JP2012087386A - Electroless nickel plating bath and electroless nickel plating method using the same - Google Patents
Electroless nickel plating bath and electroless nickel plating method using the same Download PDFInfo
- Publication number
- JP2012087386A JP2012087386A JP2010236378A JP2010236378A JP2012087386A JP 2012087386 A JP2012087386 A JP 2012087386A JP 2010236378 A JP2010236378 A JP 2010236378A JP 2010236378 A JP2010236378 A JP 2010236378A JP 2012087386 A JP2012087386 A JP 2012087386A
- Authority
- JP
- Japan
- Prior art keywords
- nickel plating
- electroless nickel
- acid
- antimony
- plating bath
- 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.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000007747 plating Methods 0.000 title claims abstract description 95
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000008139 complexing agent Substances 0.000 claims abstract description 35
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 30
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001630 malic acid Substances 0.000 claims abstract description 30
- 235000011090 malic acid Nutrition 0.000 claims abstract description 30
- 239000003381 stabilizer Substances 0.000 claims abstract description 23
- 239000001384 succinic acid Substances 0.000 claims abstract description 22
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 20
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004310 lactic acid Substances 0.000 claims abstract description 16
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000001463 antimony compounds Chemical class 0.000 claims abstract description 9
- 235000011044 succinic acid Nutrition 0.000 claims description 21
- 239000013522 chelant Substances 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- 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 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 4
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- 229940026189 antimony potassium tartrate Drugs 0.000 claims description 3
- 230000035882 stress Effects 0.000 description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 238000000151 deposition Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 235000011054 acetic acid Nutrition 0.000 description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000004471 Glycine Substances 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 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 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- XXSPKSHUSWQAIZ-UHFFFAOYSA-L 36026-88-7 Chemical compound [Ni+2].[O-]P=O.[O-]P=O XXSPKSHUSWQAIZ-UHFFFAOYSA-L 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
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100133719 Caenorhabditis elegans npr-18 gene Proteins 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- 229910004616 Na2MoO4.2H2 O Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- DQDCXYHZRIWBQD-UHFFFAOYSA-N O.O.O.[K] Chemical compound O.O.O.[K] DQDCXYHZRIWBQD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PGXZRYAHTUJRMK-UHFFFAOYSA-L dipotassium 2,3-dihydroxybutanedioate trihydrate Chemical compound O.O.O.[K+].[K+].OC(C(O)C([O-])=O)C([O-])=O PGXZRYAHTUJRMK-UHFFFAOYSA-L 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- -1 etc.) Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 150000002429 hydrazines 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
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 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
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 1
- KLDGLPRBBANWAW-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate;trihydrate Chemical compound O.O.O.[K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O KLDGLPRBBANWAW-UHFFFAOYSA-J 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 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
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000004474 valine Substances 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
Description
本発明は、無電解ニッケルめっきの技術に関し、特に応力が低いニッケルめっき皮膜を形成することが可能な無電解ニッケルめっき浴、およびそれを用いた無電解ニッケルめっき法に関する。 The present invention relates to a technique for electroless nickel plating, and particularly to an electroless nickel plating bath capable of forming a nickel plating film with low stress, and an electroless nickel plating method using the same.
無電解ニッケルめっき浴には、めっき液の安定性の向上、めっき外観や付きまわり性の改善などを目的として、有機および／または無機添加剤をめっき液中に添加することが多い。一般的に、有機添加剤を適度な濃度で添加すると、液安定性、析出速度およびめっき外観などを向上させることができるが、その一方でめっき皮膜の応力は増加する。また、めっき直後は低応力であっても、経日的にめっき皮膜の応力が増加することもある。めっき皮膜の応力の増加は、めっき処理した製品に反りやクラックを生じさせる原因となる。そのため、めっき皮膜の応力はなるべく低くなるようにすることが望ましい。 In an electroless nickel plating bath, organic and / or inorganic additives are often added to the plating solution for the purpose of improving the stability of the plating solution, improving the appearance of plating and throwing power. Generally, when an organic additive is added at an appropriate concentration, the liquid stability, the deposition rate, the plating appearance, and the like can be improved, while the stress of the plating film increases. Moreover, even if the stress is low immediately after plating, the stress of the plating film may increase over time. An increase in the stress of the plating film causes warpage and cracks in the plated product. Therefore, it is desirable to make the stress of the plating film as low as possible.
特許文献１には、無電解ニッケルめっき浴にモリブデンを適量添加することにより、ニッケル皮膜内部の応力が下がることが開示されている。特許文献２には、水溶性ニッケル塩、還元剤、モリブデンおよびアンチモンを含む無電解ニッケルめっき浴は、有害物質である鉛などを含まずとも、液安定性、析出速度およびめっき外観などに優れていることが開示されている。特許文献３には、アルミニウムまたはアルミニウム合金に無電解ニッケルめっき皮膜を形成する際に、めっき浴として水溶性のアンチモン化合物またはビスマス化合物を金属として０．０１〜１００ｐｐｍ含有する無電解ニッケルめっき浴を用いると、微小ノジュールを少なくする点から有効であることが開示されている。ただし、特許文献２および３は、得られためっき皮膜の応力に関しては何ら言及していない。 Patent Document 1 discloses that the stress inside the nickel coating is reduced by adding an appropriate amount of molybdenum to the electroless nickel plating bath. In Patent Document 2, an electroless nickel plating bath containing a water-soluble nickel salt, a reducing agent, molybdenum, and antimony is excellent in liquid stability, deposition rate, plating appearance, and the like, even without containing lead as a harmful substance. Is disclosed. Patent Document 3 uses an electroless nickel plating bath containing 0.01 to 100 ppm of a water-soluble antimony compound or bismuth compound as a metal when forming an electroless nickel plating film on aluminum or an aluminum alloy. It is disclosed that it is effective from the viewpoint of reducing minute nodules. However, Patent Documents 2 and 3 do not mention anything about the stress of the obtained plating film.
本発明は、皮膜応力が低いニッケルめっき皮膜を形成することが可能な無電解ニッケルめっき浴および該めっき浴を用いた無電解ニッケルめっき法を提供することを目的とする。 An object of the present invention is to provide an electroless nickel plating bath capable of forming a nickel plating film having a low film stress and an electroless nickel plating method using the plating bath.
本発明者らは、安定剤として金属アンチモンまたはアンチモン化合物を含み、かつ錯化剤としてリンゴ酸または乳酸とコハク酸とを所定比で含む無電解ニッケル浴を用いることにより、応力が低いめっき皮膜が形成可能であることを見出した。本発明の要旨は以下のとおりである。 By using an electroless nickel bath containing metal antimony or an antimony compound as a stabilizer and malic acid or lactic acid and succinic acid as a complexing agent in a predetermined ratio, the present inventors can form a plating film with low stress. It was found that it can be formed. The gist of the present invention is as follows.
（１）ニッケル塩と、還元剤と、金属アンチモンまたはアンチモン化合物を含む安定剤と、リンゴ酸または乳酸とコハク酸とをキレートモル比で２５：７５〜７５：２５の範囲で含む錯化剤とを含む、無電解ニッケルめっき浴。
（２）錯化剤を１リットルあたり０．３〜１．３キレートモル含む、（１）に記載の無電解ニッケルめっき浴。
（３）安定剤が金属アンチモン、塩化アンチモン、酢酸アンチモン、酸化アンチモン、酒石酸アンチモニルカリウム、またはそれらの混合物である、（１）または（２）に記載の無電解ニッケルめっき浴。
（４）還元剤が次亜リン酸または次亜リン酸ナトリウムである、（１）〜（３）のいずれかに記載の無電解ニッケルめっき浴。
（５）（１）〜（４）のいずれかに記載の無電解ニッケルめっき浴を用いる、無電解ニッケルめっき法。
(1) A nickel salt, a reducing agent, a stabilizer containing metal antimony or an antimony compound, and a complexing agent containing malic acid or lactic acid and succinic acid in a chelate molar ratio of 25:75 to 75:25. Including electroless nickel plating bath.
(2) The electroless nickel plating bath according to (1), containing a complexing agent in an amount of 0.3 to 1.3 chelate moles per liter.
(3) The electroless nickel plating bath according to (1) or (2), wherein the stabilizer is metal antimony, antimony chloride, antimony acetate, antimony oxide, potassium antimony tartrate, or a mixture thereof.
(4) The electroless nickel plating bath according to any one of (1) to (3), wherein the reducing agent is hypophosphorous acid or sodium hypophosphite.
(5) An electroless nickel plating method using the electroless nickel plating bath according to any one of (1) to (4).
本発明によれば、皮膜応力が低く、外観および付きまわり性にすぐれたニッケルめっき皮膜を形成することができる。 According to the present invention, it is possible to form a nickel plating film having a low film stress and excellent appearance and throwing power.
本発明の無電解ニッケルめっき浴は、ニッケル塩と、還元剤と、金属アンチモンまたはアンチモン化合物を含む安定剤と、リンゴ酸または乳酸とコハク酸とをキレートモル比で２５：７５〜７５：２５の範囲で含む錯化剤とを含む。 The electroless nickel plating bath of the present invention comprises a nickel salt, a reducing agent, a stabilizer containing metal antimony or an antimony compound, malic acid or lactic acid and succinic acid in a chelate molar ratio of 25:75 to 75:25. And a complexing agent.
ニッケル塩としては、無電解ニッケルめっき浴に通常使用されるものを用いることができる。ニッケル塩の具体例としては、硫酸ニッケル、塩化ニッケル、炭酸ニッケル、酢酸ニッケル、次亜リン酸ニッケル、スルファミン酸ニッケル、クエン酸ニッケルなどを挙げることができる。これらは単独で、あるいは２種以上を組み合わせて用いてもよい。ニッケル塩は、０．０１〜０．５０ｍｏｌ／Ｌ、特に０．０１〜０．３０ｍｏｌ／Ｌ、とりわけ０．０５〜０．２０ｍｏｌ／Ｌの範囲の量で用いるのが好ましい。 As the nickel salt, those usually used for an electroless nickel plating bath can be used. Specific examples of the nickel salt include nickel sulfate, nickel chloride, nickel carbonate, nickel acetate, nickel hypophosphite, nickel sulfamate, and nickel citrate. These may be used alone or in combination of two or more. The nickel salt is preferably used in an amount ranging from 0.01 to 0.50 mol / L, particularly from 0.01 to 0.30 mol / L, especially from 0.05 to 0.20 mol / L.
還元剤としては、例えば次亜リン酸、次亜リン酸ナトリウム、ＤＭＡＢ（ジメチルアミノボラン）、塩酸ヒドラジンや硫酸ヒドラジンなどのヒドラジン化合物が挙げられる。本発明では次亜リン酸または次亜リン酸ナトリウムが還元剤として最も好ましい。次亜リン酸または次亜リン酸ナトリウムを還元剤として用いると、Ｎｉ−Ｐめっき皮膜が得られる。還元剤は、０．０１〜０．５０ｍｏｌ／Ｌ、特に０．０５〜０．３０ｍｏｌ／Ｌ、とりわけ０．１０〜０．２５ｍｏｌ／Ｌの範囲の量で用いるのが好ましい。 Examples of the reducing agent include hypophosphorous acid, sodium hypophosphite, DMAB (dimethylaminoborane), hydrazine compounds such as hydrazine hydrochloride and hydrazine sulfate. In the present invention, hypophosphorous acid or sodium hypophosphite is most preferable as the reducing agent. When hypophosphorous acid or sodium hypophosphite is used as a reducing agent, a Ni-P plating film is obtained. The reducing agent is preferably used in an amount in the range of 0.01 to 0.50 mol / L, particularly 0.05 to 0.30 mol / L, especially 0.10 to 0.25 mol / L.
本発明の無電解ニッケルめっき浴に用いる安定剤は、アンチモンを金属アンチモンとして、あるいはアンチモン化合物として含む。アンチモン化合物としては、塩化アンチモン、酢酸アンチモン、酸化アンチモン、酒石酸アンチモニルカリウム、アンチモニル−Ｌ−酒石酸、アンチモン酸、アンチモン酸ナトリウム、アンチモン酸カリウムなどが挙げられる。これらの金属アンチモンあるいはアンチモン化合物は２種以上を混合して用いてもよい。好ましくは、安定剤は、金属アンチモン、塩化アンチモン、酢酸アンチモン、酸化アンチモン、酒石酸アンチモニルカリウム、またはそれらの混合物である。安定剤は、Ｓｂとして０．００１〜０．１０ｍｍｏｌ／Ｌ、特に０．００５〜０．０７５ｍｍｏｌ／Ｌ、とりわけ０．０１〜０．０５ｍｍｏｌ／Ｌの範囲の量で用いるのが好ましい。本発明においては、安定剤として塩化アンチモン（塩化アンチモン(III)として）または酒石酸アンチモニルカリウム（酒石酸アンチモニル(III)カリウム・三水和物として）を、Ｓｂとして０．１〜５０ｍｇ／Ｌ、特に０．１〜２５ｍｇ／Ｌ、とりわけ０．２〜２０ｍｇ／Ｌの範囲の量で用いるのが最も好ましい。 The stabilizer used in the electroless nickel plating bath of the present invention contains antimony as metal antimony or as an antimony compound. Examples of the antimony compound include antimony chloride, antimony acetate, antimony oxide, antimony potassium tartrate, antimonyl-L-tartaric acid, antimonic acid, sodium antimonate, and potassium antimonate. These metal antimony or antimony compounds may be used in combination of two or more. Preferably, the stabilizer is antimony metal, antimony chloride, antimony acetate, antimony oxide, potassium antimonyl tartrate, or a mixture thereof. The stabilizer is preferably used as Sb in an amount in the range of 0.001 to 0.10 mmol / L, particularly 0.005 to 0.075 mmol / L, especially 0.01 to 0.05 mmol / L. In the present invention, antimony chloride (as antimony (III) chloride) or antimony potassium tartrate (as antimony (III) potassium tartrate trihydrate) as a stabilizer and 0.1 to 50 mg / L as Sb, particularly Most preferably, it is used in an amount ranging from 0.1 to 25 mg / L, especially from 0.2 to 20 mg / L.
本発明の無電解ニッケル浴は、錯化剤としてリンゴ酸または乳酸とコハク酸とをキレートモル比で２５：７５〜７５：２５の範囲で含む。リンゴ酸または乳酸とコハク酸との比は、キレートモル比で３０：７０〜７０：３０、特に３５：６５〜６５：３５、さらに４０：６０〜６０：４０、とりわけ４５：５５〜５５：４５の範囲であるとより好ましい。錯化剤としては、リンゴ酸とコハク酸との組み合わせが最も好ましい。 The electroless nickel bath of the present invention contains malic acid or lactic acid and succinic acid as a complexing agent in a chelate molar ratio of 25:75 to 75:25. The ratio of malic acid or lactic acid to succinic acid is 30:70 to 70:30, in particular 35:65 to 65:35, in addition 40:60 to 60:40, in particular 45:55 to 55:45 in chelate molar ratio. A range is more preferable. The complexing agent is most preferably a combination of malic acid and succinic acid.
キレートモル（ｃＭ）とは、錯化剤が個々に有する配座数を考慮した濃度の単位として当業者に知られている。配座数が１の錯化剤の濃度は一般的なモル濃度と同一である。配座数が２以上である場合は、モル濃度に配座数をかけた値がキレートモルとなる。この単位を用いることにより、異なる錯化剤でもほぼ同等の濃度条件での比較が可能になる。代表的な錯化剤の配座数は次のとおりである。配座数１：酢酸、プロピオン酸など。配座数２：乳酸、グリコール酸、コハク酸、グリシンなど。配座数３：リンゴ酸、アスパラギン酸。配座数４：クエン酸。 The chelate mole (cM) is known to those skilled in the art as a unit of concentration taking into account the number of conformations each complexing agent has. The concentration of the complexing agent with a conformation number of 1 is the same as the general molar concentration. When the number of conformations is 2 or more, the value obtained by multiplying the molar concentration by the number of conformations is the chelate mole. By using this unit, different complexing agents can be compared under almost the same concentration conditions. The number of conformations of typical complexing agents is as follows. Conformation number 1: acetic acid, propionic acid, etc. Conformation number 2: lactic acid, glycolic acid, succinic acid, glycine and the like. Conformation number 3: malic acid, aspartic acid. Conformation number 4: citric acid.
錯化剤は、無電解ニッケルめっき浴中に、１リットルあたり０．３〜１．３キレートモル、特に０．４〜１．１キレートモル、とりわけ０．５〜０．９キレートモルの量で存在するのが好ましい。 The complexing agent is present in the electroless nickel plating bath in an amount of 0.3 to 1.3 chelate mole, in particular 0.4 to 1.1 chelate mole, in particular 0.5 to 0.9 chelate mole, per liter. Is preferred.
錯化剤は、リンゴ酸または乳酸とコハク酸以外の化合物を含んでいてもよい。錯化剤として用いることができる化合物としては、例えば、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸およびシュウ酸などのカルボン酸、乳酸、グリコール酸、リンゴ酸、クエン酸などのヒドロキシカルボン酸、アラニン、バリン、チロシン、グリシン、アスパラギン酸、ヒスチジンなどのアミノ酸が挙げられる。本発明において錯化剤は、好ましくはリンゴ酸または乳酸とコハク酸とのみからなり、最も好ましくはリンゴ酸とコハク酸のみからなる。 The complexing agent may contain compounds other than malic acid or lactic acid and succinic acid. Examples of the compound that can be used as the complexing agent include carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid and oxalic acid, hydroxycarboxylic acids such as lactic acid, glycolic acid, malic acid and citric acid, and alanine. , Amino acids such as valine, tyrosine, glycine, aspartic acid, histidine and the like. In the present invention, the complexing agent preferably comprises only malic acid or lactic acid and succinic acid, and most preferably comprises only malic acid and succinic acid.
本発明の無電解ニッケルめっき浴は、上記以外にも、例えば以下のような成分を含んでいてもよい：ｐＨ調整剤（水酸化カリウム、アンモニア水溶液、水酸化ナトリウムなど）、光沢剤（鉛、銅、チオ硫酸ナトリウムなど）、界面活性剤（ドデシル硫酸ナトリウム、ＰＥＧ１Ｋなど）、ｐＨ緩衝剤（塩化アンモニウム、硫酸アンモニウム、ホウ酸など）など。 In addition to the above, the electroless nickel plating bath of the present invention may contain, for example, the following components: pH adjuster (potassium hydroxide, aqueous ammonia, sodium hydroxide, etc.), brightener (lead, Copper, sodium thiosulfate, etc.), surfactant (sodium dodecyl sulfate, PEG1K, etc.), pH buffer (ammonium chloride, ammonium sulfate, boric acid, etc.), etc.
本発明は、上記の無電解ニッケルめっき浴を用いる無電解ニッケルめっき法にも関する。本発明の無電解ニッケルめっき法は、基材を本発明の無電解ニッケルめっき浴に浸し、必要に応じて加熱することにより行われる。基材としては、導電性および非導電性の物質のいずれでもよく、特に限定されるものではない。基材の具体例としては、銅、アルミニウム、鉄、またはそれらの合金からなるもの、樹脂、シリコンウエハーにアルミニウムをスパッタしたもの、などが挙げられる。基材には、めっきする前に、酸やアルカリによる脱脂ならびに活性化など、当業者に公知の前処理が施される。 The present invention also relates to an electroless nickel plating method using the above electroless nickel plating bath. The electroless nickel plating method of the present invention is performed by immersing the base material in the electroless nickel plating bath of the present invention and heating as necessary. As a base material, any of an electroconductive and nonelectroconductive substance may be sufficient, and it does not specifically limit. Specific examples of the substrate include those made of copper, aluminum, iron, or alloys thereof, resins, and silicon wafers obtained by sputtering aluminum. Prior to plating, the substrate is subjected to pretreatments known to those skilled in the art, such as degreasing and activation with acid or alkali.
本発明の無電解ニッケルめっき浴および該めっき浴を用いた無電解ニッケルめっき法によれば、皮膜応力が低く反りやクラックなどが生じない高品質なニッケルめっき皮膜を成膜することができる。本発明は、特にシリコンウエハー、自動車部品、装飾用部品、電子部品、工業用治具、型、ロールなどにニッケルめっきを施すのに有利である。 According to the electroless nickel plating bath and the electroless nickel plating method using the plating bath of the present invention, it is possible to form a high-quality nickel plating film with low film stress and without warping or cracking. The present invention is particularly advantageous for nickel plating on silicon wafers, automobile parts, decorative parts, electronic parts, industrial jigs, molds, rolls and the like.
以下、実施例を用いて本発明をより詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these Examples.
１．実験手順
基材として銅板（５０×２５ｍｍ２）と、市販のＢｅＣｕ材テストストリップ（めっき有効面積７６×１０ｍｍ２）とを用意した。銅板は次の手順で前処理した：１）６０℃で５分間アルカリ脱脂（ＮａＯＨ８ｇ／Ｌ、クエン酸ナトリウム１０ｇ／Ｌ、ナロアクティーＮ−１２０（三洋化成工業社製）２ｇ／Ｌ）、２）室温で１分間酸活性（１０％硫酸）、３）室温で１分間０．１ｇ／ＬのＰｄＣｌ２溶液で処理。テストストリップは次の手順で前処理した：１）室温で５分間酸脱脂（ＰＢ−２４２Ｄ（荏原ユージライト社製））、２）室温で１分間酸活性（１０％硫酸）、３）室温で５分間０．１ｇ／ＬのＰｄＣｌ２溶液で処理。前処理後の各基材に、無補給で３０分間めっきし、析出速度とめっき皮膜応力を測定した。
1. Experimental procedure A copper plate (50 × 25 mm 2 ) and a commercially available BeCu material test strip (plating effective area 76 × 10 mm 2 ) were prepared as substrates. The copper plate was pretreated by the following procedure: 1) Alkaline degreasing at 60 ° C. for 5 minutes (NaOH 8 g / L, sodium citrate 10 g / L, NAROACTY N-120 (manufactured by Sanyo Chemical Industries) 2 g / L), 2) 1 min at room temperature the acid activity (10% sulfuric acid), 3) PdCl 2 solution treated at room temperature for 1 minute 0.1 g / L. The test strips were pretreated by the following procedure: 1) Acid degreasing for 5 minutes at room temperature (PB-242D (Sugawara Eugleite)), 2) 1 minute acid activity at room temperature (10% sulfuric acid), 3) At room temperature Treat with 0.1 g / L PdCl 2 solution for 5 minutes. Each substrate after pretreatment was plated for 30 minutes without replenishment, and the deposition rate and plating film stress were measured.
析出速度は、精密天秤を用いて測定しためっき前後の銅板の重量差に基づいて算出しためっき膜厚（皮膜密度は７．８５ｇ／ｃｍ３とした）とめっき時間から求めた。めっき皮膜応力は、めっき後のテストストリップの両脚の先端をスケールに触れない程度にストリップ式電着応力試験器（６８３ＥＣアナライザー、エレクトロケミカル社製）にセットし、両脚間の特殊スケール目盛の合計値（開脚度）を読み、Ｓを応力（ＭＰａ）、Ｔを膜厚（μｍ）、Ｕを開脚度、ＫをテストストリップのファクターとしてＳ＝５８．２×ＵＫ／Ｔの計算式に代入して求めた。 The deposition rate was determined from the plating film thickness (film density was 7.85 g / cm 3 ) calculated based on the weight difference between the copper plates before and after plating measured using a precision balance and the plating time. The plating film stress is set on a strip-type electrodeposition stress tester (683EC analyzer, manufactured by Electrochemical Co., Ltd.) so that the tips of both legs of the test strip after plating do not touch the scale. Read (leg), substituting into S = 58.2 × UK / T, where S is stress (MPa), T is film thickness (μm), U is the degree of spread, and K is a factor of the test strip. And asked.
２．錯化剤の濃度と組み合わせの検討
表１に記載した条件に従ってめっきを行い、錯化剤の組み合わせおよび錯化剤濃度の最適条件を検討した。
2. Examination of Complexing Agent Concentration and Combination Plating was performed according to the conditions described in Table 1, and the optimum conditions for the complexing agent combination and the complexing agent concentration were examined.
表２は、錯化剤として、リンゴ酸と、コハク酸、乳酸、酢酸またはグリシンとを５０：５０のキレートモル比で用いためっき浴による結果である（表中、「as plate」とはめっき直後を意味し、比はキレートモル比である）。 Table 2 shows the results obtained by a plating bath using malic acid and succinic acid, lactic acid, acetic acid or glycine as a complexing agent in a chelate molar ratio of 50:50 (in the table, “as plate” means immediately after plating). And the ratio is the chelate molar ratio).
錯化剤として、リンゴ酸とコハク酸の組み合わせ、またはリンゴ酸と酢酸の組み合わせを用いためっき浴は、析出速度が比較的速く、めっき皮膜の応力も比較的低かった（めっき皮膜の応力は（−）は圧縮応力を、（＋）は引っ張り応力をそれぞれ示している）。ただし、リンゴ酸と酢酸の組み合わせを用いためっき浴では、総錯化剤濃度が高くなると応力が引っ張り側に移行する傾向がみられた。一方、リンゴ酸とコハク酸の組み合わせを用いた場合は、そのような傾向はみられなかった。総錯化剤濃度は、０．８ｃＭ／Ｌとした際、最も析出速度が速かった。総合的にみて、錯化剤としてリンゴ酸とコハク酸を５０：５０のキレートモル比で用い、総錯化剤濃度を０．８ｃＭ／Ｌとするのが最良であると判断された。 A plating bath using a combination of malic acid and succinic acid or a combination of malic acid and acetic acid as a complexing agent has a relatively high deposition rate and a relatively low stress of the plating film (the stress of the plating film is ( -) Indicates compressive stress, and (+) indicates tensile stress). However, in the plating bath using a combination of malic acid and acetic acid, when the total complexing agent concentration was high, the stress tended to shift to the tensile side. On the other hand, such a tendency was not observed when a combination of malic acid and succinic acid was used. When the total complexing agent concentration was 0.8 cM / L, the precipitation rate was the fastest. Overall, it was determined that it would be best to use malic acid and succinic acid as the complexing agent in a chelate molar ratio of 50:50 and a total complexing agent concentration of 0.8 cM / L.
表３は、総錯化剤濃度を０．８ｃＭ／Ｌに固定し、種々の錯化剤の５０：５０の比の組み合わせについて析出速度、めっき直後の皮膜応力、および熱処理した後の皮膜応力を調べた結果である。なお、熱処理は、数日〜十数日経過した際のめっき皮膜の状態をシミュレートするための加速劣化試験のためのものである。リンゴ酸を含む組み合わせ、およびコハク酸と乳酸の組み合わせは熱処理後の皮膜応力が低かった。しかし、リンゴ酸と乳酸、およびリンゴ酸とグリシンの組み合わせは析出速度が遅かった。リンゴ酸とコハク酸、リンゴ酸と酢酸、およびコハク酸と乳酸の組み合わせが、析出速度およびめっき皮膜応力の観点から優れていると判断された。ただし、酢酸はキレート力が弱くめっき速度促進剤として作用するため、酢酸を使用すると、析出速度が早くなる一方で、めっき浴の安定性が低下する。老化時は、新建浴時とは異なり、副生成物や蓄積物が液中に増えるため、より浴安定性が低下しやすい。その上、酢酸には臭気の問題もある。従って、錯化剤としてはリンゴ酸とコハク酸またはコハク酸と乳酸の組み合わせが好ましいと判断された。 Table 3 shows the precipitation rate, film stress immediately after plating, and film stress after heat treatment for a combination of 50:50 ratios of various complexing agents with the total complexing agent concentration fixed at 0.8 cM / L. It is the result of investigation. The heat treatment is for an accelerated deterioration test for simulating the state of the plating film when several days to several tens of days have passed. The combination containing malic acid and the combination of succinic acid and lactic acid had low film stress after heat treatment. However, the combination of malic acid and lactic acid and malic acid and glycine had a slow precipitation rate. The combination of malic acid and succinic acid, malic acid and acetic acid, and succinic acid and lactic acid was judged to be excellent from the viewpoints of deposition rate and plating film stress. However, since acetic acid has a weak chelating power and acts as a plating rate accelerator, the use of acetic acid increases the deposition rate while lowering the stability of the plating bath. When aging, unlike the new construction bath, by-products and accumulations increase in the liquid, bath stability is more likely to decrease. In addition, acetic acid has odor problems. Therefore, it was judged that the complexing agent is preferably malic acid and succinic acid or a combination of succinic acid and lactic acid.
３．錯化剤の混合比率の検討
表１に記載した条件に従ってめっきを行い、錯化剤の混合比率の最適条件を検討した。表４は、好ましい錯化剤の組み合わせであると判断されたリンゴ酸とコハク酸の混合比率を種々変更して、析出速度、めっき直後の皮膜応力、および熱処理した後の皮膜応力を調べた結果である（表中、比はキレートモル比である）。
3. Examination of the mixing ratio of the complexing agent Plating was performed according to the conditions described in Table 1, and the optimum conditions for the mixing ratio of the complexing agent were examined. Table 4 shows the results of investigating the deposition rate, the film stress immediately after plating, and the film stress after heat treatment by variously changing the mixing ratio of malic acid and succinic acid judged to be a preferable combination of complexing agents. (In the table, the ratio is the chelate molar ratio).
コハク酸の比率が高くなるにつれて、析出速度は速くなり、応力は引っ張り側に移行する傾向がみられた。リンゴ酸とコハク酸のキレートモル比は５０：５０とするのが最も好ましいと判断された。総錯化剤濃度は、やはり０．８ｃＭ／Ｌとするのが最良であった。 As the succinic acid ratio increased, the deposition rate increased and the stress tended to shift to the tensile side. It was judged that the chelate molar ratio of malic acid and succinic acid was most preferably 50:50. The total complexing agent concentration was still best at 0.8 cM / L.
４．安定剤の検討
表５に記載した条件に従ってめっきを行い、最適な安定剤の種類と量を検討した。
4). Study of Stabilizer Plating was performed according to the conditions described in Table 5, and the optimum type and amount of stabilizer were examined.
表６は、安定剤としてビスマス（硝酸ビスマス）、アンチモン（塩化アンチモン(III)）、またはチオ尿素を用いためっき浴、あるいは市販のめっき浴（エピタスＮＰＲ−１８、上村工業製）を使用した際の析出速度、めっき直後の皮膜応力、および熱処理した後の皮膜応力を調べた結果である。（ビスマス、アンチモンの濃度は、それぞれＢｉ、Ｓｂとしてのものである。）安定剤としてビスマスおよびチオ尿素を用いた場合、安定剤無添加の場合と比較して、浴安定性の向上、めっき皮膜の外観向上、析出速度の向上などの効果がみられたが、熱処理後の皮膜応力が高くなった。一方、安定剤としてアンチモンを使用した場合、熱処理後の皮膜応力が、他の安定剤を用いためっき浴および市販のめっき浴を用いた場合と比較して顕著に低くなった。 Table 6 shows that when a plating bath using bismuth (bismuth nitrate), antimony (antimony (III) chloride), or thiourea as a stabilizer, or a commercially available plating bath (Epitus NPR-18, manufactured by Uemura Kogyo Co., Ltd.) is used. This is a result of investigating the deposition rate, film stress immediately after plating, and film stress after heat treatment. (The concentrations of bismuth and antimony are those of Bi and Sb, respectively.) When bismuth and thiourea are used as stabilizers, the bath stability is improved compared to the case where no stabilizer is added, and the plating film. However, the film stress after heat treatment became high. On the other hand, when antimony was used as the stabilizer, the film stress after the heat treatment was remarkably lowered as compared with the case of using a plating bath using another stabilizer and a commercially available plating bath.
表７は、安定剤としてモリブデン（モリブデン酸ナトリウム二水和物、Ｎａ２ＭｏＯ４・２Ｈ２Ｏ）を用いためっき浴を使用した際の結果である。モリブデンを用いた場合では、熱処理後の皮膜応力を低下する効果は観察されなかった。また、モリブデンの量を増やすと、ニッケルが析出せずめっき浴として機能しなかった。 Table 7 shows the results when a plating bath using molybdenum (sodium molybdate dihydrate, Na 2 MoO 4 .2H 2 O) as a stabilizer was used. In the case of using molybdenum, the effect of reducing the film stress after the heat treatment was not observed. Further, when the amount of molybdenum was increased, nickel did not precipitate and did not function as a plating bath.
表８は、安定剤としてアンチモン（酒石酸アンチモニル(III)カリウム・三水和物、Ｃ８Ｈ４Ｋ２Ｏ１２Ｓｂ２・３Ｈ２Ｏ）とモリブデン（モリブデン酸ナトリウム二水和物、Ｎａ２ＭｏＯ４・２Ｈ２Ｏ）の混合物を用いためっき浴を使用した際の結果である。アンチモンとモリブデンを混合した場合では望ましい結果は得られなかった。 Table 8, antimony stabilizer (tartrate Anchimoniru (III) potassium trihydrate, C 8 H 4 K 2 O 12 Sb 2 · 3H 2 O) and molybdenum (sodium molybdate dihydrate, Na 2 MoO 4 is a · 2H 2 O) results when using the mixture of the plating bath used for. When antimony and molybdenum were mixed, the desired result was not obtained.
４．安定剤使用時の錯化剤の混合比率の検討
表９に記載した条件に従ってめっきを行い、安定剤としてアンチモン（酒石酸アンチモニル(III)カリウム・三水和物）を使用した場合における、最適な錯化剤の種類と量を検討した。
4). Examination of mixing ratio of complexing agent when using stabilizer The optimal complex when plating is performed according to the conditions described in Table 9 and antimony (potassium antimonyl (III) potassium tartrate trihydrate) is used as a stabilizer. The type and amount of agent were examined.
表１０は、好ましい錯化剤の組み合わせであると判断されたリンゴ酸とコハク酸の混合比率を種々変更して、析出速度、めっき直後の皮膜応力、および熱処理した後の皮膜応力を調べた結果である（表中、比はキレートモル比である）。 Table 10 shows the results of examining the deposition rate, the film stress immediately after plating, and the film stress after heat treatment by variously changing the mixing ratio of malic acid and succinic acid, which was judged to be a preferable combination of complexing agents. (In the table, the ratio is the chelate molar ratio).
安定剤（アンチモン）を使用した場合でも、リンゴ酸に対するコハク酸の混合比率が高まるにつれて析出速度の増加、引っ張り応力への移行傾向が観察された。また、還元剤の濃度が高いほど析出速度は増加し、応力にもあまり影響がなかったものの、めっき浴の安定性が低下した。リンゴ酸：コハク酸＝４９：５１、還元剤濃度を０．１７５ｍｏｌ／Ｌとするのが最も好ましいと判断された。 Even when a stabilizer (antimony) was used, an increase in precipitation rate and a tendency to shift to tensile stress were observed as the mixing ratio of succinic acid to malic acid increased. In addition, the higher the concentration of the reducing agent, the higher the deposition rate, and although there was not much influence on the stress, the stability of the plating bath decreased. It was judged that malic acid: succinic acid = 49: 51 and the reducing agent concentration was most preferably 0.175 mol / L.
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