TWI448589B - 電鍍均勻銅層之方法 - Google Patents
電鍍均勻銅層之方法 Download PDFInfo
- Publication number
- TWI448589B TWI448589B TW100146417A TW100146417A TWI448589B TW I448589 B TWI448589 B TW I448589B TW 100146417 A TW100146417 A TW 100146417A TW 100146417 A TW100146417 A TW 100146417A TW I448589 B TWI448589 B TW I448589B
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- TW
- Taiwan
- Prior art keywords
- copper
- plating
- typically
- acid
- alkyl
- Prior art date
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- 229910052802 copper Inorganic materials 0.000 title claims description 88
- 239000010949 copper Substances 0.000 title claims description 88
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 81
- 238000009713 electroplating Methods 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 30
- 238000007747 plating Methods 0.000 claims description 80
- 239000000203 mixture Substances 0.000 claims description 57
- 210000003127 knee Anatomy 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 claims description 15
- 150000001299 aldehydes Chemical class 0.000 claims description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- -1 3-sulfopropyl Chemical group 0.000 description 54
- 150000001875 compounds Chemical class 0.000 description 46
- 239000001257 hydrogen Substances 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 30
- 125000003118 aryl group Chemical group 0.000 description 29
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 24
- 239000007795 chemical reaction product Substances 0.000 description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 150000002118 epoxides Chemical class 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 16
- LSTZTHCEEPHCNQ-UHFFFAOYSA-N 3-(2,5-dioxabicyclo[2.1.0]pentan-3-yloxy)-2,5-dioxabicyclo[2.1.0]pentane Chemical compound C1(C2C(O2)O1)OC1C2C(O2)O1 LSTZTHCEEPHCNQ-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- RGZHEOWNTDJLAQ-UHFFFAOYSA-N 3,4,5-trihydroxybenzaldehyde Chemical compound OC1=CC(C=O)=CC(O)=C1O RGZHEOWNTDJLAQ-UHFFFAOYSA-N 0.000 description 4
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 3
- 125000004008 6 membered carbocyclic group Chemical group 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- 150000001556 benzimidazoles Chemical class 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 239000000460 chlorine Substances 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
- 125000005265 dialkylamine group Chemical group 0.000 description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 3
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229920000962 poly(amidoamine) Polymers 0.000 description 3
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- CRPNQSVBEWWHIJ-UHFFFAOYSA-N 2,3,4-trihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1O CRPNQSVBEWWHIJ-UHFFFAOYSA-N 0.000 description 2
- WNCNWLVQSHZVKV-UHFFFAOYSA-N 2,4,5-trihydroxybenzaldehyde Chemical compound OC1=CC(O)=C(C=O)C=C1O WNCNWLVQSHZVKV-UHFFFAOYSA-N 0.000 description 2
- IUNJCFABHJZSKB-UHFFFAOYSA-N 2,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1 IUNJCFABHJZSKB-UHFFFAOYSA-N 0.000 description 2
- CLFRCXCBWIQVRN-UHFFFAOYSA-N 2,5-dihydroxybenzaldehyde Chemical compound OC1=CC=C(O)C(C=O)=C1 CLFRCXCBWIQVRN-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 description 2
- BAMIYHILDBHASH-UHFFFAOYSA-N 4-(2,5-dioxabicyclo[2.1.0]pentan-3-yloxy)butan-1-ol Chemical compound C1(C2C(O2)O1)OCCCCO BAMIYHILDBHASH-UHFFFAOYSA-N 0.000 description 2
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-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
- 125000001054 5 membered carbocyclic group Chemical group 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000003975 aryl alkyl amines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- DKZBBWMURDFHNE-NSCUHMNNSA-N coniferyl aldehyde Chemical compound COC1=CC(\C=C\C=O)=CC=C1O DKZBBWMURDFHNE-NSCUHMNNSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 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
- 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 2
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 125000005266 diarylamine group Chemical group 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- ZTRPYTHOEREHEN-UHFFFAOYSA-N piperazine pyridine Chemical compound N1CCNCC1.N1=CC=CC=C1.N1=CC=CC=C1 ZTRPYTHOEREHEN-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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 description 2
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DKZBBWMURDFHNE-UHFFFAOYSA-N trans-coniferylaldehyde Natural products COC1=CC(C=CC=O)=CC=C1O DKZBBWMURDFHNE-UHFFFAOYSA-N 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000006526 (C1-C2) alkyl group Chemical group 0.000 description 1
- 125000006755 (C2-C20) alkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VXTJQMZXBFCVEP-UHFFFAOYSA-N 1-(2,5-dioxabicyclo[2.1.0]pentan-3-yloxy)propan-2-ol Chemical compound C1(C2C(O2)O1)OCC(C)O VXTJQMZXBFCVEP-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- FSBYOEHUNSUUTD-UHFFFAOYSA-N 2-(2,5-dioxabicyclo[2.1.0]pentan-3-yloxy)ethanol Chemical compound C1(C2C(O2)O1)OCCO FSBYOEHUNSUUTD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FMIXTGCPNDLWNP-UHFFFAOYSA-N 2-(2-methylsulfanylphenoxy)acetic acid Chemical compound CSC1=CC=CC=C1OCC(O)=O FMIXTGCPNDLWNP-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- YYAQQHMVACMQHH-UHFFFAOYSA-N 2-[[2-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1CCCCC1COCC1CO1 YYAQQHMVACMQHH-UHFFFAOYSA-N 0.000 description 1
- ZMOMCILMBYEGLD-UHFFFAOYSA-N 2-chloro-4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(Cl)=C1 ZMOMCILMBYEGLD-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- 229940006193 2-mercaptoethanesulfonic acid Drugs 0.000 description 1
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- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 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
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
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- Automation & Control Theory (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本申請依據35 U.S.C. §119(e)主張2010年12月15日提出申請之美國專利臨時申請案第61/423,407號之優先權及其所有權益,該申請案全文併入本說明書以資參考。
本發明係關於電鍍均勻銅層在基材之通孔之邊緣及壁面上之方法。更具體而言,本發明係關於藉由添加微量的3-巰基丙烷磺酸或其鹽類至銅電鍍組成物中,以電鍍均勻銅層在基材之通孔之邊緣及壁面上之方法。
通常,使物件電鍍有金屬塗層之方法包含在電鍍溶液中之兩個電極間通電流,其中一個電極為待鍍覆之物件。典型的酸銅鍍覆溶液包括溶解之銅(通常係硫酸銅)、酸電解質(如其量足以賦予浴導電性的硫酸)及專屬的添加劑,以改善鍍覆均勻性和金屬沉積物的品質。該添加劑包含促進劑、整平劑及抑制劑等。
電解銅鍍覆溶液係用於印刷電路板(“PCB”)之製造中。在PCB製造中,係將銅電鍍在先前無電銅金屬化過程中使其為導電性之通孔壁面上。電鍍該銅在通孔壁面上,以增加它們的導電度及為改善之PCB可靠性添加結構的完整性。
理想的PCB銅電鍍通孔係自PCB表面至該通孔之入口或邊緣及深入該通孔柱之長度,皆呈現實質均勻的銅厚度。尤其重要的係均勻的邊緣厚度。因其橫截面的外觀,該邊緣通常稱為膝部。由於PCB介電質(如FR-4玻璃/環氧PCB)及電鍍銅間之熱膨脹係數之失配,遂於熱偏離(如在PCB組裝和操作環境期間所見)期間產生應力。在該通孔之邊緣或膝部這些熱應力尤高。此等熱應力可能導致銅沉積物之裂縫及PCB廢品。在通孔的表面上,藉由肉眼或放大倍率下觀察到的典型現象係為擴口(flaring)或淚滴(tear dropping)。擴口係通孔周圍之銅變薄。該銅係非均勻而使得通孔的一側明顯比相反側差。此變薄係自通孔表面延伸至孔中而不未至該孔的中心,因此形成薄或脆弱的膝部。因此,該電鍍銅在膝部之厚度和均勻性(亦即電鍍均厚能力)係銅沉積物之品質的重要評量。膝部電鍍均厚能力之定義為該銅沉積物在膝部之厚度除以該銅沉積物在基板表面之厚度的比值。通孔電鍍均厚能力之定義為該銅沉積物該通孔中心之厚度除以該銅沉積物在該基板表面之厚度之比值。
整平劑係典型的銅電鍍溶液之添加劑。它們透過選擇性地抑制在高溶液攪拌且高局部電荷密度區域的鍍覆,改善銅沉積物的均勻性和提高電鍍均厚能力。然而,一些整平劑可能得到展現高的通孔電鍍均厚能力與低的膝部電鍍均厚能力之銅沉積物。對於前述的可靠性問題,低膝部電鍍均厚能力係不被期望的。因此,需要一種改善通孔之膝部電鍍均厚能力之方法。
本發明提供方法,其包括a)提供電鍍組成物,係包括一種或多種銅離子源;5至100 ppb之3-巰基丙烷磺酸、其鹽類或其混合物;一種或多種額外的亮光劑;及一種或多種整平劑;b)浸沒基材於該電鍍組成物中,該基材包含複數個通孔,其中,該複數個通孔之膝部及壁面覆有第一銅層;以及c)電鍍實質均勻的第二銅層在該複數個通孔之膝部及壁面之第一銅層上。
本發明提供組成物,其包含一種或多種銅離子源;5至100 ppb之3-巰基丙烷磺酸、其鹽類或其混合物;一種或多種額外的亮光劑;及一種或多種整平劑。
添加5至100 ppb之3-巰基丙烷磺酸、其鹽類或其混合物至包含一種或多種額外的亮光劑及一種或多種整平劑之銅電鍍組成物中,係在膝部及通孔壁面提供實質均勻的銅沉積物且增加膝部的厚度及電鍍均厚能力。
此說明書全文中,除非文意明確地另行指出否則下述縮寫具有以下涵義:A=安培;A/dm2
=每平方公寸之安培;℃=攝氏度;g=公克;mg=毫克;L=公升;ppb=十億分點;ppm=百萬分點;mmol=毫莫耳;μm=百萬分之一公尺=微米;mm=毫米;cm=公分;DI=去離子;SEM=掃描電子顯微照片;以及mL=毫升。除非另行指明,否則所有量為重量百分比且所有比為莫耳比。除了其中明顯該數值範圍受限於相加至多為100%外,所有數值範圍係包含上、下限值的且可依任何順序組合。
此說明書全文中,可互換使用“浴”及“組成物”。本說明書全文中,可互換使用“沉積”及“鍍覆”。“鹵化物”係指氟化物、氯化物、溴化物和碘化物。同樣地,“鹵基(halo)”係指氟基、氯基、溴基和碘基。術語“烷基”包含線型烷基、支鏈型烷基和環烷基。“抑制劑”係指在電鍍期間抑制金屬鍍覆速率之有機添加劑。此說明書全文中,可互換使用術語“印刷電路板”及“印刷線路板”。此說明書全文中,可互換使用術語“膝部”及“邊緣”。冠詞“一(a)”及“一(an)”係指單數和複數。
在提供基材(如印刷電路板(PCB))上實質均勻的鍍覆銅層方面,該水性電鍍組成物和方法係有用的。該組成物和方法增加厚度且改善通孔之邊緣或膝部及通孔壁面上之電鍍均厚能力。此外,該組成物和方法不抵損整體通孔之電鍍均厚能力或整體通孔之電鍍均厚能力之平衡。PCB典型地含有具有數個各種尺寸的通孔。在PCB中的通孔,可能具有多種直徑,如直徑從50μm至1 mm。該通孔之深度可能不同,如從35μm至8 mm且更大。
在銅電鍍組成物中,所包含3-巰基丙烷磺酸、其鹽類(如3-巰基丙烷磺酸、鈉鹽)或該酸及鹽類之混合物的含量為5至100 ppb或如從25至100 ppb或如從10至50 ppb。如果3-巰基丙烷磺酸或其鹽類之含量超過100 ppb,則包含膝部的電鍍均厚能力之整體通孔的電鍍均厚能力會下降。可觀察到呈現擴口之膝部的電鍍均厚能力之下降。在電鍍組成物初步製造時,係添加3-巰基丙烷磺酸、其鹽類及混合物至銅電鍍組成物中,且無需在電鍍組成物之壽命和電鍍週期期間再額外添加。在剛要電鍍前,僅添加一次3-巰基丙烷磺酸、其鹽類或其混合物。
此外,在銅電鍍組成物中,除具有亮光劑活性之3-巰基丙烷磺酸、其鹽類和其混合物外,還包含一種或多種額外的亮光劑。該亮光劑包含,但不受限於此,含硫化合物(如磺丙基二硫化物(sulfopropyldisulfide))、其鹽類(如磺丙基二硫化物鈉鹽及磺丙基二硫化物鉀鹽或其混合物)、2-巰基-乙烷磺酸(鈉鹽)及雙磺丙基二硫化物。美國專利第3,770,598、4,374,709、4,376,685、4,555,315及4,673,469號已揭露該等化合物。其他含硫亮光劑包含,但不受限於,N,N-二甲基二硫代胺甲酸(3-磺丙基)酯鈉鹽、(氧-乙基二硫代碳酸)-硫-(3-磺丙基)-酯鉀鹽、3-[(胺基-亞胺基甲基)-硫基]-1-丙烷磺酸、3-(2-苄并噻唑基硫基)-1-丙烷磺酸鈉鹽及雙磺丙基二硫化物之硫醇。該額外的亮光劑之含量為0.1 mg/L至200 mg/L或如從1 mg/L至50 mg/L。
該銅電鍍組成物也含有銅離子源、電解質及整平劑。在電鍍組成物中,也可能包含常見的添加劑,以修整電鍍過程之操作來最佳化針對特定基材之性能。
至少部分地溶解於電鍍浴中之任何銅離子源係合適。較佳地,銅離子源係溶解於電鍍浴中。合適的銅離子源為銅鹽且包含,不受限於:硫酸銅;鹵化銅如氯化銅;醋酸銅;硝酸銅;氟硼酸銅;烷基磺酸銅;芳基磺酸銅;胺磺酸銅;以及葡萄糖酸銅。例示之烷基磺酸銅包含(C1
-C6
)烷基磺酸銅,及更典型地(C1
-C3
)烷基磺酸銅。典型的烷基磺酸銅為甲烷磺酸銅、乙烷磺酸銅及丙烷磺酸銅。例示芳基磺酸銅包含,不受限於苯基磺酸銅、酚磺酸銅、對甲苯磺酸銅。典型係使用硫酸銅五水合物及甲烷磺酸銅。可使用銅離子源之混合物。一種或多種銅離子以外之其他金屬離子可有利地添加至本電鍍浴中。在銅合金的沉積中,添加該其他金屬離子源係有用的。通常,該銅鹽可自市場上取得且無需純化即可使用。
可以任何用量使用該銅鹽於水性電鍍浴中,以提供足量的銅離子濃度以供於基板上電鍍銅。典型,銅鹽係以足以在鍍覆溶液提供10至180 g/L之銅金屬的量存在。合金如銅-錫,例如,具有高達2重量%錫的銅可有利地被鍍覆。其他合適的銅合金包含,但不受限於銅-銀、錫-銅-銀及錫-銅-鉍。在該混合物中之各個金屬鹽之量係取決於待鍍覆特定合金,且為熟悉該項技藝者所周知。
電解質可能係鹼性或酸性。合適的酸性電解質包含,但不受限於硫酸、氟硼酸、烷磺酸(如甲烷磺酸、乙烷磺酸、丙烷磺酸及三氟甲烷磺酸)、芳基磺酸(如苯基磺酸、酚磺酸及甲苯磺酸)、胺磺酸、鹽酸及磷酸。在本金屬鍍覆浴中,可使用酸的混合物。典型的酸包含硫酸、甲烷磺酸、乙烷磺酸、丙烷磺酸及其混合物。該酸典型含量為1至300 g/L或如從5至250 g/L或如從10至225 g/L的範圍。通常,電解質可自市場之各種來源取得且無需純化即可使用。
該電解質可能含有鹵化物離子、錳離子、亞鐵離子或其混合物及其他常見的離子(如過渡金屬鹽的離子)之來源。典型的鹵化物離子為氯化物離子。可使用各式該等離子。典型,基於電鍍浴,該離子濃度在0至100 ppm或如從10至100 ppm或如從20至75 ppm的範圍中。該離子來源通常可自市場取得且無需純化即可使用。
可使用能夠抑制銅鍍覆速率之任何化合物,作為電鍍浴中的抑制劑。合適的抑制劑包含,但不受限於聚合材料如那些具有雜原子取代及那些具有氧取代者。例示性抑制劑係高分子量之聚醚,如那些具式R-O-(CXYCX’Y’O)n
R’者,其中,R和R’獨立地選自氫、(C2
-C20
)烷基及(C6
-C10
)芳基;各個X,Y,X’和Y’獨立地選自氫、烷基(如甲基、乙基或丙基)、芳基(如苯基)或烷芳基(如苄基);且n係5至100,000的整數。典型,一個或多個X,Y,X’和Y’為氫。較佳的抑制劑包含可自市場取得的聚丙二醇共聚物和聚乙二醇共聚物(包含環氧乙烷-環氧丙烷(“EO/PO”)共聚物及丁基醇-環氧乙烷-環氧丙烷共聚物)。合適的丁基醇-環氧乙烷-環氧丙烷共聚物係具有500至10,000之重量平均分子量,且較佳為1000至10,000。當使用該抑制劑時,典型其含量基於電鍍組成物之重量係在1至10,000 ppm的範圍,且較佳為5至10,000 ppm。
整平劑可能為聚合或非聚合。合適的整平劑包含,但不受限於聚伸乙亞胺(polyethylenimine)、聚醯胺基胺(polyamidoamine)及胺與環氧化物的反應產物。該胺可為一級、二級或三級烷基胺、芳基胺或可為雜環胺。例示性胺包含,但不受限於二烷基胺、三烷基胺、芳基烷基基胺、二芳基胺、咪唑、三唑、四唑、苯并咪唑、苯并三唑、哌啶、嗎啉、哌、吡啶、唑、苯并唑、嘧啶、喹啉和異喹啉。任何含環氧基且可與該胺反應之化合物係合適之環氧化物。合適的環氧化物包含,但不受限於環氧鹵丙烷(如環氧氣丙烷及環氧溴丙烷)及聚環氧化物化合物。
也可使用聚伸乙亞胺、聚醯胺基胺之衍生物作為整平劑。該衍生物包含,不受限於聚伸乙亞胺與環氧化物的反應產物及聚醯胺基胺與環氧化物的反應產物。
美國專利第3,320,317;4,038,161;4,336,114及6,610,192號揭露者是合適的胺與環氧化物之反應產物之實例。特定胺與特定環氧化物之反應產物之製備係周知的,例如美國專利第3,320,317號及德國專利申請案第DE 196 43 091號。美國專利第7,662,981號也揭露胺與環氧化物之反應。
在一個具體實施例中,整平劑可包含至少一個具下式之咪唑化合物之反應產物:
其中,R1
,R2
和R3
獨立地選自氫、(C1
-C12
)烷基、(C2
-C12
)烯基及芳基,限制條件為R1
和R2
不同時為氫。意即該反應產物包含至少一個咪唑,其中,R1
和R2
之至少一者為(C1
-C12
)烷基、(C2
-C12
)烯基或芳基。該咪唑化合物係經(C1
-C12
)烷基、(C2
-C12
)烯基或芳基取代於其4-和/或5-位置。較佳地,R1
,R2
和R3
獨立地選自氫、(C1
-C8
)烷基、(C2
-C7
)烯基及芳基,更佳為氫、(C1
-C6
)烷基、(C3
-C7
)烯基及芳基,甚至更佳為氫、(C1
-C4
)烷基、(C3
-C6
)烯基及芳基。各個(C1
-C12
)烷基及(C2
-C12
)烯基可視需要經一個或多個羥基、鹵素及芳基取代。較佳地,經取代的(C1
-C12
)烷基為經芳基取代之(C1
-C12
)烷基,且更佳為(C1
-C4
)烷基。例示性為(C1
-C4
)烷基,包含,但不受限於苯基、苯乙基及甲基萘基。另外,各個(C1
-C12
)烷基及(C2
-C12
)烯基可含有分別與芳基稠合之環烷基或環烯基。在本文中,術語“芳基”係指從芳香族或雜芳香族部分中移除一個氫原子,所衍生的任何有機自由基。通常,芳基含有6-12個碳原子。可選擇性以一個或多個(C1
-C4
)烷基及羥基取代本發明之芳基。例示性芳基包含,不受限於苯基、甲苯基、二甲苯基、羥基甲苯基、酚基(phenolyl)、萘基、呋喃基及噻吩基。芳基較佳為苯基、二甲苯基或萘基。例示性(C1
-C12
)烷基及經取代的(C1
-C12
)烷基包含,但不受限於甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、正戊基、2-戊基、3-戊基、2-(2-甲基)丁基、2-(2,3-二甲基)丁基、2-(2-甲基)戊基、新戊基、羥甲基、羥乙基、羥丙基、環戊基、羥基環戊基、環戊基甲基、環戊基乙基、環己基、環己基甲基、羥環己基、苯基、苯乙基、萘基甲基、四氫萘基及四氫萘基甲基。例示性(C2
-C8
)烯基包含,但不受限於烯丙基、苯乙烯基、環戊烯基、環戊基甲基、環戊烯基乙基、環己烯基、環己烯基甲基及茚基。通常,該至少一個咪唑化合物係經(C1
-C8
)烷基、(C3
-C7
)烯基或芳基取代於4-或5-位置。更典型地,該至少一個咪唑化合物係經(C1
-C6
)烷基、(C3
-C7
)烯基或芳基取代於4-或5-位置。還要更典型地,該至少一個咪唑化合物係經甲基、乙基、丙基、丁基、烯丙基或芳基取代於4-或5-位置。通常,可自市場之各種來源(如Sigma-Aldrich公司(美國密蘇里州聖路易斯))取得該有用的咪唑化合物,或者可依文獻方法製備該有用的咪唑化合物。
可使用任何合適的含環氧化物之化合物以製造反應產物。該含環氧化物之化合物可含有一個或多個環氧基,且典型含有1、2或3個環氧基,且較佳為含有1或2個環氧基。有用於本發明之適合含環氧化物的化合物係具式E-I、E-II或E-III者。
其中,Y、Y1
和Y2
獨立地選自氫及(C1
-C4
)烷基;X=鹵素;A=OR4
或R5
;R4
=((CR6
R7
)m
O)n
、(芳基-O)p
、CR6
R7
-Z-CR6
R7
O或OZ1 t
O;R5
=(CH2
)y
;A1為(C5
-C12
)環烷基;Z=5-或6-員環;Z1
為R12
OArOR12
、(R13
O)a
Ar(OR13
)a
或(R13
O)a
Cy(OR13
)a
;Cy=(C5
-C12
)環烷基;各個R6
和R7
獨立地選自氫基、CH3
及OH;各個R11
代表(C1
-C4
)烷基或(C1
-C4
)烷氧基;各個R12
代表(C1
-C8
)烷基;各個R13
代表(C2
-C6
)伸烷基氧基;各個a=1至10;m=1至6;n=1至20;p=1至6;q=1至6;r=0至4;t=1至4;以及y=0-6;其中,Y和Y1
可一起形成(C8
-C12
)環形化合物。較佳為Y=氫及X=Cl或Br,且更佳為X=Cl。Y1
和Y2
較佳獨立地選自氫及(C1
-C2
)烷基。當Y1
和Y2
未一起形成環形化合物時,典型Y1
和Y2
皆為氫。當Y1
和Y2
一起形成環形化合物時,通常A為R5
或化學鍵,且形成(C8
-C10
)碳環。典型m=2至4。典型,n=1至10。更典型當n=1至10,m=2至4。苯基-O係R4
之典型芳基-O基。典型p=1至4,更典型為1至3,且又更典型為1至2。Z典型為5-或6-員碳環,且更典型地,Z為6-員碳環。典型,y=0至4,且更典型為1至4。當A=R5
且y=0時,則A為化學鍵。典型,m=1至6,且更典型為1至4。典型q=1至4,更典型為1至3,且還要更典型為1至2。典型地,r=0且q=1,且更典型地Y1
和Y2
=氫、r=0且q=1。典型地,Z1
=R12
OArOR12
或(R13
O)a
Ar(OR13
)a
。各個R12
典型地為(C1
-C6
)烷基且更典型地為(C1
-C4
)烷基。各個R13
典型地為(C2
-C4
)伸炔基氧基。典型t=1至2。典型,a=1至8,更典型為1至6且還更典型為1至4。
例示之式E-I之含環氧化物之化合物為環氧鹵丙烷。典型,含環氧化物之化合物為環氧氯丙烷或環氧溴丙烷,且更典型為環氧氯丙烷。
其中R4
=((CR6
R7
)m
O)n
的合適式E-II化合物為具式E-IIa者:
其中,Y1
、Y2
、R6
、R7
、n和m係如上述般定義。較佳地,Y1
和Y2
皆為氫。當m=2,典型各個R6
為氫、R7
係選自氫及CH3
且n=1至10。當m=3,典型至少一個R7
選自CH3
及OH且n=1。當m=4,典型R6
和R7
皆為氫且n=1。例示性E-IIa之化合物包含,但不受限於此:1,4-丁二醇二環氧丙基醚、乙二醇二環氧丙基醚、二(乙二醇)二環氧丙基醚、聚(乙二醇)二環氧丙基醚化合物、甘油二環氧丙基醚、新戊二醇二環氧丙基醚、丙二醇二環氧丙基醚、二(丙二醇)二環氧丙基醚以及聚(丙二醇)二環氧丙基醚化合物。式E-IIa之聚(乙二醇)二環氧丙基醚化合物為其中各個R6
和R7
=氫、m=2且n=3至20之化合物,且典型n=3至15,更典型n=3至12,且還要更典型n=3至10。例示之聚(乙二醇)二環氧丙基醚化合物包含三(乙二醇)二環氧丙基醚、四(乙二醇)二環氧丙基醚、五(乙二醇)二環氧丙基醚、六(乙二醇)二環氧丙基醚、九(乙二醇)二環氧丙基醚、十(乙二醇)二環氧丙基醚、十二(乙二醇)二環氧丙基醚。式E-IIa之聚(丙二醇)二環氧丙基醚化合物為其中各個R6
=氫且一個R7
=甲基、m=2且n=3至20之化合物,且典型n=3至15,更典型=3至12,且還要更典型n=3至10。例如,聚(丙二醇)二環氧丙基醚化合物包含三(丙二醇)二環氧丙基醚、四(丙二醇)二環氧丙基醚、五(丙二醇)二環氧丙基醚、六(丙二醇)二環氧丙基醚、九(丙二醇)二環氧丙基醚、十(丙二醇)二環氧丙基醚、十二(丙二醇)二環氧丙基醚。合適的聚(乙二醇)二環氧丙基醚化合物及聚(丙二醇)二環氧丙基醚化合物,係具有350至10000之數目平均分子量的那些化合物,且典型為380至8000之數目平均分子量。
其中R4
=(芳基-O)p
之合適式E-II化合物為具有式E-IIb與E-IIc者:
其中,Y1
、Y2
和p係如上述般定義,且各個R11
代表(C1
-C4
)烷基或(C1
-C4
)烷氧基且r=0至4。E-II,r=0且p=1,且更E-IIY1
和Y2
=氫、r=0且p=1。
在其中R4
=CR6
R7
-Z-CR6
R7
O之式E-II化合物中,Z代表5-或6-員環。在該環結構中,CR6
R7
基可附接在任何位置,如在環的相鄰原子或在環的任何其他原子。其中R4
=CR6
R7
-Z-CR6
R7
O之特別合適的式E-II化合物係具有式E-IId者:
其中,Y1
、Y2
、R6
和R7
係如上述般定義且q=0或1。當q=0,該環結構為5-員碳環,且當q=1,該環結構為6-員碳環。典型,Y1
和Y2
=氫。更典型,Y1
和Y2
=氫且q=1。典型,其中R4
=CR6
R7
-Z-CR6
R7
O之式E-11化合物為1,2-環己烷二甲醇二環氧丙基醚及1,4-環己烷二甲醇二環氧丙基醚。
當A=R5
,合適的式E-II之化合物係具有式E-IIe者:
其中,Y1
、Y2
和y係如上述般定義。典型y=0至4,更典型y=1至4及y=2至4。例示性具式E-IIe之化合物包含,但不受限於1,5-二環氧基己烷、1,7-二環氧基辛烷及1,9-二環氧基癸烷。
在其中A=OZ1 t
O之式II化合物中,典型化合物係式E-IIf者:
其中,Y1
和Y2
係如上述般定義。
合適的式E-III之含環氧的化合物可為單環、螺環、稠合環及/或雙環。式E-III之含環氧化物的典型化合物包含1,5-二環氧基-環辛烷、1,6-二環氧基-環癸烷及二氧化二環戊二烯(dicyclopentadiene dioxide)。
可自市場上各種來源(如Sigma-Aldrich公司)得到有用的含環氧化物的化合物,或可使用各種本領域中周知的文獻方法製備。
藉由一種或多種以上所述的苯并咪唑化合物與一種或多種以上所述的含環氧化物的化合物反應可製備該反應產物。典型,加入所欲量的苯并咪唑及含環氧基化合物至反應瓶中,接著加水。加熱所產生的混合物至約75至95℃,4至6小時。在室溫下額外攪拌6至12小時後,以水稀釋產生的反應產物。可使用這樣的反應產物水溶液或(若需要)可純化或可分離反應產物。
一般而言,整平劑具有500至10,000之數目平均分子量(Mn),雖然可使用具有其他Mn值之反應產物。該反應產物具有重量平均分子量(Mw)值在1000至50,000之範圍,雖然可使用其他Mw值。典型,Mw係從1000至20,000。在一個具體實施例中,Mw係1500至5000。在另一個具體實施例中,Mw係5000至15,000。
典型,咪唑化合物與含環氧化物的化合物之比係從0.1:10至10:0.1。典型,該比係從0.5:5至5:0.5且更典型從0.5:1至1:0.5。可使用其他合適的咪唑化合物與含環氧化物的化合物之比來製備整平劑。
在另一個具體實施例中,在本混合物中的至少一個整平劑,係胺與環氧鹵丙烷之反應產物。通常,胺係咪唑且環氧鹵丙烷係環氧氯丙烷。然而,可使用其他環氧鹵丙烷如環氧溴丙烷。在又另一個具體實施例中,在本混合物中的至少一個整平劑係胺與聚環氧化物化合物之反應產物。在又一具體實施例中,胺係咪唑且聚環氧化物化合物係以下式(E-IIg)之二環氧化物化合物。
在印刷電路板(PCB)通孔之膝部及壁面上沉積導電晶種層方法包含無電鍍覆。在PCB上及通孔上鍍覆銅之無電方法及組成物係為本領域中周知。可使用常見的方法和無電銅鍍覆浴。美國第4,563,217及4,751,106號揭露該類方法和無電銅浴之實例。該銅層之厚度範圍為1μm至5μm。PCB係與上述的銅電鍍浴接觸,然後施加電流密度一段足以沉積第二銅層在第一銅層上之時間。
其中,R16
為(C1
-C10
)烷基;以及R14
和R15
獨立地選自氫和R16
,其中n1
=1至20。典型,n1
=1至10且更典型n1
=1至5。在一具體實施例中,n1
=1。在又一具體實施例中,R14
和R15
皆為氫。在另一個具體實施例中,R16
係視需要經取代。“經取代”意指以一或多個取代基(如羥基、(C1
-C4
)烷氧基、巰基、胺基、(C1
-C4
)烷基胺基及二(C1
-C4
)烷基胺基)置換一或多個氫。雖式(E-IIg)之聚環氧化物化合物具有兩個環氧基,但也可使用具有三或多個環氧基之聚環氧化物化合物。
雖然可使用具有其他數目平均分子量之反應產物,例示之包含選自氮、硫及氮和硫之混合物的雜原子之化合物與含有式(E-IIg)之醚鍵聯的化合物之聚環氧化物化合物之反應產物,係具有500至25,000之數目平均分子量(如藉由凝膠滲透層析術測定)。更典型,該反應產物具有1000至15,000之數目平均分子量,且還要更典型從1250至5000。一般而言,選自氮、硫及氮和硫之混合物之雜原子與含有式(E-IIg)之醚鍵聯的化合物之聚環氧化物化合物之反應產物,係具有1至5,更典型為1至4且還要更典型為1至2.5之分子量多分散性。於一具體實施例中,該多分散度為1至2。
合適的非聚合整平劑包含,不受限於非聚含硫化合物及非聚合含氮化合物。例示之含硫整平化合物包含硫脲及經取代的硫脲。例示之含氮化合物包含一級、二級或三級胺。該胺可為烷基胺、芳基胺和環胺(即具有氮作為環員之環狀化合物)。合適的胺包含,但不受限於二烷基胺、三烷基胺、芳基烷基胺、二芳基胺、咪唑、三唑、四唑、苯并咪唑、苯并三唑、哌啶、嗎啉、哌、吡啶、唑、苯并唑、嘧啶、喹啉和異喹啉。非聚合胺可為未經取代或經取代者。“經取代”意指以一或多個取代基置換一或多個氫。可使用廣泛種類取代基,包含胺基、烷基胺基、二烷基胺基、烷基、芳基、烯基、烷氧基及鹵基。其他合適的非聚合整平劑包含苯胺黑(nigrosine)、五甲基-對-玫瑰苯胺氫鹵化物、六甲基-對-玫瑰苯胺氫鹵化物及含有式N-R17
-S之官能基之化合物,其中,R17
為經取代的烷基、未經取代的烷基、經取代的芳基或未經取代的芳基。典型,該烷基為(C1
-C6
)烷基且典型為(C1
-C4
)烷基。一般而言,該芳基包含(C6
-C20
)芳基,典型地為(C6
-C10
)芳基。該芳基可能復包含雜原子,如硫、氮及氧。典型,該芳基為苯基或萘基。
整平劑也可能具有能夠充當抑制劑之功能。該化合物可為雙種功能,即它們可當作整平劑和抑制劑。
電鍍浴可視需要含有可與上述的整平劑組合使用之額外的整平劑,包含,但不受限於,美國專利第6,610,192(Step et al.)、7,128,822(Wang et al.)、7,374,652(Hayashi et al.)及6,800,188號(Hagiwara et al.)所揭露的那些。
在電鍍浴中整平劑之用量可取決於所選擇之特定的整平劑、在電鍍浴中之金屬離子的濃度、所使用之特定的電解質、電解質的濃度及所施加之電流密度。一般而言,雖然可使用更多或更少之量,在電鍍浴中,基於電鍍浴之總重,整平劑之總量係從0.01 ppm至5000 ppm。典型,整平劑之總量係從0.25至5000 ppm,且更典型從0.25至1000 ppm,且還要更典型從0.25至100 ppm。
視需要地,在銅電鍍組成物中,可能包含一種或多種醛、一種或多種羧酸或其混合物以安定組成物。也可能包含酸酐。在電鍍循環期間,3-巰基丙烷磺酸及其鹽類可能分解至低於5 ppb的水平。添加一種或多種醛或一種或多種羧酸或酸酐或其混合物至電鍍組成物中係抑制3-巰基丙烷磺酸及其鹽類的分解,並在電鍍期間,保持它們在5至100 ppb的理想水平。在電鍍組成物中,係包含25 ppm且更多,或如25 ppm至100 ppm,或如從50 ppm至75 ppm之醛及酸。典型,包含醛以安定組成物。藉由在鍍覆領域中周知的常見的碳拋光過程,可保持醛及羧酸水平。
在組成物中可包含的羧酸包含,但不受限於單羧酸及多羧酸,包含二羧酸和三羧酸。羧酸之實例為醋酸和其酐、甲酸、檸檬酸、琥珀酸、酒石酸、丙酸、丁酸、異丁酸、戊酸、異戊酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、延胡索酸、檸康酸和中康酸(mesaconic acid)。
醛包含,但不受限於R18
-CHO,其中,R18
為氫、(C1
-C20
)線型、支鏈型或環狀烷基;(C2
-C20
)線型、支鏈型或環狀烯基;(C2
-C20
)線型或支鏈型炔基;(C1
-C20
)烷基-O(C2
-C3
O)x1
R19
;(C1
-C12
)烷基苯基-O(C2
-C3
O)x1
R19
;或-苯基-O(C2
-C3
O)x1
R19
;其中,x1係從1至500的整數且R19
為氫、(C1
-C4
)烷基或苯基;該(C1
-C20
)烷基、(C2
-C20
)烯基及(C2
-C20
)炔基可未經取代或經取代。
在(C1
-C20
)烷基、(C2
-C20
)烯基及(C2
-C20
)炔基上的取代基包含,但不受限於鹵素、芳基、-SH、-CN、-SCN、-C=NS、矽基、矽烷、-Si(OH)3
、-NO2
、SO3
M、-PO3
M、-P(R22
)2
、-OH、-COOH、-CHO、-COO(C1
-C12
)烷基、-CO(C1
-C12
)烷基或NR21
R20
,其中R20
和R21
為獨立地氫、芳基或(C1
-C12
)烷基;且M為氫或鹼金屬鋰、鈉、鉀、銣、或銫之相反離子;且R22
為氫或鹵素氟、氯、溴或碘。
環狀烯基及芳基包含,但不受限於苯基、聯苯基、萘基、蒽基、菲基、呋喃基、吡啶基和嘧啶基。
典型,醛為脂環醛及芳香醛,如(C1
-C20
)環烷基及(C2
-C20
)環烯基或帶有芳基取代基之醛。芳香基包含,但不受限於苯基、聯苯基、萘基及呋喃基。
具體之醛的實例為甲醛、乙醛、戊二醛、2,3,4-三羥基苯甲醛、3-羥基苯甲醛、3,4,5-三羥基苯甲醛、2,4-二羥基苯甲醛、4-羥基-3-甲氧基肉桂醛、3,4,5-三羥基苯甲醛單水合物、丁香醛、2,5-二羥基苯甲醛、2,4,5-三羥基苯甲醛、3,5-羥基苯甲醛、3,4-二羥基苯甲醛、4-羥基苯甲醛、4-羧基苯甲醛、2-氯-4-羥基苯甲醛、3-呋喃醛和苯甲醛。
其他之醛的實例包含,但不受限於吡啶甲醛、苯甲醛、萘甲醛、聯苯基甲醛、蒽甲醛、菲甲醛、2-甲醯基苯氧基醋酸、2,3,4-三羥基苯甲醛、3-羥基苯甲醛、3,4,5-三羥基苯甲醛、2,4-二羥基苯甲醛、4-羥基-3-甲氧基肉桂醛、3,4,5-三羥基苯甲醛單水合物及丁香醛。
在印刷電路板(PCB)之通孔之膝部和壁面上沉積導電晶種層之方法包含無電鍍覆。在PCB上及通孔上鍍覆銅之無電方法及組成物係為本領域中周知。可使用常見的方法和無電銅鍍覆浴。美國第4,563,217及4,751,106號揭露該類方法和無電銅浴之實例。該銅層之厚度可為1μm至5μm。PCB係與上述的銅電鍍浴接觸,然後施加電流密度一段足以沉積第二銅層在第一銅層上之時間。
電鍍浴可在任何溫度下使用,如從10至65℃或更高。典型,鍍覆浴的溫度係從10至35℃且更典型從15至30℃。
一般而言,在使用期間,係攪拌該水性電鍍浴。任何合適的攪拌方法可與本發明一起使用且該方法係為本領域中周知。合適的攪拌方法包含,但不受限於空氣注入法、工作件攪拌和衝擊攪拌。
典型,係藉由基材與電鍍浴接觸而電鍍基材。該基材通常當作陰極。該鍍覆浴含有係為可溶的或不可溶的陽極。典型係施加電位至陰極。施加足夠的電流密度及實行鍍覆一段足以沉積具有所欲厚度之銅層於該基板上及通孔之膝部和壁面上之時間。合適的電流密度包含,但不受限於0.05至10 A/dm2
或如1 A/dm2
至5 A/dm2
之範圍。特定的電流密度係部分取決於待電鍍的基材和所選擇的整平劑。該電流密度的選擇係屬熟悉該項技術者之技能。
銅電鍍組成物中添加5至100 ppb,或如從25至100 ppb,或如從10至50 ppb之3-巰基丙烷磺酸、其鹽類或其混合物以及一種或多種額外的亮光劑,提供實質均勻的銅沉積物在通孔之膝部及壁面上,藉此改善膝部及通孔之電鍍均厚能力。膝部之電鍍均厚能力範圍可能從80%且更高,或如從85%且更高,或如從85%至90%。整體的通孔之電鍍均厚能力範圍可能從80%且更高,或如從85%且更高,或如從85%至90%。因此,該方法提供膝部與通孔之電鍍均厚能力的良好平衡。在熱偏離期間(如在迴流、組裝和/或最終使用的環境期間),整個表面上實質均勻的銅改善可靠性,即耐裂性。係定義通孔和膝部兩者之更高電鍍均厚能力意指基材上具有實質均勻的銅厚度。
下述實例用以進一步說明本發明,但不欲受限其範疇。
藉由組合75 g/L的銅(以硫酸銅五水合物)、240 g/L的硫酸、50 ppm的氯化物離子、0.3 g/L的硫酸錳水溶液、1 mg/L的磺丙基二硫化物、100 ppb的3-巰基丙烷磺酸鈉鹽及1.5 g/L的鈉鹽及抑制劑,製備電鍍浴。該抑制劑為具有分子量小於5,000和末端羥基之EO/PO共聚物。該電鍍浴也含有5 mg/L的整平劑,其為63 mmol的1,4-丁二醇二環氧丙基醚、25 mmol的咪唑和75 mmol的4-苯基咪唑之反應產物。反應產物的分析顯示於以下的峰值:δppm:9.22-7.22(m,24H,H arom
);4.52-3.00(m,37.2H(2.65 x 14 H)
,4CH2
-O,2CH-OH,2CH2
-N);以及1.74-1.24(m,10.6H(2.653 x 4H)
,2CH2
)。
使用常見的無電銅鍍覆浴,先無電電鍍1至3μm的薄銅晶種層於具有平均直徑為0.3 mm之通孔之雙側FR4 PCB(5×9.5 cm)的樣本(2.4 mm厚)。之後在使用實施例1的銅鍍覆浴之哈林電池(Haring cell)中鍍覆該樣本。浴的溫度為25℃。施加2 A/dm2
之電流密度至樣本,80分鐘。分析經銅鍍覆樣本,以測定膝部和通孔之電鍍均厚能力。在樣本之多處取得橫截面樣本並視覺比較和測量在膝部和通孔壁面表面的銅沉積物之厚度。第1圖係以徠卡顯微鏡拍攝一個通孔之5000X SEM。該SEM顯示在膝部和通孔壁面之兩側上,銅沉積物之厚度係實質一致的。測得通孔之平均電鍍均厚能力為80%,且膝部之平均電鍍均厚能力為87%。
使用相同類型與相同的尺寸的PCB樣本重複實施例2之方法。如同實施例2以銅無電鍍覆樣本,然後以實施例1之相同的銅電鍍浴(除了不添加3-巰基丙烷磺酸鈉鹽至銅電鍍浴的組成中)電鍍樣本。在如同實施例2之相同的條件及電鍍參數下實行銅電鍍。在樣本之多處取得橫截面樣本並視覺比較和測量樣本表面及通孔壁面表面之銅積層厚度以測定膝部和通孔壁面之電鍍均厚能力。測得膝部之平均電鍍均厚能力為55%,且測得通孔之平均電鍍均厚能力為80%。第2圖係一個通孔壁面之5000X SEM。在膝部和通孔左側壁面之厚度比在右側薄。雖然通孔之電鍍均厚能力良好,但膝部之電鍍均厚能力差。該於製造浴時未添加3-巰基丙烷磺酸鈉鹽至浴的銅電鍍浴中之銅電鍍浴,比在實施例2中之於製造浴時添加3-巰基丙烷磺酸鈉鹽至銅電鍍浴的板之電鍍均厚能力低。
第1圖係FR-4/玻璃-環氧PCB之直徑為0.3 mm的通孔之5000X橫截面,其在各膝部和通孔壁面上有均勻銅沉積物。
第2圖係FR-4/玻璃-環氧PCB之直徑為0.3 mm的通孔之5000X橫截面,其在各膝部和通孔壁面上有不均勻銅沉積物。
該代表圖無元件符號及其所代表之意義。
Claims (8)
- 一種方法,包括:a)提供電鍍組成物,係包括一種或多種銅離子源;5至100 ppb之3-巰基丙烷磺酸、其鹽類或其混合物;一種或多種額外的亮光劑;及一種或多種整平劑;b)浸沒基材於該電鍍組成物中,該基材包含複數個通孔,其中,該複數個通孔之膝部及壁面塗覆有第一銅層;以及c)電鍍實質均勻的第二銅層在該複數個通孔之膝部及壁面之第一銅層上。
- 如申請專利範圍第1項所述之方法,其中,該電鍍組成物復包括一種或多種醛類。
- 如申請專利範圍第1項所述之方法,其中,該電鍍組成物復包括一種或多種羧酸。
- 如申請專利範圍第1項所述之方法,其中,該膝部之電鍍均厚能力為80%及更高。
- 如申請專利範圍第1項所述之方法,其中,該該複數個通孔壁面之電鍍均厚能力為80%及更高。
- 一種電鍍組成物,包括一種或多種銅離子源;5至100 ppb之3-巰基丙烷磺酸、其鹽類或其混合物;一種或多種額外的亮光劑;及一種或多種整平劑。
- 如申請專利範圍第6項所述之電鍍組成物,其中,復包括一種或多種醛。
- 如申請專利範圍第6項所述之電鍍組成物,其中,復包括一種或多種羧酸。
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2011
- 2011-12-13 EP EP11193194A patent/EP2465976B1/en active Active
- 2011-12-13 JP JP2011271940A patent/JP2012127003A/ja active Pending
- 2011-12-15 US US13/326,846 patent/US9365943B2/en not_active Expired - Fee Related
- 2011-12-15 TW TW100146417A patent/TWI448589B/zh active
- 2011-12-15 CN CN201110463058.6A patent/CN102534702B/zh active Active
- 2011-12-15 KR KR1020110135733A patent/KR101839822B1/ko active IP Right Grant
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CN102534702A (zh) | 2012-07-04 |
TW201231736A (en) | 2012-08-01 |
KR20120067315A (ko) | 2012-06-25 |
CN102534702B (zh) | 2015-06-03 |
EP2465976B1 (en) | 2013-04-03 |
JP2012127003A (ja) | 2012-07-05 |
US20120318676A1 (en) | 2012-12-20 |
JP2016216830A (ja) | 2016-12-22 |
EP2465976A1 (en) | 2012-06-20 |
KR101839822B1 (ko) | 2018-03-19 |
JP6227722B2 (ja) | 2017-11-08 |
US9365943B2 (en) | 2016-06-14 |
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