KR20230005394A - Catalyst-applied liquid for electroless plating - Google Patents
Catalyst-applied liquid for electroless plating Download PDFInfo
- Publication number
- KR20230005394A KR20230005394A KR1020227043461A KR20227043461A KR20230005394A KR 20230005394 A KR20230005394 A KR 20230005394A KR 1020227043461 A KR1020227043461 A KR 1020227043461A KR 20227043461 A KR20227043461 A KR 20227043461A KR 20230005394 A KR20230005394 A KR 20230005394A
- Authority
- KR
- South Korea
- Prior art keywords
- electroless plating
- electroless
- plating
- catalyst
- application liquid
- Prior art date
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- 238000007772 electroless plating Methods 0.000 title claims abstract description 88
- 239000007788 liquid Substances 0.000 title claims abstract description 65
- 238000007747 plating Methods 0.000 claims abstract description 91
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 38
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 33
- 239000010931 gold Substances 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 28
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 25
- 229910052737 gold Inorganic materials 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- -1 amine compound Chemical class 0.000 claims description 23
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 150000001412 amines Chemical class 0.000 claims description 20
- 229910000085 borane Inorganic materials 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000013077 target material Substances 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 150000002429 hydrazines Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 12
- 230000004888 barrier function Effects 0.000 abstract description 10
- 239000007769 metal material Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 27
- 238000011156 evaluation Methods 0.000 description 20
- 239000000758 substrate Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005238 degreasing Methods 0.000 description 10
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- 229920005989 resin Polymers 0.000 description 10
- 159000000000 sodium salts Chemical class 0.000 description 10
- 150000003863 ammonium salts Chemical class 0.000 description 9
- 235000015165 citric acid Nutrition 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910001020 Au alloy Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 8
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 8
- 239000003353 gold alloy Substances 0.000 description 8
- 159000000001 potassium salts Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- 229910001252 Pd alloy Inorganic materials 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 4
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 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
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910010277 boron hydride 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
- 239000000919 ceramic Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000006179 pH buffering agent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-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
- 239000011800 void material Substances 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910020674 Co—B Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229910017262 Mo—B Inorganic materials 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- CJXQLDHMQRJPJJ-UHFFFAOYSA-L N.[Co](Cl)Cl Chemical compound N.[Co](Cl)Cl CJXQLDHMQRJPJJ-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- RSBNPUNXBGVNNB-UHFFFAOYSA-M S(=O)(=O)([O-])[O-].[NH4+].[Co+] Chemical compound S(=O)(=O)([O-])[O-].[NH4+].[Co+] RSBNPUNXBGVNNB-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- VDTVZBCTOQDZSH-UHFFFAOYSA-N borane N-ethylethanamine Chemical compound B.CCNCC VDTVZBCTOQDZSH-UHFFFAOYSA-N 0.000 description 1
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- RECCKCFXMJNLFO-ZVGUSBNCSA-L cobalt(2+);(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Co+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O RECCKCFXMJNLFO-ZVGUSBNCSA-L 0.000 description 1
- VPUKOWSPRKCWBV-UHFFFAOYSA-L cobalt(2+);2-hydroxypropanoate Chemical compound [Co+2].CC(O)C([O-])=O.CC(O)C([O-])=O VPUKOWSPRKCWBV-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- JIPRFNBGGBDGIY-UHFFFAOYSA-L potassium;cobalt(2+);sulfate Chemical compound [K+].[Co+2].[O-]S([O-])(=O)=O JIPRFNBGGBDGIY-UHFFFAOYSA-L 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- C23C18/16—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 by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
-
- 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
- C23C18/16—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 by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
-
- 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
- C23C18/16—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 by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
-
- 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
- C23C18/16—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 by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- 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
- C23C18/16—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 by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
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- 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
- C23C18/16—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 by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- 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
- C23C18/16—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 by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
-
- 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
- C23C18/16—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 by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
금속 재료 상에 무전해 도금을 실시할 때의 전처리에 사용하는 촉매 부여액으로서, 도금 석출성, 선택 석출성, 배리어 특성, 접합성 등이 보다 우수한 무전해 도금 피막을 형성하기 위해 유용하고, 또한 욕 안정성이 보다 우수한 촉매 부여액을 제공하는 것. 코발트 화합물 및 환원제를 함유하는 무전해 도금용 촉매 부여액.As a catalyst application liquid used for pretreatment in electroless plating on a metal material, it is useful for forming an electroless plating film with excellent plating deposition properties, selective deposition properties, barrier properties, bonding properties, etc. To provide a catalyst-applied liquid having more excellent stability. A catalyst application liquid for electroless plating containing a cobalt compound and a reducing agent.
Description
본 발명은 무전해 도금용 촉매 부여액 등에 관한 것이다.The present invention relates to a catalyst application liquid for electroless plating and the like.
프린트 배선판, 반도체 패키지, 전자 부품 등의 일렉트로니스 관련 분야에 있어서, 제조 시에서의 최종 공정의 하나에, 도체 회로, 단자 부분 등에 무전해 니켈 도금을 실시하고, 또한 무전해 금 도금을 실시하는 처리가 있다. 이 방법으로 형성되는 무전해 니켈／금 도금 피막은 동 회로 표면의 산화를 방지하여 양호한 땜납 접속 성능을 발휘시키는 것이나, 반도체 패키지와 그 위에 실장되는 전자 부품의 와이어 본딩성을 향상시키는 것 등을 목적으로 하여 이용되고 있다. 무전해 니켈 도금 피막을 형성한 후, 치환 금 도금 피막을 형성하는 경우에는, 기초의(underlying) 니켈 도금 피막의 상태에 따라서는, 니켈이 국소적으로 용해하여, 니켈의 부식, 이른바 블랙 패드가 발생하는 것이나, 열처리에 의한 기초 금속 확산에 의하여 Au표면이 오염되는 것 등의 문제점이 있다. 이와 같은 문제점을 해결하는 수단으로서, 무전해 니켈 도금과 금 도금의 사이에 배리어 피막으로서 무전해 팔라듐 도금을 실시하는, 무전해 니켈／팔라듐／금 도금 처리가 증가하고 있다. 또한, 프린트 배선판의 고밀도화에 동반하는 동 배선의 미세화에 대응하기 위해, 가장 막두께가 높은 무전해 니켈 도금 피막을 생략한 무전해 팔라듐／금 도금 처리가 개발되고 있다(하기 특허문헌 1 참조). In electronics-related fields such as printed wiring boards, semiconductor packages, and electronic components, one of the final steps in manufacturing is a process in which electroless nickel plating is applied to conductor circuits, terminals, etc., followed by electroless gold plating. there is The purpose of the electroless nickel/gold plating film formed by this method is to prevent oxidation of the copper circuit surface to exhibit good solder connection performance, and to improve wire bonding of semiconductor packages and electronic components mounted thereon. It is being used as In the case where a substitution gold plating film is formed after the electroless nickel plating film is formed, depending on the state of the underlying nickel plating film, nickel is locally dissolved and nickel corrosion, a so-called black pad, occurs. There are problems such as contamination of the surface of Au due to diffusion of the base metal by heat treatment. As a means to solve such a problem, an electroless nickel/palladium/gold plating process in which electroless palladium plating is applied as a barrier film between electroless nickel plating and gold plating is increasing. In addition, in order to cope with miniaturization of copper wiring accompanying the increase in density of printed wiring boards, an electroless palladium/gold plating process omitting the electroless nickel plating film having the highest film thickness has been developed (see Patent Document 1 below).
기판의 금속 재료 상에 무전해 도금을 실시할 때에, 도금 석출성 등을 향상시킬 목적으로, 금속 재료 상에 치환 반응으로 촉매핵으로 되는 팔라듐 금속을 석출시키는 촉매 부여 처리를 실시하는 일이 있다. 본 발명자는 연구를 진행하는 중에, 이 촉매 부여 처리를 실시하는 경우, 도금 석출성은 양호하지만, 배리어 특성 및 접합성에서 불충분한 것을 발견했다. 이 원인에 대하여 조사해 가는 중에, 상기 촉매 부여 처리를 실시하는 경우, 금속 재료의 과잉 용해가 발생하는 경우가 있고, 그 후에 무전해 도금(니켈이나 팔라듐 등) 처리를 실시하면, 석출한 도금 피막과 금속 재료의 사이의 곳곳에 미소한 공극(보이드)이 발생하는 것을 발견했다.When electroless plating is performed on a metal material of a substrate, a catalyst imparting treatment for depositing palladium metal serving as a catalytic nucleus by a substitution reaction is sometimes performed on the metal material for the purpose of improving plating deposition properties and the like. In the course of research, the present inventors have found that when this catalyst imparting treatment is performed, the plating depositability is good, but the barrier characteristics and bondability are insufficient. While investigating the cause, excessive dissolution of the metal material may occur in the case of performing the above catalyst imparting treatment, and then, if electroless plating (nickel, palladium, etc.) treatment is performed, the deposited plating film and It was discovered that minute voids (voids) were generated in various places between metal materials.
이 때문에, 본 발명자는 치환 반응은 아니고, 환원 반응에 의해 팔라듐 금속을 석출시키는 촉매 부여 처리를 시도했다. 그러나 도금 석출성, 선택 석출성, 욕 안정성, 배리어 특성, 접합성 등의 특성의 몇 가지에서 불충분했다.For this reason, the present inventors attempted a catalyst imparting treatment in which palladium metal was deposited by a reduction reaction rather than a substitution reaction. However, some of the properties, such as plating precipitation properties, selective precipitation properties, bath stability, barrier properties, and bonding properties, were insufficient.
그래서 본 발명은 금속 재료 상에 무전해 도금을 실시할 때의 전처리에 사용하는 촉매 부여액으로서, 도금 석출성, 선택 석출성, 배리어 특성, 접합성 등이 보다 우수한 무전해 도금 피막을 형성하기 위해 유용하고, 또한, 욕 안정성이 보다 우수한 촉매 부여액을 제공하는 것을 과제로 한다.Therefore, the present invention is a catalyst-applied liquid used for pretreatment in performing electroless plating on a metal material, and is useful for forming an electroless plating film having better plating deposition properties, selective deposition properties, barrier properties, bondability, and the like. In addition, it is an object to provide a catalyst-applied liquid having better bath stability.
본 발명자는 상기 과제를 감안하여 예의 연구를 진행한 결과, 코발트 화합물 및 환원제를 함유하는 무전해 도금용 촉매 부여액이면, 상기 과제를 해결할 수 있는 것을 발견했다. 본 발명자는 이 지견에 기초하여 더욱 연구를 진행한 결과, 본 발명을 완성시켰다. 즉, 본 발명은 하기의 양태를 포함한다.As a result of intensive research in view of the above problems, the present inventors have found that the above problems can be solved if it is a catalyst application liquid for electroless plating containing a cobalt compound and a reducing agent. As a result of further research based on this knowledge, the present inventors completed the present invention. That is, the present invention includes the following aspects.
항 1. 코발트 화합물 및 환원제를 함유하는 무전해 도금용 촉매 부여액.Item 1. A catalyst application liquid for electroless plating containing a cobalt compound and a reducing agent.
항 2. 상기 환원제가 아민 화합물을 포함하는 항 1에 기재된 무전해 도금용 촉매 부여액.Item 2. The catalyst application liquid for electroless plating according to Item 1, wherein the reducing agent contains an amine compound.
항 3. 상기 아민 화합물이 아민보란, 히드라진 및 히드라진 유도체로 이루어지는 군으로부터 선택되는 적어도 1종을 포함하는 항 2에 기재된 무전해 도금용 촉매 부여액.Item 3. The catalyst-applied liquid for electroless plating according to Item 2, wherein the amine compound contains at least one selected from the group consisting of amine borane, hydrazine and hydrazine derivatives.
항 4. 착화제를 함유하는 항 1 내지 3 중 어느 한 항에 기재된 무전해 도금용 촉매 부여액.Item 4. The catalyst application liquid for electroless plating according to any one of Items 1 to 3 containing a complexing agent.
항 5. 상기 착화제가 카르복실산을 포함하는 항 4에 기재된 무전해 도금용 촉매 부여액.Item 5. The catalyst application liquid for electroless plating according to Item 4, wherein the complexing agent contains a carboxylic acid.
항 6. 상기 카르복실산이 히드록시카르복실산 또는 디카르복실산을 포함하는 항 5에 기재된 무전해 도금용 촉매 부여액.Item 6. The catalyst-applied liquid for electroless plating according to Item 5, wherein the carboxylic acid contains a hydroxycarboxylic acid or a dicarboxylic acid.
항 7. 상기 환원제가 붕소 함유 화합물 및 인 함유 화합물로 이루어지는 군으로부터 선택되는 적어도 1종을 포함하는 항 1 내지 6 중 어느 한 항에 기재된 무전해 도금용 촉매 부여액.Item 7. The catalyst-applied liquid for electroless plating according to any one of Items 1 to 6, wherein the reducing agent contains at least one selected from the group consisting of boron-containing compounds and phosphorus-containing compounds.
항 8. 금속염을 더 함유하는 항 1 내지 7 중 어느 한 항에 기재된 무전해 도금용 촉매 부여액.Item 8. The catalyst application liquid for electroless plating according to any one of Items 1 to 7 further containing a metal salt.
항 9. 코발트 함유량이 금속 100질량％에 대하여 50질량％ 이상인 항 1 내지 8 중 어느 한 항에 기재된 무전해 도금용 촉매 부여액.Item 9. The catalyst-applied liquid for electroless plating according to any one of Items 1 to 8, wherein the cobalt content is 50% by mass or more with respect to 100% by mass of the metal.
항 10. 상기 환원제가 붕소 함유 화합물 및 인 함유 화합물로 이루어지는 군으로부터 선택되는 적어도 1종을 포함하고, 또한,Item 10. The reducing agent contains at least one selected from the group consisting of boron-containing compounds and phosphorus-containing compounds, and
상기 무전해 도금이 동 및／또는 동 합금이 표면에 노출되어 있는 재료에 대한 무전해 팔라듐 도금, 무전해 니켈 도금 및 무전해 금 도금으로 이루어지는 군으로부터 선택되는 적어도 1종의 무전해 도금인 항 1 내지 9 중 어느 한 항에 기재된 무전해 도금용 촉매 부여액.Item 1, wherein the electroless plating is at least one type of electroless plating selected from the group consisting of electroless palladium plating, electroless nickel plating, and electroless gold plating on a material having copper and/or copper alloy exposed on its surface. The catalyst application liquid for electroless plating according to any one of 9 to 9.
항 11. (1) 무전해 도금 대상 재료와, 항 1 내지 10 중 어느 한 항에 기재된 무전해 도금용 촉매 부여액을 접촉시키는 공정을 포함하는, 촉매핵을 포함하는 무전해 도금 대상 재료를 제조하는 방법.Item 11. (1) Manufacture of an electroless plating target material containing a catalyst core, including a step of bringing the electroless plating target material into contact with the electroless plating catalyst-applying liquid according to any one of items 1 to 10 How to.
항 12. (1) 무전해 도금 대상 재료와, 항 1 내지 10 중 어느 한 항에 기재된 무전해 도금용 촉매 부여액을 접촉시키는 공정 및,Item 12. (1) Step of bringing the material to be electroless plating into contact with the electroless plating catalyst-applying liquid according to any one of Items 1 to 10;
(2) 공정(1) 후에, 무전해 도금 처리하는 공정을 포함하는 무전해 도금 피막을 포함하는 재료를 제조하는 방법.(2) A method for producing a material containing an electroless plating film including a step of performing an electroless plating treatment after step (1).
항 13. 금속이 표면에 노출되어 있는 재료, 상기 금속 상의 촉매핵(1) 및 상기 촉매핵(1) 상의 피막(2)을 포함하고, 또한Item 13. A material having a metal exposed on the surface, a catalytic core 1 on the metal, and a coating 2 on the catalytic core 1, and
상기 촉매핵(1)이 코발트를 함유하고,The catalyst core 1 contains cobalt,
상기 피막(2)이 무전해 도금 피막인 재료.The material in which the film (2) is an electroless plating film.
본 발명에 따르면, 금속 재료 상에 무전해 도금을 실시할 때의 전처리에 사용하는 촉매 부여액으로서, 도금 석출성, 선택 석출성, 배리어 특성, 접합성 등이 보다 우수한 무전해 도금 피막을 형성하기 위해 유용하고, 또한, 욕 안정성이 보다 우수한 촉매 부여액을 제공할 수 있다.According to the present invention, as a catalyst-applied liquid used for pretreatment in electroless plating on a metal material, to form an electroless plating film having better plating deposition properties, selective deposition properties, barrier properties, bondability, etc. It is possible to provide a catalyst-applied liquid that is useful and has more excellent bath stability.
본 명세서 중에서 “함유” 및 “포함하는”의 표현에 대해서는, “함유”, “포함하는”, “실질적으로 이루어지는” 및 “만으로 이루어지는”이라는 개념을 포함한다.In this specification, the expressions "containing" and "comprising" include the concepts of "contains", "comprising", "consisting essentially of" and "consisting only of".
1. 촉매 부여액1. Catalyst applied liquid
본 발명은, 그 일 양태에 있어서, 코발트 화합물 및 환원제를 함유하는 무전해 도금 촉매 부여액(본 명세서에 있어서, “본 발명의 촉매 부여액”으로 나타내는 일도 있다.)에 관한 것이다. 이하에, 이에 대하여 설명한다.In one aspect, the present invention relates to an electroless plating catalyst application liquid (sometimes referred to as “catalyst application liquid of the present invention” in this specification) containing a cobalt compound and a reducing agent. Below, this is demonstrated.
코발트 화합물은 도금액에 가용성인 것인 한, 특별히 제한되지 않는다. 코발트 화합물로서는, 예를 들면, 유기 또는 무기의 코발트염을 들 수 있고, 보다 구체적으로는, 예를 들면, 황산코발트, 염화코발트, 질산코발트, 브롬화코발트, 요드화코발트, 차아인산코발트, 인산코발트, 황산코발트암모늄, 염화코발트암모늄, 황산코발트칼륨, 설파민산코발트, 아세트산코발트, 탄산코발트, 코발트아세틸아세토네이트, 포름산코발트, 옥살산코발트, 스테아르산코발트, 시트르산코발트, 타르타르산코발트, 락트산코발트 등을 들 수 있다. 이들 중에서도, 본 발명의 효과의 관점에서, 바람직하게는 무기코발트염을 들 수 있고, 보다 바람직하게는 황산코발트, 염화코발트, 질산코발트, 인산코발트, 차아인산코발트 등을 들 수 있고, 더욱 바람직하게는 황산코발트, 염화코발트를 들 수 있다.The cobalt compound is not particularly limited as long as it is soluble in the plating solution. Examples of the cobalt compound include organic or inorganic cobalt salts, and more specifically, for example, cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt bromide, cobalt iodide, cobalt hypophosphite, cobalt phosphate. , ammonium cobalt sulfate, ammonium cobalt chloride, potassium cobalt sulfate, cobalt sulfamate, cobalt acetate, cobalt carbonate, cobalt acetylacetonate, cobalt formate, cobalt oxalate, cobalt stearate, cobalt citrate, cobalt tartrate, cobalt lactate, etc. there is. Among these, from the viewpoint of the effect of the present invention, inorganic cobalt salts are preferably used, and cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt phosphate, and hypophosphite are more preferably used. may include cobalt sulfate and cobalt chloride.
코발트 화합물은 1종 단독으로 또는 2종 이상을 조합하여 이용할 수 있다.A cobalt compound can be used individually by 1 type or in combination of 2 or more types.
본 발명의 촉매 부여액 중의 코발트 농도는 예를 들면, 0.05g／L 이상이다. 해당 코발트 농도는 본 발명의 효과의 관점에서, 바람직하게는 0.05∼50g／L, 보다 바람직하게는 0.1∼30g／L, 더욱 바람직하게는 0.2∼20g／L, 더한층 바람직하게는 0.4∼15g／L, 그 중에서도 바람직하게는 0.6∼10g／L, 특히 바람직하게는 0.7∼6g／L이다.The cobalt concentration in the catalyst application liquid of the present invention is, for example, 0.05 g/L or more. From the viewpoint of the effect of the present invention, the cobalt concentration is preferably 0.05 to 50 g/L, more preferably 0.1 to 30 g/L, still more preferably 0.2 to 20 g/L, still more preferably 0.4 to 15 g/L. , Among them, preferably 0.6 to 10 g/L, particularly preferably 0.7 to 6 g/L.
본 발명의 촉매 부여액 중의 코발트 함유량은, 코발트를 포함하는 천이 금속 원소의 함유량 100질량％에 대하여, 예를 들면, 50질량％ 이상, 바람직하게는 60질량％ 이상, 보다 바람직하게는 70질량％이고, 또는 80질량％ 이상, 또는 90질량％ 이상이다.The cobalt content in the catalyst-applied liquid of the present invention is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass relative to 100% by mass of the content of the transition metal element containing cobalt. , or 80% by mass or more, or 90% by mass or more.
환원제로서는, 코발트 금속을 석출시키는 것이 가능한 환원제인 한, 특별히 제한되지 않고, 환원 도금에서 사용될 수 있는 환원제를 사용할 수 있다. 환원제로서는, 예를 들면, 아민 화합물, 붕소 함유 화합물, 인 함유 화합물 등을 들 수 있다. 환원제는, 이들의 복수에 속하는 것도 존재한다. 예를 들면, 아민 화합물이고, 또한 붕소 함유 화합물인 환원제도 존재한다. 그 경우, 그 환원제를 함유하는 경우에는, 아민 화합물을 함유한다고 할 수 있고, 또한 붕소 함유 화합물을 함유한다고 할 수 있다.The reducing agent is not particularly limited as long as it is a reducing agent capable of depositing cobalt metal, and a reducing agent that can be used in reduction plating can be used. Examples of the reducing agent include amine compounds, boron-containing compounds, and phosphorus-containing compounds. As for the reducing agent, there are also those belonging to a plurality of these. For example, a reducing agent that is an amine compound and is a boron-containing compound also exists. In that case, when the reducing agent is contained, it can be said to contain an amine compound, and furthermore, it can be said to contain a boron-containing compound.
아민 화합물로서는, 예를 들면, 아민보란, 히드라진, 히드라진 유도체 등을 들 수 있다.As an amine compound, an amine borane, hydrazine, a hydrazine derivative etc. are mentioned, for example.
아민보란은 보란(예를 들면, BH3)과 아민의 착체인 아민보란 착체이다. 아민보란을 구성하는 아민으로서는, 쇄상 아민(비환상 아민), 환상 아민의 어느 쪽이어도 좋지만, 바람직하게는 쇄상 아민이고, 보다 바람직하게는 쇄상 아민 중에서도, 일반식(1):An amine borane is an amine borane complex which is a complex of a borane (eg, BH 3 ) and an amine. As the amine constituting the amine borane, either a chain amine (non-cyclic amine) or a cyclic amine may be used, but a chain amine is preferred, and among the chain amines, general formula (1) is preferred:
[화학식 1][Formula 1]
[식 중, R1, R2 및 R3은 동일 또는 다르고, 수소 원자 또는 알킬기를 나타낸다.][In the formula, R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom or an alkyl group.]
로 표시되는 쇄상 아민을 들 수 있다.and chain amines represented by
알킬기에는, 직쇄상, 분기쇄상 및 환상의 어느 쪽의 것도 포함된다. 알킬기는 바람직하게는 직쇄상 또는 분기쇄상이고, 보다 바람직하게는 직쇄상이다. 해당 알킬기의 탄소수는 특별히 제한되지 않지만, 예를 들면, 1∼8, 바람직하게는 1∼6, 보다 바람직하게는 1∼4, 더욱 바람직하게는 1∼2, 더한층 바람직하게는 1이다. 해당 알킬기의 구체예로서는, 메틸기, 에틸기, n―프로필기, 이소프로필기, n―부틸기, 이소부틸기, tert―부틸기, sec―부틸기, n―펜틸기, 네오펜틸기, n―헥실기, 3―메틸펜틸기, 시클로헥실기 등을 들 수 있다.The alkyl group includes any of linear, branched and cyclic. The alkyl group is preferably straight-chain or branched-chain, more preferably straight-chain. The number of carbon atoms in the alkyl group is not particularly limited, but is, for example, 1 to 8, preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2, still more preferably 1. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, n-hex. A real group, a 3-methylpentyl group, a cyclohexyl group, etc. are mentioned.
본 발명의 바람직한 일 양태에 있어서는, R1, R2 및 R3 중, 어느 2개 또는 전부(보다 바람직하게는 2개)가 알킬기이고, 나머지는 수소 원자이다.In a preferred aspect of the present invention, any two or all (more preferably two) of R 1 , R 2 and R 3 are alkyl groups, and the others are hydrogen atoms.
보란 착체를 구성하는 아민의 구체예로서는, 디메틸아민, 디에틸아민, 트리메틸아민, 트리에틸아민, 메톡시에틸아민, 디시클로헥실아민, t―부틸아민, 아미노피리딘, 에틸렌디아민, 모르폴린, 피리딘, 피페리딘, 이미다졸 등을 들 수 있다. 이들 중에서도, 바람직하게는 디메틸아민, 디에틸아민, 트리메틸아민, 메톡시에틸아민, 디시클로헥실아민 등을 들 수 있고, 보다 바람직하게는 디메틸아민 등을 들 수 있다.Specific examples of the amine constituting the borane complex include dimethylamine, diethylamine, trimethylamine, triethylamine, methoxyethylamine, dicyclohexylamine, t-butylamine, aminopyridine, ethylenediamine, morpholine, pyridine, Piperidine, imidazole, etc. are mentioned. Among these, dimethylamine, diethylamine, trimethylamine, methoxyethylamine, dicyclohexylamine, etc. are preferable, and dimethylamine etc. are mentioned more preferably.
아민보란의 적합한 구체예로서는, 디메틸아민보란, 디에틸아민보란, 트리메틸아민보란 등을 들 수 있다.As a suitable specific example of an amine borane, a dimethylamine borane, a diethylamine borane, a trimethylamine borane, etc. are mentioned.
히드라진 유도체로서는, 무전해 도금의 환원제로서 사용할 수 있는 것이면, 특별히 제한되지 않는다.The hydrazine derivative is not particularly limited as long as it can be used as a reducing agent for electroless plating.
붕소 함유 화합물로서는, 예를 들면, 수소화 붕소 화합물, 보다 구체적으로는, 예를 들면, 아민 화합물이기도 한 상기 아민보란, 아민보란 이외의 보란 착체(보란과 다른 화합물의 착체), 수소화 붕소 알칼리 금속염(예를 들면, 나트륨염 등) 등을 들 수 있다.As the boron-containing compound, for example, a boron hydride compound, more specifically, for example, the amine borane that is also an amine compound, a borane complex other than amine borane (a complex of borane and other compounds), an alkali metal salt of boron hydride ( For example, sodium salt etc.) etc. are mentioned.
인 함유 화합물로서는, 예를 들면, 차아인산, 차아인산염(예를 들면, 나트륨염, 칼륨염, 암모늄염 등), 아인산, 아인산염(예를 들면, 나트륨염, 칼륨염, 암모늄염 등), 그들의 수화물 등을 들 수 있다.Examples of the phosphorus-containing compound include hypophosphorous acid, hypophosphite (eg, sodium salt, potassium salt, ammonium salt, etc.), phosphorous acid, phosphite (eg, sodium salt, potassium salt, ammonium salt, etc.), hydrates thereof etc. can be mentioned.
환원제는 본 발명의 효과의 관점에서, 아민 화합물을 포함하는 것이 바람직하다. 또한, 이 경우, 아민 화합물은 아민보란, 히드라진 및 히드라진 유도체로 이루어지는 군으로부터 선택되는 적어도 1종을 포함하는 것이 보다 바람직하고, 아민보란 및 히드라진으로 이루어지는 군으로부터 선택되는 적어도 1종을 포함하는 것이 더욱 바람직하고, 아민보란을 포함하는 것이 더한층 바람직하다. 또한, 환원제가 아민 화합물을 포함하는 경우, 환원제는 인 함유 화합물을 더 포함하는 것이 보다 바람직하다.The reducing agent preferably contains an amine compound from the viewpoint of the effects of the present invention. Further, in this case, the amine compound more preferably contains at least one selected from the group consisting of amine borane, hydrazine and hydrazine derivatives, and more preferably contains at least one selected from the group consisting of amine borane and hydrazine. It is preferable, and the one containing an amine borane is still more preferable. Moreover, when a reducing agent contains an amine compound, it is more preferable that a reducing agent further contains a phosphorus containing compound.
환원제는 본 발명의 효과의 관점에서, 붕소 함유 화합물 및 인 함유 화합물로 이루어지는 군으로부터 선택되는 적어도 1종을 포함하는 것이 바람직하다.It is preferable that a reducing agent contains at least 1 sort(s) selected from the group which consists of a boron-containing compound and a phosphorus-containing compound from a viewpoint of the effect of this invention.
환원제는 1종 단독으로 또는 2종 이상을 조합하여 이용할 수 있다.A reducing agent can be used individually by 1 type or in combination of 2 or more types.
본 발명의 촉매 부여액 중의 환원제의 농도는 예를 들면, 0.05g／L 이상이다. 해당 농도는 본 발명의 효과의 관점에서, 바람직하게는 0.05∼100g／L, 보다 바람직하게는 0.2∼50g／L, 더욱 바람직하게는 0.5∼30g／L이다. 환원제가 아민 화합물을 포함하는 경우, 본 발명의 촉매 부여액 중의 해당 아민 화합물의 농도는 본 발명의 효과의 관점에서, 바람직하게는 0.05∼25g／L, 보다 바람직하게는 0.1∼20g／L, 더욱 바람직하게는 0.2∼15g／L, 더한층 바람직하게는 0.4∼10g／L, 특히 바람직하게는 0.6∼8g／L이다. 환원제가 인 함유 화합물을 포함하는 경우, 본 발명의 촉매 부여액 중의 해당 인 함유 화합물의 농도는 본 발명의 효과의 관점에서, 바람직하게는 1∼200g／L, 보다 바람직하게는 5∼150g／L, 더욱 바람직하게는 10∼100g／L, 더한층 바람직하게는 20∼80g／L이다.The concentration of the reducing agent in the catalyst-applied liquid of the present invention is, for example, 0.05 g/L or more. From the viewpoint of the effect of the present invention, the concentration is preferably 0.05 to 100 g/L, more preferably 0.2 to 50 g/L, still more preferably 0.5 to 30 g/L. When the reducing agent contains an amine compound, the concentration of the amine compound in the catalyst-applied liquid of the present invention is preferably 0.05 to 25 g/L, more preferably 0.1 to 20 g/L, and furthermore, from the viewpoint of the effect of the present invention. It is preferably 0.2 to 15 g/L, more preferably 0.4 to 10 g/L, and particularly preferably 0.6 to 8 g/L. When the reducing agent contains a phosphorus-containing compound, the concentration of the phosphorus-containing compound in the catalyst-applied liquid of the present invention is preferably 1 to 200 g/L, more preferably 5 to 150 g/L, from the viewpoint of the effect of the present invention. , more preferably 10 to 100 g/L, still more preferably 20 to 80 g/L.
본 발명의 촉매 부여액은 본 발명의 효과의 관점에서, 착화제를 더 함유하는 것이 바람직하다.It is preferable that the catalyst application liquid of this invention further contains a complexing agent from a viewpoint of the effect of this invention.
착화제로서는, 특별히 제한되지 않고, 무전해 도금(특히, 환원 도금)에서 사용될 수 있는 착화제를 사용할 수 있다. 착화제로서는, 예를 들면, 아세트산, 포름산 등의 모노카르복실산, 이들의 암모늄염, 칼륨염, 나트륨염 등; 말론산, 석신산, 아디프산, 말레산, 푸마르산 등의 디카르복실산, 이들의 암모늄염, 칼륨염, 나트륨염 등; 말산, 락트산, 글리콜산, 글루콘산, 시트르산, 타르타르산 등의 히드록시카르복실산, 이들의 암모늄염, 칼륨염, 나트륨염 등; 에틸렌디아민디아세트산, 1―히드록시에틸리덴―1, 1―디포스폰산, 이들의 암모늄염, 칼륨염, 나트륨염 등; 에틸렌디아민테트라아세트산, 디에틸렌트리아민펜타아세트산 등의 아미노폴리카르복실산이나 그들의 나트륨염, 칼륨염, 암모늄염 등; 피로인산 등의 포스폰산류나 그들의 나트륨염, 칼륨염, 암모늄염 등; 글리신, 글루타민산 등의 아미노산류 등을 들 수 있다.The complexing agent is not particularly limited, and any complexing agent that can be used in electroless plating (particularly, reduction plating) can be used. Examples of the complexing agent include monocarboxylic acids such as acetic acid and formic acid, ammonium salts, potassium salts, and sodium salts thereof; dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid and fumaric acid, ammonium salts, potassium salts and sodium salts thereof; hydroxycarboxylic acids such as malic acid, lactic acid, glycolic acid, gluconic acid, citric acid, and tartaric acid, ammonium salts, potassium salts, and sodium salts thereof; ethylenediaminediacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ammonium salts, potassium salts, sodium salts and the like thereof; aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, and sodium salts, potassium salts, and ammonium salts thereof; phosphonic acids such as pyrophosphoric acid, sodium salts, potassium salts, and ammonium salts thereof; and amino acids such as glycine and glutamic acid.
착화제는 본 발명의 효과의 관점에서, 카르복실산을 포함하는 것이 바람직하다. 이 경우, 카르복실산은 본 발명의 효과의 관점에서, 히드록시카르복실산이나 디카르복실산을 포함하는 것이 보다 바람직하다. 히드록시카르복실산이나 디카르복실산 중에서도, 더욱 바람직하게는 말산, 시트르산, 타르타르산, 락트산, 아디프산, 석신산, 말론산, 글루콘산 등을 들 수 있고, 더한층 바람직하게는 말산, 시트르산, 타르타르산 등을 들 수 있다.The complexing agent preferably contains a carboxylic acid from the viewpoint of the effects of the present invention. In this case, it is more preferable that carboxylic acid contains hydroxycarboxylic acid or dicarboxylic acid from a viewpoint of the effect of this invention. Among hydroxycarboxylic acids and dicarboxylic acids, more preferably malic acid, citric acid, tartaric acid, lactic acid, adipic acid, succinic acid, malonic acid, gluconic acid, etc. are mentioned, and still more preferably malic acid, citric acid, Tartaric acid etc. are mentioned.
착화제는 1종 단독으로 또는 2종 이상을 조합하여 이용할 수 있다.A complexing agent can be used individually by 1 type or in combination of 2 or more types.
본 발명의 촉매 부여액이 착화제를 함유하는 경우, 본 발명의 촉매 부여액 중의 착화제의 농도는 예를 들면, 0.5g／L 이상이다. 해당 코발트 농도는 본 발명의 효과의 관점에서, 바람직하게는 1∼200g／L, 보다 바람직하게는 2∼150g／L, 더욱 바람직하게는 4∼120g／L, 더한층 바람직하게는 6∼100g／L, 특히 바람직하게는 7∼70g／L이다.When the catalyst application liquid of the present invention contains a complexing agent, the concentration of the complexing agent in the catalyst application liquid of the present invention is, for example, 0.5 g/L or more. From the viewpoint of the effect of the present invention, the cobalt concentration is preferably 1 to 200 g/L, more preferably 2 to 150 g/L, still more preferably 4 to 120 g/L, still more preferably 6 to 100 g/L. , particularly preferably 7 to 70 g/L.
본 발명의 촉매 부여액은 본 발명의 효과의 관점에서, 금속염을 더 함유하는 것이 바람직하다.It is preferable that the catalyst application liquid of this invention further contains a metal salt from a viewpoint of the effect of this invention.
금속염으로서는, 특별히 제한되지 않지만, 예를 들면, 코발트 이외의 천이 금속 원소를 포함하는 염을 들 수 있다. 천이 금속 원소로서는, 예를 들면, 금, 팔라듐, 니켈, 텅스텐, 몰리브덴, 레늄 등의 금속 원소를 들 수 있다. 금속염으로서 보다 구체적으로는, 예를 들면, 황산니켈, 염화니켈, 황산팔라듐, 염화팔라듐, 텅스텐산나트륨, 몰리브덴산2나트륨, 시안화 금칼륨, 아황산 금나트륨, 과레늄산암모늄 등을 들 수 있다.The metal salt is not particularly limited, and examples thereof include salts containing transition metal elements other than cobalt. Examples of the transition metal element include metal elements such as gold, palladium, nickel, tungsten, molybdenum, and rhenium. More specific examples of the metal salt include nickel sulfate, nickel chloride, palladium sulfate, palladium chloride, sodium tungstate, disodium molybdate, potassium gold cyanide, gold sodium sulfite, and ammonium perrhenate.
금속염은 1종 단독으로 또는 2종 이상을 조합하여 이용할 수 있다.A metal salt can be used individually by 1 type or in combination of 2 or more types.
본 발명의 촉매 부여액이 금속염을 함유하는 경우, 해당 금속염에 포함되는 금속의, 본 발명의 촉매 부여액 중의 농도는 예를 들면, 0.005g／L 이상이다. 해당 농도는 본 발명의 효과의 관점에서, 바람직하게는 0.005∼5g／L, 보다 바람직하게는 0.01∼3g／L, 더욱 바람직하게는 0.02∼2g／L, 더한층 바람직하게는 0.03∼1g／L이다. 해당 농도는 본 발명의 촉매 부여액 중의 코발트 농도의 예를 들면, 0.8／1 이하, 바람직하게는 0.6／1 이하이고, 또는 0.5／1 이하, 0.3／1 이하, 0.2／1 이하, 0.15／1 이하이다.When the catalyst application liquid of the present invention contains a metal salt, the concentration of the metal contained in the metal salt in the catalyst application liquid of the present invention is, for example, 0.005 g/L or more. From the viewpoint of the effect of the present invention, the concentration is preferably 0.005 to 5 g/L, more preferably 0.01 to 3 g/L, still more preferably 0.02 to 2 g/L, still more preferably 0.03 to 1 g/L. . The concentration is, for example, 0.8/1 or less, preferably 0.6/1 or less, or 0.5/1 or less, 0.3/1 or less, 0.2/1 or less, or 0.15/1 or less of the cobalt concentration in the catalyst-applied liquid of the present invention. below
본 발명의 촉매 부여액은 용매로서 주로 물을 함유한다. 물 이외의 용매도 함유하는 경우, 그 함유량은 물을 포함하는 용매 100질량％에 대하여, 예를 들면, 10질량％ 이하, 5질량％ 이하, 1질량％, 0.1질량％ 이하이다.The catalyst application liquid of the present invention mainly contains water as a solvent. When a solvent other than water is also contained, the content is, for example, 10% by mass or less, 5% by mass or less, 1% by mass, or 0.1% by mass or less with respect to 100% by mass of the solvent containing water.
본 발명의 촉매 부여액에는, 그 밖에 필요에 따라서 각종 첨가제를 배합할 수 있다. 첨가제로서는, 예를 들면, 안정제, pH완충제, 계면 활성제 등을 들 수 있다.In addition, various additives can be blended with the catalyst-applied liquid of the present invention as needed. Examples of additives include stabilizers, pH buffering agents, and surfactants.
안정제로서, 예를 들면, 질산납, 아세트산납 등의 납염; 질산비스무트, 아세트산비스무트 등의 비스무트염; 티오황산나트륨 등의 유황 화합물 등을 1종 단독 또는 2종 이상 혼합하여 첨가할 수 있다. 안정제를 첨가하는 경우, 그 첨가량은 특별히 한정적이지는 않지만, 예를 들면, 0.01∼100㎎／L 정도로 할 수 있다.Examples of the stabilizer include lead salts such as lead nitrate and lead acetate; bismuth salts such as bismuth nitrate and bismuth acetate; Sulfur compounds, such as sodium thiosulfate, etc. can be added individually by 1 type or in mixture of 2 or more types. When adding a stabilizer, the addition amount is not particularly limited, but can be, for example, about 0.01 to 100 mg/L.
pH완충제로서, 예를 들면, 아세트산, 붕산, 인산, 아인산, 탄산, 그들의 나트륨염, 칼륨염, 암모늄염 등을 1종 단독 또는 2종 이상 혼합하여 첨가할 수 있다. pH완충제를 첨가하는 경우, 그 첨가량은 특별히 한정적이지는 않지만, 욕 안정성 등의 관점에서, 0.002∼1㏖／L 정도로 할 수 있다.As the pH buffering agent, for example, acetic acid, boric acid, phosphoric acid, phosphorous acid, carbonic acid, and sodium salts, potassium salts, and ammonium salts thereof may be added alone or in combination of two or more. When adding a pH buffer, the addition amount is not particularly limited, but can be set to about 0.002 to 1 mol/L from the viewpoint of bath stability and the like.
계면 활성제로서, 예를 들면, 노니온성, 어니온성, 카티온성, 양성 등의 각종 계면 활성제를 이용할 수 있다. 예를 들면, 방향족 또는 지방족 설폰산알칼리염, 방향족 또는 지방족 카르복실산알칼리 금속염 등을 들 수 있다. 계면 활성제는 1종 단독 또는 2종 이상 혼합하여 이용할 수 있다. 계면 활성제를 첨가하는 경우, 그 첨가량은 특별히 한정적이지는 않지만, 예를 들면, 0.01∼1000㎎／L 정도로 할 수 있다.As surfactant, various surfactants, such as nonionic, anionic, cationic, and amphoteric, can be used, for example. For example, an aromatic or aliphatic sulfonic acid alkali salt, an aromatic or aliphatic carboxylic acid alkali metal salt, etc. are mentioned. Surfactant can be used individually by 1 type or in mixture of 2 or more types. When adding a surfactant, the addition amount is not particularly limited, but can be, for example, about 0.01 to 1000 mg/L.
본 발명의 무전해 도금액의 pH는 통상, 2∼12 정도로 하면 좋고, 바람직하게는 6∼10 정도, 보다 바람직하게는 6.5∼9 정도, 더욱 바람직하게는 6.9(또는 7.0)∼8.5 정도이다.The pH of the electroless plating solution of the present invention is usually about 2 to 12, preferably about 6 to 10, more preferably about 6.5 to 9, still more preferably about 6.9 (or 7.0) to 8.5.
2. 촉매 부여 방법2. Catalyst imparting method
본 발명은, 그 일 양태에 있어서, (1) 무전해 도금 대상 재료와, 본 발명의 촉매 부여액을 접촉시키는 공정을 포함하는, 촉매핵을 포함하는 무전해 도금 대상 재료를 제조하는 방법, 또는 무전해 도금 대상 재료를 촉매 부여 처리하는 방법(본 명세서에 있어서, “본 발명의 방법 1”로 나타내는 일도 있다.)에 관한 것이다. 이하, 이에 대하여 설명한다.In one aspect of the present invention, (1) a method for producing an electroless plating target material containing catalyst nuclei, including a step of bringing the electroless plating target material into contact with the catalyst-applying liquid of the present invention, or It relates to a method of applying a catalyst to a material to be electroless plated (in this specification, it is sometimes referred to as "Method 1 of the present invention"). Hereinafter, this will be described.
무전해 도금 대상 재료는 금속이 표면에 노출되어 있는 재료인 한, 특별히 제한되지 않는다. 예를 들면, 소재로서, 유리 섬유 강화 에폭시, 폴리이미드, PET 등의 플라스틱류, 유리, 세라믹, 금속 산화물, 금속, 종이, 합성, 또는 천연 섬유 등의 재질을 1종으로 또는 조합하여 이루어지는 것이고, 그 형상으로서는, 판, 필름, 직물상, 섬유상, 튜브 등의 어느 쪽이어도 좋다. 표면에 노출되어 있는 금속으로서는, 예를 들면, 동, 동 합금, 은, 은 합금, 금, 금 합금, 백금, 백금 합금, 몰리브덴, 텅스텐 등을 들 수 있다. 이들 중에서, 동 합금, 은 합금, 금 합금 및 백금 합금으로서는, 각각 예를 들면, 동, 은, 금, 또는 백금을 50중량％ 이상 포함하는 합금에 대하여 적용할 수 있다. 무전해 도금 대상 재료로서 구체적으로는, 예를 들면, 프린트 배선판, 반도체 패키지, 전자 부품, 세라믹 기판 등을 들 수 있다. 이들의 재료에 있어서, 표면에 노출되어 있는 금속은 배선을 구성할 수 있다.The material to be subjected to electroless plating is not particularly limited as long as it is a material in which metal is exposed on the surface. For example, materials such as glass fiber reinforced epoxy, polyimide, plastics such as PET, glass, ceramics, metal oxides, metals, paper, synthetic or natural fibers are used alone or in combination, As the shape, any of a plate, film, fabric, fiber, tube or the like may be used. Examples of the metal exposed on the surface include copper, copper alloy, silver, silver alloy, gold, gold alloy, platinum, platinum alloy, molybdenum, and tungsten. Among these, as a copper alloy, a silver alloy, a gold alloy, and a platinum alloy, respectively, it is applicable with respect to the alloy containing 50 weight% or more of copper, silver, gold, or platinum, respectively, for example. Specific examples of the material to be subjected to electroless plating include printed wiring boards, semiconductor packages, electronic components, ceramic substrates, and the like. In these materials, the metal exposed on the surface can constitute wiring.
무전해 도금 대상 재료는 탈지 처리, 소프트 에칭 처리 등의 전처리가 실시된 것인 것이 바람직하다.It is preferable that the material to be subjected to electroless plating has been subjected to pretreatment such as degreasing treatment and soft etching treatment.
본 발명의 촉매 부여액을 무전해 도금 대상 재료에 접촉시키기 위한 구체적인 방법에 대해서는, 특별히 한정적이지는 않지만, 통상은 본 발명의 촉매 부여액 중에 피처리물을 침지하면 좋다. 그 밖에, 무전해 도금 대상 재료의 표면에 해당 촉매 부여액을 분무하는 방법 등에 의해서도 촉매 부여 처리를 실시할 수 있다.A specific method for bringing the catalyst-applied liquid of the present invention into contact with the material to be electroless plated is not particularly limited, but usually the object to be treated may be immersed in the catalyst-applied liquid of the present invention. In addition, the catalyst imparting treatment can also be carried out by a method of spraying the catalyst imparting liquid onto the surface of the material to be electroless plated.
본 발명의 촉매 부여액을 침지법에 의하여 실시하는 경우에는, 본 발명의 촉매 부여액의 액온은 통상, 10∼90℃ 정도로 하는 것이 바람직하고, 40∼80℃ 정도로 하는 것이 보다 바람직하고, 60∼80℃로 하는 것이 더욱 바람직하다.When the catalyst-applied liquid of the present invention is applied by an immersion method, the liquid temperature of the catalyst-applied liquid of the present invention is usually preferably about 10 to 90°C, more preferably about 40 to 80°C, and preferably 60 to 90°C. It is more preferable to set it as 80 degreeC.
처리 시간에 대해서는, 30초∼20분 정도로 하는 것이 바람직하고, 1분∼5분 정도로 하는 것이 보다 바람직하다.About processing time, it is preferable to set it as about 30 second - 20 minutes, and it is more preferable to set it as about 1 minute - 5 minutes.
본 발명의 방법 1에 의해, 무전해 도금 대상 재료의 표면 금속 상에 코발트를 포함하는 촉매핵이 형성된다. 촉매핵은 본 발명의 무전해 도금액 중의 성분에 따른 조성을 가진다. 예를 들면, 본 발명의 촉매 부여액 중의 환원제가 붕소 함유 화합물 및／또는 인 함유 화합물을 포함하는 경우, 촉매핵은 Co 및 B 및／또는 P를 포함한다. 또한, 본 발명의 촉매 부여액이 금속 원소 함유 화합물을 포함하는 경우, 촉매핵은 Co 및 해당 금속을 포함한다.By method 1 of the present invention, catalyst nuclei containing cobalt are formed on the surface metal of the material to be electroless plated. The catalyst core has a composition according to the components in the electroless plating solution of the present invention. For example, when the reducing agent in the catalyst-applied liquid of the present invention contains a boron-containing compound and/or a phosphorus-containing compound, the catalyst core contains Co and B and/or P. Further, when the catalyst application liquid of the present invention contains a compound containing a metal element, the catalyst core contains Co and the metal.
촉매핵 중의 Co함유량은 예를 들면, 50질량％ 이상, 바람직하게는 60질량％ 이상, 보다 바람직하게는 70질량％이고, 또는 80질량％ 이상, 또는 90질량％ 이상이다.The Co content in the catalyst core is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass, or 80% by mass or more, or 90% by mass or more.
촉매핵이 B를 포함하는 경우, 그 함유량은 예를 들면, 2질량％ 이하, 바람직하게는 1질량％ 이하, 보다 바람직하게는 0.5질량％ 이하, 더욱 바람직하게는 0.2질량％ 이하이다. 해당 함유량의 하한은 예를 들면, 0.01질량％, 0.05질량％, 또는 0.07질량％이다.When the catalyst core contains B, its content is, for example, 2% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less. The lower limit of the content is, for example, 0.01% by mass, 0.05% by mass, or 0.07% by mass.
촉매핵이 P를 포함하는 경우, 그 함유량은 예를 들면, 0.5∼20질량％, 바람직하게는 1.5∼15질량％, 보다 바람직하게는 3∼10질량％이다.When the catalyst core contains P, its content is, for example, 0.5 to 20% by mass, preferably 1.5 to 15% by mass, and more preferably 3 to 10% by mass.
촉매핵 중의 각 원소의 함유량은 에너지 분산형 X선 분석 장치(EDX, HORIBA제 EMAX X―act)에 의한 측정, 또는 고주파 유도 결합 플라즈마(ICP) 발광 분광 분석 장치(히타치 하이테크 사이언스제 PS3500DDII)를 사용한 용해법에 의해 동정(同定)한다.The content of each element in the catalyst core was measured by an energy dispersive X-ray analyzer (EDX, EMAX X-act manufactured by HORIBA) or by using a high-frequency inductively coupled plasma (ICP) emission spectrometer (PS3500DDII manufactured by Hitachi High-Tech Sciences). It is identified by the dissolution method.
해당 촉매핵을 포함하는 무전해 도금 대상 재료를 무전해 도금 처리함으로써 도금 석출성, 선택 석출성, 배리어 특성, 접합성 등이 보다 우수한 무전해 도금 피막을 형성할 수 있다. 촉매핵은 표면 활성화의 목적이기 때문에, 그 두께는 예를 들면, 0.05㎛ 이하, 0.005∼0.05㎛일 수 있다.By electroless plating the target material for electroless plating including the catalyst core, it is possible to form an electroless plated film having better plating deposition properties, selective deposition properties, barrier properties, bondability, and the like. Since the catalyst core is for surface activation, its thickness may be, for example, 0.05 μm or less, or 0.005 to 0.05 μm.
3. 무전해 도금 방법3. Electroless plating method
본 발명은, 그 일 양태에 있어서, (1) 무전해 도금 대상 재료와, 본 발명의 촉매 부여액을 접촉시키는 공정 및 (2) 공정(1) 후에, 무전해 도금 처리하는 공정을 포함하는, 무전해 도금 피막을 포함하는 재료를 제조하는 방법, 또는 무전해 도금 대상 재료를 무전해 도금하는 방법(본 명세서에 있어서, “본 발명의 방법 2”로 나타내는 일도 있다.)에 관한 것이다. 이하, 이에 대하여 설명한다.The present invention, in one aspect thereof, includes (1) a step of contacting a material to be electroless plating with a catalyst-applying liquid of the present invention, and (2) a step of performing an electroless plating treatment after step (1), It relates to a method for producing a material containing an electroless plating film or a method for electroless plating a material to be electroless plated (in this specification, it is sometimes referred to as “method 2 of the present invention”). Hereinafter, this will be described.
공정(1)에 대해서는, 상기 “2. 촉매 부여 방법”과 같다.Regarding process (1), above “2. Catalyst imparting method”.
무전해 도금 처리는 공정(1)에서 얻어진 촉매핵을 포함하는 무전해 도금 대상 재료를 무전해 도금액과 접촉시킴으로써 실시할 수 있다.The electroless plating treatment can be carried out by bringing the material to be electroless plated containing catalyst cores obtained in step (1) into contact with an electroless plating solution.
무전해 도금액으로서는, 특별히 한정은 없고, 자기 촉매성의 무전해 도금액을 이용할 수 있다. 예를 들면, 무전해 팔라듐 도금액, 무전해 팔라듐 합금 도금액, 무전해 동 도금액, 무전해 동 합금 도금액, 무전해 은 도금액, 무전해 은 합금 도금액, 무전해 니켈 도금액, 무전해 니켈 합금 도금액, 무전해 금 도금액, 무전해 금 합금 도금액 등을 이용할 수 있다. 이들의 무전해 도금액의 구체적인 조성에 대해서는, 특별히 한정은 없고, 환원제 성분을 포함하는 공지의 조성의 자기 촉매성의 무전해 도금액을 이용하면 좋다. 도금 조건에 대해서도, 사용하는 도금액의 종류에 따라서, 통상의 도금 조건에 따르면 좋다.The electroless plating solution is not particularly limited, and a self-catalytic electroless plating solution can be used. For example, electroless palladium plating solution, electroless palladium alloy plating solution, electroless copper plating solution, electroless copper alloy plating solution, electroless silver plating solution, electroless silver alloy plating solution, electroless nickel plating solution, electroless nickel alloy plating solution, electroless A gold plating solution, an electroless gold alloy plating solution, or the like can be used. The specific composition of these electroless plating solutions is not particularly limited, and a self-catalytic electroless plating solution having a known composition containing a reducing agent component may be used. Regarding the plating conditions, it is good to follow the normal plating conditions according to the type of plating solution to be used.
본 발명의 방법 2의 공정(2)에서는 무전해 도금액으로서, 무전해 팔라듐 도금액, 무전해 팔라듐 합금 도금액, 무전해 니켈 도금액, 무전해 니켈 합금 도금액 등, 무전해 금 도금액, 무전해 금 합금 도금액을 사용하는 것이 바람직하다. 공정(2)에서 무전해 팔라듐 도금액 또는 무전해 팔라듐 합금 도금액을 사용한 경우에는, 무전해 금 도금 또는 무전해 금 합금 도금을 더 실시하는 것이 바람직하다. 또한, 공정(2)에서 무전해 니켈 도금액 또는 무전해 니켈 합금 도금액을 사용한 경우에는, 무전해 팔라듐 도금 또는 무전해 팔라듐 합금 도금을 더 실시하는 것이 바람직하고, 이에 계속하여 무전해 금 도금 또는 무전해 금 합금 도금을 더 실시하는 것이 보다 바람직하다. 또한, 공정(2)에서 무전해 니켈 도금액 또는 무전해 니켈 합금 도금액을 사용한 경우에는, 이에 계속하여 무전해 금 도금 또는 무전해 금 합금 도금을 더 실시하는 것도 가능하다. 또한, 공정(2)에서 무전해 금 도금액, 무전해 금 합금 도금액만을 실시하는 것도 가능하다.In step (2) of Method 2 of the present invention, an electroless gold plating solution or an electroless gold alloy plating solution, such as an electroless palladium plating solution, an electroless palladium alloy plating solution, an electroless nickel plating solution, or an electroless nickel alloy plating solution, is selected as an electroless plating solution. It is preferable to use When an electroless palladium plating solution or an electroless palladium alloy plating solution is used in step (2), it is preferable to further perform electroless gold plating or electroless gold alloy plating. In addition, when an electroless nickel plating solution or an electroless nickel alloy plating solution is used in step (2), it is preferable to further perform electroless palladium plating or electroless palladium alloy plating, followed by electroless gold plating or electroless nickel alloy plating. It is more preferable to further perform gold alloy plating. In addition, when an electroless nickel plating solution or an electroless nickel alloy plating solution is used in step (2), it is also possible to further perform electroless gold plating or electroless gold alloy plating subsequent to this. It is also possible to apply only the electroless gold plating solution and the electroless gold alloy plating solution in step (2).
본 발명의 방법 2에 의해, 도금 석출성, 선택 석출성, 배리어 특성, 접합성 등이 보다 우수한 무전해 도금 피막을 형성할 수 있다. 본 발명의 방법 2에 의해, 이와 같은 무전해 도금 피막을 구비하는 재료, 구체적으로는, 금속이 표면에 노출되어 있는 재료, 상기 금속 상의 촉매핵(1) 및 상기 촉매핵(1) 상의 피막(2)을 포함하고, 또한 상기 촉매핵(1)이 코발트를 함유하고, 상기 피막(2)이 무전해 도금 피막인 재료를 얻을 수 있다.According to the method 2 of the present invention, an electroless plated film having better plating deposition properties, selective deposition properties, barrier properties, bondability, and the like can be formed. By method 2 of the present invention, a material having such an electroless plating film, specifically, a material having a metal exposed on the surface, a catalyst core 1 on the metal, and a film on the catalyst core 1 ( 2), the catalyst core 1 contains cobalt, and the film 2 is an electroless plating film.
(실시예)(Example)
이하에, 실시예에 기초하여 본 발명을 상세하게 설명하지만, 본 발명은 이들의 실시예에 의하여 한정되는 것은 아니다.Below, the present invention will be described in detail based on examples, but the present invention is not limited by these examples.
(1) 촉매 부여액의 조제(1) Preparation of catalyst application liquid
이하에 나타내는 조성으로 이루어지는 무전해 도금용 촉매 부여액을 조제했다. 용매로서는 물을 사용했다.A catalyst application liquid for electroless plating comprising the composition shown below was prepared. Water was used as a solvent.
(1―1) 실시예 1∼8: Co 함유(1-1) Examples 1 to 8: Co-containing
(실시예 1) Co―B(Example 1) Co-B
황산코발트ㆍ7수화물 5g／L(코발트로서 1g／L)Cobalt sulfate heptahydrate 5g/L (1g/L as cobalt)
DL―말산 10g／LDL-Malic Acid 10g/L
디메틸아민보란 3.0g／LDimethylamine borane 3.0g/L
pH 7.5, 욕온 70℃.pH 7.5, bath temperature 70°C.
(실시예 2) Co―Ni―B(Example 2) Co-Ni-B
황산코발트ㆍ7수화물 5g／L(코발트로서 1g／L)Cobalt sulfate heptahydrate 5g/L (1g/L as cobalt)
황산니켈ㆍ6수화물 0.45g／L(니켈로서 0.1g／L)Nickel sulfate hexahydrate 0.45 g/L (0.1 g/L as nickel)
DL―말산 10g／LDL-Malic Acid 10g/L
디메틸아민보란 3.0g／LDimethylamine borane 3.0g/L
pH 7.5, 욕온 70℃.pH 7.5, bath temperature 70°C.
(실시예 3) Co―Pd―B(Example 3) Co-Pd-B
황산코발트ㆍ7수화물 5g／L(코발트로서 1g／L)Cobalt sulfate heptahydrate 5g/L (1g/L as cobalt)
염화팔라듐 0.08g／L(팔라듐으로서 0.05g／L)Palladium chloride 0.08 g/L (0.05 g/L as palladium)
시트르산 50g／LCitric acid 50g／L
디메틸아민보란 1.0g／LDimethylamine borane 1.0g/L
pH 7.5, 욕온 70℃.pH 7.5, bath temperature 70°C.
(실시예 4) Co―W―B(Example 4) Co-W-B
황산코발트ㆍ7수화물 5g／L(코발트로서 1g／L)Cobalt sulfate heptahydrate 5g/L (1g/L as cobalt)
텅스텐산나트륨ㆍ2수화물 1g／L(텅스텐으로서 0.55g／L)시트르산 50g／LSodium tungstate/dihydrate 1g/L (0.55g/L as tungsten) Citric acid 50g/L
디메틸아민보란 1.0g／LDimethylamine borane 1.0g/L
pH 7.5, 욕온 70℃.pH 7.5, bath temperature 70°C.
(실시예 5) Co―Mo―B(Example 5) Co-Mo-B
황산코발트ㆍ7수화물 20g／L(코발트로서 4g／L)Cobalt sulfate heptahydrate 20g/L (4g/L as cobalt)
몰리브덴산2나트륨ㆍ2수화물 0.5g／L(몰리브덴으로서 0.2g／L)시트르산 50g／LDisodium molybdate/dihydrate 0.5 g/L (0.2 g/L as molybdenum) Citric acid 50 g/L
디메틸아민보란 1.0g／LDimethylamine borane 1.0g/L
pH 7.5, 욕온 70℃.pH 7.5, bath temperature 70°C.
(실시예 6) Co―B―P(Example 6) Co-B-P
황산코발트ㆍ7수화물 20g／L(코발트로서 4g／L)Cobalt sulfate heptahydrate 20g/L (4g/L as cobalt)
시트르산 50g／LCitric acid 50g／L
디메틸아민보란 1.0g／LDimethylamine borane 1.0g/L
차아인산나트륨 60g／LSodium hypophosphite 60g/L
pH 7.5, 욕온 70℃.pH 7.5, bath temperature 70°C.
(실시예 7) Co―B―P(Example 7) Co-B-P
황산코발트ㆍ7수화물 20g／L(코발트로서 4g／L)Cobalt sulfate heptahydrate 20g/L (4g/L as cobalt)
시트르산 50g／LCitric acid 50g／L
붕산 10g／LBoric acid 10g／L
디메틸아민보란 1.0g／LDimethylamine borane 1.0g/L
차아인산나트륨 20g／LSodium hypophosphite 20g/L
pH 8.0, 욕온 70℃.pH 8.0, bath temperature 70°C.
(실시예 8) Co―P(Example 8) Co—P
황산코발트ㆍ7수화물 20g／L(코발트로서 4g／L)Cobalt sulfate heptahydrate 20g/L (4g/L as cobalt)
시트르산 50g／LCitric acid 50g／L
붕산 10g／LBoric acid 10g／L
히드라진 2.0g／LHydrazine 2.0g／L
차아인산나트륨 20g／LSodium hypophosphite 20g/L
pH 8.0, 욕온 70℃.pH 8.0, bath temperature 70°C.
(1―2) 비교예 1∼5: Co 비함유(1-2) Comparative Examples 1 to 5: Co-free
(비교예 1) Ni―B(Comparative Example 1) Ni—B
황산니켈ㆍ6수화물 4.5g／L(니켈로서 1.0g／L)Nickel sulfate hexahydrate 4.5 g/L (1.0 g/L as nickel)
DL―말산 10g／LDL-Malic Acid 10g/L
디메틸아민보란 5.0g／LDimethylamine borane 5.0g/L
pH 7.5, 욕온 60℃.pH 7.5, bath temperature 60°C.
(비교예 2) Ni―B(Comparative Example 2) Ni—B
황산니켈ㆍ6수화물 0.45g／L(니켈로서 0.1g／L)Nickel sulfate hexahydrate 0.45 g/L (0.1 g/L as nickel)
DL―말산 10g／LDL-Malic Acid 10g/L
디메틸아민보란 5.0g／LDimethylamine borane 5.0g/L
pH 7.5, 욕온 60℃.pH 7.5, bath temperature 60°C.
(비교예 3) Ni―B―P(Comparative Example 3) Ni-B-P
황산니켈ㆍ6수화물 0.45g／L(니켈로서 0.1g／L)Nickel sulfate hexahydrate 0.45 g/L (0.1 g/L as nickel)
DL―말산 10g／LDL-Malic Acid 10g/L
디메틸아민보란 5.0g／LDimethylamine borane 5.0g/L
차아인산나트륨 10g／LSodium hypophosphite 10g/L
pH 7.5, 욕온 60℃.pH 7.5, bath temperature 60°C.
(비교예 4) Pd―B(Comparative Example 4) Pd-B
염화팔라듐 0.83g／L(팔라듐으로서 0.5g／L)Palladium chloride 0.83 g/L (0.5 g/L as palladium)
에틸렌디아민 10g／LEthylenediamine 10g/L
디메틸아민보란 1.0g／LDimethylamine borane 1.0g/L
pH 7.5, 욕온 40℃.pH 7.5, bath temperature 40°C.
(비교예 5) Pd(Comparative Example 5) Pd
염화팔라듐 0.83g／L(팔라듐으로서 0.5g／L)Palladium chloride 0.83 g/L (0.5 g/L as palladium)
에틸렌디아민 10g／LEthylenediamine 10g/L
히드라진 1.0g／LHydrazine 1.0g／L
pH 7.5, 욕온 40℃.pH 7.5, bath temperature 40°C.
(1―3) 비교예 6∼7: 치환 반응에 의한 Pd촉매 부여 처리(종래 기술)(1-3) Comparative Examples 6 to 7: Pd catalyst imparting treatment by substitution reaction (prior art)
(비교예 6)(Comparative Example 6)
염화팔라듐 0.17g／L(팔라듐으로서 0.1g／L)Palladium chloride 0.17g/L (0.1g/L as palladium)
35％ 염산 100㎖／L35% hydrochloric acid 100mL/L
욕온 30℃.Bath temperature 30 ℃.
(비교예 7)(Comparative Example 7)
염화팔라듐 0.19g／L(팔라듐으로서 0.1g／L)Palladium chloride 0.19g/L (0.1g/L as palladium)
98％ 황산 20㎖／L98% sulfuric acid 20㎖/L
욕온 30℃.Bath temperature 30 ℃.
(2) 평가 시험(2) evaluation test
이하의 평가 시험에서는 무전해 도금 대상 재료를 전처리(산성 탈지, 소프트 에칭) 후에, 상기한 촉매 부여액에 의해 금속 표면 상에 촉매핵을 형성하고, 이어서, 무전해 팔라듐 도금, 무전해 금 도금의 차례로 처리했다. 각 처리의 상세는 특별히 언급이 없는 한, 이하와 같다. 각 공정 사이에 유수 수세 1분 처리를 실시했다.In the following evaluation test, after pretreatment (acidic degreasing, soft etching) of the material to be electroless plating, catalyst nuclei are formed on the metal surface with the above-mentioned catalyst application liquid, and then electroless palladium plating and electroless gold plating are performed. processed in turn. Details of each process are as follows unless otherwise specified. Between each process, running water washing treatment was performed for 1 minute.
(a) 산성 탈지(a) Acid degreasing
황산 및 계면 활성제를 함유하는 산성 탈지액(상표명: ICP클린 S―135K)에 40℃에서 5분간 침지했다.It was immersed in an acidic degreasing solution (trade name: ICP Clean S-135K) containing sulfuric acid and a surfactant at 40°C for 5 minutes.
(b) 소프트 에칭(b) soft etching
과황산나트륨 100g／L과 98％ 황산 10㎖／L을 함유하는 수용액 중에 실온에서 1분간 침지했다.It was immersed for 1 minute at room temperature in an aqueous solution containing 100 g/L of sodium persulfate and 10 ml/L of 98% sulfuric acid.
(c) 촉매 부여 처리(c) Catalyst imparting treatment
실시예 1∼8 및 비교예 1∼5에 대해서는, 촉매핵의 두께가 0.01㎛로 되도록 촉매 부여액 중에 1∼5분간 침지했다. 비교예 6 및 7에 대해서는 1분간 침지로 했다.For Examples 1 to 8 and Comparative Examples 1 to 5, they were immersed in the catalyst-applying solution for 1 to 5 minutes so that the thickness of the catalyst core was 0.01 μm. About Comparative Examples 6 and 7, it was set as immersion for 1 minute.
(d) 무전해 팔라듐 도금(d) electroless palladium plating
무전해 팔라듐 도금액(상표명: 톱 팔라스PD, 오쿠노 제약 공업(제)) 중에 65℃에서 5분간 침지하여 막두께 약 0.1㎛의 도금 피막을 얻었다.It was immersed in an electroless palladium plating solution (trade name: Top Palace PD, manufactured by Okuno Pharmaceutical Industry Co., Ltd.) at 65°C for 5 minutes to obtain a plated film having a film thickness of about 0.1 µm.
(e) 무전해 금 도금(e) electroless gold plating
무전해 금 도금(상표명: 톱 팔라스AU, 오쿠노 제약 공업(제)) 중에 80℃에서 10분간 침지했다. 막두께 약 0.05㎛의 도금 피막을 얻었다.It was immersed at 80 degreeC for 10 minutes in electroless gold plating (trade name: Top Palace AU, Okuno Pharmaceutical Co., Ltd.). A plated film with a film thickness of about 0.05 μm was obtained.
(2―1) 촉매핵의 조성 측정(2-1) Measurement of catalyst core composition
무전해 도금 대상 재료로서 동장(Cooper-clad) 에폭시 기판을 사용하고, 산성 탈지, 소프트 에칭, 촉매 부여 처리를 실시한 후, 에너지 분산형 X선 분석 장치(EDX, HORIBA제 EMAX X―act)에 의한 측정, 또는 고주파 유도 결합 플라즈마(ICP) 발광 분광 분석 장치(히타치 하이테크 사이언스제 PS3500DDII)를 사용한 용해법에 의해 조성을 동정했다.After using a copper-clad epoxy substrate as a material for electroless plating, acid degreasing, soft etching, and catalyst imparting treatment, energy dispersive X-ray analyzer (EDX, EMAX X-act manufactured by HORIBA) The composition was identified by measurement or a dissolution method using a high frequency induction coupled plasma (ICP) emission spectrometer (PS3500DDII manufactured by Hitachi High-Tech Sciences).
(2―2) 도금 석출성의 평가(2-2) Evaluation of plating precipitation
무전해 도금 대상 재료로서, 수지 기재 상에 오버 레지스트 타입의 미소(微小) 동 패드(직경 0.2㎜, 패드수 30개)를 가지는 BGA(Ball Grid Array)수지 기판을 이용했다. 무전해 도금 대상 재료를 산성 탈지, 소트프 에칭, 촉매 부여 처리, 무전해 팔라듐 도금, 무전해 금 도금의 차례로 처리했다. 각 패드에서의 도금 석출의 유무를 마이크로스코프(KEYENCE제 VHX―1000)에 의해 판정하고, 이하의 평가 기준에 따라서 평가했다.As a material to be electroless plated, a BGA (Ball Grid Array) resin substrate having overresist type micro copper pads (0.2 mm in diameter, 30 pads) on a resin substrate was used. The material to be subjected to electroless plating was subjected to acid degreasing, soft etching, catalyst imparting treatment, electroless palladium plating, and electroless gold plating in this order. The presence or absence of plating precipitation on each pad was determined with a microscope (VHX-1000 manufactured by KEYENCE), and evaluated according to the following evaluation criteria.
＜도금 석출성의 평가 기준＞<Evaluation Criteria for Plating Precipitation>
○: 전체 패드 정상적으로 석출.○: All pads normally precipitated.
×: 도금 미석출의 패드 있음.x: There is a pad of non-plating precipitation.
(2―3) 선택 석출성의 평가(2-3) Evaluation of Selective Precipitation
무전해 도금 대상 재료로서, SAP법으로 제작한 배선폭／배선 간격(L／S)＝20／20㎛의 동배선 패턴을 가지는 수지 기판을 이용했다. 무전해 도금 대상 재료를 산성 탈지, 소프트 에칭, 촉매 부여 처리, 무전해 팔라듐 도금, 무전해 금 도금의 차례로 처리했다. 배선 패턴 사이(수지부)로의 도금 석출의 유무를 주사형 전자 현미경(SEM, 히타치 하이테크 사이언스제 S―3400N)에 의해 판정하고, 이하의 평가 기준에 따라서 평가했다.As the material to be electroless plated, a resin substrate having a copper wiring pattern of wiring width/wiring spacing (L/S) = 20/20 µm produced by the SAP method was used. The material to be subjected to electroless plating was subjected to acid degreasing, soft etching, catalyst imparting treatment, electroless palladium plating, and electroless gold plating in this order. The presence or absence of plating precipitation between wiring patterns (resin portion) was determined by a scanning electron microscope (SEM, S-3400N manufactured by Hitachi High-Tech Sciences), and evaluated according to the following evaluation criteria.
＜선택 석출성의 평가 기준＞<Evaluation Criteria for Selective Precipitation>
○: 배선 패턴 사이로의 도금 석출 없음.○: No plating precipitation between wiring patterns.
△: 배선 패턴 사이로 약간 도금 석출.△: Slight plating precipitation between wiring patterns.
×: 배선 패턴 사이에 전면 석출.x: All-over precipitation between wiring patterns.
(2―4) 욕 안정성의 평가(2-4) Evaluation of bath stability
도금 석출성의 평가에서 사용 후의 촉매 부여액을 촉매 부여 처리의 욕온＋5℃로 가온하여, 72시간 방치했다. 욕 분해의 유무를 육안에 의해 판정하고, 이하의 평가 기준에 따라서 평가했다.In evaluation of plating deposition property, the catalyst-applied liquid after use was heated at the bath temperature of the catalyst-applying treatment + 5°C, and left to stand for 72 hours. The presence or absence of bath decomposition was visually determined and evaluated according to the following evaluation criteria.
＜욕 안정성의 평가 기준＞<Evaluation criteria for bath stability>
○: 욕 분해하지 않음.○: No bath decomposition.
×: 욕 분해.×: Bath decomposition.
(2－5) 공극(보이드)의 확인(2-5) Confirmation of air gaps (voids)
무전해 도금 대상 재료로서, 수지 기재 상에 오버 레지스트 타입의 동 패드를 가지는 BGA(Ball Grid Array)수지 기판을 이용했다. 무전해 도금 대상 재료를 산성 탈지, 소프트 에칭, 촉매 부여 처리, 무전해 팔라듐 도금, 무전해 금 도금의 차례로 처리했다. 이어서, 집속 이온 빔 가공 관찰 장치를 이용하여 단면 가공하고, 주사 이온 현미경에 의해 보이드의 유무를 관찰했다(FIB／SIM, 히타치 하이테크놀로지즈제 FB2200).As a material for electroless plating, a BGA (Ball Grid Array) resin substrate having an overresist type copper pad on a resin substrate was used. The material to be subjected to electroless plating was subjected to acid degreasing, soft etching, catalyst imparting treatment, electroless palladium plating, and electroless gold plating in this order. Subsequently, cross-section processing was performed using a focused ion beam processing observation device, and the presence or absence of voids was observed with a scanning ion microscope (FIB/SIM, FB2200 manufactured by Hitachi High-Technologies).
＜보이드의 평가 기준＞＜Void Evaluation Criteria＞
○: 보이드 없음.○: No voids.
×: 보이드 있음.×: Void present.
(2―6) 배리어 특성의 평가(2-6) Evaluation of barrier properties
무전해 도금 대상 재료로서, 수지 기재 상에 오버 레지스트 타입의 동 패드를 가지는 BGA(Ball Grid Array)수지 기판을 이용했다. 무전해 도금 대상 재료를 산성 탈지, 소프트 에칭, 촉매 부여 처리, 무전해 팔라듐 도금, 무전해 금 도금의 차례로 처리했다. 이어서, 처리 기판을 175℃에서 16시간 열처리한 후, Au도금 표면의 원소 조성을 X선 광전자 분광 분석 장치(얼백ㆍ파이 주식회사, PHI5000VersaProbe Ⅲ)로 측정했다. Au피막 표면에서의 기초 금속(Cu, Co, Ni, Pd) 검출의 유무에 기초하여 이하의 평가 기준에 따라서 평가했다.As a material for electroless plating, a BGA (Ball Grid Array) resin substrate having an overresist type copper pad on a resin substrate was used. The material to be subjected to electroless plating was subjected to acid degreasing, soft etching, catalyst imparting treatment, electroless palladium plating, and electroless gold plating in this order. Subsequently, the treated substrate was subjected to heat treatment at 175° C. for 16 hours, and then the elemental composition of the Au plating surface was measured with an X-ray photoelectron spectroscopy analyzer (Eolbaek Pi Co., Ltd., PHI5000VersaProbe III). Based on the presence or absence of detection of base metals (Cu, Co, Ni, Pd) on the surface of the Au film, evaluation was performed according to the following evaluation criteria.
＜배리어 특성의 평가 기준＞<Evaluation criteria for barrier properties>
○: Au피막 표면에서 기초 금속(Cu, Co, Ni, Pd)이 검출되지 않는다.○: Base metals (Cu, Co, Ni, Pd) are not detected on the surface of the Au film.
×: Au피막 표면에서 기초 금속(Cu, Co, Ni, Pd)이 검출.×: Base metals (Cu, Co, Ni, Pd) were detected on the surface of the Au film.
(2―7) 접합성의 평가(2-7) Evaluation of adhesion
무전해 도금 대상 재료로서, 수지 기재 상에 오버 레지스트 타입의 미소 동 패드(직경 0.6㎜, 패드수 20개)를 가지는 BGA수지 기판을 이용했다. 무전해 도금 대상 재료를 산성 탈지, 소프트 에칭, 촉매 부여 처리, 무전해 팔라듐 도금, 무전해 금 도금의 차례로 처리했다. 그 후, Sn―3Ag―0.5Cu의 땜납 볼(ø0.76㎜)을 탑재하고, 리플로 장치에서 가열(피크 온도 250℃)한 후, 땜납 볼 풀 시험 장치(Dage사제 ＃4000)를 이용하여 풀 속도 5000㎛／초로 땜납 볼 풀 시험을 실시했다. 땜납 내부에서 파단이 발생하거나, 또는 기재가 파괴되는 모드를 양호, 땜납 볼과 도금 피막의 접합 계면에서 파괴되는 모드를 불량으로 판단하고, 이하의 평가 기준에 따라서 평가했다.As a material for electroless plating, a BGA resin substrate having overresist type micro copper pads (0.6 mm in diameter, 20 pads) on a resin substrate was used. The material to be subjected to electroless plating was subjected to acid degreasing, soft etching, catalyst imparting treatment, electroless palladium plating, and electroless gold plating in this order. After that, a Sn-3Ag-0.5Cu solder ball (ø0.76 mm) was mounted, heated in a reflow device (peak temperature: 250°C), and then, using a solder ball paste tester (#4000 manufactured by Dage), A solder ball paste test was conducted at a paste speed of 5000 µm/second. The mode in which breakage occurred inside the solder or the substrate was destroyed was judged to be good, and the mode in which the solder ball and the plated film bonded to each other was judged to be poor, and evaluated according to the following evaluation criteria.
＜접합성의 평가 기준＞<Evaluation Criteria for Adhesion>
○: 양호 모드 50％ 이상.○: 50% or more of good mode.
△: 양호 모드 0％ 초과 50％ 미만.△: Good mode more than 0% and less than 50%.
×: 모두 불량 모드(양호 모드 0％).x: All bad mode (good mode 0%).
(3) 결과(3) Results
결과를 표 1에 나타낸다.The results are shown in Table 1.
[표 1][Table 1]
Claims (13)
무전해 도금용 촉매 부여액.
containing a cobalt compound and a reducing agent
A catalyst application liquid for electroless plating.
상기 환원제가 아민 화합물을 포함하는
무전해 도금용 촉매 부여액.
According to claim 1,
The reducing agent comprises an amine compound
A catalyst application liquid for electroless plating.
상기 아민 화합물이 아민보란, 히드라진 및 히드라진 유도체로 이루어지는 군으로부터 선택되는 적어도 1종을 포함하는
무전해 도금용 촉매 부여액.
According to claim 2,
The amine compound contains at least one selected from the group consisting of amine borane, hydrazine and hydrazine derivatives.
A catalyst application liquid for electroless plating.
착화제를 함유하는
무전해 도금용 촉매 부여액.According to any one of claims 1 to 3,
containing a complexing agent
A catalyst application liquid for electroless plating.
상기 착화제가 카르복실산을 포함하는
무전해 도금용 촉매 부여액.
According to claim 4,
The complexing agent comprises a carboxylic acid
A catalyst application liquid for electroless plating.
상기 카르복실산이 히드록시카르복실산 또는 디카르복실산을 포함하는
무전해 도금용 촉매 부여액.
According to claim 5,
Where the carboxylic acid includes a hydroxycarboxylic acid or a dicarboxylic acid
A catalyst application liquid for electroless plating.
상기 환원제가 붕소 함유 화합물 및 인 함유 화합물로 이루어지는 군으로부터 선택되는 적어도 1종을 포함하는
무전해 도금용 촉매 부여액.
According to any one of claims 1 to 6,
The reducing agent contains at least one selected from the group consisting of boron-containing compounds and phosphorus-containing compounds.
A catalyst application liquid for electroless plating.
금속염을 더 함유하는
무전해 도금용 촉매 부여액.According to any one of claims 1 to 7,
containing more metal salts
A catalyst application liquid for electroless plating.
코발트 함유량이 금속 100질량％에 대하여 50질량％ 이상인
무전해 도금용 촉매 부여액.
According to any one of claims 1 to 8,
The cobalt content is 50% by mass or more with respect to 100% by mass of the metal.
A catalyst application liquid for electroless plating.
상기 환원제가 붕소 함유 화합물 및 인 함유 화합물로 이루어지는 군으로부터 선택되는 적어도 1종을 포함하고, 또한,
상기 무전해 도금이 동 및／또는 동 합금이 표면에 노출되어 있는 재료에 대한 무전해 팔라듐 도금, 무전해 니켈 도금 및 무전해 금 도금으로 이루어지는 군으로부터 선택되는 적어도 1종의 무전해 도금인
무전해 도금용 촉매 부여액.
According to any one of claims 1 to 9,
The reducing agent includes at least one selected from the group consisting of boron-containing compounds and phosphorus-containing compounds, and
The electroless plating is at least one kind of electroless plating selected from the group consisting of electroless palladium plating, electroless nickel plating, and electroless gold plating on a material in which copper and/or copper alloy is exposed on the surface.
A catalyst application liquid for electroless plating.
촉매핵을 포함하는 무전해 도금 대상 재료를 제조하는 방법.
(1) Including a step of bringing the electroless plating target material into contact with the electroless plating catalyst application liquid according to any one of claims 1 to 10,
A method for manufacturing a material to be electroless plated containing a catalytic nucleus.
(2) 공정(1) 후에, 무전해 도금 처리하는 공정을 포함하는,
무전해 도금 피막을 포함하는 재료를 제조하는 방법.
(1) a step of bringing the material to be electroless plating into contact with the electroless plating catalyst application liquid according to any one of claims 1 to 10;
(2) After step (1), including a step of electroless plating treatment,
A method for producing a material containing an electroless plating film.
상기 촉매핵(1)이 코발트를 함유하고,
상기 피막(2)이 무전해 도금 피막인
재료.It includes a material having a metal exposed on its surface, a catalytic core 1 on the metal, and a coating 2 on the catalytic core 1, and
The catalyst core 1 contains cobalt,
The film 2 is an electroless plating film
ingredient.
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| PCT/JP2021/022772 WO2022004367A1 (en) | 2020-07-03 | 2021-06-16 | Catalyst-imparting solution for electroless plating |
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| US4232060A (en) * | 1979-01-22 | 1980-11-04 | Richardson Chemical Company | Method of preparing substrate surface for electroless plating and products produced thereby |
| JP3826544B2 (en) * | 1998-02-27 | 2006-09-27 | 奥野製薬工業株式会社 | Catalyst composition for electroless plating |
| JP2002167675A (en) * | 2000-12-01 | 2002-06-11 | Okuno Chem Ind Co Ltd | Method for imparting catalyst for electroless plating |
| JP4670064B2 (en) * | 2001-02-07 | 2011-04-13 | 奥野製薬工業株式会社 | Method for applying catalyst for electroless plating |
| JP4143385B2 (en) * | 2002-03-05 | 2008-09-03 | 株式会社大和化成研究所 | Pretreatment liquid for imparting catalyst for electroless plating, pretreatment method using the liquid, electroless plating film and / or plating coating produced using the method |
| JPWO2009142126A1 (en) * | 2008-05-21 | 2011-09-29 | 日本高純度化学株式会社 | Catalyst application liquid for solder plating |
| WO2010004856A1 (en) * | 2008-07-08 | 2010-01-14 | 日本高純度化学株式会社 | Catalyst-imparting liquid for palladium plating |
| JP5568811B2 (en) * | 2011-04-01 | 2014-08-13 | 学校法人 関西大学 | Substrate intermediate, substrate and through via electrode forming method |
| JP6466521B2 (en) * | 2017-06-28 | 2019-02-06 | 小島化学薬品株式会社 | Electroless plating process |
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