其中R19、R20、R21、R22、R23及R24獨立地選自氫及羥基。具有式(VI)之較佳醌為苯醌且具有式(VII)之較佳醌為萘-1,4-二酮。
本發明之反應產物可藉由邁克爾加成來製備。可遵循習知邁克爾加成程序以製備本發明之反應產物。胺充當邁克爾加成供體且醌為邁克爾加成受體。一般而言,添加足量醌至反應容器中,接著添加足量溶劑,諸如乙醇、二氯甲烷、乙酸乙酯、丙酮、水或其混合物。接著添加足量胺至反應容器中。通常,反應容器中醌與胺之量的莫耳比為0.75-1:1;然而,此比率可視特定反應物而改變。可進行少量實驗以發現特定反應物之較佳反應物莫耳比。可在室溫至110℃或諸如室溫至60℃下進行反應20-24小時或4-6小時。
包含所述反應產物中之一或多者的鍍覆浴及方法適用於在諸如印刷電路板或半導體晶片之基板上提供實質
上齊平的鍍覆金屬層。另外,鍍覆浴及方法適用於用金屬填充基板中之孔口。銅沈積物的均鍍能力良好且團塊形成減少。
對於含有所述反應產物之銅鍍覆浴,上面可電鍍銅的任何基板均可用作基板。此類基板包含(但不限於):印刷線路板、積體電路、半導體封裝、引線框架及互連件。積體電路基板可為用於雙鑲嵌製造方法中之晶圓。此類基板通常含有多個具有各種尺寸之特徵(尤其孔口)。PCB中之通孔可具有各種直徑,諸如直徑為50μm至350μm。此類通孔之深度可不同,諸如0.8mm至10mm。PCB可含有具各種尺寸之盲通道,諸如直徑高達200μm且深度為150μm或大於150μm。
銅鍍覆浴含有銅離子源、電解質及調平劑,其中所述調平劑為如上所述之一或多種胺與一或多種丙烯醯胺的反應產物。銅鍍覆浴可含有鹵離子源、促進劑及抑制劑。除銅以外,電鍍浴可視情況包含一或多種錫來源用於電鍍銅/錫合金。較佳地,電鍍浴為銅電鍍浴。
適合之銅離子源為銅鹽且包含(但不限於):硫酸銅;鹵化銅,諸如氯化銅;乙酸銅;硝酸銅;四氟硼酸銅;烷基磺酸銅;芳基磺酸銅;胺基磺酸銅;過氯酸銅及葡糖酸銅。例示性烷磺酸銅包含(C1-C6)烷磺酸銅且更佳地(C1-C3)烷磺酸銅。較佳的烷磺酸銅為甲磺酸銅、乙磺酸銅及丙磺酸銅。例示性芳基磺酸銅包含(但不限於)苯磺酸銅及對甲苯磺酸銅。可使用銅離子源之混合物。可向本發明電鍍浴中添加除銅離子以外之金屬離子的一或多種鹽。通常,銅鹽的存在量足以提供10至400g/L鍍覆溶液之銅金屬的量。
適合之錫化合物包含(但不限於)鹽,諸如鹵化錫、硫酸錫、烷磺酸錫(諸如甲烷磺酸錫)、芳基磺酸錫(諸如苯磺酸錫及對甲苯磺酸錫)。此等電解質組合物中錫化合物之量通常為提供在5至150g/L範圍內之錫含量的量。錫化合物之混合物可以如上所述之量使用。
適用於本發明之電解質為酸性的。較佳地,電解質之pH2。適合之酸性電解質包含(但不限於):硫酸、乙酸、氟硼酸、烷磺酸(諸如甲磺酸、乙磺酸、丙磺酸及三氟甲烷磺酸)、芳基磺酸(諸如苯磺酸、對甲苯磺酸)、胺磺酸、鹽酸、氫溴酸、過氯酸、硝酸、鉻酸及磷酸。酸之混合物適宜用於本發明金屬鍍覆浴中。較佳之酸包含硫酸、甲磺酸、乙磺酸、丙磺酸、鹽酸及其混合物。酸可以1至400g/L範圍內之量存在。電解質一般可購自各種來源且可未經進一步純化即使用。
此類電解質可視情況含有鹵離子源。通常使用氯離子。例示性氯離子源包含氯化銅、氯化錫、氯化鈉、氯化鉀及鹽酸。可在本發明中使用廣泛範圍之鹵離子濃度。通常,鹵離子濃度以鍍覆浴計在0至100ppm範圍內。此類鹵離子源一般為市售的且可未經進一步純化即使用。
鍍覆組合物通常含有促進劑。任何促進劑(亦稱為增亮劑)均適用於本發明。此類促進劑為本領域中熟習此項技術者所熟知。促進劑包含(但不限於)N,N-二甲基-二硫基胺基甲酸-(3-磺丙基)酯;3-巰基-丙基磺酸-(3-磺丙基)酯;3-巰基-丙基磺酸鈉鹽;碳酸二硫基-O-乙酯-S-酯與3-巰基-1-丙烷磺酸鉀鹽;雙磺丙基二硫化物;雙-(鈉磺丙基)-二硫化
物;3-(苯并噻唑基-S-硫基)丙基磺酸鈉鹽;吡啶鎓丙基磺基甜菜鹼;1-鈉-3-巰基丙烷-1-磺酸鹽;N,N-二甲基-二硫基胺基甲酸-(3-磺乙基)酯;3-巰基-乙基丙基磺酸-(3-磺乙基)酯;3-巰基-乙基磺酸鈉鹽;碳酸-二硫基-O-乙酯-S-酯與3-巰基-1-乙烷磺酸鉀鹽;雙磺乙基二硫化物;3-(苯并噻唑基-S-硫基)乙基磺酸鈉鹽;吡啶鎓乙基磺基甜菜鹼;及1-鈉-3-巰基乙烷-1-磺酸鹽。促進劑可以各種量使用。一般而言,促進劑以在0.1ppm至1000ppm範圍內之量使用。
任何能夠抑制金屬鍍覆速率之化合物均可用作本發明電鍍組合物中之抑制劑。適合之抑制劑包含(但不限於)聚丙二醇共聚物及聚乙二醇共聚物,包含環氧乙烷-環氧丙烷(「EO/PO」)共聚物及丁醇-環氧乙烷-環氧丙烷共聚物。適合之丁醇-環氧乙烷-環氧丙烷共聚物為重量平均分子量為100至100,000g/mol、較佳500至10,000g/mol之彼等丁醇-環氧乙烷-環氧丙烷共聚物。當使用此類抑制劑時,其通常以組合物之重量計以在1至10,000ppm且更通常5至10,000ppm範圍內之量存在。本發明之調平劑亦可具有能夠充當抑制劑之功能。
一般而言,反應產物之數目平均分子量(Mn)為200至100,000g/mol、通常300至50,000g/mol、較佳500至30,000g/mol,但仍可使用具有其他Mn值之反應產物。此類反應產物之重量平均分子量(Mw)值可在1000至50,000g/mol、通常5000至30,000g/mol範圍內,但仍可使用其他Mw值。
電鍍浴中所用之反應產物(亦即調平劑)的量取
決於所選特定調平劑、電鍍浴中金屬離子之濃度、所用特定電解質、電解質之濃度及所施加之電流密度。一般而言,電鍍浴中調平劑之總量介於以鍍覆浴之總重量計0.01ppm至1000ppm、較佳0.1ppm至100ppm、最佳0.5ppm至50ppm範圍內,但仍可使用更大或更小的量。
電鍍浴可藉由以任何順序組合組分來製備。較佳地,首先將諸如金屬離子源、水、電解質及視情況選用之鹵離子源之無機組分添加至浴容器中,接著添加有機組分,諸如調平劑、促進劑、抑制劑及任何其他有機組分。
電鍍浴可視情況含有至少一種額外調平劑。此類額外調平劑可為本發明之另一調平劑,或者可為任何習知調平劑。可與本發明調平劑組合使用之適合的習知調平劑包含(但不限於)Step等人之美國專利第6,610,192號、Wang等人之美國專利第7,128,822號、Hayashi等人之美國專利第7,374,652號及Hagiwara等人之美國專利第6,800,188號中所揭示之彼等調平劑。調平劑之此類組合可用於調整鍍覆浴之特徵,包含調平能力及均鍍能力。
通常,鍍覆浴可在10至65℃或高於65℃之任何溫度下使用。鍍覆浴之溫度較佳為10至35℃且更佳為15至30℃。
一般而言,在使用期間攪拌電鍍浴。可使用任何適合之攪拌方法且此類方法為此項技術中熟知的。適合之攪拌方法包含(但不限於):空氣噴射、工件攪拌及衝擊。
通常,藉由使基板與鍍覆浴接觸來電鍍基板。基板通常充當陰極。鍍覆浴含有陽極,其可為可溶或不溶的。
通常向電極施加電勢。施加足夠的電流密度且進行鍍覆一段時間,所述時間足以在基板上沈積具有所需厚度之金屬層以及填充盲通道、溝槽及通孔或保形鍍覆通孔。電流密度可介於0.05至10A/dm2範圍內,但可使用更高及更低的電流密度。特定電流密度部分取決於待鍍覆之基板、鍍覆浴之組成及所需表面金屬厚度。此類電流密度選擇在本領域中熟習此項技術者的能力內。
本發明之優勢為在PCB上獲得實質上齊平的金屬沈積物。PCB中之通孔、盲通道或其組合經實質上填充或通孔以理想的均鍍能力經保形鍍覆。本發明之另一優勢為廣泛範圍之孔口及孔口尺寸可經填充或以理想的均鍍能力經保形鍍覆。
均鍍能力定義為鍍覆在通孔中心之金屬的平均厚度與鍍覆在PCB樣品表面之金屬的平均厚度相比的比率且以百分比形式報導。均鍍能力愈高,鍍覆浴愈佳能夠保形鍍覆通孔。本發明之金屬鍍覆組合物的均鍍能力45%、較佳50%。
反應產物在基板上、甚至在具有小特徵之基板上及在具有多種特徵尺寸之基板上提供具有實質上齊平表面之銅層及銅/錫層。鍍覆方法有效地將金屬沈積於通孔中,使得電鍍浴具有良好的均鍍能力。
雖然本發明之方法已大體上參照印刷電路板製造加以描述,但應瞭解,本發明可適用於任何需要本質上齊平或平坦的銅或銅/錫沈積物及經填充或經保形鍍覆之孔口的電解製程。此類製程包含半導體封裝及互連件製造。
以下實例意欲進一步說明本發明但並不意欲限制其範疇。
將22.5mmol苯醌添加至100mL三頸燒瓶中,接著添加30mL乙醇及水之混合物。接著將30mmol 2,2'-(伸乙二氧基)雙(乙胺)添加至反應混合物中。在室溫下進行反應隔夜。在反應完全之後,減壓移除所有溶劑,留下固體物質。反應產物1未經純化即使用。
將22.5mmol苯醌添加至100mL三頸燒瓶中,接著添加30mL乙醇及水之混合物。接著將30mmol 6,8,11,15,17-五甲基-4,7,10,13,16,19-六氧雜二十二烷-2,21-二胺添加至反應混合物中。在室溫下進行反應。反應混合物保持在室溫下隔夜。減壓移除所有溶劑,留下固體物質。反應產物2未經純化即使用。
將22.5mmol萘-1,4-二酮添加至100mL三頸燒瓶中,接著添加30mL乙醇及水之混合物。接著將30mmol 6,8,11,15,17-五甲基-4,7,10,13,16,19-六氧雜二十二烷-2,21-二胺添加至反應混合物中。在110℃下經4-5小時進行反應。減壓移除所有溶劑,留下固體物質。反應產物3未經純化即使用。
藉由組合75g/L呈五水合硫酸銅形式之銅、240g/L硫酸、60ppm氯離子、1ppm促進劑及1.5g/L抑制劑來製備多個銅電鍍浴。促進劑為雙(鈉-磺丙基)二硫化物。抑制劑
為重量平均分子量<5,000且具有末端羥基的EO/PO共聚物。各電鍍浴亦含有2ppm至20ppm之量的反應產物1-3中之一者,如下文實例5之表中所示。反應產物未經純化即使用。
具有多個通孔之3.2mm厚的雙面FR4 PCB(5cm×9.5cm)樣品在哈林槽(Haring cell)中使用實例4之銅電鍍浴電鍍銅。樣品具有0.25mm直徑的通孔。各浴之溫度為25℃。將3A/dm2之電流密度施加至樣品40分鐘。分析經銅鍍覆之樣品以測定電鍍浴之均鍍能力(「TP」)及銅沈積物上之團塊數。
均鍍能力藉由測定鍍覆在通孔中心之銅的平均厚度與鍍覆在PCB樣品表面之銅的平均厚度相比之比率來計算。均鍍能力在表中以百分比形式報導。
結果顯示,均鍍能力超過45%表明反應產物之均鍍能力表現良好。另外,所有樣品顯示銅沈積物上之團塊顯著減少。
Claims (10)
- 一種包括胺與醌之反應產物的化合物,其中所述胺具有下式:
- 如申請專利範圍第1項所述的化合物,其中所述胺具有下式:
- 如申請專利範圍第1項所述的化合物,其中所述胺具有下式:
- 如申請專利範圍第1項所述的化合物,其中所述醌具有下式:
- 如申請專利範圍第1項所述的化合物,其中所述醌具有下式:
- 一種電鍍浴,其包括一或多種銅離子源、一或多種促進劑、一或多種抑制劑、一或多種電解質及一或多種如申請專利範圍第1項所述的化合物。
- 如申請專利範圍第6項所述的電鍍浴,其另外包括一或多種錫離子源。
- 一種電鍍方法,其包括:a)提供基板;b)將所述基板浸沒於如申請專利範圍第6項所述的電鍍浴中;c)施加電流至所述基板及所述電鍍浴;及d)將銅電鍍於所述基板上。
- 如申請專利範圍第8項所述的方法,其中如申請專利範圍第6項所述的電鍍浴另外包括一或多種錫離子源。
- 如申請專利範圍第8項所述的方法,其中所述基板包括多個通孔及盲通道中之一或多者。
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