JP6841462B1 - Catalyst-imparting liquid for electroless plating - Google Patents
Catalyst-imparting liquid for electroless plating Download PDFInfo
- Publication number
- JP6841462B1 JP6841462B1 JP2020115474A JP2020115474A JP6841462B1 JP 6841462 B1 JP6841462 B1 JP 6841462B1 JP 2020115474 A JP2020115474 A JP 2020115474A JP 2020115474 A JP2020115474 A JP 2020115474A JP 6841462 B1 JP6841462 B1 JP 6841462B1
- Authority
- JP
- Japan
- Prior art keywords
- electroless
- plating
- catalyst
- electroless plating
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000007772 electroless plating Methods 0.000 title claims abstract description 70
- 239000007788 liquid Substances 0.000 title claims abstract description 34
- 238000007747 plating Methods 0.000 claims abstract description 94
- 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 63
- 239000003054 catalyst Substances 0.000 claims description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 32
- 229910052763 palladium Inorganic materials 0.000 claims description 32
- 239000010931 gold Substances 0.000 claims description 30
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 28
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052737 gold Inorganic materials 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 229910017052 cobalt Inorganic materials 0.000 claims description 24
- 239000010941 cobalt Substances 0.000 claims description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 24
- -1 amine compound Chemical class 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 17
- 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
- 229910000085 borane Inorganic materials 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
- 239000013077 target material Substances 0.000 claims description 9
- 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
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 150000002429 hydrazines Chemical class 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims 4
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 238000001556 precipitation Methods 0.000 abstract description 21
- 230000004888 barrier function Effects 0.000 abstract description 10
- 239000007769 metal material Substances 0.000 abstract description 7
- 238000010586 diagram Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 58
- 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
- 238000011282 treatment Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000005238 degreasing Methods 0.000 description 10
- 159000000000 sodium salts Chemical class 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 229910001020 Au alloy Inorganic materials 0.000 description 9
- 150000003863 ammonium salts Chemical class 0.000 description 9
- 235000015165 citric acid Nutrition 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 239000003353 gold alloy Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 229940044175 cobalt sulfate Drugs 0.000 description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004094 surface-active agent Substances 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
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 159000000001 potassium salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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
- 238000011276 addition treatment Methods 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- KFHRUBBWOSPNDP-UHFFFAOYSA-N cobalt heptahydrate Chemical compound O.O.O.O.O.O.O.[Co] KFHRUBBWOSPNDP-UHFFFAOYSA-N 0.000 description 4
- 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 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
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000012360 testing method 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
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-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
- 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
- 239000006174 pH buffer Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 230000001376 precipitating effect Effects 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
- 238000006467 substitution reaction Methods 0.000 description 3
- SDVHRXOTTYYKRY-UHFFFAOYSA-J tetrasodium;dioxido-oxo-phosphonato-$l^{5}-phosphane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)P([O-])([O-])=O SDVHRXOTTYYKRY-UHFFFAOYSA-J 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
- 239000011800 void material 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000010953 base metal Substances 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
- 238000005516 engineering process 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
- 125000004435 hydrogen atom Chemical group [H]* 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
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 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
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 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
- 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
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 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
- 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 235000001014 amino acid Nutrition 0.000 description 1
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- 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
- SXFQDYORBVIULR-UHFFFAOYSA-N azane;cobalt(2+) Chemical compound N.[Co+2] SXFQDYORBVIULR-UHFFFAOYSA-N 0.000 description 1
- VCNSVJZBSHPMSH-UHFFFAOYSA-N azanium;cobalt;chloride Chemical compound [NH4+].[Cl-].[Co] VCNSVJZBSHPMSH-UHFFFAOYSA-N 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
- 238000007796 conventional method 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
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NRCFFPOQRUJEOG-UHFFFAOYSA-J dipotassium;cobalt(2+);disulfate Chemical compound [K+].[K+].[Co+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NRCFFPOQRUJEOG-UHFFFAOYSA-J 0.000 description 1
- 238000004090 dissolution 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
- 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
- 238000010438 heat treatment Methods 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
- 238000007654 immersion Methods 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
- 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
- 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
- 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
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 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
- 229940095064 tartrate Drugs 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
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
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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
-
- 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
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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
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
【課題】金属材料上に無電解めっきを行う際の前処理に使用する触媒付与液であって、めっき析出性、選択析出性、バリア特性、接合性等がより優れた無電解めっき皮膜を形成するために有用であり、また浴安定性がより優れた触媒付与液を提供すること。【解決手段】コバルト化合物及び還元剤を含有する、無電解めっき用触媒付与液。【選択図】なしPROBLEM TO BE SOLVED: To form an electroless plating film which is a catalyst-imparting liquid used for pretreatment when performing electroless plating on a metal material and has more excellent plating precipitation property, selective precipitation property, barrier property, bondability and the like. To provide a catalyst-imparting solution that is useful for the purpose and has better bath stability. SOLUTION: A catalyst-imparting liquid for electroless plating containing a cobalt compound and a reducing agent. [Selection diagram] None
Description
本発明は、無電解めっき用触媒付与液等に関する。 The present invention relates to a catalyst-imparting liquid for electroless plating and the like.
プリント配線板、半導体パッケージ、電子部品等のエレクトロニクス関連分野において、製造時における最終工程の一つに、導体回路、端子部分等に無電解ニッケルめっきを施し、更に無電解金めっきを行う処理がある。この方法で形成される無電解ニッケル/金めっき皮膜は、銅回路表面の酸化を防止して良好なはんだ接続性能を発揮させることや、半導体パッケージとその上に実装される電子部品とのワイヤーボンディング性を向上させることなどを目的として用いられている。無電解ニッケルめっき皮膜を形成した後、置換金めっき皮膜を形成する場合には、下地のニッケルめっき皮膜の状態によっては、ニッケルが局所的に溶解して、ニッケルの腐食、いわゆるブラックパッドが発生することや、熱処理による下地金属拡散によってAu表面が汚染されることなどの問題点がある。この様な問題点を解決する手段として、無電解ニッケルめっきと金めっきの間に、バリア皮膜として無電解パラジウムめっきを行う、無電解ニッケル/パラジウム/金めっき処理が増加している。更に、プリント配線板の高密度化に伴う銅配線の微細化に対応するために、最も膜厚の高い無電解ニッケルめっき皮膜を省略した無電解パラジウム/金めっき処理が開発されている(下記特許文献1参照)。 In electronics-related fields such as printed wiring boards, semiconductor packages, and electronic components, one of the final processes during manufacturing is electroless nickel plating on conductor circuits, terminal parts, etc., and then electroless gold plating. .. The electroless nickel / gold plating film formed by this method prevents oxidation of the copper circuit surface to exhibit good solder connection performance, and wire bonding between the semiconductor package and the electronic components mounted on it. It is used for the purpose of improving the sex. When an electroless nickel plating film is formed and then a replacement gold plating film is formed, nickel is locally dissolved depending on the state of the underlying nickel plating film, and nickel corrosion, so-called black pad, occurs. In addition, there are problems such as the Au surface being contaminated by the diffusion of the base metal by heat treatment. As a means for solving such a problem, electroless nickel / palladium / gold plating treatment in which electroless palladium plating is performed as a barrier film between electroless nickel plating and gold plating is increasing. Further, in order to cope with the miniaturization of copper wiring due to the high density of printed wiring boards, an electroless palladium / gold plating process has been developed in which the electroless nickel plating film having the highest film thickness is omitted (the following patent). Reference 1).
基板の金属材料上に無電解めっきを行う際に、めっき析出性等を向上させる目的で、金属材料上に置換反応にて触媒核となるパラジウム金属を析出させる触媒付与処理を行うことがある。本発明者は研究を進める中で、この触媒付与処理を行う場合、めっき析出性は良好であるものの、バリア特性及び接合性において不十分であることを見出した。この原因について調べていく中で、上記触媒付与処理を行う場合、金属材料の過剰溶解が生じる場合があり、その後に無電解めっき(ニッケルやパラジウムなど)処理を行うと析出しためっき皮膜と金属材料の間に、ところどころに微小な空隙(ボイド)が生じることを見出した。 When electroless plating is performed on a metal material of a substrate, a catalyst addition treatment for precipitating palladium metal as a catalyst core by a substitution reaction may be performed on the metal material for the purpose of improving plating precipitation. In the course of research, the present inventor has found that when this catalyst-imparting treatment is performed, the plating precipitation property is good, but the barrier properties and bondability are insufficient. While investigating the cause of this, when the above catalyst application treatment is performed, excessive dissolution of the metal material may occur, and when electroless plating (nickel, palladium, etc.) is performed after that, the precipitated plating film and metal material It was found that minute voids were generated in some places between the two.
このため、本発明者は、置換反応ではなく、還元反応によりパラジウム金属を析出させる触媒付与処理を試みた。しかし、めっき析出性、選択析出性、浴安定性、バリア特性、接合性等の特性のいくつかにおいて不十分であった。 Therefore, the present inventor has attempted a catalyst addition treatment for precipitating palladium metal by a reduction reaction rather than a substitution reaction. However, some of the properties such as plating precipitation property, selective precipitation property, bath stability, barrier property, and bondability were insufficient.
そこで、本発明は、金属材料上に無電解めっきを行う際の前処理に使用する触媒付与液であって、めっき析出性、選択析出性、バリア特性、接合性等がより優れた無電解めっき皮膜を形成するために有用であり、また浴安定性がより優れた触媒付与液を提供することを課題とする。 Therefore, the present invention is an electroless plating which is a catalyst-imparting liquid used for pretreatment when performing electroless plating on a metal material, and has more excellent plating precipitation property, selective precipitation property, barrier property, bondability and the like. It is an object of the present invention to provide a catalyst-imparting solution which is useful for forming a film and has more excellent bath stability.
本発明者は上記課題に鑑みて鋭意研究を進めた結果、コバルト化合物及び還元剤を含有する、無電解めっき用触媒付与液、であれば、上記課題を解決できることを見出した。本発明者はこの知見に基づいてさらに研究を進めた結果、本発明を完成させた。即ち、本発明は、下記の態様を包含する。 As a result of diligent research in view of the above problems, the present inventor has found that a catalyst-imparting solution for electroless plating containing a cobalt compound and a reducing agent can solve the above problems. The present inventor has completed the present invention as a result of further research based on this finding. That is, the present invention includes the following aspects.
項1. コバルト化合物及び還元剤を含有する、無電解めっき用触媒付与液。 Item 1. A catalyst-imparting solution for electroless plating containing a cobalt compound and a reducing agent.
項2. 前記還元剤がアミン化合物を含む、項1に記載の無電解めっき用触媒付与液。 Item 2. Item 2. The catalyst-imparting solution for electroless plating, wherein the reducing agent contains an amine compound.
項3. 前記アミン化合物が、アミンボラン、ヒドラジン、及びヒドラジン誘導体からなる群より選択される少なくとも1種を含む、項2に記載の無電解めっき用触媒付与液。 Item 3. Item 2. The electroless plating catalyst-imparting solution according to Item 2, wherein the amine compound contains at least one selected from the group consisting of amine borane, hydrazine, and hydrazine derivatives.
項4. 錯化剤を含有する、項1〜3のいずれかに記載の無電解めっき用触媒付与液。 Item 4. Item 2. The catalyst-imparting solution for electroless plating according to any one of Items 1 to 3, which contains a complexing agent.
項5. 前記錯化剤がカルボン酸を含む、項4に記載の無電解めっき用触媒付与液。 Item 5. Item 4. The catalyst-imparting solution for electroless plating, wherein the complexing agent contains a carboxylic acid.
項6. 前記カルボン酸がヒドロキシカルボン酸又はジカルボン酸を含む、項5に記載の無電解めっき用触媒付与液。 Item 6. Item 5. The catalyst-imparting solution for electroless plating according to Item 5, wherein the carboxylic acid contains a hydroxycarboxylic acid or a dicarboxylic acid.
項7. 前記還元剤が、ホウ素含有化合物及びリン含有化合物からなる群より選択される少なくとも1種を含む、項1〜6のいずれかに記載の無電解めっき用触媒付与液。 Item 7. Item 2. The catalyst-imparting solution 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 a boron-containing compound and a phosphorus-containing compound.
項8. さらに、金属塩を含有する、項1〜7のいずれかに記載の無電解めっき用触媒付与液。 Item 8. Item 4. The electroless plating catalyst-imparting liquid according to any one of Items 1 to 7, further containing a metal salt.
項9. コバルト含有量が金属100質量%に対して50質量%以上である、項1〜8のいずれかに記載の無電解めっき用触媒付与液。 Item 9. Item 2. The catalyst-imparting solution 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.
項10. 前記還元剤が、ホウ素含有化合物及びリン含有化合物からなる群より選択される少なくとも1種を含み、且つ
前記無電解めっきが、銅及び/又は銅合金が表面に露出している材料に対する、無電解パラジウムめっき、無電解ニッケルめっき、及び無電解金めっきからなる群より選択される少なくとも1種の無電解めっきである、
項1〜9のいずれかに記載の無電解めっき用触媒付与液。
Item 10. The reducing agent contains at least one selected from the group consisting of boron-containing compounds and phosphorus-containing compounds, and the electroless plating is electroless for materials in which copper and / or copper alloys are exposed on the surface. At least one electroless plating selected from the group consisting of palladium plating, electroless nickel plating, and electroless gold plating.
Item 4. The catalyst-imparting solution for electroless plating according to any one of Items 1 to 9.
項11. (1)無電解めっき対象材料と、項1〜10のいずれかに記載の無電解めっき用触媒付与液とを接触させる工程を含む、触媒核を含む無電解めっき対象材料を製造する方法。 Item 11. (1) A method for producing an electroless plating target material containing a catalyst nucleus, which comprises a step of bringing the electroless plating target material into contact with the electroless plating catalyst-imparting liquid according to any one of Items 1 to 10.
項12. (1)無電解めっき対象材料と、項1〜10のいずれかに記載の無電解めっき用触媒付与液とを接触させる工程、及び
(2)工程(1)後に、無電解めっき処理する工程
を含む、無電解めっき皮膜を含む材料を製造する方法。
Item 12. (1) A step of contacting the material to be electroless plated with the electroless plating catalyst-applying liquid according to any one of Items 1 to 10, and a step of performing electroless plating after step (2) and step (1). A method for producing a material containing an electroless plating film, including.
項13. 金属が表面に露出している材料、前記金属上の触媒核1、及び前記触媒核1上の皮膜2を含み、且つ
前記触媒核1がコバルトを含有し、
前記皮膜2が無電解めっき皮膜である、
材料。
Item 13. A material in which the metal is exposed on the surface, a catalyst nucleus 1 on the metal, and a film 2 on the catalyst nucleus 1 are included, and the catalyst nucleus 1 contains cobalt.
The film 2 is an electroless plating film.
material.
本発明によれば、金属材料上に無電解めっきを行う際の前処理に使用する触媒付与液であって、めっき析出性、選択析出性、バリア特性、接合性等がより優れた無電解めっき皮膜を形成するために有用であり、また浴安定性がより優れた触媒付与液を提供することができる。 According to the present invention, it is an electroless plating which is a catalyst-imparting liquid used for pretreatment when performing electroless plating on a metal material and has more excellent plating precipitation property, selective precipitation property, barrier property, bondability and the like. It is possible to provide a catalyst-imparting solution that is useful for forming a film and has better bath stability.
本明細書中において、「含有」及び「含む」なる表現については、「含有」、「含む」、「実質的にからなる」及び「のみからなる」という概念を含む。 In the present specification, the expressions "contains" and "contains" include the concepts of "contains", "contains", "substantially consists" and "consists of only".
1.触媒付与液
本発明は、その一態様において、コバルト化合物及び還元剤を含有する、無電解めっき用触媒付与液(本明細書において、「本発明の触媒付与液」と示すこともある。)に関する。以下に、これについて説明する。
1. 1. Catalyst-imparting liquid In one aspect of the present invention, the present invention relates to a catalyst-imparting liquid for electroless plating containing a cobalt compound and a reducing agent (in the present specification, it may be referred to as “catalyst-imparting liquid of the present invention”). .. This will be described below.
コバルト化合物は、めっき液に可溶性であるものである限り、特に制限されない。コバルト化合物としては、例えば有機又は無機のコバルト塩が挙げられ、より具体的には例えば硫酸コバルト、塩化コバルト、硝酸コバルト、臭化コバルト、ヨウ化コバルト、次亜リン酸コバルト、リン酸コバルト、硫酸コバルトアンモニウム、塩化コバルトアンモニウム、硫酸コバルトカリウム、スルファミン酸コバルト、酢酸コバルト、炭酸コバルト、コバルトアセチルアセトネート、ギ酸コバルト、シュウ酸コバルト、ステアリン酸コバルト、クエン酸コバルト、酒石酸コバルト、乳酸コバルトなどが挙げられる。これらの中でも、本発明の効果の観点から、好ましくは無機コバルト塩が挙げられ、より好ましくは硫酸コバルト、塩化コバルト、硝酸コバルト、リン酸コバルト、次亜リン酸コバルト等が挙げられ、さらに好ましくは硫酸コバルト、塩化コバルトが挙げられる。 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, sulfuric acid. Examples include cobalt ammonium, cobalt ammonium chloride, cobalt potassium sulfate, cobalt sulfamate, cobalt acetate, cobalt carbonate, cobalt acetylacetonate, cobalt formate, cobalt oxalate, cobalt stearate, cobalt citrate, cobalt tartrate, cobalt lactate and the like. .. Among these, from the viewpoint of the effect of the present invention, an inorganic cobalt salt is preferable, and cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt phosphate, cobalt hypophosphite and the like are more preferable, and more preferably. Examples include cobalt sulfate and cobalt chloride.
コバルト化合物は、1種単独で又は2種以上を組合わせて用いることができる。 The cobalt compound may be used alone or in combination of two or more.
本発明の触媒付与液中のコバルト濃度は、例えば0.05g/L以上である。該コバルト濃度は、本発明の効果の観点から、好ましくは0.05〜50g/L、より好ましくは0.1〜30g/L、さらに好ましくは0.2〜20g/L、よりさらに好ましくは0.4〜15g/L、とりわけ好ましくは0.6〜10g/L、特に好ましくは0.7〜6g/Lである。 The cobalt concentration in the catalyst-imparting solution 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. It is .4 to 15 g / L, particularly preferably 0.6 to 10 g / L, and particularly preferably 0.7 to 6 g / L.
本発明の触媒付与液中のコバルト含有量は、コバルトを含む遷移金属元素の含有量100質量%に対して、例えば50質量%以上、好ましくは60質量%以上、より好ましくは70質量%であり、或いは80質量%以上、又は90質量%以上である。 The cobalt content in the catalyst-imparting liquid of the present invention is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass with respect to 100% by mass of the content of the transition metal element containing cobalt. , 80% by mass or more, or 90% by mass or more.
還元剤としては、コバルト金属を析出させることが可能な還元剤である限り特に制限されず、還元めっきで使用され得る還元剤を使用することができる。還元剤としては、例えばアミン化合物、ホウ素含有化合物、リン含有化合物等が挙げられる。還元剤は、これらの複数に属するものも存在する。例えば、アミン化合物であり且つホウ素含有化合物である還元剤も存在する。その場合、その還元剤を含有する場合は、アミン化合物を含有するといえ、且つホウ素含有化合物を含有するといえる。 The reducing agent is not particularly limited as long as it is a reducing agent capable of precipitating 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, phosphorus-containing compounds and the like. Some reducing agents belong to a plurality of these. For example, there are reducing agents that are amine compounds and boron-containing compounds. In that case, when the reducing agent is contained, it can be said that the amine compound is contained and the boron-containing compound is contained.
アミン化合物としては、例えばアミンボラン、ヒドラジン、ヒドラジン誘導体等が挙げられる。 Examples of the amine compound include amine borane, hydrazine, and hydrazine derivatives.
アミンボランは、ボラン(例えばBH3)とアミンとの錯体であるアミンボラン錯体である。アミンボランを構成するアミンとしては、鎖状アミン(非環状アミン)、環状アミンのいずれでもよいが、好ましくは鎖状アミンであり、より好ましくは鎖状アミンの中でも、一般式(1): Amineborane is an amineborane complex that is a complex of borane (eg, BH 3) and an amine. The amine constituting the amine borane may be either a chain amine (non-cyclic amine) or a cyclic amine, but is preferably a chain amine, and more preferably, among the chain amines, the general formula (1):
[式中、R1、R2及びR3は同一又は異なって、水素原子又はアルキル基を示す。]
で表される鎖状アミンが挙げられる。
[In the formula, R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom or an alkyl group. ]
Examples thereof include chain amines represented by.
アルキル基には、直鎖状、分枝鎖状、及び環状のいずれのものも包含される。アルキル基は、好ましくは直鎖状又は分岐鎖状であり、より好ましくは直鎖状である。該アルキル基の炭素数は、特に制限されないが、例えば1〜8、好ましくは1〜6、より好ましくは1〜4、さらに好ましくは1〜2、よりさらに好ましくは1である。該アルキル基の具体例としては、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、tert−ブチル基、sec−ブチル基、n−ペンチル基、ネオペンチル基、n−ヘキシル基、3−メチルペンチル基、シクロヘキシル基等が挙げられる。 Alkyl groups include linear, branched, and cyclic groups. The alkyl group is preferably linear or branched chain, and more preferably linear. The number of carbon atoms of 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, and even more preferably 1. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, neopentyl group, n. -Hexyl group, 3-methylpentyl group, cyclohexyl group and the like can be mentioned.
本発明の好ましい一態様においては、R1、R2及びR3の内、いずれか2つ又は全て(より好ましくは2つ)がアルキル基であり、残りは水素原子である。 In a preferred embodiment of the present invention, any two or all (more preferably two) of R 1 , R 2 and R 3 are alkyl groups and the rest are hydrogen atoms.
ボラン錯体を構成するアミンの具体例としては、ジメチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン、メトキシエチルアミン、ジシクロへキシルアミン、t−ブチルアミン、アミノピリジン、エチレンジアミン、モルホリン、ピリジン、ピペリジン、イミダゾール等が挙げられる。これらの中でも、好ましくはジメチルアミン、ジエチルアミン、トリメチルアミン、メトキシエチルアミン、ジシクロへキシルアミン等が挙げられ、より好ましくはジメチルアミン等が挙げられる。 Specific examples of amines constituting the borane complex include dimethylamine, diethylamine, trimethylamine, triethylamine, methoxyethylamine, dicyclohexylamine, t-butylamine, aminopyridine, ethylenediamine, morpholine, pyridine, piperidine, imidazole and the like. Among these, dimethylamine, diethylamine, trimethylamine, methoxyethylamine, dicyclohexylamine and the like are preferable, and dimethylamine and the like are more preferable.
アミンボランの好適に具体例としては、ジメチルアミンボラン、ジエチルアミンボラン、トリメチルアミンボラン等が挙げられる。 Preferable specific examples of amine borane include dimethylamine borane, diethylamine borane, trimethylamine borane and the like.
ヒドラジン誘導体としては、無電解めっきの還元剤として使用し得るものであれば、特に制限されない。 The hydrazine derivative is not particularly limited as long as it can be used as a reducing agent for electroless plating.
ホウ素含有化合物としては、例えば水素化ホウ素化合物、より具体的には、例えばアミン化合物でもある上記アミンボラン、アミンボラン以外のボラン錯体(ボランと他の化合物との錯体)、水素化ホウ素アルカリ金属塩(例えばナトリウム塩等)等が挙げられる。 Examples of the boron-containing compound include a boron hydride compound, more specifically, the above-mentioned amine borane which is also an amine compound, a borane complex other than amine borane (complex of borane and other compounds), and a boron hydride alkali metal salt (for example). (Sodium salt, etc.) and the like.
リン含有化合物としては、例えば次亜リン酸、次亜リン酸塩(例えば、ナトリウム塩、カリウム塩、アンモニウム塩等)、亜リン酸、亜リン酸塩(例えば、ナトリウム塩、カリウム塩、アンモニウム塩等)、それらの水和物等が挙げられる。 Examples of phosphorus-containing compounds include hypophosphorous acid, hypophosphite (eg, sodium salt, potassium salt, ammonium salt, etc.), phosphorous acid, phosphite (eg, sodium salt, potassium salt, ammonium salt, etc.). Etc.), their hydrates and the like.
還元剤は、本発明の効果の観点から、アミン化合物を含むことが好ましい。また、この場合、アミン化合物は、アミンボラン、ヒドラジン、及びヒドラジン誘導体からなる群より選択される少なくとも1種を含むことがより好ましく、アミンボラン及びヒドラジンからなる群より選択される少なくとも1種を含むことがさらに好ましく、アミンボランを含むことがよりさらに好ましい。また、還元剤がアミン化合物を含む場合、還元剤は、さらにリン含有化合物を含むことがより好ましい。 The reducing agent preferably contains an amine compound from the viewpoint of the effect 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 may contain at least one selected from the group consisting of amine borane and hydrazine. It is even more preferable, and it is even more preferable to contain amine borane. When the reducing agent contains an amine compound, it is more preferable that the reducing agent further contains a phosphorus-containing compound.
還元剤は、本発明の効果の観点から、ホウ素含有化合物及びリン含有化合物からなる群より選択される少なくとも1種を含むことが好ましい。 From the viewpoint of the effect of the present invention, the reducing agent preferably contains at least one selected from the group consisting of boron-containing compounds and phosphorus-containing compounds.
還元剤は、1種単独で又は2種以上を組合わせて用いることができる。 The reducing agent may be used alone or in combination of two or more.
本発明の触媒付与液中の還元剤の濃度は、例えば0.05g/L以上である。該濃度は、本発明の効果の観点から、好ましくは0.05〜100g/L、より好ましくは0.2〜50g/L、さらに好ましくは0.5〜30g/Lである。還元剤がアミン化合物を含む場合、本発明の触媒付与液中の該アミン化合物の濃度は、本発明の効果の観点から、好ましくは0.05〜25g/L、より好ましくは0.1〜20g/L、さらに好ましくは0.2〜15g/L、よりさらに好ましくは0.4〜10g/L、とりわけ好ましくは0.6〜8g/Lである。還元剤がリン含有化合物を含む場合、本発明の触媒付与液中の該リン含有化合物の濃度は、本発明の効果の観点から、好ましくは1〜200g/L、より好ましくは5〜150g/L、さらに好ましくは10〜100g/L、よりさらに好ましくは20〜80g/Lである。 The concentration of the reducing agent in the catalyst-imparting 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, and further preferably 0.5 to 30 g / L. When the reducing agent contains an amine compound, the concentration of the amine compound in the catalyst-imparting solution of the present invention is preferably 0.05 to 25 g / L, more preferably 0.1 to 20 g, from the viewpoint of the effect of the present invention. / L, more preferably 0.2 to 15 g / L, even 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-imparting solution 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, and even more preferably 20 to 80 g / L.
本発明の触媒付与液は、本発明の効果の観点から、さらに錯化剤を含有することが好ましい。 From the viewpoint of the effect of the present invention, the catalyst-imparting liquid of the present invention preferably further contains a complexing agent.
錯化剤としては、特に制限されず、無電解めっき(特に還元めっき)で使用され得る錯化剤を使用することができる。錯化剤としては、例えば、酢酸、蟻酸等のモノカルボン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等; マロン酸、コハク酸、アジピン酸、マレイン酸、フマール酸等のジカルボン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等; リンゴ酸、乳酸、グリコール酸、グルコン酸、クエン酸、酒石酸等のヒドロキシカルボン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等; エチレンジアミンジ酢酸、1−ヒドロキシエチリデン−1,1−ジホスホン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等; エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸等のアミノポリカルボン酸やそれらのナトリウム塩、カリウム塩、アンモニウム塩等; ピロリン酸等のホスホン酸類やそれらのナトリウム塩、カリウム塩、アンモニウム塩等; グリシン、グルタミン酸等のアミノ酸類等が挙げられる。 The complexing agent is not particularly limited, and a 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, sodium salts and the like; dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid and fumaric acid, among others. Ammonium salt, potassium salt, sodium salt, etc .; hydroxycarboxylic acids such as malic acid, lactic acid, glycolic acid, gluconic acid, citric acid, tartrate acid, etc., ammonium salt, potassium salt, sodium salt, etc.; ethylenediaminediacetic acid, 1-hydroxy Ethiliden-1,1-diphosphonic acid, ammonium salts, potassium salts, sodium salts, etc.; Aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc. and their sodium salts, potassium salts, ammonium salts, etc.; Phosphonic acids and their sodium salts, potassium salts, ammonium salts, etc .; Amino acids such as glycine and glutamic acid can be mentioned.
錯化剤は、本発明の効果の観点から、カルボン酸を含むことが好ましい。この場合、カルボン酸は、本発明の効果の観点から、ヒドロキシカルボン酸やジカルボン酸を含むことがより好ましい。ヒドロキシカルボン酸やジカルボン酸の中でも、さらに好ましくはリンゴ酸、クエン酸、酒石酸、乳酸、アジピン酸、コハク酸、マロン酸、グルコン酸等が挙げられ、よりさらに好ましくはリンゴ酸、クエン酸、酒石酸等が挙げられる。 The complexing agent preferably contains a carboxylic acid from the viewpoint of the effect of the present invention. In this case, the carboxylic acid more preferably contains a hydroxycarboxylic acid or a dicarboxylic acid from the viewpoint of the effect of the present invention. Among the hydroxycarboxylic acids and dicarboxylic acids, malic acid, citric acid, tartaric acid, lactic acid, adipic acid, succinic acid, malonic acid, gluconic acid and the like are more preferable, and malic acid, citric acid, tartaric acid and the like are even more preferable. Can be mentioned.
錯化剤は、1種単独で又は2種以上を組合わせて用いることができる。 The complexing agent may be used alone or in combination of two or more.
本発明の触媒付与液が錯化剤を含有する場合、本発明の触媒付与液中の錯化剤の濃度は、例えば0.5g/L以上である。該コバルト濃度は、本発明の効果の観点から、好ましくは1〜200g/L、より好ましくは2〜150g/L、さらに好ましくは4〜120g/L、よりさらに好ましくは6〜100g/L、とりわけ好ましくは7〜70g/Lである。 When the catalyst-imparting liquid of the present invention contains a complexing agent, the concentration of the complexing agent in the catalyst-imparting 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, further preferably 4 to 120 g / L, still more preferably 6 to 100 g / L, in particular. It is preferably 7 to 70 g / L.
本発明の触媒付与液は、本発明の効果の観点から、さらに金属塩を含有することが好ましい。 From the viewpoint of the effect of the present invention, the catalyst-imparting liquid of the present invention preferably further contains a metal salt.
金属塩としては、特に制限されないが、例えばコバルト以外の遷移金属元素を含む塩が挙げられる。遷移金属元素としては、例えば金、パラジウム、ニッケル、タングステン、モリブデン、レニウム等の金属元素が挙げられる。金属塩として、より具体的には、例えば硫酸ニッケル、塩化ニッケル、硫酸パラジウム、塩化パラジウム、タングステン酸ナトリウム、モリブデン酸2ナトリウム、シアン化金カリウム、亜硫酸金ナトリウム、過レニウム酸アンモニウム等が挙げられる。 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 molybdenate, potassium gold cyanide, sodium gold sulfite, ammonium perrhenate and the like.
金属塩は、1種単独で又は2種以上を組合わせて用いることができる。 The metal salt may be used alone or in combination of two or more.
本発明の触媒付与液が金属塩を含有する場合、当該金属塩に含まれる金属の、本発明の触媒付与液中の濃度は、例えば0.005g/L以上である。該濃度は、本発明の効果の観点から、好ましくは0.005〜5g/L、より好ましくは0.01〜3g/L、さらに好ましくは0.02〜2g/L、よりさらに好ましくは0.03〜1g/Lである。該濃度は、本発明の触媒付与液中のコバルト濃度の、例えば0.8/1 以下、好ましくは0.6/1 以下であり、或いは0.5/1 以下、0.3/1 以下、0.2/1 以下、0.15/1 以下である。 When the catalyst-imparting solution of the present invention contains a metal salt, the concentration of the metal contained in the metal salt in the catalyst-imparting solution 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. It is 03-1 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, which is the cobalt concentration in the catalyst-imparting solution of the present invention. It is 0.2 / 1 or less and 0.15 / 1 or less.
本発明の触媒付与液は、溶媒として主に水を含有する。水以外の溶媒も含有する場合、その含有量は、水を含む溶媒100質量%に対して、例えば10質量%以下、5質量%以下、1質量%、0.1質量%以下である。 The catalyst-imparting liquid of the present invention mainly contains water as a solvent. When a solvent other than water is also contained, the content thereof 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.
本発明の触媒付与液には、その他必要に応じて、各種の添加剤を配合することができる。添加剤としては、例えば安定剤、pH緩衝剤、界面活性剤等が挙げられる。 Various additives can be added to the catalyst-imparting liquid of the present invention, if necessary. Examples of the additive include a stabilizer, a pH buffer, a surfactant and the like.
安定剤として、例えば硝酸鉛、酢酸鉛等の鉛塩;硝酸ビスマス、酢酸ビスマス等のビスマス塩;チオ硫酸ナトリウム等の硫黄化合物等を1種単独又は2種以上混合して添加することができる。安定剤を添加する場合、その添加量は、特に限定的ではないが、例えば、0.01〜100mg/L程度とすることができる。 As the stabilizer, for example, lead salts such as lead nitrate and lead acetate; bismuth salts such as bismuth nitrate and bismuth acetate; and sulfur compounds such as sodium thiosulfate can be added alone or in admixture of two or more. When the stabilizer is added, the amount of the stabilizer added is not particularly limited, but can be, for example, about 0.01 to 100 mg / L.
pH緩衝剤として、例えば酢酸、ホウ酸、リン酸、亜リン酸、炭酸、それらのナトリウム塩、カリウム塩、アンモニウム塩等を1種単独又は2種以上混合して添加することができる。pH緩衝剤を添加する場合、その添加量は特に限定的ではないが、浴安定性等の観点から、0.002〜1mol/L程度とすることができる。 As the pH buffer, for example, acetic acid, boric acid, phosphoric acid, phosphorous acid, carbonic acid, their sodium salts, potassium salts, ammonium salts and the like can be added alone or in combination of two or more. When a pH buffer is added, the amount thereof is not particularly limited, but it can be about 0.002 to 1 mol / L from the viewpoint of bath stability and the like.
界面活性剤として、例えばノニオン性、アニオン性、カチオン性、両性等の各種界面活性剤を用いることができる。例えば、芳香族又は脂肪族スルホン酸アルカリ塩、芳香族又は脂肪族カルボン酸アルカリ金属塩等が挙げられる。界面活性剤は、一種単独又は二種以上混合して用いることができる。界面活性剤を添加する場合、その添加量は特に限定的ではないが、例えば0.01〜1000mg/L程度とすることができる。 As the surfactant, for example, various surfactants such as nonionic, anionic, cationic and amphoteric can be used. For example, an aromatic or aliphatic sulfonic acid alkali salt, an aromatic or aliphatic carboxylic acid alkali metal salt and the like can be mentioned. The surfactant may be used alone or in combination of two or more. When a surfactant is added, the amount of the surfactant added is not particularly limited, but can be, for example, about 0.01 to 1000 mg / L.
本発明の無電解めっき液のpHは、通常、2〜12程度とすればよく、好ましくは6〜10程度、より好ましくは6.5〜9程度、さらに好ましくは6.9(又は7.0)〜8.5程度である。 The pH of the electroless plating solution of the present invention may be usually about 2 to 12, preferably about 6 to 10, more preferably about 6.5 to 9, and even more preferably about 6.9 (or 7.0). ) ~ 8.5.
2.触媒付与方法
本発明は、その一態様において、(1)無電解めっき対象材料と、本発明の触媒付与液とを接触させる工程を含む、触媒核を含む無電解めっき対象材料を製造する方法、或いは、無電解めっき対象材料を触媒付与処理する方法(本明細書において、「本発明の方法1」と示すこともある。)に関する。以下、これについて説明する。
2. 2. Catalyst application method In one aspect of the present invention, a method for producing an electroless plating target material containing a catalyst nucleus, which comprises (1) a step of contacting an electroless plating target material with the catalyst application solution of the present invention. Alternatively, the present invention relates to a method for applying a catalyst to a material to be electroless plated (in this specification, it may be referred to as "method 1 of the present invention"). This will be described below.
無電解めっき対象材料は、金属が表面に露出している材料である限り、特に制限されない。例えば、素材として、ガラス繊維強化エポキシ、ポリイミド、PET等のプラスチック類、ガラス、セラミック、金属酸化物、金属、紙、合成又は天然繊維などの材質を1種で又は組み合わせてなるものであり、その形状としては、板、フィルム、布状、繊維状、チューブ等のいずれであってもよい。表面に露出している金属としては、例えば、銅、銅合金、銀、銀合金、金、金合金、白金、白金合金、モリブデン、タングステン等が挙げられる。これらの内で、銅合金、銀合金、金合金及び白金合金としては、それぞれ、例えば、銅、銀、金又は白金を50重量%以上含む合金に対して適用できる。無電解めっき対象材料として、具体的には、例えばプリント配線板、半導体パッケージ、電子部品、セラミック基板等が挙げられる。これらの材料において、表面に露出している金属は、配線を構成し得る。 The material to be electroless plated is not particularly limited as long as the metal is exposed on the surface. For example, as a material, plastics such as glass fiber reinforced epoxy, polyimide, PET, and materials such as glass, ceramic, metal oxide, metal, paper, synthetic or natural fiber are used alone or in combination. The shape may be any of a plate, a film, a cloth, a fiber, a tube and the like. Examples of the metal exposed on the surface include copper, copper alloy, silver, silver alloy, gold, gold alloy, platinum, platinum alloy, molybdenum, tungsten and the like. Among these, the copper alloy, silver alloy, gold alloy and platinum alloy can be applied to alloys containing, for example, copper, silver, gold or platinum in an amount of 50% by weight or more, respectively. Specific examples of the material to be electroless plated include a printed wiring board, a semiconductor package, an electronic component, a ceramic substrate, and the like. In these materials, the metal exposed on the surface can constitute the wiring.
無電解めっき対象材料は、脱脂処理、ソフトエッチング処理等の前処理が施されたものであることが好ましい。 The material to be electroless plated is preferably one that has been subjected to pretreatment such as degreasing treatment and soft etching treatment.
本発明の触媒付与液を無電解めっき対象材料に接触させるための具体的な方法については、特に限定的ではないが、通常は、本発明の触媒付与液中に被処理物を浸漬すればよい。その他、無電解めっき対象材料の表面に該触媒付与液を噴霧する方法などによっても触媒付与処理を行うことができる。 The specific method for bringing the catalyst-imparting 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-imparting liquid of the present invention. .. In addition, the catalyst addition treatment can also be performed by a method of spraying the catalyst application liquid on the surface of the electroless plating target material.
本発明の触媒付与液を浸漬法によって行う場合には、本発明の触媒付与液の液温は、通常、10〜90℃程度とすることが好ましく、40〜80℃程度とすることがより好ましく、60〜80℃とすることがさらに好ましい。 When the catalyst-imparting liquid of the present invention is carried out by an immersion method, the liquid temperature of the catalyst-imparting liquid of the present invention is usually preferably about 10 to 90 ° C, more preferably about 40 to 80 ° C. , 60 to 80 ° C. is more preferable.
処理時間については、30秒〜20分程度とすることが好ましく、1分〜5分程度とすることがより好ましい。 The treatment time is preferably about 30 seconds to 20 minutes, more preferably about 1 minute to 5 minutes.
本発明の方法1により、無電解めっき対象材料の表面金属上にコバルトを含む触媒核が形成される。触媒核は、本発明の無電解めっき液中の成分に応じた組成を有する。例えば、本発明の触媒付与液中の還元剤がホウ素含有化合物及び/又はリン含有化合物を含む場合、触媒核は、Co、並びにB及び/又はPを含む。また、本発明の触媒付与液が金属元素含有化合物を含む場合、触媒核は、Co、及び当該金属を含む。 According to the method 1 of the present invention, a catalyst nucleus containing cobalt is formed on the surface metal of the material to be electroless plated. The catalyst nucleus has a composition corresponding to the components in the electroless plating solution of the present invention. For example, when the reducing agent in the catalyst-imparting solution of the present invention contains a boron-containing compound and / or a phosphorus-containing compound, the catalyst nucleus contains Co and B and / or P. When the catalyst-imparting liquid of the present invention contains a metal element-containing compound, the catalyst nucleus contains Co and the metal.
触媒核中のCo含有量は、例えば50質量%以上、好ましくは60質量%以上、より好ましくは70質量%であり、或いは80質量%以上、又は90質量%以上である。 The Co content in the catalyst nucleus is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, or 80% by mass or more, or 90% by mass or more.
触媒核がBを含む場合、その含有量は、例えば2質量%以下、好ましくは1質量%以下、より好ましくは0.5質量%以下、さらに好ましくは0.2質量%以下である。該含有量の下限は、例えば0.01質量%、0.05質量%、又は0.07質量%である。 When the catalyst nucleus contains B, the content thereof 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.
触媒核がPを含む場合、その含有量は、例えば0.5〜20質量%、好ましくは1.5〜15質量%、より好ましくは3〜10質量%である。 When the catalyst nucleus contains P, the content thereof is, for example, 0.5 to 20% by mass, preferably 1.5 to 15% by mass, and more preferably 3 to 10% by mass.
触媒核中の各元素の含有量は、エネルギー分散型X線分析装置(EDX,HORIBA製EMAX X−act)による測定、もしくは高周波誘導結合プラズマ(ICP)発光分光分析装置(日立ハイテクサイエンス製PS3500DDII)を使用した溶解法により同定する。 The content of each element in the catalyst nucleus is measured by an energy dispersive X-ray analyzer (EDX, EMAX X-act manufactured by HORIBA) or a high frequency inductively coupled plasma (ICP) emission spectroscopic analyzer (PS3500DDII manufactured by Hitachi High-Tech Science). Is identified by the dissolution method using.
該触媒核を含む無電解めっき対象材料を無電解めっき処理することにより、めっき析出性、選択析出性、バリア特性、接合性等がより優れた無電解めっき皮膜を形成することができる。触媒核は表面活性化の目的であるので、その厚みは、例えば0.05μm以下、0.005〜0.05μmであることができる。 By electroless plating the material to be electroless plated containing the catalyst nucleus, an electroless plating film having more excellent plating precipitation property, selective precipitation property, barrier property, bondability and the like can be formed. Since the catalyst nucleus is for the purpose of surface activation, its thickness can be, for example, 0.05 μm or less, 0.005 to 0.05 μm.
3.無電解めっき方法
本発明は、その一態様において、(1)無電解めっき対象材料と、本発明の触媒付与液とを接触させる工程、及び(2)工程(1)後に、無電解めっき処理する工程を含む、無電解めっき皮膜を含む材料を製造する方法、或いは、無電解めっき対象材料を無電解めっきする方法(本明細書において、「本発明の方法2」と示すこともある。)に関する。以下、これについて説明する。
3. 3. Electroless plating method In one aspect of the present invention, electroless plating is performed after (1) a step of bringing the material to be electroless plating into contact with the catalyst-imparting liquid of the present invention, and (2) step (1). The present invention relates to a method for producing a material containing an electroless plating film including a step, or a method for electroless plating a material to be electroless plated (in the present specification, it may be referred to as "method 2 of the present invention"). .. This will be described below.
工程(1)については、上記「2.触媒付与方法」の通りである。 The step (1) is as described in "2. Catalyst application method" above.
無電解めっき処理は、工程(1)で得られた触媒核を含む無電解めっき対象材料を、無電解めっき液と接触させることにより行うことができる。 The electroless plating treatment can be performed by bringing the electroless plating target material containing the catalyst nucleus obtained in the step (1) into contact with the electroless plating solution.
無電解めっき液としては特に限定はなく、自己触媒性の無電解めっき液を用いることができる。例えば、無電解パラジウムめっき液、無電解パラジウム合金めっき液、無電解銅めっき液、無電解銅合金めっき液、無電解銀めっき液、無電解銀合金めっき液、無電解ニッケルめっき液、無電解ニッケル合金めっき液、無電解金めっき液、無電解金合金めっき液等を用いることができる。これらの無電解めっき液の具体的な組成については、特に限定はなく、還元剤成分を含む公知の組成の自己触媒性の無電解めっき液を用いればよい。めっき条件についても、使用するめっき液の種類に応じて、通常のめっき条件に従えばよい。 The electroless plating solution is not particularly limited, and an autocatalytic 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. An electroless gold plating solution, an electroless gold alloy 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. As for the plating conditions, normal plating conditions may be followed according to the type of plating solution used.
本発明の方法2の工程(2)では、無電解めっき液として、無電解パラジウムめっき液、無電解パラジウム合金めっき液、無電解ニッケルめっき液、無電解ニッケル合金めっき液等、無電解金めっき液、無電解金合金めっき液を使用することが好ましい。工程(2)で無電解パラジウムめっき液又は無電解パラジウム合金めっき液を使用した場合は、さらに無電解金めっき又は無電解金合金めっきを行うことが好ましい。また、工程(2)で無電解ニッケルめっき液又は無電解ニッケル合金めっき液を使用した場合は、さらに無電解パラジウムめっき又は無電解パラジウム合金めっきを行うことが好ましく、これに続いてさらに無電解金めっき又は無電解金合金めっきを行うことがより好ましい。また工程(2)で無電解ニッケルめっき液又は無電解ニッケル合金めっき液を使用した場合は、これに続いてさらに無電解金めっき又は無電解金合金めっきを行うことも可能である。また工程(2)で無電解金めっき液、無電解金合金めっき液のみを行うことも可能である。 In the step (2) of the method 2 of the present invention, as the electroless plating solution, an electroless gold plating solution such as an electroless palladium plating solution, an electroless palladium alloy plating solution, an electroless nickel plating solution, an electroless nickel alloy plating solution, etc. , It is preferable to use an electroless gold alloy plating solution. When the electroless palladium plating solution or the electroless palladium alloy plating solution is used in the step (2), it is preferable to further perform electroless gold plating or electroless gold alloy plating. When an electroless nickel plating solution or an electroless nickel alloy plating solution is used in the step (2), it is preferable to further perform electroless palladium plating or electroless palladium alloy plating, followed by electroless gold. It is more preferable to perform plating or electroless gold alloy plating. When the electroless nickel plating solution or the electroless nickel alloy plating solution is used in the step (2), it is also possible to further perform electroless gold plating or electroless gold alloy plating. It is also possible to perform only the electroless gold plating solution and the electroless gold alloy plating solution in the step (2).
本発明の方法2により、めっき析出性、選択析出性、バリア特性、接合性等がより優れた無電解めっき皮膜を形成することができる。本発明の方法2により、このような無電解めっき皮膜を供える材料、具体的には、金属が表面に露出している材料、前記金属上の触媒核1、及び前記触媒核1上の皮膜2を含み、且つ前記触媒核1がコバルトを含有し、前記皮膜2が無電解めっき皮膜である、材料、を得ることができる。 According to the method 2 of the present invention, an electroless plating film having more excellent plating precipitation property, selective precipitation property, barrier property, bondability and the like can be formed. According to the method 2 of the present invention, a material provided with such an electroless plating film, specifically, a material in which a metal is exposed on the surface, a catalyst nucleus 1 on the metal, and a film 2 on the catalyst nucleus 1. , And the catalyst nucleus 1 contains cobalt, and the film 2 is an electroless plating film.
以下に、実施例に基づいて本発明を詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.
(1)触媒付与液の調製
以下に示す組成からなる無電解めっき用触媒付与液を調製した。溶媒としては水を使用した。
(1) Preparation of catalyst-imparting liquid A catalyst-imparting liquid for electroless plating having the composition shown below was prepared. Water was used as the solvent.
(1−1)実施例1〜8:Co含有
(実施例1)Co−B
硫酸コバルト・7水和物 5g/L(コバルトとして1g/L)
DL−リンゴ酸 10g/L
ジメチルアミンボラン 3.0g/L
pH 7.5、浴温 70℃。
(1-1) Examples 1-8: Co-containing
(Example 1) Co-B
Cobalt sulfate / heptahydrate 5 g / L (1 g / L as cobalt)
DL-malic acid 10g / L
Dimethylamine borane 3.0 g / L
pH 7.5, bath temperature 70 ° C.
(実施例2)Co−Ni−B
硫酸コバルト・7水和物 5g/L(コバルトとして1g/L)
硫酸ニッケル・6水和物 0.45g/L(ニッケルとして0.1g/L)
DL−リンゴ酸 10g/L
ジメチルアミンボラン 3.0g/L
pH 7.5、浴温 70℃。
(Example 2) Co-Ni-B
Cobalt sulfate / heptahydrate 5 g / L (1 g / L as cobalt)
Nickel sulfate hexahydrate 0.45 g / L (0.1 g / L as nickel)
DL-malic acid 10g / L
Dimethylamine borane 3.0 g / L
pH 7.5, bath temperature 70 ° C.
(実施例3)Co−Pd−B
硫酸コバルト・7水和物 5g/L(コバルトとして1g/L)
塩化パラジウム 0.08g/L(パラジウムとして0.05g/L)
クエン酸 50g/L
ジメチルアミンボラン 1.0g/L
pH 7.5、浴温 70℃。
(Example 3) Co-Pd-B
Cobalt sulfate / heptahydrate 5 g / L (1 g / L as cobalt)
Palladium chloride 0.08 g / L (0.05 g / L as palladium)
Citric acid 50g / L
Dimethylamine borane 1.0 g / L
pH 7.5, bath temperature 70 ° C.
(実施例4)Co−W−B
硫酸コバルト・7水和物 5g/L(コバルトとして1g/L)
タングステン酸ナトリウム・2水和物 1g/L(タングステンとして0.55g/L)
クエン酸 50g/L
ジメチルアミンボラン 1.0g/L
pH 7.5、浴温 70℃。
(Example 4) Co-WB
Cobalt sulfate / heptahydrate 5 g / L (1 g / L as cobalt)
Sodium tungstate / dihydrate 1 g / L (0.55 g / L as tungsten)
Citric acid 50g / L
Dimethylamine borane 1.0 g / L
pH 7.5, bath temperature 70 ° C.
(実施例5)Co−Mo−B
硫酸コバルト・7水和物 20g/L(コバルトとして4g/L)
モリブデン酸2ナトリウム・2水和物 0.5g/L(モリブデンとして0.2g/L)
クエン酸 50g/L
ジメチルアミンボラン 1.0g/L
pH 7.5、浴温 70℃。
(Example 5) Co-Mo-B
Cobalt sulfate heptahydrate 20 g / L (4 g / L as cobalt)
Disodium molybdate / dihydrate 0.5 g / L (0.2 g / L as molybdenum)
Citric acid 50g / L
Dimethylamine borane 1.0 g / L
pH 7.5, bath temperature 70 ° C.
(実施例6)Co−B−P
硫酸コバルト・7水和物 20g/L(コバルトとして4g/L)
クエン酸 50g/L
ジメチルアミンボラン 1.0g/L
次亜リン酸ナトリウム 60g/L
pH 7.5、浴温 70℃。
(Example 6) Co-BP
Cobalt sulfate heptahydrate 20 g / L (4 g / L as cobalt)
Citric acid 50g / L
Dimethylamine borane 1.0 g / L
Sodium hypophosphate 60 g / L
pH 7.5, bath temperature 70 ° C.
(実施例7)Co−B−P
硫酸コバルト・7水和物 20g/L(コバルトとして4g/L)
クエン酸 50g/L
ホウ酸 10g/L
ジメチルアミンボラン 1.0g/L
亜リン酸ナトリウム 20g/L
pH 8.0、浴温 70℃。
(Example 7) Co-BP
Cobalt sulfate heptahydrate 20 g / L (4 g / L as cobalt)
Citric acid 50g / L
Boric acid 10g / L
Dimethylamine borane 1.0 g / L
Sodium phosphite 20 g / L
pH 8.0, bath temperature 70 ° C.
(実施例8)Co−P
硫酸コバルト・7水和物 20g/L(コバルトとして4g/L)
クエン酸 50g/L
ホウ酸 10g/L
ヒドラジン 2.0g/L
次亜リン酸ナトリウム 20g/L
pH 8.0、浴温 70℃。
(Example 8) Co-P
Cobalt sulfate heptahydrate 20 g / L (4 g / L as cobalt)
Citric acid 50g / L
Boric acid 10g / L
Hydrazine 2.0g / L
Sodium hypophosphate 20 g / L
pH 8.0, bath temperature 70 ° C.
(1−2)比較例1〜5:Co非含有
(比較例1)Ni−B
硫酸ニッケル・6水和物 4.5g/L(ニッケルとして1.0g/L)
DL−リンゴ酸 10g/L
ジメチルアミンボラン 5.0g/L
pH 7.5、浴温 60℃。
(1-2) Comparative Examples 1 to 5: Co-free
(Comparative Example 1) Ni-B
Nickel sulfate hexahydrate 4.5 g / L (1.0 g / L as nickel)
DL-malic acid 10g / L
Dimethylamine borane 5.0 g / L
pH 7.5, bath temperature 60 ° C.
(比較例2)Ni−B
硫酸ニッケル・6水和物 0.45g/L(ニッケルとして0.1g/L)
DL−リンゴ酸 10g/L
ジメチルアミンボラン 5.0g/L
pH 7.5、浴温 60℃。
(Comparative Example 2) Ni-B
Nickel sulfate hexahydrate 0.45 g / L (0.1 g / L as nickel)
DL-malic acid 10g / L
Dimethylamine borane 5.0 g / L
pH 7.5, bath temperature 60 ° C.
(比較例3)Ni−B−P
硫酸ニッケル・6水和物 0.45g/L(ニッケルとして0.1g/L)
DL−リンゴ酸 10g/L
ジメチルアミンボラン 5.0g/L
次亜リン酸ナトリウム 10g/L
pH 7.5、浴温 60℃。
(Comparative Example 3) Ni-BP
Nickel sulfate hexahydrate 0.45 g / L (0.1 g / L as nickel)
DL-malic acid 10g / L
Dimethylamine borane 5.0 g / L
Sodium hypophosphate 10 g / L
pH 7.5, bath temperature 60 ° C.
(比較例4)Pd−B
塩化パラジウム 0.83g/L(パラジウムとして0.5g/L)
エチレンジアミン 10g/L
ジメチルアミンボラン 1.0g/L
pH 7.5、浴温 40℃。
(Comparative Example 4) Pd-B
Palladium chloride 0.83 g / L (0.5 g / L as palladium)
Ethylenediamine 10g / L
Dimethylamine borane 1.0 g / L
pH 7.5, bath temperature 40 ° C.
(比較例5)Pd
塩化パラジウム 0.83g/L(パラジウムとして0.5g/L)
エチレンジアミン 10g/L
ヒドラジン 1.0g/L
pH 7.5、浴温 40℃。
(Comparative Example 5) Pd
Palladium chloride 0.83 g / L (0.5 g / L as palladium)
Ethylenediamine 10g / L
Hydrazine 1.0g / L
pH 7.5, bath temperature 40 ° C.
(1−3)比較例6〜7:置換反応によるPd触媒付与処理(従来技術)
(比較例6)
塩化パラジウム 0.17g/L(パラジウムとして0.1g/L)
35%塩酸 100 ml/L
浴温 30℃。
(1-3) Comparative Examples 6 to 7: Pd catalyst addition treatment by substitution reaction (conventional technique)
(Comparative Example 6)
Palladium chloride 0.17 g / L (0.1 g / L as palladium)
35% hydrochloric acid 100 ml / L
Bath temperature 30 ° C.
(比較例7)
硫酸パラジウム 0.19g/L(パラジウムとして0.1g/L)
98%硫酸 20 ml/L
浴温 30℃。
(Comparative Example 7)
Palladium sulfate 0.19 g / L (0.1 g / L as palladium)
98% sulfuric acid 20 ml / L
Bath temperature 30 ° C.
(2)評価試験
以下の評価試験では、無電解めっき対象材料を前処理(酸性脱脂、ソフトエッチング)後に、上記した触媒付与液により金属表面上に触媒核を形成し、次いで無電解パラジウムめっき、無電解金めっきの順に処理した。各処理の詳細は、特に断りのない限り以下の通りである。各工程間に流水水洗1分処理を実施した。
(2) Evaluation test In the following evaluation tests, after pretreatment (acid degreasing, soft etching) of the material to be electroless plated, catalyst nuclei are formed on the metal surface with the above-mentioned catalyst-imparting solution, and then electroless palladium plating is performed. The treatment was performed in the order of electroless gold plating. Details of each process are as follows unless otherwise specified. A 1-minute wash with running water was performed between each step.
(a)酸性脱脂
硫酸および界面活性剤を含有する酸性脱脂液(商標名:ICPクリーンS−135K)に、40℃で5分間浸漬した。
(A) Acid Solvent Degreasing 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)ソフトエッチング
過硫酸ナトリウム100g/L と98%硫酸10 ml/Lを含有する水溶液中に、室温で1分間浸漬した。
(B) Soft etching Immersed in an aqueous solution containing 100 g / L of sodium persulfate and 10 ml / L of 98% sulfuric acid at room temperature for 1 minute.
(c)触媒付与処理
実施例1〜8及び比較例1〜5については、触媒核の厚みが0.01μmとなるよう、触媒付与液中に1〜5分間浸漬した。比較例6および7については1分間浸漬とした。
(C) Catalyst-imparting treatment Examples 1 to 8 and Comparative Examples 1 to 5 were immersed in the catalyst-imparting solution for 1 to 5 minutes so that the thickness of the catalyst nucleus was 0.01 μm. Comparative Examples 6 and 7 were immersed for 1 minute.
(d)無電解パラジウムめっき
無電解パラジウムめっき液(商標名:トップパラスPD、奥野製薬工業(製))中に、65℃で5分間浸漬して、膜厚約0.1μmのめっき皮膜を得た。
(D) Electroless Palladium Plating Immerse in electroless palladium plating solution (trade name: Top Pallas PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 65 ° C. for 5 minutes to obtain a plating film with a film thickness of about 0.1 μm. It was.
(e)無電解金めっき
無電解金めっき(商標名:トップパラスAU、奥野製薬工業(製))中に、80℃で10分間浸漬した。膜厚約0.05μmのめっき皮膜を得た。
(E) Electroless gold plating Electroless gold plating (trade name: Top Pallas AU, Okuno Pharmaceutical Co., Ltd.) was immersed at 80 ° C. for 10 minutes. A plating film having a film thickness of about 0.05 μm was obtained.
(2−1)触媒核の組成測定
無電解めっき対象材料として銅張エポキシ基板を使用し、酸性脱脂、ソフトエッチング、触媒付与処理を実施した後、エネルギー分散型X線分析装置(EDX,HORIBA製EMAX X−act)による測定、もしくは高周波誘導結合プラズマ(ICP)発光分光分析装置(日立ハイテクサイエンス製PS3500DDII)を使用した溶解法により組成を同定した。
(2-1) Measurement of composition of catalyst nucleus Using a copper-clad epoxy substrate as the target material for electroless plating, after performing acid degreasing, soft etching, and catalyst application treatment, an energy dispersive X-ray analyzer (EDX, manufactured by HORIBA) The composition was identified by measurement by EMAX X-act) or by a dissolution method using a high frequency inductively coupled plasma (ICP) emission spectroscopic analyzer (PS3500DDII manufactured by Hitachi High-Tech Science).
(2−2)めっき析出性の評価
無電解めっき対象材料として、樹脂基材上に、オーバーレジストタイプの微小銅パッド(直径0.2mm、パッド数30個)を有するBGA(Ball Grid Array)樹脂基板を用いた。無電解めっき対象材料を、酸性脱脂、ソフトエッチング、触媒付与処理、無電解パラジウムめっき、無電解金めっきの順に処理した。各パッドにおけるめっき析出の有無をマイクロスコープ(KEYENCE製VHX−1000)により判定し、以下の評価基準に従って評価した。
(2-2) Evaluation of Plating Precipitability A BGA (Ball Grid Array) resin having an overresist type micro copper pad (diameter 0.2 mm, number of pads: 30) on a resin substrate as an electroless plating target material. A substrate was used. The material to be electroless plated was treated in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. The presence or absence of plating precipitation on each pad was determined by a microscope (VHX-1000 manufactured by KEYENCE), and evaluated according to the following evaluation criteria.
<めっき析出性の評価基準>
〇:全パッド正常に析出。
×:めっき未析出のパッド有。
<Evaluation criteria for plating precipitation>
〇: All pads are deposited normally.
X: There is a pad that has not been plated.
(2−3)選択析出性の評価
無電解めっき対象材料として、SAP法にて作製した配線幅/配線間隔(L/S)=20/20μmの銅配線パターンを有する樹脂基板を用いた。無電解めっき対象材料を、酸性脱脂、ソフトエッチング、触媒付与処理、無電解パラジウムめっき、無電解金めっきの順に処理した。配線パターン間(樹脂部)へのめっき析出の有無を走査型電子顕微鏡(SEM,日立ハイテクノロジーズ製S−3400N)により判定し、以下の評価基準に従って評価した。
(2-3) Evaluation of Selective Precipitation As the material to be electroless plated, a resin substrate having a copper wiring pattern of wiring width / wiring interval (L / S) = 20/20 μm produced by the SAP method was used. The material to be electroless plated was treated in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. 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-Technologies Corporation), and evaluated according to the following evaluation criteria.
<選択析出性の評価基準>
〇:配線パターン間へのめっき析出なし。
△:配線パターン間へわずかにめっき析出。
×:配線パターン間に全面析出。
<Evaluation criteria for selective precipitation>
〇: No plating precipitation between wiring patterns.
Δ: Slight plating deposits between the wiring patterns.
X: The entire surface is deposited between the wiring patterns.
(2−4)浴安定性の評価
めっき析出性の評価で使用後の触媒付与液を、触媒付与処理の浴温+5℃に加温して、72時間放置した。浴分解の有無を目視により判定し、以下の評価基準に従って評価した。
(2-4) Evaluation of Bath Stability In the evaluation of plating precipitation property, the catalyst-imparting liquid after use was heated to the bath temperature of the catalyst-impartment treatment + 5 ° C. and left for 72 hours. The presence or absence of bath decomposition was visually determined and evaluated according to the following evaluation criteria.
<浴安定性の評価基準>
〇:浴分解せず。
×:浴分解。
<Evaluation criteria for bath stability>
〇: No bath decomposition.
×: Bath decomposition.
(2−5)空隙(ボイド)の確認
無電解めっき対象材料として、樹脂基材上に、オーバーレジストタイプの銅パッドを有するBGA(Ball Grid Array)樹脂基板を用いた。無電解めっき対象材料を、酸性脱脂、ソフトエッチング、触媒付与処理、無電解パラジウムめっき、無電解金めっきの順に処理した。続いて、集束イオンビーム加工観察装置を用いて断面加工し,走査イオン顕微鏡によりボイドの有無を観察した(FIB/SIM,日立ハイテクノロジーズ製FB2200)。
〈ボイドの評価基準〉
〇:ボイドなし。
×:ボイドあり。
(2-5) Confirmation of voids As a material to be electroless plated, a BGA (Ball Grid Array) resin substrate having an overresist type copper pad was used on a resin base material. The material to be electroless plated was treated in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. Subsequently, the cross section was processed 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 Corporation).
<Void evaluation criteria>
〇: No void.
×: There is a void.
(2−6)バリア特性の評価
無電解めっき対象材料として、樹脂基材上に、オーバーレジストタイプの銅パッドを有するBGA(Ball Grid Array)樹脂基板を用いた。無電解めっき対象材料を、酸性脱脂、ソフトエッチング、触媒付与処理、無電解パラジウムめっき、無電解金めっきの順に処理した。続いて、処理基板を熱処理175℃、16 hした後、Auめっき表面の元素組成を X線光電子分光分析装置(アルバック・ファイ株式会社、PHI5000VersaProbe III)で測定した。Au皮膜表面における下地金属(Cu、Co、Ni、Pd)検出の有無に基づいて、以下の評価基準に従って評価した。
(2-6) Evaluation of Barrier Characteristics A BGA (Ball Grid Array) resin substrate having an overresist type copper pad was used as a material to be electroless plated. The material to be electroless plated was treated in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. Subsequently, the treated substrate was heat-treated at 175 ° C. for 16 hours, and then the elemental composition of the Au-plated surface was measured with an X-ray photoelectron spectroscopy analyzer (Albac Phi Co., Ltd., PHI5000 VersaProbe III). The evaluation was made according to the following evaluation criteria based on the presence or absence of detection of the base metal (Cu, Co, Ni, Pd) on the surface of the Au film.
<バリア特性の評価基準>
〇:Au皮膜表面にて下地金属(Cu、Co、Ni、Pd)が検出されず。
×:Au皮膜表面にて下地金属(Cu、Co、Ni、Pd)が検出。
<Evaluation criteria for barrier characteristics>
〇: Underlayer metal (Cu, Co, Ni, Pd) was not detected on the surface of the Au film.
X: Underlayer metal (Cu, Co, Ni, Pd) is detected on the surface of Au film.
(2−7)接合性の評価
無電解めっき対象材料として、樹脂基材上に、オーバーレジストタイプの微小銅パッド(直径0.6mm、パッド数20個)を有するBGA樹脂基板を用いた。無電解めっき対象材料を、酸性脱脂、ソフトエッチング、触媒付与処理、無電解パラジウムめっき、無電解金めっきの順に処理した。その後、Sn−3Ag−0.5Cuのはんだボール(φ0.76mm)を搭載し、リフロー装置にて加熱(ピーク温度250℃)した後、はんだボールプル試験装置(Dage社製#4000)を用いてプル速度5000μm/秒にてはんだボールプル試験を行った。はんだ内部で破断が生じるもしくは基材が破壊されるモードを良好、はんだボールとめっき皮膜の接合界面で破壊されるモードを不良と判断し、以下の評価基準に従って評価した。
(2-7) Evaluation of Bondability As a material to be electroless plated, a BGA resin substrate having an overresist type micro copper pad (diameter 0.6 mm, number of pads 20) was used on a resin base material. The material to be electroless plated was treated in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. After that, a solder ball (φ0.76 mm) of Sn-3Ag-0.5Cu was mounted, heated by a reflow device (peak temperature 250 ° C.), and then pulled using a solder ball pull test device (# 4000 manufactured by Dage). A solder ball pull test was performed at a speed of 5000 μm / sec. The mode in which breakage occurred inside the solder or the base material was broken was judged to be good, and the mode in which the base material was broken at the bonding interface between the solder ball and the plating film was judged to be defective, and evaluated according to the following evaluation criteria.
<接合性の評価基準>
〇:良好モード50%以上。
△:良好モード0%超50%未満。
×:すべて不良モード(良好モード0%)。
<Evaluation criteria for bondability>
〇: Good mode 50% or more.
Δ: Good mode more than 0% and less than 50%.
X: All in bad mode (good mode 0%).
(3)結果
結果を表1に示す。
(3) Results The results are shown in Table 1.
Claims (13)
無電解パラジウムめっき、無電解ニッケルめっき、及び無電解金めっきからなる群より選択される少なくとも1種の無電解めっき(但し、触媒金属として銀を使用する無電解めっきを除く)に用いるための触媒付与液。 Contains cobalt compounds and reducing agents,
Electroless palladium plating, electroless nickel plating, and at least one of the electroless plating is selected from the group consisting of electroless gold plating (excluding electroless plating using silver as catalyst metal) to have use in Catalyzing solution.
前記無電解めっきが、銅及び/又は銅合金が表面に露出している材料に対する無電解めっきである、
請求項1〜9のいずれかに記載の触媒付与液。 Wherein the reducing agent comprises at least one member selected from the group consisting of boron-containing compounds and phosphorus-containing compounds, and the electroless plating, against the material copper and / or copper alloy is exposed to the surface no Electroless plating,
Catalysts applied solution according to any one of claims 1 to 9.
(2)工程(1)後に、無電解めっき処理する工程
を含む、無電解めっき皮膜を含む材料を製造する方法。 Comprising (1) and electroless plating subject material, the step of contacting the catalytic applying solution according to any one of claims 1 to 10, and (2) after the step (1), the electroless plating process to step, A method of manufacturing a material containing an electroless plating film.
前記触媒核1がコバルトを含有し、
前記皮膜2が無電解パラジウムめっき皮膜、無電解ニッケルめっき皮膜、及び無電解金めっき皮膜からなる群より選択される少なくとも1種の無電解めっき皮膜である、材料。 A material whose surface is exposed to a metal, a catalyst nucleus 1 on the metal (excluding a catalyst nucleus containing silver as a catalyst metal) , and a film 2 on the catalyst nucleus 1 and the catalyst nucleus 1 Contains cobalt,
A material in which the film 2 is at least one electroless plating film selected from the group consisting of an electroless palladium plating film, an electroless nickel plating film, and an electroless gold plating film.
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JP2020115474A JP6841462B1 (en) | 2020-07-03 | 2020-07-03 | Catalyst-imparting liquid for electroless plating |
CN202180046353.3A CN115735022A (en) | 2020-07-03 | 2021-06-16 | Catalyst imparting liquid for electroless plating |
KR1020227043461A KR20230005394A (en) | 2020-07-03 | 2021-06-16 | Catalyst-applied liquid for electroless plating |
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 |
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JP3826544B2 (en) * | 1998-02-27 | 2006-09-27 | 奥野製薬工業株式会社 | Catalyst composition for electroless plating |
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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 |
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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 |
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