TWI843003B - 無電解鍍敷用觸媒賦予液 - Google Patents
無電解鍍敷用觸媒賦予液 Download PDFInfo
- Publication number
- TWI843003B TWI843003B TW110123581A TW110123581A TWI843003B TW I843003 B TWI843003 B TW I843003B TW 110123581 A TW110123581 A TW 110123581A TW 110123581 A TW110123581 A TW 110123581A TW I843003 B TWI843003 B TW I843003B
- Authority
- TW
- Taiwan
- Prior art keywords
- electroless
- plating
- catalyst
- electroless plating
- cobalt
- Prior art date
Links
- 238000007772 electroless plating Methods 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims description 67
- 239000007788 liquid Substances 0.000 title description 25
- 238000007747 plating Methods 0.000 claims abstract description 101
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 31
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 53
- -1 amine compound Chemical class 0.000 claims description 36
- 229910052763 palladium Inorganic materials 0.000 claims description 35
- 239000010931 gold Substances 0.000 claims description 33
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 29
- 229910052737 gold Inorganic materials 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 239000013077 target material Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 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
- 239000000463 material Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 12
- 239000000203 mixture 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
- 150000003839 salts Chemical class 0.000 claims description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 229910000085 borane Inorganic materials 0.000 claims description 7
- 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
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 238000001556 precipitation Methods 0.000 abstract description 22
- 230000004888 barrier function Effects 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 8
- 239000007769 metal material Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 64
- 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 23
- 230000000694 effects Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- 229940044175 cobalt sulfate Drugs 0.000 description 11
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 11
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 159000000000 sodium salts Chemical class 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000005238 degreasing Methods 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 150000003863 ammonium salts Chemical class 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 159000000001 potassium salts Chemical class 0.000 description 9
- 229910000679 solder Inorganic materials 0.000 description 9
- 229910001020 Au alloy Inorganic materials 0.000 description 8
- 239000003353 gold alloy Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 229910001252 Pd alloy Inorganic materials 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 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
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NHYSHMZGBQMTLC-UHFFFAOYSA-N [amino(methyl)boranyl]methane Chemical compound CB(C)N NHYSHMZGBQMTLC-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
- 238000002149 energy-dispersive X-ray emission spectroscopy 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
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000006174 pH buffer Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000002585 base Substances 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
- 235000015165 citric acid Nutrition 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
- 230000008021 deposition Effects 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
- 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
- 150000002739 metals Chemical class 0.000 description 2
- 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 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000009864 tensile test Methods 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
- 238000012360 testing method Methods 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
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020674 Co—B Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- 229910017262 Mo—B Inorganic materials 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- CJXQLDHMQRJPJJ-UHFFFAOYSA-L N.[Co](Cl)Cl Chemical compound N.[Co](Cl)Cl CJXQLDHMQRJPJJ-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- RSBNPUNXBGVNNB-UHFFFAOYSA-M S(=O)(=O)([O-])[O-].[NH4+].[Co+] Chemical compound S(=O)(=O)([O-])[O-].[NH4+].[Co+] RSBNPUNXBGVNNB-UHFFFAOYSA-M 0.000 description 1
- YWNYNHHYXJOUIH-UHFFFAOYSA-N [amino(ethyl)boranyl]ethane Chemical compound CCB(N)CC YWNYNHHYXJOUIH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 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
- 238000012790 confirmation 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
- 238000009792 diffusion process Methods 0.000 description 1
- GMLFPSKPTROTFV-UHFFFAOYSA-N dimethylborane Chemical compound CBC GMLFPSKPTROTFV-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000004744 fabric Substances 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
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 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
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- 229940046892 lead acetate Drugs 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
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- BORTXUKGEOWSPS-UHFFFAOYSA-N n-dimethylboranylmethanamine Chemical compound CNB(C)C BORTXUKGEOWSPS-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
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- 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
- 239000002736 nonionic surfactant Substances 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
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- JIPRFNBGGBDGIY-UHFFFAOYSA-L potassium;cobalt(2+);sulfate Chemical compound [K+].[Co+2].[O-]S([O-])(=O)=O JIPRFNBGGBDGIY-UHFFFAOYSA-L 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 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
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 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
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
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- 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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- 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
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- 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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- 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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- 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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- 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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- 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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Abstract
提供一種觸媒賦予液，該觸媒賦予液為在金屬材料上進行無電解鍍敷時之前處理中所使用的觸媒賦予液，其有助於用以形成鍍敷析出性、選擇析出性、障壁特性、接合性等更加優異之無電解鍍敷皮膜，且該觸媒賦予液之浴安定性更加優異。無電解鍍敷用觸媒賦予液含有鈷化合物及還原劑。
Description
本發明係關於無電解鍍敷用觸媒賦予液等。
在印刷配線板、半導體封裝體、電子零件等電子相關領域中，製造時之最後步驟之一，有一於導體電路、端子部分等施予無電解鎳鍍敷並進一步進行無電解金鍍敷之處理。以此方法形成之無電解鎳/金鍍敷皮膜係為了下述目的使用：防止銅電路表面的氧化而使其發揮良好的焊料連接性能、提升半導體封裝體與安裝於其上的電子零件之焊線接合性等。在形成無電解鎳鍍敷皮膜後，要形成取代金鍍敷皮膜時會有下述問題點，即：依據基底的鎳鍍敷皮膜的狀態，鎳局部地溶解而發生鎳的腐蝕、即黑墊(Black pad)；因熱處理所致之基底金屬擴散，Au表面被污染等。作為解決如此之問題點的手段，增加了一種在無電解鎳鍍敷與金鍍敷之間進行無電解鈀鍍敷以作為障壁皮膜的無電解鎳/鈀/金鍍敷處理。進一步地，為了對應伴隨著印刷配線板高密度化而起的銅配線細微化，已開發了省略膜厚最大之無電解鎳鍍敷皮膜之無電解鈀/金鍍敷處理(參照下述專利文獻1)。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開平5-327187號公報
發明概要
[發明所欲解決之課題]
於基板的金屬材料上進行無電解鍍敷時，以提升鍍敷析出性等為目的，有進行一藉由取代反應使會成為觸媒核之鈀金屬析出於金屬材料上之觸媒賦予處理。本發明人在研究進行之中發現，進行此觸媒賦予處理時，雖然鍍敷析出性良好，但於障壁特性及接合性上則並不充分。針對其原因進行調查之過程中發現，在進行上述觸媒賦予處理時，會有發生金屬材料過度溶解的情況，若在其後進行無電解鍍敷(鎳、鈀等)處理，則在析出之鍍敷皮膜與金屬材料之間，會處處產生微小的空隙(void)。
因此，本發明人嘗試了不藉由取代反應，而是藉由還原反應使鈀金屬析出之觸媒賦予處理。但是，於鍍敷析出性、選擇析出性、浴安定性、障壁特性、接合性等特性中有數者並不充分。
於是，本發明係以提供下述觸媒賦予液為課題，該觸媒賦予液為在金屬材料上進行無電解鍍敷時之前處理中所使用的觸媒賦予液，其有助於用以形成鍍敷析出性、選擇析出性、障壁特性、接合性等更加優異之無電解鍍敷皮膜，且該觸媒賦予液之浴安定性更加優異。
[用以解決課題之手段]
本發明人鑑於上述課題進行精闢研討之結果，發現了若為含有鈷化合物及還原劑之無電解鍍敷用觸媒賦予液，可以解決上述課題。本發明人基於此見解進一步進行研究之結果，完成了本發明。即，本發明包含下述態樣。
項1.一種無電解鍍敷用觸媒賦予液，含有鈷化合物及還原劑。
項2.如項1之無電解鍍敷用觸媒賦予液，其中前述還原劑包含胺化合物。
項3.如項2之無電解鍍敷用觸媒賦予液，其中前述胺化合物包含選自於由硼烷胺、聯胺、及聯胺衍生物所構成群組中之至少1種。
項4.如項1至3中任一項之無電解鍍敷用觸媒賦予液，其含有錯合劑。
項5.如項4之無電解鍍敷用觸媒賦予液，其中前述錯合劑包含羧酸。
項6.如項5之無電解鍍敷用觸媒賦予液，其中前述羧酸包含羥基羧酸或二羧酸。
項7.如項1至6中任一項之無電解鍍敷用觸媒賦予液，其中前述還原劑包含選自於由含硼化合物及含磷化合物所構成群組中之至少1種。
項8.如請求項1至7中任一項之無電解鍍敷用觸媒賦予液，其更含有金屬鹽。
項9.如項1至8中任一項之無電解鍍敷用觸媒賦予液，其中鈷含量相對於金屬100質量%為50質量%以上。
項10.如項1至9中任一項之無電解鍍敷用觸媒賦予液，其中前述還原劑包含選自於由含硼化合物及含磷化合物所構成群組中之至少1種，且前述無電解鍍敷係針對表面露出銅及/或銅合金之材料者，並為選自於由無電解鈀鍍敷、無電解鎳鍍敷、及無電解金鍍敷所構成群組中之至少1種無電解鍍敷。
項11.一種製造包含觸媒核之無電解鍍敷對象材料之方法，包含以下步驟：(1)使無電解鍍敷對象材料與如項1至10中任一項之無電解鍍敷用觸媒賦予液接觸之步驟。
項12.一種製造包含無電解鍍敷皮膜之材料之方法，包含以下步驟：(1)使無電解鍍敷對象材料與如項1至10中任一項之無電解鍍敷用觸媒賦予液接觸之步驟；及(2)於步驟(1)後，進行無電解鍍敷處理之步驟。
項13.一種材料，包含：表面露出金屬之材料、前述金屬上之觸媒核1、及前述觸媒核1上之皮膜2，且前述觸媒核1含有鈷，前述皮膜2為無電解鍍敷皮膜。
[發明效果]
根據本發明，可以提供一種觸媒賦予液，該觸媒賦予液為在金屬材料上進行無電解鍍敷時之前處理中所使用的觸媒賦予液，其有助於用以形成鍍敷析出性、選擇析出性、障壁特性、接合性等更加優異之無電解鍍敷皮膜，且該觸媒賦予液之浴安定性更加優異。
用以實施發明之形態
在本說明書中，關於所稱「含有」及「包含」之表現，其等包括：「含有」、「包含」、「實質上由…構成」及「僅由…構成」之概念。
1.觸媒賦予液
本發明其中一態樣，係關於含有鈷化合物及還原劑之無電解鍍敷用觸媒賦予液(本說明書中，亦有表示為「本發明之觸媒賦予液」)。以下對此進行說明。
鈷化合物只要是對鍍敷液為可溶性者，則無特別限制。作為鈷化合物，可舉例如有機或無機之鈷鹽，更具體而言，例如可列舉：硫酸鈷、氯化鈷、硝酸鈷、溴化鈷、碘化鈷、次磷酸鈷、磷酸鈷、硫酸鈷銨、氯化鈷銨、硫酸鈷鉀、胺磺酸鈷、醋酸鈷、碳酸鈷、乙醯丙酮鈷、蟻酸鈷、草酸鈷、硬脂酸鈷、檸檬酸鈷、酒石酸鈷、乳酸鈷等。於此等中，由本發明之效果的觀點來看，又宜舉出無機鈷鹽，較佳可列舉硫酸鈷、氯化鈷、硝酸鈷、磷酸鈷、次磷酸鈷等，更佳可列舉硫酸鈷、氯化鈷。
鈷化合物可單獨使用1種或組合2種以上使用。
本發明之觸媒賦予液中之鈷濃度，例如為0.05g/L以上。由本發明之效果的觀點來看，該鈷濃度宜為0.05~50g/L，較佳為0.1~30g/L，更佳為0.2~20g/L，又更佳為0.4~15g/L，尤宜為0.6~10g/L，且0.7~6g/L特佳。
本發明之觸媒賦予液中之鈷含量，相對於包含鈷之過渡金屬元素之含量100質量%，例如為50質量%以上，宜為60質量%，較佳為70質量%，抑或為80質量%以上，或為90質量%以上。
作為還原劑，只要為可使鈷金屬析出之還原劑則無特別限制，可以使用可被用於還原鍍敷之還原劑。作為還原劑，例如可列舉胺化合物、含硼化合物、含磷化合物等。還原劑亦存在屬於其中數種者。例如，亦存在既為胺化合物且為含硼化合物之還原劑。該情況下，若含有該還原劑，可以說是含有胺化合物，且亦可說含是有含硼化合物。
作為胺化合物，例如可列舉硼烷胺、聯胺、聯胺衍生物等。
硼烷胺為硼烷(例如BH
3)與胺之錯合物、即硼烷胺錯合物。作為構成硼烷胺之胺，為鏈狀胺(非環狀胺)、環狀胺之任一者皆可，但宜為鏈狀胺，而鏈狀胺之中，較佳可舉出通式(1)所示之鏈狀胺：
[化學式1]
[式中，R
1、R
2及R
3為相同或相異，表示氫原子或烷基]。
烷基包含直鏈狀、支鏈狀、及環狀中之任一者。烷基宜為直鏈狀或支鏈狀，較佳為直鏈狀。該烷基之碳數無特別限制，例如為1~8，宜為1~6，較佳為1~4，更佳為1~2，又更佳為1。作為該烷基之具體例，可列舉：甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、tert-丁基、sec-丁基、n-戊基、新戊基、n-己基，3-甲基戊基、環己基等。
在本發明之較佳一態樣，R
1、R
2及R
3之中，任2個或全部(較佳為2個)為烷基，其餘為氫原子。
作為構成硼烷錯合物之胺的具體例，可列舉：二甲基胺、二乙基胺、三甲基胺、三乙基胺、甲氧基乙基胺、二環己基胺、t-丁基胺、胺吡啶、乙二胺、嗎福林、吡啶、哌啶、咪唑等。此等之中，又宜舉出二甲基胺、二乙基胺、三甲基胺、甲氧基乙基胺、二環己基胺等，較佳可舉出二甲基胺等。
作為硼烷胺之適宜具體例，可列舉二甲基硼烷胺、二乙基硼烷胺、三甲基硼烷胺等。
作為聯胺衍生物，只要為可作為無電解鍍敷之還原劑使用者，則無特別限制。
作為含硼化合物，可舉例如氫化硼化合物，更具體而言，可舉例如：亦為胺化合物之上述硼烷胺、硼烷胺以外之硼烷錯合物(硼烷與其他化合物之錯合物)、氫化硼鹼金屬鹽(例如鈉鹽等)。
作為含磷化合物，例如可列舉：次磷酸、次磷酸鹽(例如鈉鹽、鉀鹽、銨鹽等)、亞磷酸、亞磷酸鹽(例如鈉鹽、鉀鹽、銨鹽等)、其等之水合物等。
還原劑由本發明之效果的觀點來看，宜包含胺化合物。又，此情況下，胺化合物較佳為包含選自於由硼烷胺、聯胺、及聯胺衍生物所構成群組中之至少1種，更佳為包含選自於由硼烷胺及聯胺所構成群組中之至少1種，又更佳為包含硼烷胺。又，還原劑包含胺化合物時，還原劑較佳為更包含含磷化合物。
還原劑由本發明之效果的觀點來看，宜包含選自於由含硼化合物及含磷化合物所構成群組中之至少1種。
還原劑可單獨使用1種或組合2種以上使用。
本發明之觸媒賦予液中之還原劑的濃度，例如為0.05g/L以上。由本發明之效果的觀點來看，該濃度宜為0.05~100g/L，較佳為0.2~50g/L，更佳為0.5~30g/L。還原劑包含胺化合物時，本發明之觸媒賦予液中之該胺化合物的濃度，由本發明之效果的觀點來看，宜為0.05~25g/L，較佳為0.1~20g/L，更佳為0.2~15g/L，又更佳為0.4~10g/L，尤宜為0.6~8g/L。還原劑包含含磷化合物時，本發明之觸媒賦予液中之該含磷化合物的濃度，由本發明之效果的觀點來看，宜為1~200g/L，較佳為5~150g/L，更佳為10~100g/L，又更佳為20~80g/L。
本發明之觸媒賦予液，由本發明之效果的觀點來看，宜更含有錯合劑。
作為錯合劑並無特別限制，可使用可用於無電解鍍敷(特別是還原鍍敷)之錯合劑。作為錯合劑，例如可列舉：醋酸、蟻酸等單羧酸及此等之銨鹽、鉀鹽、鈉鹽等；丙二酸、琥珀酸、己二酸、馬來酸、延胡索酸酸等二羧酸及此等之銨鹽、鉀鹽、鈉鹽等；蘋果酸、乳酸、乙醇酸、葡萄糖酸、檸檬酸、酒石酸等羥基羧酸及此等之銨鹽、鉀鹽、鈉鹽等；乙二胺二醋酸、1-羥基亞乙基-1,1-二膦酸及此等之銨鹽、鉀鹽、鈉鹽等；乙二胺四醋酸、二伸乙基三胺五醋酸等胺基多元羧酸及其等之鈉鹽、鉀鹽、銨鹽等；焦磷酸等膦酸類及其等之鈉鹽、鉀鹽、銨鹽等；甘胺酸、麩胺酸等胺基酸類等。
錯合劑由本發明之效果的觀點來看，宜包含羧酸。此情況下，羧酸由本發明之效果的觀點來看，較佳為包含羥基羧酸、二羧酸。於羥基羧酸、二羧酸之中，更佳又可舉出蘋果酸、檸檬酸、酒石酸、乳酸、己二酸、琥珀酸、丙二酸、葡萄糖酸等，又更佳可舉出蘋果酸、檸檬酸、酒石酸等。
錯合劑可單獨使用1種或組合2種以上使用。
本發明之觸媒賦予液含有錯合劑時，本發明之觸媒賦予液中之錯合劑的濃度，例如為0.5g/L以上。該鈷濃度由本發明之效果的觀點來看，宜為1~200g/L，較佳為2~150g/L，更佳為4~120g/L，又更佳為6~100g/L，尤宜為7~70g/L。
本發明之觸媒賦予液，由本發明之效果的觀點來看，宜更含有金屬鹽。
作為金屬鹽，雖無特別限制，但可舉例如包含鈷以外之過渡金屬元素之鹽。作為過渡金屬元素，例如可列舉：金、鈀、鎳、鎢、鉬、錸等金屬元素。作為金屬鹽，更具體而言，例如可列舉：硫酸鎳、氯化鎳、硫酸鈀、氯化鈀、鎢酸鈉、鉬酸2鈉、氰化金鉀、亞硫酸金鈉、過錸酸銨等。
金屬鹽可單獨使用1種或組合2種以上使用。
本發明之觸媒賦予液含有金屬鹽時，該金屬鹽所含金屬於本發明之觸媒賦予液中之濃度，例如為0.005g/L以上。由本發明之效果的觀點來看，該濃度宜為0.005~5g/L，較佳為0.01~3g/L，更佳為0.02~2g/L，又更佳為0.03~1g/L。該濃度例如為本發明之觸媒賦予液中之鈷濃度的0.8/1以下，宜為0.6/1以下，抑或為0.5/1以下、0.3/1以下、0.2/1以下、0.15/1以下。
本發明之觸媒賦予液在溶劑方面主要含有水。也含有水以外之溶劑時，其含量相對於包含水之溶劑100質量%，例如為10質量%以下、5質量%以下、1質量%、0.1質量%以下。
本發明之觸媒賦予液可因應其他需求摻合各種添加劑。作為添加劑，例如可列舉安定劑、pH緩衝劑、界面活性劑等。
作為安定劑，可取下列1種單獨添加，或取下列2種以上混合添加，例如：硝酸鉛、醋酸鉛等鉛鹽；硝酸鉍、醋酸鉍等鉍鹽；硫代硫酸鈉等硫化合物等。添加安定劑時，其添加量雖無特別限定，但例如可設為0.01~100mg/L左右。
作為pH緩衝劑，可取下列1種單獨添加，或取下列2種以上混合添加，例如：醋酸、硼酸、磷酸、亞磷酸、碳酸及其等之鈉鹽、鉀鹽、銨鹽等。添加pH緩衝劑時，其添加量雖無特別限定，但由浴安定性等之觀來看，可設為0.002~1mol/L左右。
作為界面活性劑，例如可使用非離子性、陰離子性、陽離子性、兩性等各種界面活性劑。例如可列舉：芳香族或脂肪族磺酸鹼鹽、芳香族或脂肪族羧酸鹼金屬鹽等。界面活性劑可單獨使用一種或混合二種以上使用。添加界面活性劑時，其添加量雖無特別限定，但例如可設為0.01~1000mg/L左右。
本發明之無電解鍍敷液之pH通常設為2~12左右即可，宜為6~10左右，較佳為6.5~9左右，更佳為6.9(或7.0)~8.5左右。
2.觸媒賦予方法
本發明之其中一態樣，係關於製造包含觸媒核之無電解鍍敷對象材料的方法，或是對無電解鍍敷對象材料進行觸媒賦予處理的方法(本說明書中，亦有表示為「本發明之方法1」)，前述方法包含下述步驟：(1)使無電解鍍敷對象材料與本發明之觸媒賦予液接觸之步驟。以下，對此進行說明。
無電解鍍敷對象材料只要為表面露出金屬之材料，則無特別限制。例如，作為素材為下述材質之1種或組合下述材質而成者：玻璃纖維強化環氧、聚醯亞胺、PET等塑膠類；玻璃、陶瓷、金屬氧化物、金屬、紙、合成或天然纖維等；其形狀可為板、薄膜、布狀、纖維狀、管等之任一者。作為於表面露出之金屬，例如可列舉：銅、銅合金、銀、銀合金、金、金合金、白金、白金合金、鉬、鎢等。其等之中，作為銅合金、銀合金、金合金及白金合金，例如各自可針對包含50重量%以上之銅、銀、金或白金之合金來應用。作為無電解鍍敷對象材料，具體而言，例如可列舉印刷配線板、半導體封裝體、電子零件、陶瓷基板等。此等材料中，於表面露出之金屬可構成配線。
無電解鍍敷對象材料宜為已施以脫脂處理、軟蝕刻(soft etching)處理等前處理者。
針對用以使本發明之觸媒賦予液與無電解鍍敷對象材料接觸之具體方法，雖無特別限定，但通常將被處理物浸漬於本發明之觸媒賦予液中即可。此外也可藉由於無電解鍍敷對象材料之表面噴霧該觸媒賦予液之方法等來進行觸媒賦予處理。
藉由浸漬法來進行本發明之觸媒賦予液時，本發明之觸媒賦予液的液溫，通常宜設為10~90℃左右，較佳設為40~80℃左右，更佳設為60~80℃。
關於處理時間，宜設為30秒~20分左右，較佳設為1分~5分左右。
藉由本發明之方法1，於無電解鍍敷對象材料之表面金屬上會形成包含鈷之觸媒核。觸媒核具有與本發明之無電解鍍敷液中之成分相應的組成。例如，本發明之觸媒賦予液中之還原劑包含含硼化合物及/或含磷化合物時，觸媒核包含Co以及B及/或P。又，本發明之觸媒賦予液包含含金屬元素之化合物時，觸媒核包含Co及該金屬。
觸媒核中之Co含量，例如為50質量%以上，宜為60質量%以上，較佳為70質量%，抑或為80質量%以上或90質量%以上。
觸媒核包含B時，其含量例如為2質量%以下，宜為1質量%以下，較佳為0.5質量%以下，更佳為0.2質量%以下。該含量之下限，例如為0.01質量%、0.05質量%、或0.07質量%。
觸媒核包含P時，其含量例如為0.5~20質量%，宜為1.5~15質量%，較佳為3~10質量%。
觸媒核中各元素之含量係藉由能量分散型X射線分析裝置(EDX,HORIBA製EMAX X-act) 來測定，抑或是藉由使用高頻感應耦合電漿(ICP)發光分光分析裝置(日立High tech science製PS3500DDII)之溶解法來鑑定。
藉由將包含該觸媒核之無電解鍍敷對象材料進行無電解鍍敷處理，可形成鍍敷析出性、選擇析出性、障壁特性、接合性等更加優異之無電解鍍敷皮膜。因觸媒核係為了表面活化之目的，故其厚度例如可為0.05μm以下，且為0.005~0.05μm。
3.無電解鍍敷方法
本發明之其中一態樣，係關於製造包含無電解鍍敷皮膜之材料的方法，或是對無電解鍍敷對象材料進行無電解鍍敷的方法(本說明書中，亦有表示為「本發明之方法2」)，前述方法包含下述步驟：(1)使無電解鍍敷對象材料與本發明之觸媒賦予液接觸之步驟；及(2)於步驟(1)後，進行無電解鍍敷處理之步驟。以下，對此進行說明。
關於步驟(1)，如上述「2.觸媒賦予方法」所述。
無電解鍍敷處理可藉由使於步驟(1)所得之包含觸媒核之無電解鍍敷對象材料與無電解鍍敷液接觸來進行。
作為無電解鍍敷液並無特別限定，可使用自觸媒性之無電解鍍敷液。例如可使用：無電解鈀鍍敷液、無電解鈀合金鍍敷液、無電解銅鍍敷液、無電解銅合金鍍敷液、無電解銀鍍敷液、無電解銀合金鍍敷液、無電解鎳鍍敷液、無電解鎳合金鍍敷液、無電解金鍍敷液、無電解金合金鍍敷液等。針對此等無電解鍍敷液之具體組成並無特別限定，使用包含還原劑成分之公知組成的自觸媒性無電解鍍敷液即可。針對鍍敷條件亦是因應所使用之鍍敷液的種類，遵從通常之鍍敷條件即可。
於本發明之方法2之步驟(2)，作為無電解鍍敷液，宜使用無電解鈀鍍敷液、無電解鈀合金鍍敷液、無電解鎳鍍敷液、無電解鎳合金鍍敷液等、無電解金鍍敷液、無電解金合金鍍敷液。於步驟(2)使用無電解鈀鍍敷液或無電解鈀合金鍍敷液時，宜進一步進行無電解金鍍敷或無電解金合金鍍敷。又，於步驟(2)使用無電解鎳鍍敷液或無電解鎳合金鍍敷液時，宜進一步進行無電解鈀鍍敷或無電解鈀合金鍍敷，較佳為繼而進一步進行無電解金鍍敷或無電解金合金鍍敷。又，於步驟(2)使用無電解鎳鍍敷液或無電解鎳合金鍍敷液時，亦可繼而進一步進行無電解金鍍敷或無電解金合金鍍敷。又，於步驟(2)亦可只進行無電解金鍍敷液、無電解金合金鍍敷液。
藉由本發明之方法2，可形成鍍敷析出性、選擇析出性、障壁特性、接合性等更加優異之無電解鍍敷皮膜。藉由本發明之方法2可獲得能提供如此之無電解鍍敷皮膜之材料，具體而言，可獲得一種材料，其包含：表面露出金屬之材料、前述金屬上之觸媒核1、及前述觸媒核1上之皮膜2，且前述觸媒核1含有鈷，前述皮膜2為無電解鍍敷皮膜。
[實施例]
以下，基於實施例詳細說明本發明，但本發明並非限定於此等實施例者。
(1)觸媒賦予液之調製
調製由以下所示組成所構成之無電解鍍敷用觸媒賦予液。使用水作為溶劑。
(1-1)實施例1~8：含有Co
(實施例1)Co-B
硫酸鈷・7水合物 5g/L(鈷1g/L)
DL-蘋果酸 10g/L
二甲基硼烷胺 3.0g/L
pH 7.5，浴溫 70℃。
(實施例2)Co-Ni-B
硫酸鈷・7水合物 5g/L(鈷1g/L)
硫酸鎳・6水合物 0.45g/L(鎳0.1g/L)
DL-蘋果酸 10g/L
二甲基硼烷胺 3.0g/L
pH 7.5，浴溫 70℃。
(實施例3)Co-Pd-B
硫酸鈷・7水合物 5g/L(鈷1g/L)
氯化鈀 0.08g/L(鈀0.05g/L)
檸檬酸 50g/L
二甲基硼烷胺 1.0g/L
pH 7.5，浴溫 70℃。
(實施例4)Co-W-B
硫酸鈷・7水合物 5g/L(鈷1g/L)
鎢酸鈉・2水合物 1g/L(鎢0.55g/L)
檸檬酸 50g/L
二甲基硼烷胺 1.0g/L
pH 7.5，浴溫 70℃。
(實施例5)Co-Mo-B
硫酸鈷・7水合物 20g/L(鈷4g/L)
鉬酸2鈉・2水合物 0.5g/L(鉬0.2g/L)
檸檬酸 50g/L
二甲基硼烷胺 1.0g/L
pH 7.5，浴溫 70℃。
(實施例6)Co-B-P
硫酸鈷・7水合物 20g/L(鈷4g/L)
檸檬酸 50g/L
二甲基硼烷胺 1.0g/L
次磷酸鈉 60g/L
pH 7.5，浴溫 70℃。
(實施例7)Co-B-P
硫酸鈷・7水合物 20g/L(鈷4g/L)
檸檬酸 50g/L
硼酸 10g/L
二甲基硼烷胺 1.0g/L
亞磷酸鈉 20g/L
pH 8.0，浴溫 70℃。
(實施例8)Co-P
硫酸鈷・7水合物 20g/L(鈷4g/L)
檸檬酸 50g/L
硼酸 10g/L
聯胺 2.0g/L
次磷酸鈉 20g/L
pH 8.0，浴溫 70℃。
(1-2)比較例1~5：不含有Co
(比較例1)Ni-B
硫酸鎳・6水合物 4.5g/L(鎳1.0g/L)
DL-蘋果酸 10g/L
二甲基硼烷胺 5.0g/L
pH 7.5，浴溫 60℃。
(比較例2)Ni-B
硫酸鎳・6水合物 0.45g/L(鎳0.1g/L)
DL-蘋果酸 10g/L
二甲基硼烷胺 5.0g/L
pH 7.5，浴溫 60℃。
(比較例3)Ni-B-P
硫酸鎳・6水合物 0.45g/L(鎳0.1g/L)
DL-蘋果酸 10g/L
二甲基硼烷胺 5.0g/L
次磷酸鈉 10g/L
pH 7.5，浴溫 60℃。
(比較例4)Pd-B
氯化鈀 0.83g/L(鈀0.5g/L)
乙二胺 10g/L
二甲基硼烷胺 1.0g/L
pH 7.5，浴溫 40℃。
(比較例5)Pd
氯化鈀 0.83g/L(鈀0.5g/L)
乙二胺 10g/L
聯胺 1.0g/L
pH 7.5，浴溫 40℃。
(1-3)比較例6~7：藉由取代反應之Pd觸媒賦予處理(習知技術)
(比較例6)
氯化鈀 0.17g/L(鈀0.1g/L)
35%鹽酸 100 ml/L
浴溫 30℃。
(比較例7)
硫酸鈀 0.19g/L(鈀0.1g/L)
98%硫酸 20 ml/L
浴溫 30℃。
(2)評價試驗
於以下之評價試驗，係在將無電解鍍敷對象材料進行前處理(酸性脫脂、軟蝕刻)後，藉由上述觸媒賦予液於金屬表面上形成觸媒核，接著以無電解鈀鍍敷、無電解金鍍敷之順序進行處理。各處理之詳細情形，只要無特別聲明則如以下所述。於各步驟間有實施流水水洗1分鐘處理。
(a)酸性脫脂
在40℃下於含有硫酸及界面活性劑之酸性脫脂液(商標名：ICP CLEAN S-135K)中浸漬5分鐘。
(b)軟蝕刻
在室溫下於含有過硫酸鈉100g/L與98%硫酸10ml/L之水溶液中浸漬1分鐘。
(c)觸媒賦予處理
對於實施例1~8及比較例1~5，係於觸媒賦予液中浸漬1~5分鐘，以使觸媒核之厚度成為0.01μm。對於比較例6及7係浸漬1分鐘。
(d)無電解鈀鍍敷
在65℃下於無電解鈀鍍敷液(商標名：TOP PALLAS PD，奥野製藥工業(製))中浸漬5分鐘，獲得膜厚約0.1μm之鍍敷皮膜。
(e)無電解金鍍敷
在80℃下於無電解金鍍敷(商標名：TOP PALLAS AU，奥野製藥工業(製))中浸漬10分鐘。獲得膜厚約0.05μm之鍍敷皮膜。
(2-1)觸媒核之組成測定
使用銅包環氧基板作為無電解鍍敷對象材料，實施酸性脫脂、軟蝕刻、觸媒賦予處理後，藉由能量分散型X射線分析裝置(EDX,HORIBA製EMAX X-act)之測定，抑或是藉由使用高頻感應耦合電漿(ICP)發光分光分析裝置(日立High tech science製PS3500DDII)之溶解法來鑑定組成。
(2-2)鍍敷析出性之評價
作為無電解鍍敷對象材料，係使用於樹脂基材上具有過阻焊(Over Resist)型微小銅墊(直徑0.2mm，墊數30個)的BGA(Ball Grid Array)樹脂基板。將無電解鍍敷對象材料以酸性脫脂、軟蝕刻、觸媒賦予處理、無電解鈀鍍敷、無電解金鍍敷之順序進行處理。藉由顯微鏡(KEYENCE製VHX-1000)來判定各墊中有無鍍敷析出，並遵從以下評價基準進行評價。
＜鍍敷析出性之評價基準＞
〇：全部的墊皆正常析出。
×：有鍍敷未析出之墊。
(2-3)選擇析出性之評價
作為無電解鍍敷對象材料，係使用具有銅配線圖型的樹脂基板，該銅配線圖型係以SAP法製作且配線寬/配線間隔(L/S)＝20/20μm者。將無電解鍍敷對象材料以酸性脫脂、軟蝕刻、觸媒賦予處理、無電解鈀鍍敷、無電解金鍍敷之順序進行處理。藉由掃描型電子顯微鏡(SEM,日立High technologies製S-3400N)來判定有無往配線圖型間(樹脂部分)之鍍敷析出，並遵從以下評價基準進行評價。
＜選擇析出性之評價基準＞
〇：無往配線圖型間之鍍敷析出。
△：往配線圖型間有少許鍍敷析出。
×：全面析出至配線圖型間。
(2-4)浴安定性之評價
將使用於鍍敷析出性之評價後的觸媒賦予液加溫至觸媒賦予處理之浴溫＋5℃，並放置72小時。藉由目視來判定有無浴分解，並遵從以下評價基準進行評價。
＜浴安定性之評價基準＞
〇：無浴分解。
×：浴分解。
(2-5)空隙(void)之確認
作為無電解鍍敷對象材料，係使用於樹脂基材上具有過阻焊型銅墊的BGA(Ball Grid Array)樹脂基板。將無電解鍍敷對象材料以酸性脫脂、軟蝕刻、觸媒賦予處理、無電解鈀鍍敷、無電解金鍍敷之順序進行處理。接著，使用聚焦離子束加工觀察裝置進行截面加工，藉由掃描離子顯微鏡觀察有無空隙(FIB/SIM,日立High technologies製FB2200)。
〈空隙之評價基準〉
〇：無空隙。
×：有空隙。
(2-6)障壁特性之評價
作為無電解鍍敷對象材料，係使用於樹脂基材上具有過阻焊型銅墊的BGA(Ball Grid Array)樹脂基板。將無電解鍍敷對象材料以酸性脫脂、軟蝕刻、觸媒賦予處理、無電解鈀鍍敷、無電解金鍍敷之順序進行處理。接著，將處理基板進行熱處理175℃、16h後，以X射線光電子分光分析裝置(ULVAC・PHI(股)公司，PHI5000VersaProbe III)測定Au鍍敷表面之元素組成。基於在Au皮膜表面有無檢測出基底金屬(Cu、Co、Ni、Pd)，遵從以下評價基準進行評價。
＜障壁特性之評價基準＞
〇：在Au皮膜表面無檢測出基底金屬(Cu、Co、Ni、Pd)。
×：在Au皮膜表面有檢測出基底金屬(Cu、Co、Ni、Pd)。
(2-7)接合性之評價
作為無電解鍍敷對象材料，係使用於樹脂基材上具有過阻焊型微小銅墊(直徑0.6mm，墊數20個)的BGA樹脂基板。將無電解鍍敷對象材料以酸性脫脂、軟蝕刻、觸媒賦予處理、無電解鈀鍍敷、無電解金鍍敷之順序進行處理。其後，搭載Sn-3Ag-0.5Cu之焊料球(φ0.76mm)並以回焊裝置加熱(峰值溫度250℃)後，使用焊料球拉力試驗裝置(Dage公司製＃4000)以拉速5000μm/秒進行焊料球拉力試驗。將焊料內部發生破斷或是基材被破壞之模式判斷為良好，將焊料球與鍍敷皮膜之接合界面被破壞之模式判斷為不良，並遵從以下評價基準進行評價。
＜接合性之評價基準＞
〇：良好模式50%以上。
△：良好模式高於0%且低於50%。
×：全部為不良模式(良好模式0%)。
(3)結果
結果表示於表1。
[表1]
Claims (13)
- 一種含有鈷化合物及還原劑之組成物之用途，係將該組成物用作觸媒賦予液，且該觸媒賦予液係用於：選自於由無電解鈀鍍敷、無電解鎳鍍敷、及無電解金鍍敷所構成群組中之至少1種無電解鍍敷。
- 如請求項1之用途，其中前述還原劑包含胺化合物。
- 如請求項2之用途，其中前述胺化合物包含選自於由硼烷胺、聯胺、及聯胺衍生物所構成群組中之至少1種。
- 如請求項1之用途，其中前述組成物含有錯合劑。
- 如請求項4之用途，其中前述錯合劑包含羧酸。
- 如請求項5之用途，其中前述羧酸包含羥基羧酸或二羧酸。
- 如請求項1至6中任一項之用途，其中前述還原劑包含選自於由含硼化合物及含磷化合物所構成群組中之至少1種。
- 如請求項1至6中任一項之用途，其中前述組成物更含有金屬鹽。
- 如請求項1至6中任一項之用途，其中前述組成物之鈷含量相對於金屬100質量%為50質量%以上。
- 如請求項1至6中任一項之用途，其中前述還原劑包含選自於由含硼化合物及含磷化合物所構成群組中之至少1種，且前述無電解鍍敷係針對表面露出銅及/或銅合金之材料所進行之下列無電解鍍敷：選自於由無電解鈀鍍敷、無電解鎳鍍敷、及無電解金鍍敷所構成群組中之至少1種無電解鍍敷。
- 一種製造包含觸媒核之無電解鍍敷對象材料之方法，包含以下步驟：(1)使不含觸媒核之無電解鍍敷對象材料與含有鈷化合物及還原劑之無電解鍍敷用觸媒賦予液接觸之步驟； 前述無電解鍍敷係選自於由無電解鈀鍍敷、無電解鎳鍍敷、及無電解金鍍敷所構成群組中之至少1種無電解鍍敷。
- 一種製造包含無電解鍍敷皮膜之材料之方法，包含以下步驟：(1)使不含觸媒核之無電解鍍敷對象材料與含有鈷化合物及還原劑之無電解鍍敷用觸媒賦予液接觸之步驟；及(2)於步驟(1)後，進行無電解鍍敷處理之步驟；前述無電解鍍敷係選自於由無電解鈀鍍敷、無電解鎳鍍敷、及無電解金鍍敷所構成群組中之至少1種無電解鍍敷。
- 一種包含觸媒核之材料，包含：表面露出金屬且不含觸媒核之材料、前述金屬上之觸媒核1、及前述觸媒核1上之皮膜2，且前述觸媒核1含有鈷，前述皮膜2為無電解鍍敷皮膜；前述無電解鍍敷係選自於由無電解鈀鍍敷、無電解鎳鍍敷、及無電解金鍍敷所構成群組中之至少1種無電解鍍敷。
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| TW110123581A TWI843003B (zh) | 2020-07-03 | 2021-06-28 | 無電解鍍敷用觸媒賦予液 |
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| Country | Link |
|---|---|
| JP (1) | JP6841462B1 (zh) |
| KR (1) | KR20230005394A (zh) |
| CN (1) | CN115735022A (zh) |
| TW (1) | TWI843003B (zh) |
| WO (1) | WO2022004367A1 (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55102297A (en) * | 1979-01-22 | 1980-08-05 | Richardson Chemical Co | Method of controlling to electrolessly plate surface of support and product fabricated thereby |
| JP2012216722A (ja) * | 2011-04-01 | 2012-11-08 | Kansai Univ | 基板中間体、基板及び貫通ビア電極形成方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05327187A (ja) | 1992-05-18 | 1993-12-10 | Ishihara Chem Co Ltd | プリント配線板及びその製造法 |
| JP3826544B2 (ja) * | 1998-02-27 | 2006-09-27 | 奥野製薬工業株式会社 | 無電解めっき用触媒組成物 |
| JP2002167675A (ja) * | 2000-12-01 | 2002-06-11 | Okuno Chem Ind Co Ltd | 無電解めっき用触媒付与方法 |
| JP4670064B2 (ja) * | 2001-02-07 | 2011-04-13 | 奥野製薬工業株式会社 | 無電解めっき用触媒付与方法 |
| JP4143385B2 (ja) * | 2002-03-05 | 2008-09-03 | 株式会社大和化成研究所 | 無電解めっきの触媒付与のための前処理液、該液を使用する前処理方法、該方法を使用して製造した無電解めっき皮膜及び（又は）めっき被覆体 |
| JPWO2009142126A1 (ja) * | 2008-05-21 | 2011-09-29 | 日本高純度化学株式会社 | はんだめっき用触媒付与液 |
| WO2010004856A1 (ja) * | 2008-07-08 | 2010-01-14 | 日本高純度化学株式会社 | パラジウムめっき用触媒付与液 |
| JP6466521B2 (ja) * | 2017-06-28 | 2019-02-06 | 小島化学薬品株式会社 | 無電解めっきプロセス |
-
2020
- 2020-07-03 JP JP2020115474A patent/JP6841462B1/ja active Active
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2021
- 2021-06-16 WO PCT/JP2021/022772 patent/WO2022004367A1/ja active Application Filing
- 2021-06-16 KR KR1020227043461A patent/KR20230005394A/ko not_active IP Right Cessation
- 2021-06-16 CN CN202180046353.3A patent/CN115735022A/zh active Pending
- 2021-06-28 TW TW110123581A patent/TWI843003B/zh active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55102297A (en) * | 1979-01-22 | 1980-08-05 | Richardson Chemical Co | Method of controlling to electrolessly plate surface of support and product fabricated thereby |
| JP2012216722A (ja) * | 2011-04-01 | 2012-11-08 | Kansai Univ | 基板中間体、基板及び貫通ビア電極形成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115735022A (zh) | 2023-03-03 |
| TW202212628A (zh) | 2022-04-01 |
| WO2022004367A1 (ja) | 2022-01-06 |
| JP6841462B1 (ja) | 2021-03-10 |
| JP2022013121A (ja) | 2022-01-18 |
| KR20230005394A (ko) | 2023-01-09 |
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