CN117779011B - Wafer electroless tungsten plating alloy solution, preparation method and electroless tungsten plating method - Google Patents
Wafer electroless tungsten plating alloy solution, preparation method and electroless tungsten plating method Download PDFInfo
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- CN117779011B CN117779011B CN202410199826.9A CN202410199826A CN117779011B CN 117779011 B CN117779011 B CN 117779011B CN 202410199826 A CN202410199826 A CN 202410199826A CN 117779011 B CN117779011 B CN 117779011B
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- plating
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- tungsten
- nickel
- electroless
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- 238000007747 plating Methods 0.000 title claims abstract description 280
- 238000000034 method Methods 0.000 title claims abstract description 64
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims description 33
- 229910052721 tungsten Inorganic materials 0.000 title claims description 33
- 239000010937 tungsten Substances 0.000 title claims description 33
- 239000000956 alloy Substances 0.000 title claims description 13
- 229910045601 alloy Inorganic materials 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910001080 W alloy Inorganic materials 0.000 claims abstract description 77
- 239000000126 substance Substances 0.000 claims abstract description 36
- 238000007772 electroless plating Methods 0.000 claims abstract description 31
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 12
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 158
- 238000012360 testing method Methods 0.000 claims description 100
- ACVSDIKGGNSZDR-UHFFFAOYSA-N [P].[W].[Ni] Chemical compound [P].[W].[Ni] ACVSDIKGGNSZDR-UHFFFAOYSA-N 0.000 claims description 58
- 238000009713 electroplating Methods 0.000 claims description 54
- 229910001096 P alloy Inorganic materials 0.000 claims description 51
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 37
- 239000010931 gold Substances 0.000 claims description 37
- 229910052737 gold Inorganic materials 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- 238000011282 treatment Methods 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 10
- 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 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- -1 nitro, amino Chemical group 0.000 claims description 6
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 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 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 4
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 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 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- BJZOJDVXMSHAMP-UHFFFAOYSA-K tripotassium 2-phosphonobutane-1,2,4-tricarboxylate Chemical compound [K+].P(=O)(O)(O)C(CC(=O)[O-])(CCC(=O)[O-])C(=O)[O-].[K+].[K+] BJZOJDVXMSHAMP-UHFFFAOYSA-K 0.000 claims description 3
- QXDQVFCXPRBVFR-UHFFFAOYSA-N 1-phosphanylethanamine Chemical compound CC(N)P QXDQVFCXPRBVFR-UHFFFAOYSA-N 0.000 claims description 2
- LDBLRXFNVJQRSI-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;nickel(3+);hydrate Chemical compound O.[Ni+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O LDBLRXFNVJQRSI-UHFFFAOYSA-K 0.000 claims description 2
- LJASZMIARXGOCH-UHFFFAOYSA-N 2-phosphanylethanamine Chemical compound NCCP LJASZMIARXGOCH-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 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 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 2
- XFWCDQMDZATIEY-UHFFFAOYSA-L benzenesulfonate;nickel(2+);hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 XFWCDQMDZATIEY-UHFFFAOYSA-L 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- LQJMXNQEJAVYNB-UHFFFAOYSA-L dibromonickel;hydrate Chemical compound O.Br[Ni]Br LQJMXNQEJAVYNB-UHFFFAOYSA-L 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- OIPXXWBYRWQVLJ-UHFFFAOYSA-G heptasodium;[2-[2-[bis(phosphonatomethyl)amino]ethyl-(phosphonatomethyl)amino]ethyl-(phosphonomethyl)amino]methyl-hydroxyphosphinate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])CN(CP([O-])([O-])=O)CCN(CP([O-])(=O)O)CCN(CP(O)([O-])=O)CP([O-])([O-])=O OIPXXWBYRWQVLJ-UHFFFAOYSA-G 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- GVVGQWPLZQAOSX-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;sodium Chemical compound [Na].NCCNCCN GVVGQWPLZQAOSX-UHFFFAOYSA-N 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- DVWAOMBFCAJFPW-UHFFFAOYSA-L nickel(2+) disulfamate hydrate Chemical compound O.S(N)([O-])(=O)=O.[Ni+2].S(N)([O-])(=O)=O DVWAOMBFCAJFPW-UHFFFAOYSA-L 0.000 claims description 2
- ZBQNIFVEJKLWAA-UHFFFAOYSA-L nickel(2+);carbonate;hydrate Chemical compound [OH-].[Ni+2].OC([O-])=O ZBQNIFVEJKLWAA-UHFFFAOYSA-L 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- CPSVKYWGRAHIGK-UHFFFAOYSA-N nickel(3+) borate hydrate Chemical compound O.[Ni+3].[O-]B([O-])[O-] CPSVKYWGRAHIGK-UHFFFAOYSA-N 0.000 claims description 2
- VBMJUZHLTOKWGA-UHFFFAOYSA-K nickel(3+) phosphate hydrate Chemical compound O.P(=O)([O-])([O-])[O-].[Ni+3] VBMJUZHLTOKWGA-UHFFFAOYSA-K 0.000 claims description 2
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001444 polymaleic acid Polymers 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- GHTWQCXOBQMUHR-UHFFFAOYSA-M potassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [K+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O GHTWQCXOBQMUHR-UHFFFAOYSA-M 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 235000011046 triammonium citrate Nutrition 0.000 claims description 2
- 239000001393 triammonium citrate Substances 0.000 claims description 2
- XKWFRVVFRZYIFP-UHFFFAOYSA-N triazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O XKWFRVVFRZYIFP-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 13
- 239000004065 semiconductor Substances 0.000 abstract description 11
- 230000008054 signal transmission Effects 0.000 abstract description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 56
- 235000012431 wafers Nutrition 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 50
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- 239000011248 coating agent Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 25
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- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 19
- 150000003839 salts Chemical class 0.000 description 12
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
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- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
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- 230000007935 neutral effect Effects 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
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- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 2
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
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- JFGLJTFTVBZOCB-UHFFFAOYSA-N (4-bromo-1-methylpyrazol-3-yl)methanol Chemical compound CN1C=C(Br)C(CO)=N1 JFGLJTFTVBZOCB-UHFFFAOYSA-N 0.000 description 1
- ZEWJFUNFEABPGL-UHFFFAOYSA-N 1,2,4-triazole-3-carboxamide Chemical compound NC(=O)C=1N=CNN=1 ZEWJFUNFEABPGL-UHFFFAOYSA-N 0.000 description 1
- CDCHBOQVXIGZHA-UHFFFAOYSA-N 1,2-dihydropyrrol-5-one Chemical compound O=C1NCC=C1 CDCHBOQVXIGZHA-UHFFFAOYSA-N 0.000 description 1
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- BHTZCIGVYSJBQB-UHFFFAOYSA-N 1-(1h-pyrazol-5-yl)ethanone Chemical compound CC(=O)C=1C=CNN=1 BHTZCIGVYSJBQB-UHFFFAOYSA-N 0.000 description 1
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- DVLGEHCERRWDIX-UHFFFAOYSA-N 1-Ethyl-1H-pyrrole-2-carboxaldehyde Chemical compound CCN1C=CC=C1C=O DVLGEHCERRWDIX-UHFFFAOYSA-N 0.000 description 1
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- REFNCKLJAUXDRN-UHFFFAOYSA-N 1-methyl-1,2,4-triazole-3,5-diamine Chemical compound CN1N=C(N)N=C1N REFNCKLJAUXDRN-UHFFFAOYSA-N 0.000 description 1
- YKEKIXBCQILKAU-UHFFFAOYSA-N 1-methylpyrrolidine-2-carbaldehyde Chemical compound CN1CCCC1C=O YKEKIXBCQILKAU-UHFFFAOYSA-N 0.000 description 1
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- ICFGFAUMBISMLR-UHFFFAOYSA-N 1h-pyrazole-5-carbaldehyde Chemical compound O=CC=1C=CNN=1 ICFGFAUMBISMLR-UHFFFAOYSA-N 0.000 description 1
- BNYCHCAYYYRJSH-UHFFFAOYSA-N 1h-pyrazole-5-carboxamide Chemical compound NC(=O)C1=CC=NN1 BNYCHCAYYYRJSH-UHFFFAOYSA-N 0.000 description 1
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- AQGHRKDJMJXRLK-UHFFFAOYSA-N 1h-pyrrole-2,4-dicarbaldehyde Chemical compound O=CC1=CNC(C=O)=C1 AQGHRKDJMJXRLK-UHFFFAOYSA-N 0.000 description 1
- MKVBQBLIGAFRIY-UHFFFAOYSA-N 1h-pyrrole-2,5-dicarbaldehyde Chemical compound O=CC1=CC=C(C=O)N1 MKVBQBLIGAFRIY-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Chemically Coating (AREA)
Abstract
The invention relates to the technical field of electroless plating, in particular to a tungsten alloy solution for wafer electroless plating, a preparation method and an electroless plating method. The electroless tungsten alloy plating solution comprises the following components in concentration: 70-560 mmol/L of tungstate, 7-56 mmol/L of first stabilizer, 25-480 mmol/L of hypophosphorous acid, 30-240 mmol/L of nickel salt and 0.2-1.6 mmol/L of additive. The invention adopts the method of adding the additive to improve the stability of the chemical plating solution, can ensure that the tungsten alloy plating deposited in the wafer plating area has compact amorphous morphology, has no pinholes and cracks, has a flat and smooth surface, can effectively prevent the defects of unstable signal transmission, high resistance, excessive power loss and the like caused by the defects of pinholes or cracks, and further improves the stability and the reliability of the semiconductor wafer chip product.
Description
Technical Field
The invention relates to the technical field of wafer electroless plating, in particular to a wafer electroless plating tungsten alloy solution, a preparation method and an electroless plating method.
Background
The wafer is an important raw material of chips used for semiconductor circuits, and the wafer electroplating process is a special manufacturing technology in the nano precise manufacturing process of semiconductor electronic components. The application fields comprise wafer chip electroplating, printed board electroplating, lead frame electroplating, connector electroplating, microwave device and other electronic component manufacturing, and the method is the only key technology capable of realizing nanoscale electronic logic interconnection and micro-nano structure manufacturing, processing and forming. The method can deposit a metal coating on the surface of the wafer, and the metal coating can be used for manufacturing electrodes, conductive circuits, reflectors and other electronic devices. It can improve the conductivity and reflection performance of the semiconductor chip. The wafer electroplated product is a chip base electronic material which is not separated from the modern information society, and is widely applied to various aspects of high-tech fields such as aerospace, new energy automobiles, communication electronic industry and the like.
The miniaturization and multifunction of semiconductor electronic products continuously push the development of wafer chips to the direction of line miniaturization and volume miniaturization, and the mainstream products are an HDI (high density interconnection) board and an IC (integrated circuit) substrate. In order to meet the requirements of high density and high integration of HDI and IC substrates, the wafer manufacturing industry chain opens up the nanometer precision manufacturing technology of electronic plating.
Along with the improvement of the requirements of the nano-precision manufacturing technology of electronic plating, the improvement of the electroplating process and the continuous updating of the electroplating solution in the nano-precision manufacturing technology of electronic plating are particularly important, and the high-end semiconductor chip product has very strict requirements on the excellent compactness and high uniformity of a metal coating and the strong corrosion resistance under various severe environments, so that the requirements are important technical indexes for measuring the manufacturing process of the wafer deposited nano-metal coating.
The tungsten alloy coating is summarized in non-patent documents (electroplating and coating, 1998, 17 (3): pp 22), has the characteristics of compact and bright surface, high hardness, good wear resistance, strong corrosion resistance and the like, and is widely applied to electronic products such as new energy automobiles, aerospace, communication and the like and high-precision grinding tool products; however, the alloy plating layer which is electroplated by the tungsten alloy electroplating process has the defects of rough surface, non-uniformity, pitting, high corrosion resistance, substandard performance and the like; severely restricting the application and development of the semiconductor wafer chip in the field of manufacturing high-end semiconductor wafer chip electronic products.
In the prior art, solutions to problems of tungsten alloy electroplating deposited materials focus on research and exploration from three aspects of tungsten alloy electroplating solutions, electroplating equipment and electroplating processes. Patent CN 112111765A provides a method for forming nickel-tungsten alloy coating which can prolong the service life of electroplating solution and form a coating with compact and bright surface on a workpiece; however, the service life of the electroplating solution is only 2000KAh/L, and the continuous electroplating production requirement cannot be met. The nickel-tungsten alloy electroplating solution provided by the patent CN 114959812A relates to an insoluble anode system, which improves the current efficiency of a coating, can effectively reduce the stress in the coating and reduces the generation of cracks after heat treatment; but as core content of the insoluble anode system: the anode material, no specific information is disclosed herein, and therefore, the beneficial effects of the invention are not verified. Patent CN 115323448A provides a tungsten alloy electroplating solution and an electroplating process, the tungsten alloy electrodeposition solution electrodeposits nickel tungsten alloy with excellent corrosion resistance and wear resistance; however, the plating process using stainless steel as an inert anode does not disclose film thickness distribution uniformity data of tungsten alloy of 30 x 60cm for the plated article.
It is known that the plating film thickness of the plated workpiece has a phenomenon that the peripheral edge is high and the middle is low, which is commonly called as a 'pool effect', and the prior art cannot solve the problem. However, the existing electrolytic nickel-tungsten technology does not solve the defects of rough, uneven, pitting and the like of the nickel-tungsten alloy plating layer. To date, no literature report on solutions has been found; the existence of the scientific problems and the technical difficulties in the technical field of the wafer chemical plating tungsten alloy prevents the continuous innovation and increase of the requirements of the aerospace, new energy automobiles and communication electronic industry on high-end electronic component materials, and is a research subject with urgent need for innovation and breakthrough.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects in the prior art and provides a wafer electroless tungsten alloy plating solution, a preparation method and an electroless tungsten alloy plating method. The electroless tungsten alloy plating solution is suitable for special electroplating processing of high-end precise electronic plating parts, and achieves the aim of manufacturing tungsten alloy plating products by electroless plating of the high-end precise electronic plating parts; the chemical plating method is easy to operate, can simply and efficiently manufacture the high-end precise electronic device with high uniformity, excellent compactness, strong corrosion resistance under various severe environments, solves the defects of rough surface, non-uniformity, pits, high corrosion resistance, and the like of a tungsten plating layer, provides various high-end precise electronic devices with complex shapes, and can be widely applied to the field of high-end electronic product electroplating such as wafer chip manufacture, three-dimensional integration and device packaging, sensor, micro-nano device manufacture, micro-electromechanical systems, components and the like.
The technical scheme adopted for solving the technical problems is as follows:
a wafer electroless tungsten alloy plating solution comprising the following concentrations of components:
Tungstate 70-560 mmol/L
7-56 Mmol/L of first stabilizer
30-240 Mmol/L nickel salt
Hypophosphorous acid 25-480 mmol/L
Additives of 0.2-1.6 mmol/L
The solvent is deionized water.
Further, the tungstate is selected from one or more of sodium tungstate dihydrate, sodium metatungstate hydrate, potassium tungstate, ammonium metatungstate and ammonium metatungstate hydrate.
Further, the stabilizer is selected from one or more of sodium formate, tri-ammonium ethylenediamine tetraacetate, potassium ethylenediamine tetraacetate, tri-ammonium citrate, butane-2-1, 2, 4-tricarboxylic acid sodium salt, butane-2, 4-tricarboxylic acid tetrasodium salt, butane-2-phosphono-1, 2, 4-tricarboxylic acid potassium salt, pentasodium diethylenetriamine pentaacetate, heptasodium diethylenetriamine pentamethylenephosphonate, sodium diethylenetriamine pentamethylenephosphonate, diethylenetriamine pentaacetic acid, butane-2, 4-tricarboxylic acid, 2, 3-dihydroxysuccinic acid, butane-2, 4-tricarboxylic acid potassium salt, 3-carboxy-3-hydroxypentanedioic acid, triethylenetetramine hexaacetic acid.
Further, the nickel salt is selected from one or more of nickel sulfate heptahydrate, nickel chloride hexahydrate, nickel nitrate hexahydrate, nickel sulfamate hydrate, nickel benzenesulfonate salt hexahydrate, nickel citrate hydrate, nickel carbonate hydrate, nickel bromide hydrate, nickel phosphate hydrate and nickel borate hydrate.
Further, the hypophosphorous acid is selected from one or more of sodium hypophosphite, potassium hypophosphite, 2-aminoethylphosphine, ammonium hypophosphite and 1-aminoethylphosphine.
Further, the additive comprises a second stabilizer and a metal surfactant, wherein the second stabilizer is a five-membered heterocyclic compound with a substituent R, and the substituent R is one or more selected from methyl, nitro, amino and acyl;
the metal surfactant is selected from one or more of polyacrylic acid with average molecular weight less than 2000, 50wt% of sodium polyacrylate aqueous solution, 40wt% of ammonium polyacrylate aqueous solution, hydroxypropyl acrylate polymer, acrylic acid maleic acid copolymer with molecular weight of 1000, polymaleic acid with molecular weight of 300, heptapolyethylene glycol, octapolyethylene glycol, decapolyethylene glycol, amino polyethylene glycol hydroxyl with molecular weight of 400, polyethylene glycol dicarboxylic acid with molecular weight of 600, polyethylene glycol dicarboxylic acid with molecular weight of 1000, amino-heptapolyethylene glycol-carboxylic acid, amino-nonapolyethylene glycol-carboxylic acid, and polyethylene glycol diacrylate with molecular weight of 1000.
Further, the five-membered heterocyclic compound is selected from one or more of pyrrole, pyrazole, imidazole, triazole and tetrazole;
The pyrrole is selected from one or more of 3-nitropyrrole, 2-aminopyrrole, 3-aminopyrrole, 1-methyl-2-pyrrolidinemethanol, 5-bromopyrrole-3-formaldehyde, 2-propionylpyrrole, pyrrole-3-formaldehyde, 2-acetylpyrrole, pyrrole-2-formaldehyde, 3-pyrrolin-2-one, 3-acetylpyrrole, 1-formylpyrrolidine, 5-bromopyrrole-2-formaldehyde, 2-aldehyde-3-bromopyrrole, (1H-pyrrol-3-yl) methanol, 1H-pyrrole-2, 5-dicarboxaldehyde, 5-methylpyrroline-2-formaldehyde, N-methyl-2-pyrrolidinecarboxaldehyde, 4-bromo-1H-pyrrole-2-formaldehyde, 1H-pyrrole-2, 4-dicarboxaldehyde, 1-ethyl-1H-pyrrole-2-formaldehyde;
The pyrazole is selected from one or more of 3-aminopyrazole, 4-pyrazole formamide, pyrazole-3-formamide, 3-acetamidopyrazole, 1H-pyrazole-3, 5-diamine, 3-nitropyrazole, 4-nitropyrazole, pyrazolone, 3-pyrazole formaldehyde, 1H-pyrazole-5-formaldehyde, 3-acetyl pyrazole, 4-chloro-3-pyrazole formaldehyde, 1-pyrazole methanol, (4-bromo-1-methyl-3-pyrazolyl) methanol;
The imidazole is selected from one or more of 4-nitroimidazole, 2, 4-dinitroimidazole, 2-aminoimidazole sulfate, 1, 5-dimethyl-4-aminoimidazole hydrochloride and 4-imidazole formaldehyde;
the triazole is selected from one or more of 4-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole, 1H-1, 2, 4-triazole-5-amine, 1,2, 4-triazole-3-formamide, 4-amino-4H-1, 2, 4-triazole, 1-methyl-1, 2, 4-1H-triazole-3, 5-diamine;
the tetrazole is selected from one or more of 5-aminotetrazole and 2-methyl-5-amino-2H-tetrazole.
Further, the temperature of the bath solution is 75-85 ℃ during the electroless plating of the wafer electroless plating tungsten alloy solution
The preparation method of the wafer electroless tungsten plating alloy solution specifically comprises the following steps:
Adding deionized water with half of the capacity of a tank into a PP material electrolytic tank, heating to 50 ℃, adding nickel salt a small amount for multiple times under the running condition of a circulating pump, and uniformly dissolving to obtain a solution A, wherein the concentration of the nickel salt in the solution A is 30-240 mmol/L;
Step (2), a 5-liter beaker made of PP material is additionally taken, deionized water with half of the beaker capacity is added, the beaker is heated to 50 ℃, a small amount of first stabilizer is added for many times under the magnetic stirring condition, and solution B is prepared after the solution B is uniformly dissolved, wherein the concentration of the first stabilizer in the solution B is 7-56 mmol/L;
step (3), adding tungstate into the solution A prepared in the step (1) for a small amount for many times, and uniformly dissolving to prepare a solution C, wherein the concentration of the tungstate in the solution C is 25-480 mmol/L;
Step (4), adding hypophosphorous acid into the solution C prepared in the step (3) for a small amount for multiple times, and uniformly dissolving to prepare a solution D, wherein the concentration of the phosphorous acid in the solution D is 25-480 mmol/L;
Step (5), adding additives into the solution D prepared in the step (4) for a small amount for multiple times, and uniformly dissolving to prepare a solution E, wherein the concentration of the additives in the solution E is 0.2-1.6 mmol/L;
Step (6), adding the solution B prepared in the step (2) into the solution E prepared in the step (5) a small amount for many times, and uniformly stirring and mixing to prepare a solution F;
Step (7), adding the rest deionized water into the solution F prepared in the step (6) to prepare a required volume to prepare a solution G;
And (8) continuously operating the pump for 15 minutes, uniformly stirring the solution G prepared in the step (7), and testing the pH value of the solution G to be 4.5-5.5 to obtain the finished wafer electroless tungsten alloy plating solution.
The electroless plating method of the wafer electroless plating tungsten alloy solution comprises the following steps:
step S1, performing alkali degreasing and acid activation treatment on a plated part;
S2, performing bottom nickel plating treatment on the plated piece;
S3, selecting the control temperature and the treatment time of the corresponding electroless plating tungsten alloy solution according to the size of the electroplating area and the thickness of the plating layer required by the plating piece, and placing the plating piece in an electroless plating tank;
Step S4, detecting the nickel concentration, the tungsten concentration, the hypophosphorous acid concentration and the pH value of the tungsten plating alloy solution at regular time, judging the difference from the standard value, and automatically supplementing corresponding chemical components to the insufficient part to finish the tungsten plating nickel phosphorus alloy process;
S5, further carrying out gold plating treatment on the surface of the tungsten nickel phosphorus alloy plating piece obtained in the step S4;
and S6, completing the electroplating process on the plated piece.
Wherein, in the step S3, the chemical plating device can use a single-sided chemical plating mould or a double-sided chemical plating mould.
The beneficial effects of the invention are as follows: the invention has reasonable design, the adopted additive can improve the stability of the chemical plating solution, the tungsten alloy plating deposited in the wafer plating area has compact amorphous morphology, no pinholes and no cracks, has a flat and smooth surface, can effectively prevent the defects of unstable signal transmission, high resistance, excessive power loss and the like caused by the defects of pinholes or cracks, and further improves the stability and the reliability of the semiconductor wafer chip product.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a solution electroless plating method for electroless plating tungsten alloys on wafers in accordance with the present invention;
FIG. 2 is a schematic view of a plated article to be processed in example 1;
FIG. 3 is a schematic diagram of test points of the plating area in the plated item of example 1;
FIG. 4 is an electron microscope scan of example 12;
fig. 5 is an electron microscope scan of comparative example 3.
In the figure: 20. plating member, 21. Plating area.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular forms also include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The electroless plating method of the wafer electroless plating tungsten alloy solution specifically comprises the following steps:
step S1, performing alkali degreasing and acid activation treatment on a plated part;
S2, performing bottom nickel plating treatment on the plated piece;
S3, selecting the control temperature and the treatment time of the corresponding electroless plating tungsten alloy solution according to the size of the electroplating area and the thickness of the plating layer required by the plating piece, and placing the plating piece in an electroless plating tank;
Step S4, detecting the nickel concentration, the tungsten concentration, the hypophosphorous acid concentration and the pH value of the tungsten plating alloy solution at regular time, judging the difference from the standard value, and automatically supplementing corresponding chemical components to the insufficient part to finish the tungsten plating nickel phosphorus alloy process;
S5, further carrying out gold plating treatment on the surface of the tungsten nickel phosphorus alloy plating piece obtained in the step S4;
and S6, completing the electroplating process on the plated piece.
Wherein, in the step S3, the chemical plating device can use a single-sided chemical plating mould or a double-sided chemical plating mould.
The invention applies the tungsten alloy chemical plating solution to the wafer chemical plating processing on the basis of utilizing the precise electroplating mould, thereby realizing the aim of manufacturing the tungsten-nickel-phosphorus alloy plating product by chemical plating on the high-end precise electronic plating piece. The invention is easy to operate, and can simply and efficiently manufacture high-end precise electronic devices with compact amorphous morphology, high uniformity of plating distribution, high corrosion resistance and excellent friction resistance of tungsten nickel phosphorus alloy plating; the invention adopts the method of the additive to improve the stability of the electroplating solution, can ensure that the tungsten alloy plating deposited in the wafer plating area has compact amorphous morphology, no pinholes or cracks, has smooth and flat surface, can effectively prevent difficult problems of unstable signal transmission, high resistance, excessive power loss and the like caused by the defects of pinholes or cracks, further improves the stability and the reliability of semiconductor wafer chip products, and is used for meeting the requirements of high-tech, high-quality and high-precision electronic electroplating product fields and development trend of high-end precision tungsten alloy materials.
Example 1
A wafer electroless tungsten alloy plating solution comprising the following concentrations of components:
the preparation method of the tungsten alloy electroplating solution specifically comprises the following steps:
adding deionized water with half of the capacity of a tank into a PP material electrolytic tank, heating to 50 ℃, adding nickel sulfate heptahydrate for a small amount for multiple times under the running condition of a circulating pump, and uniformly dissolving to obtain a solution A, wherein the concentration of the nickel sulfate heptahydrate in the solution A is 30mmol/L;
Step (2), adding pure water with the capacity of half of that of a PP (polypropylene) beaker, heating to 50 ℃, adding 2-phosphonobutane-1, 2, 4-tricarboxylic acid a small amount of the pure water for multiple times under the condition of magnetic stirring, adding 2-phosphonobutane-1, 2, 4-tricarboxylic acid potassium salt a small amount of the pure water after the pure water is uniformly dissolved, and preparing a solution B after the pure water is uniformly dissolved, wherein the concentration of the 2-phosphonobutane-1, 2, 4-tricarboxylic acid in the solution B is 3.3mmol/L, the concentration of the 2-phosphonobutane-1, 2, 4-tricarboxylic acid potassium salt in the solution B is 3.7mmol/L, and the total concentration of a stabilizer in the solution B is 7.0mmol/L;
adding sodium tungstate dihydrate into the solution A prepared in the step (1) a small amount for many times, and uniformly dissolving to prepare a solution C, wherein the concentration of the sodium tungstate dihydrate in the solution C is 70mmol/L;
Step (4), adding sodium hypophosphite into the solution C prepared in the step (3) a small amount for many times, and uniformly dissolving to prepare a solution D, wherein the concentration of the sodium hypophosphite in the solution D is 25mmol/L;
Adding a small amount of 50wt% sodium polyacrylate aqueous solution into the solution D prepared in the step (4) for a small amount of times, adding a small amount of times after the solution D is uniformly dissolved, adding a small amount of times again, and uniformly dissolving the solution E to obtain a solution E, wherein the concentration of the 50wt% sodium polyacrylate aqueous solution in the solution E is 0.08mmol/L, the concentration of 5-methylpyrrole-2-formaldehyde is 0.12mmol/L, and the total concentration of a stabilizer in the solution E is 0.20mmol/L;
Step (6), adding the solution B prepared in the step (2) into the solution E prepared in the step (5) a small amount for many times, and uniformly stirring and mixing to prepare a solution F;
Step (7), adding the rest deionized water into the solution F prepared in the step (6) to prepare a required volume to prepare a solution G;
And (8) after the pump continues to run for 15 minutes, testing the pH value of the solution G, wherein the pH value is 5.0, and obtaining the finished wafer electroless tungsten alloy plating solution.
Fig. 2 shows a plated part 20 to be processed in this embodiment, which is made of 8 inch (20.32 mm) round copper material with a thickness of 0.35mm, and is obtained by sticking one side of the plated part to a dry film, protecting the other side of the plated part with a 3M dedicated adhesive tape, performing 1) mask exposure, 2) development, 3) demolding, 4) neutralization, 5) cleaning, 6) drying to obtain a single-sided test piece 20 shown in fig. 2 with 58 plating areas 21, wherein only 58 plating areas 21 are contacted with a plating solution during plating, the surface area of each plating area is 6×13=78 mm 2, and the total surface area of the test piece 20 is 58×78mm 2/each=4524 mm 2.
Preparation of the plated article 20 in this example:
Firstly, immersing a plating piece 20 into a prepared tungsten alloy chemical plating solution of the embodiment 1, setting the temperature of a bath solution at 75 ℃ during chemical plating, and treating the plating piece for 13 minutes, wherein the thickness target of a tungsten nickel phosphorus alloy plating layer of a plating piece experimental piece is set to be 700nm;
Secondly, after the obtained tungsten-nickel-phosphorus alloy plating piece 20 is washed by deionized water, the tungsten-nickel-phosphorus alloy plating piece is immediately immersed in a gold plating solution tank, and a high-frequency electroplating power supply is adopted, and a sample of the plating piece 20 in the example 1 is obtained after electroplating for 13 seconds at the current density of 2.0A/dm 2; the preparation conditions of example 1 are listed in table 1.
TABLE 1 preparation conditions for example 1
Example 1 film thickness test of plated article 20 the center black point ∈21 of each of the plated areas I-vii of plated article 20 according to fig. 3 was shown as ∈c-c: column I, 4 (3.24 mm,15.62 mm), 8 (3.24, 12), 12 (3.24,8.32), 16 (3.24,4.64); column II, 3 (5.55, 16.54), 7 (5.55, 12.86), 13 (5.55,7.43), 17 (5.55,3.80); column iii, 2 (7.86 mm,17.46 mm), 6 (7.86, 18.38), 10 (7.86, 10.16), 14 (7.86,6.52), 18 (7.86,2.89); column IV, 1 (10.16 mm,18.35 mm), 5 (10.16, 14.71), 9 (10.16, 11.07), 11 (10.16,9.25), 15 (10.16,5.61), 19 (10.16,1.97); column v, 4 (12.47 mm,15.62 mm), 8 (12.47, 12), 12 (12.47,8.36), 16 (12.47,4.72); 3 (14.78 mm,16.54 mm), 7 (14.78, 12.90), 13 (12.47,7.44), 17 (12.47,3.80) of column VI; column VII, 6 (14.78 mm,18.38 mm), 10 (17.09, 10.16), 14 (17.09,6.52).
The film thickness test of the prepared plating piece 20 of the embodiment 1 adopts a FISCHERSCOPE X-RAY XDV-SDD detector manufactured by Fischer, and the automatic detection is carried out according to the test position of the plating piece 20 shown in figure 3, so that the tungsten-nickel-phosphorus alloy and the gold-plating film thickness data can be simultaneously detected; the tungsten-nickel-phosphorus alloy film thickness test data Max, min, ave, max-Min values for example 1 are listed in table 2, as are the gold-plated film thickness test data in table 3.
TABLE 2 film thickness test results (nm) for tungsten-nickel-phosphorus alloy of example 1
TABLE 3 gold plating film thickness test results (nm)
Examples 2 to 10
In order to investigate the optimal range of the amount of sodium hypophosphite used in the tungsten alloy plating solution, the components of example 1 were the same as those of example 1 except that the sodium hypophosphite concentration was varied in the range of 25 to 70mmol/L, and the details thereof were not repeated. The specific test conditions for the amount of sodium hypophosphite used are shown in Table 4.
TABLE 4 amounts (mmol/L) of sodium hypophosphite used in examples 1 to 10
Examples 2-10 corresponding plated article samples were obtained for appearance and various test measurements in the same manner as in example 1.
Appearance was examined using a 40-fold optical microscope and further observed using an electron microscope at 5000-fold magnification, and the results are shown in table 5.
Table 5 results of appearance inspection of examples 1 to 10
The same preparation conditions as in example 1 were used to perform the tungsten plating and gold plating treatments as in examples 2 to 10, and the tungsten nickel phosphorus alloy film and gold plating film thickness data processing methods were the same as in example 1, and the tungsten nickel phosphorus alloy film thickness data Max, min, ave, max-Min of examples 1 to 10 are shown in table 6, and the gold plating film thickness data Max, min, ave, max-Min are shown in table 7.
TABLE 6 film thickness test results (nm) for tungsten-nickel-phosphorus alloys of examples 1-10
TABLE 7 gold plating film thickness test results (nm) for examples 1 to 10
The sulfur dioxide gas corrosion tests of examples 1 to 10 are carried out according to the national standard GB2423.33-2005, saturated sulfur dioxide test method; the results of examining the ratio of the corrosion area to the entire plating area after 24 hours of test and washing with pure water and drying are shown in Table 8.
Table 8 sulfur dioxide test corrosion (%) examination results
By combining the data shown in tables 4 to 8, the hypophosphorous acid used in examples 3 to 8 was in the optimum range, i.e., the hypophosphorous acid used was 35 to 60mmol/L; when the surface corrosion is lower than 35mmol/L, the corrosion rate of sulfur dioxide test is very high, which indicates that the formed tungsten alloy plating layer has poor compactness, and tiny similar pinhole-shaped areas are observed by an electron microscope, and gaps between similar pinholes or lattices are easy to be invaded by sulfur dioxide gas, so that the substrate metal is corroded; when the amount of hypophosphorous acid used is higher than 60mmol/L, pinholes and irregular bar-shaped areas are observed under an electron microscope, so that the tungsten alloy coating has poor compactness, and sulfur dioxide gas is easy to invade to corrode the substrate metal.
In examples 1 to 10, the total amount of tungsten metal and nickel metal was 100mmol/L; according to the results of the screening experimental conditions, the optimum use range of hypophosphite is 35-60 mmol/L, therefore, the optimum ratio of the hypophosphite to the total metal (tungsten metal and nickel metal) used amount is (0.35-0.60): 1.
The optimum ratio according to the amount of hypophosphite to total metal used is (0.35 to 0.60): 1, wherein the use range of the tungsten compound is 70-560 mmol/L, the use range of the nickel salt is 30-240 mmol/L, the average is divided into 8 equal parts, and the ratio is (0.35-0.60): 1 was also divided into 8 parts to give examples 11 to 17.
Example 11
A wafer electroless tungsten alloy plating solution comprising the following concentrations of components:
example 12
A wafer electroless tungsten alloy plating solution comprising the following concentrations of components:
Example 13
A wafer electroless tungsten alloy plating solution comprising the following concentrations of components:
Example 14
A wafer electroless tungsten alloy plating solution comprising the following concentrations of components:
Example 15
A wafer electroless tungsten alloy plating solution comprising the following concentrations of components:
Example 16
A wafer electroless tungsten alloy plating solution comprising the following concentrations of components:
Example 17
A wafer electroless tungsten alloy plating solution comprising the following concentrations of components:
The tungsten-nickel-phosphorus alloy plated articles 20 prepared in example 3 and example 11 to example 17 were further subjected to the gold plating conditions shown in table 1 of example 1, and the plated articles 20 having the tungsten-nickel-phosphorus alloy and gold plating layer of example 3, example 11 to example 17 were obtained for the subsequent evaluation test.
The amounts of hypophosphorous acid used in example 3, example 11 to example 17 and electroless plating conditions to be applied are shown in Table 9.
Table 9 phosphorous acid usage amount and electroless plating conditions of example 3, example 11 to example 17
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The preparation method and specific steps of the electroplating solutions of examples 11 to 17 are similar to those of example 1, and detailed processes are not repeated.
In example 3 and examples 11 to 17, a plating method was employed in which the plating material 20 was immersed in a wafer plating tungsten alloy solution, and the plating material 20 was subjected to a tungsten-nickel-phosphorus alloy film thickness and gold plating film thickness test and a sulfur dioxide corrosion test in the same manner as in example 1. The film thickness test results of the tungsten-nickel-phosphorus alloy are shown in Table 10, the film thickness test results of the gold plating are shown in Table 11, and the sulfur dioxide corrosion test results are shown in Table 12.
Table 10 film thickness test results (nm) of tungsten-nickel-phosphorus alloys of example 3, example 11 to example 17
As can be seen from the data in Table 10, in order to meet the requirement that the plating specification of the tungsten-nickel-phosphorus alloy product is more than or equal to 700nm, when the minimum value Min range 704-707 nm meets the specification requirement, the distribution of the film thickness Max range 725-729 nm at the periphery edge of the plating piece is higher, the Max-Min difference value data is in the range of 20-22 nm, and for the target plating film thickness of 700nm, the film thickness error is 2.8-3.1%, and the film thickness error is not more than 4%; wherein:
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TABLE 11 gold plating film thickness test results (nm) for example 3, example 11 to example 17
As can be seen from the data in Table 11, in order to meet the requirement that the gold plating film thickness specification is more than or equal to 30nm, when the minimum value Min range of 32-35 nm meets the specification requirement, the distribution of the film thickness Max range of 38-41 nm at the periphery edge of the plating piece is higher, the Max-Min difference data is in the range of 5-7 nm, and for the target plating film thickness of 30nm, the film thickness error is 16.6-23.3%, and the film thickness error is shown to be not more than 24%.
Table 12 test results of sulfur dioxide test corrosion rate (%) in example 3, example 11 to example 17
As can be seen from the data in table 12, the sulfur dioxide experiments of examples 3 and 11 to 17 show excellent results of being completely non-corroding, it is known that the gold plating layer and the nitric acid vapor are metals which are completely non-reactive, and the gold plating layer has a plurality of micro pinholes because the gold plating thickness is only about 30nm, sulfur dioxide gas easily invades the pinholes during the experiment, the surface of the tungsten alloy plating layer of the bottom layer is contacted with sulfur dioxide gas, if the compactness of the tungsten alloy plating layer of 500nm is poor, pinholes, pits or roughness caused by uneven film thickness are formed on the surface, the gold plating layer or the copper surface of the material is invaded by sulfur dioxide gas, and the metal nickel and copper are easily corroded by sulfur dioxide gas; the corrosion phenomenon is not observed in the plating parts 20 of the embodiment 3 and the embodiment 11 to the embodiment 17 under the experimental conditions, and the tungsten alloy plating layer obtained by the electroplating method has excellent compactness, and has no appearance of pinholes, no cracks or uneven film thickness on the surface of the plating layer, so that sulfur dioxide gas can be completely prevented from penetrating through the tungsten nickel phosphorus alloy plating layer, and the bottom nickel plating layer or the copper material is protected from being oxidized and corroded by the sulfur dioxide gas.
The plating methods of the immersion solution method adopted in the above examples 3, 11 to 17 show that the tungsten-nickel-phosphorus alloy plating layer of the present invention has excellent compactness, plating uniformity and strong corrosion resistance.
Comparative example 1
Comparative example 1 sample preparation was carried out by immersion solution plating in the same manner as in examples 1 to 17; the difference is that: the plating conditions of comparative example 1 are shown in Table 13, except that commercial tungsten-nickel plating solutions were used instead of the electroless tungsten alloy plating solutions of the present invention, and the plating times were different. Comparative example 1 the plating samples prepared according to the plating conditions shown in table 13 were tested for the film thickness of the tungsten-nickel-phosphorus alloy, the test data are shown in table 14, and the test results of the film thickness of the gold plating are shown in table 15.
TABLE 13 comparative example 1 electroplating conditions
Table 14 comparative example 1 tungsten Nickel phosphorus alloy film thickness test results (nm)
As can be seen from the data in Table 14, in order to meet the requirement that the product coating specification is more than or equal to 700nm, when the minimum value of 705nm meets the specification requirement, the film thickness distribution of the peripheral edge of the coated part is higher, the maximum value of the film thickness distribution reaches 842nm, the difference between Max and Min is 137nm, and the film thickness error is 19.6% for the target coating film thickness of 700 nm.
Table 15 comparative example 1 gold plating film thickness test results (nm)
As can be seen from the data in Table 15, in order to meet the requirement that the thickness of the gold plating film is not less than 30nm, when the minimum value Min 32nm meets the requirement, the film thickness Max at the peripheral edge of the plated article is 40nm, the difference data of Max-Min is 8nm, and the film thickness error is 26.6% for the target plating film thickness of 30 nm.
Comparative examples 2 to 8
The treatment conditions of comparative examples 2 to 8 are the same as those of comparative example 1, the treatment conditions are shown in Table 16, the results of the film thickness test of the tungsten-nickel-phosphorus alloy of comparative examples 1 to 8 are shown in Table 17, and the results of the film thickness test of the gold plating of comparative examples 1 to 8 are shown in Table 18.
TABLE 16 tungsten plating conditions for comparative examples 1 to 8
Table 17 comparative examples 1 to 8 tungsten-nickel-phosphorus alloy film thickness test results (nm)
As can be seen from the data in Table 17, in order to meet the requirement that the plating specification of the tungsten alloy product is more than or equal to 700nm, when the minimum value Min 702-706 nm meets the specification requirement, the film thickness Max of the periphery edge of the plating part is 840-845 nm, the difference value data of Max-Min is in the range of 135-142 nm, and for the target plating film thickness of 700nm, the film thickness error is 19.2-20.3%, and the film thickness error is not more than 21%.
TABLE 18 comparative examples 1-8 gold plating film thickness test results (nm)
As can be seen from the data in Table 18, in order to meet the requirement that the specification of the gold plating film thickness is more than or equal to 30nm, when the minimum value Min range of 32-35 nm meets the specification requirement, the distribution of the film thickness Max range of the peripheral edge of the plating piece is higher, the difference data of Max-Min is in the range of 6-9 nm, and the film thickness error is 20.0-30.0% for the target plating film thickness of 30 nm.
The results of comparing the film thicknesses Max-Min of the tungsten-nickel-phosphorus alloys of example 3, 11-17 in Table 10 with those of the tungsten-nickel-phosphorus alloys of comparative examples 1-8 in Table 17 are shown in Table 19.
TABLE 19 results of testing film thicknesses Max-Min (nm) of tungsten-plated alloys of examples and comparative examples
As shown in the comparison result of Max-Min data of examples and comparative examples shown in Table 19, the electroplating method of immersing in the electroplating solution by electroplating the tungsten alloy solution by using the wafer of the invention is compared with the tungsten nickel electroplating solution method of the prior art, the Max-Min data range of 20-22 nm of the examples is far lower than the Max-Min data range of 135-142 nm of the comparative examples, the film thickness error of the examples is 2.8-3.1% and the film thickness error of the comparative examples is 19.2-20.3% when compared with the standard of more than or equal to 700nm, and the film thickness error of the examples is far lower than the film thickness error of the comparative examples, thereby indicating that the uniformity of the surface of the plated part of the invention is better.
Example 18
The plating samples prepared in example 3, example 11 to example 17 and comparative examples 1 to 8 were subjected to sulfur dioxide test, plating product surface roughness test, plating product friction test, plating hardness test and plating neutral salt spray test.
(1) Sulfur dioxide gas test for tungsten-nickel-phosphorus/gold plating
The sulfur dioxide gas test is carried out according to the national standard GB2423.33-2005 and the saturated sulfur dioxide test method.
Experimental time: 48 hours.
Test sample: example 3, examples 11 to 17, comparative examples 1 to 8 were tungsten nickel phosphorus/gold plating.
The test results are shown in% corrosion and are shown in Table 20
Table 20 test results of sulfur dioxide gas test corrosion (%) for examples and comparative examples
As shown in Table 20, the comparative results of the sulfur dioxide gas test corrosion rates of example 3, example 11 to example 17 and comparative examples 1 to 8 indicate that the corrosion rate of the tungsten-nickel-phosphorus alloy of the present invention is 0.00%, and the corrosion rate of the tungsten-nickel-metal plating layer of the present invention is stronger and more excellent than that of the tungsten-nickel-metal plating layer of the prior art of 6.39 to 7.52%.
(2) Surface roughness test of tungsten-nickel-phosphorus/gold plating
The surface roughness test of the plated product is implemented according to the national standard GB3505-83, and the surface roughness is measured by adopting a 3D contour measuring instrument VR-6000 manufactured by Kidney.
Test sample: example 3, examples 11 to 17, comparative examples 1 to 8 were tungsten nickel phosphorus/gold plating.
The test results are shown in nm units and are shown in Table 21.
Table 21 results of surface roughness (Ra) test of examples and comparative examples
As is clear from Table 21, the results of comparison of the surface roughness of examples 3, 11 to 17 and comparative examples 1 to 8 show that the surface roughness of the plating article is in a very low range compared with 329 to 339nm of the prior art tungsten alloy plating solution method by the electroless plating method of the present invention, and thus the surface compactness and the smoothness of the surface of the plating article are more advantageous.
(3) Friction test of tungsten-nickel-phosphorus/gold coating
The sliding friction and wear test of the coating is implemented according to the national standard GB-T12444-2006, and CSM ball friction and wear test equipment is adopted.
Test sample: example 3, examples 11 to 17, comparative examples 1 to 8 were tungsten nickel phosphorus/gold plating.
The test results are expressed in terms of the loss amount (mg) of the weight difference before and after the friction test, and the results are shown in Table 22
Table 22 results of the friction loss (mg) test for examples and comparative examples
Table 22 shows that, in the results of the plating friction loss amounts of examples 3, 11 to 17 and comparative examples 1 to 8, the friction loss amounts of examples were 0.01 to 0.03mg, the friction loss amounts of comparative examples were 9.2 to 9.9mg, and the friction loss amounts of examples were significantly smaller than those of comparative examples. Therefore, compared with the tungsten metal plating layer in the prior art, the tungsten-nickel-phosphorus alloy has stronger friction resistance.
(4) Hardness test of tungsten-nickel-phosphorus/gold coating
Test sample: example 3, examples 11 to 17, comparative examples 1 to 8 were tungsten nickel phosphorus/gold plating.
The detection purpose is as follows: resistance to mechanical effects such as impact, scoring; and the compactness of the coating, the better the compactness, the higher the hardness of the coating, the poor the compactness and the reduced the hardness of the coating.
The test method comprises the following steps: and measuring the plating layer by adopting a triangular pressure head of a microhardness meter.
Performing a standard; GB/T9790-2021 microhardness test of metallic materials, metals and other inorganic coverings.
Test equipment: wilson hardness tester.
Evaluation criteria: hardness unit kg/mm 2, expressed as HV.
The test results are shown in Table 23 as plating hardness (Hv).
Table 23 plating hardness (Hv) test results for examples and comparative examples
As is clear from Table 23, in the results of the hardness (Hv) tests of the plating layers of examples 11 to 17 and comparative examples 1 to 8, the vickers hardness of the plating layers deposited in the comparative examples was as high as 1123 to 1146Hv, and the internal stress was strong, and thus the plating layers were liable to peel and the plating cracks were liable to occur. The tungsten-nickel-phosphorus alloy plating layer of the invention achieves the purpose of reducing the Vickers hardness of the tungsten plating layer by forming alloy with nickel, phosphorus and tungsten with the Vickers hardness of 901-908 Hv; meanwhile, as phosphorus enters the tungsten nickel alloy, the binding force between the phosphorus and the bottom nickel layer on the surface of the plating piece is greatly improved, and the difficult problem of pinholes or cracks existing in the tungsten plating layer is solved.
(5) Neutral salt spray test of tungsten nickel phosphorus coating
Performing a standard; GB/T2423.17-2008 "basic environmental test protocol test for Electrical and electronic products Ka: salt spray test method, GB/T2423.18-2000, electrical and electronic product Environment test part 2: test Kb: salt mist, alternation (sodium chloride solution)
Test sample: example 3, examples 11 to 17, comparative examples 1 to 8.
Test time: 96 hours.
Test equipment: MRT-YWX-90 type salt spray corrosion testing machine.
The test content is as follows: defects such as corrosion spots, bubbles, skinning, cracking, discoloration and the like of the appearance of the sample.
The evaluation method comprises the following steps: and observing the whole surface area of the gold plating under the condition of amplifying by 70 times by using an electron microscope, wherein the corroded area is expressed by percent, the greater the numerical value is, the greater the corroded area is, the poorer the corrosion resistance is, and conversely, the smaller the numerical value is, the smaller the corroded area is, and the corrosion resistance is stronger.
The test results are shown in% corrosion area and are shown in Table 24.
Table 24 results of salt spray test corrosion rate (%) test of examples and comparative examples
Table 24 shows that, for the neutral salt spray test results of the tungsten-nickel-phosphorus alloy plating layers of examples 3, 11 to 17, and comparative examples 1 to 8, the salt spray test corrosion rate of examples is 0.00 to 0.01%, and the salt spray test corrosion rate of comparative examples is 1.17 to 1.82%; the tungsten nickel phosphorus alloy plating layer prepared by the electroplating method for the wafer chemical plating tungsten alloy solution has better corrosion resistance; the plating layer compactness of the electronic plating tungsten alloy solution is superior to that of the tungsten nickel alloy plating method in the prior art.
The tungsten nickel phosphorus alloy plating layers prepared by the electroplating method of the wafer electroless tungsten alloy plating solution of the invention have better corrosion resistance performance by combining the appearance test results (fig. 4 and 5) of an electron microscope, the plating layers of the tungsten nickel phosphorus alloy plating and the gold plating of comparative examples 1 to 8 and the test results of sulfur dioxide gas, the surface roughness and the friction loss amount; the plating layer compactness of the wafer electroplated tungsten alloy solution is superior to that of the tungsten nickel alloy electroplating method in the prior art.
In summary, the beneficial effects of the invention are as follows:
(1) The experimental results of the examples and the comparative examples are combined, and it can be observed that the maximum value of the thickness of the tungsten-nickel alloy plating film of all the comparative examples is far higher than that of the tungsten-nickel-phosphorus alloy plating film of the examples; also, the average value of the plating film thickness of all comparative examples was far higher than that of the examples; therefore, the tungsten nickel phosphorus plating solution for the wafer tungsten alloy has better uniform distribution performance by adopting an immersion plating method;
(2) The results of electron microscope tests on the surfaces of the plating layers of the embodiment and the comparative example adopting the immersion plating method show that the comparative example in the prior art is a composite plating layer of a tungsten nickel/gold plating layer or a tungsten nickel alloy single plating layer, and the compactness of the surface of the plating layer is poor due to the influence of the characteristics of plating solution; according to the chemical plating solution for the wafer tungsten alloy, through the combination of the selected chemical plating solution and hypophosphorous acid, the electrolytic precipitated tungsten-nickel-phosphorus alloy plating layer forms an amorphous structure, so that the compactness of the surface of the plating layer is greatly improved, and the surface of the plating layer is flat and smooth;
(3) The ratio of the molar amount of hypophosphorous acid used to the total molar amount of metallic tungsten and metallic nickel used in the above examples was (0.35 to 0.60): 1; in the above range, the plating layer precipitated by immersion type chemical plating of the tungsten alloy chemical plating solution of the invention has high uniformity of distribution, high corrosion resistance and excellent friction resistance; the defects of unstable signal transmission, high resistance, excessive power loss and the like caused by the defects of pinholes or cracks on the surface of a plating layer in the existing tungsten-nickel plating technology are overcome;
(4) Compared with the prior art, the sulfur dioxide gas test result of the prepared electroplating product is far more corrosion-resistant than the prior art electroplating method; from the corrosion state of the test sample after sulfur dioxide gas test, pinhole-shaped corrosive oozes out from the surface of the sample of the comparative example, and corrosion of a coating crack area, wherein the existence of pinholes and cracks indicates that the uniformity of an electroplating film layer on the surface of a plating piece is insufficient, so that the compactness performance of a metal coating is poor; meanwhile, the surface roughness of the electroplated product in the prior art is too high, pinholes and surface cracks on the surface of the electroplated part are easy to invade the surface of the internal substrate when being attacked by sulfur dioxide under the test condition of sulfur dioxide, and the electroplated part is corroded with metallic nickel or metallic copper with poor corrosion resistance, so that the product is damaged from the inside, and the electronic product cannot meet the corrosion resistance requirement;
(5) Compared with the prior art, the chemical plating method has the core technical method that the combination proportion and the total use quantity of the stabilizing agents in the tungsten-nickel-phosphorus alloy plating solution are regulated, and the chemical plating method not only solves the problem of uneven thickness of the plating film of the plating product, but also can coordinate and maintain the long-term stability of the tungsten-nickel-phosphorus alloy plating solution, and ensures that the tungsten-nickel-phosphorus alloy plating layer of the plating product manufactured by continuous electroplating has high distribution uniformity, high corrosion resistance and excellent friction resistance; the technical problems of unstable signal transmission, high resistance, excessive power loss and the like caused by defects of plating pinholes or cracks in the existing tungsten-nickel plating technology are solved; the method provides a feasible solution for solving a series of difficult problems that the uniformity of a tungsten nickel alloy coating in the electroplating industry is poor, the compactness of the coating is not up to the requirements and the corrosion resistance are low, and pinholes or cracks are easy to be generated in the tungsten nickel alloy coating;
(6) The electroless plating solution and the electroless plating method for the wafer tungsten alloy can be suitable for electroless plating production and processing in various modes immersed in the electroplating solution, such as single-piece electroplating products of the wafer plating piece and continuously running terminal products of the embodiment of the invention; the method can also be applied to plating equipment for plating, and the partial areas of various precise electronic plating products can be processed by electrolysis to provide feasible plating process routes;
(7) The chemical plating solution and the chemical plating method for the wafer tungsten alloy fully show that the tungsten nickel phosphorus alloy plating layer prepared by the chemical plating method for the chemical plating tungsten alloy solution has better corrosion resistance by carrying out the appearance test result of an electron microscope, the sulfur dioxide gas test result, the surface roughness test result, the friction loss test result and the plating hardness test result on the plating piece 20 with the plating layer of the plating tungsten nickel phosphorus alloy and the gold plating; the plating compactness of the electroless tungsten alloy plating solution is superior to that of the tungsten nickel alloy plating method in the prior art; in addition, the neutral salt spray experimental result of the plating solution for the wafer chemical plating of the tungsten alloy is shown that the tungsten nickel phosphorus alloy plating layer prepared by the plating method for the wafer chemical plating of the tungsten alloy has better corrosion resistance; the plating compactness of the electroless tungsten alloy plating solution is superior to that of the tungsten nickel alloy plating method in the prior art;
(8) The tungsten nickel phosphorus alloy plating layer provided by the chemical plating solution and the chemical plating method for the wafer tungsten alloy is characterized in that atoms of the tungsten nickel phosphorus alloy plating layer are not arranged in a period in a reduction forming process during chemical precipitation, so that a long-range disordered amorphous state is formed, and the periodic and symmetrical arrangement of the atoms of a metal material is different from that of the atoms of the metal material under normal conditions, so that the tungsten nickel phosphorus alloy plating layer is called amorphous alloy; therefore, the tungsten nickel phosphorus alloy plating layer has the inherent characteristics of an amorphous structure, has high compactness, good surface smoothness and glossiness, excellent plating layer distribution uniformity and strong corrosion resistance to sulfur dioxide gas and salt fog acceleration test conditions; the tungsten alloy solution for wafer chemical plating provided by the invention is organically combined with various precise electroplating dies, so that various precise nano electroplating methods formed in an optimized manner have very wide application prospects in high-precision electronic industry and semiconductor manufacturing industry, especially in high-speed development of the high-precision wafer electroplating industry;
(9) The chemical plating solution and the chemical plating method for the wafer tungsten alloy provided by the invention provide an excellent scheme for selectively plating the tungsten alloy in order to solve a series of problems existing in the existing tungsten plating and electroplating methods; in addition to the performance characteristics of the tungsten nickel phosphorus alloy plating layer precipitated by the various tungsten plating alloy solutions, in the tungsten plating alloy of the invention, expensive tungsten metal resources can be saved by the participation of nickel and phosphorus.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (7)
1. The wafer electroless tungsten plating alloy solution is characterized in that: comprises the following components in concentration:
Tungstate 70-560 mmol/L
7-56 Mmol/L of first stabilizer
30-240 Mmol/L nickel salt
Hypophosphorous acid 25-480 mmol/L
Additives of 0.2-1.6 mmol/L
The solvent is deionized water;
The first stabilizer is selected from one or more of sodium formate, tri-ammonium ethylenediamine tetraacetate, potassium ethylenediamine tetraacetate, tri-ammonium citrate, sodium salt of 2-phosphonobutane-1, 2, 4-tricarboxylic acid, potassium salt of 2-phosphonobutane-1, 2, 4-tricarboxylic acid, pentasodium diethylenetriamine pentaacetate, heptasodium diethylenetriamine pentamethylenephosphonate, sodium diethylenetriamine pentamethylenephosphonate, diethylenetriamine pentaacetic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 2, 3-dihydroxysuccinic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid potassium salt, 3-carboxyl-3-hydroxypentanedioic acid, triethylenetetramine hexaacetic acid;
The additive comprises a second stabilizer and a metal surfactant, wherein the second stabilizer is a five-membered heterocyclic compound with a substituent R, and the substituent R is one or more selected from methyl, nitro, amino and acyl;
The metal surfactant is selected from one or more of polyacrylic acid with average molecular weight less than 2000, 50wt% of sodium polyacrylate aqueous solution, 40wt% of ammonium polyacrylate aqueous solution, hydroxypropyl acrylate polymer, acrylic acid maleic acid copolymer with molecular weight of 1000, polymaleic acid with molecular weight of 300, heptapolyethylene glycol, octapolyethylene glycol, decapolyethylene glycol, amino polyethylene glycol hydroxyl with molecular weight of 400, polyethylene glycol dicarboxylic acid with molecular weight of 600, polyethylene glycol dicarboxylic acid with molecular weight of 1000, amino-heptapolyethylene glycol-carboxylic acid, amino-nonapolyethylene glycol-carboxylic acid, and polyethylene glycol diacrylate with molecular weight of 1000;
The five-membered heterocyclic compound is selected from one or more of pyrrole, pyrazole, imidazole, triazole and tetrazole.
2. The electroless tungsten wafer plating solution according to claim 1, wherein: the tungstate is selected from one or more of sodium tungstate dihydrate, sodium metatungstate hydrate, potassium tungstate, ammonium metatungstate and ammonium metatungstate hydrate.
3. The electroless tungsten wafer plating solution according to claim 1, wherein: the nickel salt is selected from one or more of nickel sulfate heptahydrate, nickel chloride hexahydrate, nickel nitrate hexahydrate, nickel sulfamate hydrate, nickel benzenesulfonate hexahydrate, nickel citrate hydrate, nickel carbonate hydrate, nickel bromide hydrate, nickel phosphate hydrate and nickel borate hydrate.
4. The electroless tungsten wafer plating solution according to claim 1, wherein: the hypophosphorous acid is selected from one or more of sodium hypophosphite, potassium hypophosphite, 2-aminoethylphosphine, ammonium hypophosphite and 1-aminoethylphosphine.
5. The electroless tungsten wafer plating solution according to claim 1, wherein: the temperature of the bath solution for electroless plating of the wafer electroless plating tungsten alloy solution is 75-85 ℃.
6. A method for preparing a wafer electroless tungsten alloy plating solution according to any one of claims 1 to 5, wherein: the method specifically comprises the following steps:
Adding deionized water with half of the capacity of a tank into a PP material electrolytic tank, heating to 50 ℃, adding nickel salt a small amount for multiple times under the running condition of a circulating pump, and uniformly dissolving to obtain a solution A, wherein the concentration of the nickel salt in the solution A is 30-240 mmol/L;
Step (2), a 5-liter beaker made of PP material is additionally taken, deionized water with half of the beaker capacity is added, the beaker is heated to 50 ℃, a small amount of first stabilizer is added for many times under the magnetic stirring condition, and solution B is prepared after the solution B is uniformly dissolved, wherein the concentration of the first stabilizer in the solution B is 7-56 mmol/L;
step (3), adding tungstate into the solution A prepared in the step (1) for a small amount for many times, and uniformly dissolving to prepare a solution C, wherein the concentration of the tungstate in the solution C is 25-480 mmol/L;
Step (4), adding hypophosphorous acid into the solution C prepared in the step (3) for a small amount for multiple times, and uniformly dissolving to prepare a solution D, wherein the concentration of the phosphorous acid in the solution D is 25-480 mmol/L;
Step (5), adding additives into the solution D prepared in the step (4) for a small amount for multiple times, and uniformly dissolving to prepare a solution E, wherein the concentration of the additives in the solution E is 0.2-1.6 mmol/L;
Step (6), adding the solution B prepared in the step (2) into the solution E prepared in the step (5) a small amount for many times, and uniformly stirring and mixing to prepare a solution F;
Step (7), adding the rest deionized water into the solution F prepared in the step (6) to prepare a required volume to prepare a solution G;
And (8) continuously operating the pump for 15 minutes, uniformly stirring the solution G prepared in the step (7), and testing the pH value of the solution G to be 4.5-5.5 to obtain the finished wafer electroless tungsten alloy plating solution.
7. An electroless plating method of a wafer electroless plating tungsten alloy solution according to any one of claims 1 to 5, characterized in that: the method specifically comprises the following steps:
step S1, performing alkali degreasing and acid activation treatment on a plated part;
S2, performing bottom nickel plating treatment on the plated piece;
S3, selecting the control temperature and the treatment time of the corresponding electroless plating tungsten alloy solution according to the size of the electroplating area and the thickness of the plating layer required by the plating piece, and placing the plating piece in an electroless plating tank;
Step S4, detecting the nickel concentration, the tungsten concentration, the hypophosphorous acid concentration and the pH value of the tungsten plating alloy solution at regular time, judging the difference from the standard value, and automatically supplementing corresponding chemical components to the insufficient part to finish the tungsten plating nickel phosphorus alloy process;
S5, further carrying out gold plating treatment on the surface of the tungsten nickel phosphorus alloy plating piece obtained in the step S4;
and S6, completing the electroplating process on the plated piece.
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