TW201406992A - 用於鎳層無電沈積之鍍浴 - Google Patents
用於鎳層無電沈積之鍍浴 Download PDFInfo
- Publication number
- TW201406992A TW201406992A TW102119832A TW102119832A TW201406992A TW 201406992 A TW201406992 A TW 201406992A TW 102119832 A TW102119832 A TW 102119832A TW 102119832 A TW102119832 A TW 102119832A TW 201406992 A TW201406992 A TW 201406992A
- Authority
- TW
- Taiwan
- Prior art keywords
- plating bath
- nickel
- electroless plating
- group
- aqueous
- Prior art date
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000007747 plating Methods 0.000 title claims abstract description 64
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 48
- 230000008021 deposition Effects 0.000 title claims abstract description 23
- 239000003381 stabilizer Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 20
- 238000007772 electroless plating Methods 0.000 claims description 33
- 238000000151 deposition Methods 0.000 claims description 25
- 239000003638 chemical reducing agent Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- -1 C 4 alkane Chemical class 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 229910002065 alloy metal Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 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 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000000138 intercalating agent Substances 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000000956 alloy Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000012312 sodium hydride Substances 0.000 description 7
- 229910000104 sodium hydride Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000087 stabilizing effect Effects 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229910001096 P alloy Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 229910000085 borane Inorganic materials 0.000 description 5
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical group [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- 230000002378 acidificating effect Effects 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- YGTZTXICKXYYBD-UHFFFAOYSA-N 3-(prop-2-ynylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCNCC#C YGTZTXICKXYYBD-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- NEEDEQSZOUAJMU-UHFFFAOYSA-N but-2-yn-1-ol Chemical compound CC#CCO NEEDEQSZOUAJMU-UHFFFAOYSA-N 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229960002449 glycine Drugs 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- TVGVYYLGHGAKNU-UHFFFAOYSA-M sodium 2-prop-2-ynoxyacetate Chemical compound [Na+].[O-]C(=O)COCC#C TVGVYYLGHGAKNU-UHFFFAOYSA-M 0.000 description 2
- POIGZCIVRUKYCD-UHFFFAOYSA-M sodium 2-prop-2-ynoxypropanoate Chemical compound [Na+].CC(OCC#C)C([O-])=O POIGZCIVRUKYCD-UHFFFAOYSA-M 0.000 description 2
- QVZMIHUVEFXHBC-UHFFFAOYSA-M sodium 4-but-3-ynoxybutane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCCOCCC#C QVZMIHUVEFXHBC-UHFFFAOYSA-M 0.000 description 2
- VWXGNFUAUQOLGU-UHFFFAOYSA-M sodium 4-prop-2-ynoxybutane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCCOCC#C VWXGNFUAUQOLGU-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- LDHXNOAOCJXPAH-UHFFFAOYSA-M sodium;prop-2-yne-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC#C LDHXNOAOCJXPAH-UHFFFAOYSA-M 0.000 description 2
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- HOZBSSWDEKVXNO-DKWTVANSSA-N 2-aminobutanedioic acid;(2s)-2-aminobutanedioic acid Chemical compound OC(=O)C(N)CC(O)=O.OC(=O)[C@@H](N)CC(O)=O HOZBSSWDEKVXNO-DKWTVANSSA-N 0.000 description 1
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- ULHLNVIDIVAORK-UHFFFAOYSA-N 2-hydroxybutanedioic acid Chemical compound OC(=O)C(O)CC(O)=O.OC(=O)C(O)CC(O)=O ULHLNVIDIVAORK-UHFFFAOYSA-N 0.000 description 1
- OORRCVPWRPVJEK-UHFFFAOYSA-N 2-oxidanylethanoic acid Chemical compound OCC(O)=O.OCC(O)=O OORRCVPWRPVJEK-UHFFFAOYSA-N 0.000 description 1
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 1
- KVZLHPXEUGJPAH-UHFFFAOYSA-N 2-oxidanylpropanoic acid Chemical compound CC(O)C(O)=O.CC(O)C(O)=O KVZLHPXEUGJPAH-UHFFFAOYSA-N 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
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000005299 abrasion 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
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- OTJZCIYGRUNXTP-UHFFFAOYSA-N but-3-yn-1-ol Chemical compound OCCC#C OTJZCIYGRUNXTP-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- KDOWHHULNTXTNS-UHFFFAOYSA-N hex-3-yne-2,5-diol Chemical compound CC(O)C#CC(C)O KDOWHHULNTXTNS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 description 1
- 229940005631 hypophosphite ion Drugs 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- CXIHYTLHIDQMGN-UHFFFAOYSA-L methanesulfonate;nickel(2+) Chemical compound [Ni+2].CS([O-])(=O)=O.CS([O-])(=O)=O CXIHYTLHIDQMGN-UHFFFAOYSA-L 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 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
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009662 stress testing Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000000080 wetting agent 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
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Abstract
本發明係關於用於鎳及鎳合金沈積之水性鍍浴組合物,其利用具有碳碳參鍵及官能基之新穎穩定劑來增強該浴效能。
Description
本發明係關於用於鎳及鎳合金之無電沈積之水性鍍浴組合物。由本發明獲得之鎳塗層展示出較高均一性及較高硬度、良好的耐磨性及耐腐蝕性。此類塗層適合在航空、汽車、電力及化學工業中作為功能性塗層。自此類鍍浴沈積之金屬層亦適合在半導體裝置、印刷電路板、IC基板及其類似物中作為障壁及頂蓋層。
障壁層用於諸如半導體裝置、印刷電路板、IC基板及其類似物之電子裝置中,以分隔不同組合物層,且進而防止在該等不同組合物層之間的非所需擴散。
典型的障壁層材料為二元鎳合金,諸如Ni-P合金,其通常藉由無電電鍍而沈積至第一組合物之第一層上,隨後將第二組合物之第二層沈積至障壁層上。該第一層可由銅或鋁組成。
障壁層材料在電子裝置中之另一應用為作為頂蓋層,例如將其沈積至銅上以防止銅腐蝕。
鎳及鎳合金沈積物之另一應用為針對各種基板之腐蝕保護。
用於無電鍍鎳溶液之組合物為此項技術中已知。舉例而言,美國專利2,658,841教示可溶性有機酸鹽作為用於無電鍍鎳溶液之緩衝劑之用途。美國專利2,658,842教示短鏈二羧酸作為EN浴之激發劑之用
途。美國專利2,762,723教示將硫化物及含硫添加劑用於無電鍍鎳浴以用於改良浴穩定性。
美國專利2,847,327已介紹穩定無電鍍鎳溶液之其他手段。此等手段包括使用較高純度之起始物質;來自諸如Pb、Sb、Bi、Cu及Se之重金屬類別之較有效的穩定劑;無機化合物,諸如碘酸鹽,及硫代化合物;有機化合物,諸如不飽和烯烴與炔烴及其他。
本發明之目標為提供用於鎳及鎳合金沈積之無電鍍浴,其具有對抗非所需分解之較高穩定性且提供均一塗層。
此目標藉由提供一種用於鎳及鎳合金之無電沈積之水性鍍浴組合物而得以解決,該鍍浴包含(i)鎳離子之來源,(ii)至少一種錯合劑,(iii)至少一種還原劑,(iv)式(1)之穩定劑:
其中X係選自O及NR4,n在1至6範圍內,m在1至8範圍內;R1、R2、R3及R4係獨立地選自氫及C1至C4烷基;Y係選自-SO3R5、-CO2R5及-PO3R5 2,且R5係選自氫、C1-C4烷基及適合之相對離子。
本發明進一步關於一種藉由將待電鍍之基板浸沒至上述電鍍液中來沈積鎳及鎳合金之方法。
圖1展示具有用於無電鎳沈積之銅襯墊之測試基板。
圖2展示在儲存時間(亦稱為閒置時間)期間,含有本發明穩定劑(樣品1至3)或比較化合物(樣品6)之無電鎳沈積浴之穩定性。
用於施加鎳塗層之無電鍍鎳組合物為此項技術中所熟知,且電鍍方法及組合物描述於大量公開案中,諸如美國專利第2,935,425號;第3,338,726號;第3,597,266號;第3,717,482號;第3,915,716號;第4,467,067號;第4,466,233號及第4,780,342號。無電電鍍通常描述不使用外部電流源來還原金屬離子之方法。通常將後者描述為電解或電化電鍍法。在無電電鍍溶液中,使用如次磷酸鹽、硼烷或甲醛之化學還原劑將金屬離子還原成其金屬形式,且進而在基板上形成沈積物。
一種常用之鎳合金沈積物為鎳磷(NiP)合金。一般而言,NiP沈積溶液包含溶解於溶劑(通常為水)中之至少四種成分。該等成分為(1)鎳離子之來源,(2)還原劑,(3)提供需要之pH值之酸或氫氧化物pH值調節劑,及(4)足以防止金屬離子在溶液中沈澱之金屬離子之錯合劑。用於NiP溶液之大量適合之錯合劑描述於以上提到之公開案中。若使用次磷酸鹽作為還原劑,則沈積物將含有鎳及磷。類似地,若採用胺硼烷,則沈積物將含有鎳及硼,如美國專利第3,953,654號中所示。
鎳離子可藉由使用任何可溶性鹽來提供,諸如硫酸鎳、氯化鎳、乙酸鎳、甲基磺酸鎳及其混合物。溶液中鎳之濃度可廣泛變化,且為約0.1至60g/l,較佳為約2至50g/l,例如4至10g/l。
還原劑通常且較佳為次磷酸根離子,其藉由任何適合之來源(諸如次磷酸鈉、次磷酸鉀、次磷酸銨及次磷酸鎳)提供至浴中。亦可適當採用其他還原劑,諸如胺硼烷、硼氫化物、肼及其衍生物及甲醛。還原劑之濃度通常莫耳濃度超過足以還原浴中之鎳之量。還原劑之濃
度通常在0.05至0.35mol/l範圍內。
浴可為酸性、中性或鹼性,且酸性或鹼性pH值調節劑可選自廣泛範圍之物質,諸如氫氧化銨、氫氧化鈉、鹽酸及其類似物。浴之pH值可在約2至12範圍內,且較佳為酸性浴。建議較佳3.5至7、更佳4至6.5之弱酸性pH值範圍。
用於鎳及鎳合金電鍍之鍍浴組合物中包括錯合劑(有時亦稱為螯合劑)或錯合劑之混合物。
在一個實施例中,羧酸、羥基羧酸、胺基羧酸及前述之鹽或其混合物可用作錯合劑。適用之羧酸包括單-、雙-、三-及四-羧酸。羧酸可經各種取代基部分(諸如羥基或胺基)取代,且該等酸可以其鈉鹽、鉀鹽或銨鹽形式引入鍍浴中。舉例而言,某些錯合劑,諸如乙酸亦可充當pH值緩衝劑,且考慮到該等添加劑組分之雙重功能性,該等組分之適合濃度可經最佳化以用於任何鍍浴。
適用作本發明鍍浴中之錯合劑或螯合劑之此類羧酸之實例包括:單羧酸,諸如乙酸、羥基乙酸(乙醇酸)、胺基乙酸(甘胺酸)、2-胺基丙酸(丙胺酸);2-羥基丙酸(乳酸);二羧酸,諸如丁二酸、胺基丁二酸(天冬胺酸)、羥基丁二酸(蘋果酸)、丙二酸(propanedioic acid、malonic acid)、酒石酸;三羧酸,諸如2-羥基-1,2,3丙烷三羧酸(檸檬酸);及四羧酸,諸如乙二胺四乙酸(EDTA)。在一個實施例中,在本發明之鍍浴中使用上述錯合劑/螯合劑中之兩者或兩者以上之混合物。
烷基胺亦可用作為錯合劑,例如單-、雙-及三烷基胺。較佳為C1-C3烷基胺,例如三乙醇胺。
錯合劑之濃度,或在使用超過一種錯合劑之情況下所有錯合劑一起之濃度較佳在0.01至3.0mol/l範圍內,更佳為0.1至1.0mol/l,且甚至更佳為0.2-0.6mol/l。
在次磷酸鹽化合物用作還原劑之情況下,獲得Ni-P合金沈積物。基於硼烷之化合物作為還原劑產生Ni-B合金沈積物,且次磷酸鹽與基於硼烷之化合物之混合物作為還原劑產生三元Ni-B-P合金沈積物。基於氮之還原劑(諸如肼及其衍生物)以及甲醛作為還原劑產生鎳沈積物。
其他金屬離子可存在於鍍鎳溶液中,在此情況下相應鎳合金以沈積物形式獲得。
適合之電鍍組合物可藉由將成分溶解於水中且將pH值調整至所需範圍而形成。
待鍍鎳或鎳合金之部件可藉由將該部件浸沒於鍍鎳浴中而電鍍至所需厚度及沈積物量,該鍍鎳浴維持在約20℃至100℃、較佳70℃至95℃或90℃之溫度範圍內。視應用而定,可採用高達60μm或60μm以上之沈積物厚度。
對於耐腐蝕塗層,通常需要在30-60μm之間的較高厚度,而對於電子應用,通常施加在5-14μm之間的厚度。
熟習此項技術者應瞭解,電鍍速率可受許多因素影響,該等因素包括(1)電鍍液之pH值,(2)還原劑之濃度,(3)鍍浴之溫度,(4)可溶性鎳之濃度,(5)浴之體積與所電鍍之表面積之比率,及(6)溶液攪拌之方法與設計,且上述參數僅為給出用於實踐本發明之一般導引而提供。
高磷NiP合金在本文中定義為含有低於90wt.% Ni及等於或超過10wt.% P(例如10.5wt.%)之金屬塗層。高磷合金通常含有高達15wt.% P。已知含有超過約10.5%磷之鎳磷(NiP)合金為高磷NiP塗層且當電鍍時其為順磁性的(非磁性的)。
中磷NiP合金在本文中定義為含有5-9wt.% P之金屬塗層。
本發明之無電鍍浴適於提供具有在5-15wt.% P之間的廣泛P含量
範圍之鎳磷合金塗層。
NiP沈積物之厚度通常可在5-60μm範圍內。厚度視技術應用而定,且對於某些應用可較高或較低。舉例而言,若沈積NiP層以提供耐腐蝕塗層,則通常需要在30-60μm之間的厚度。
此外,鍍浴組合物含有式(1)之穩定劑:
其中X係選自O及NR4,n在1至6範圍內,m在1至8範圍內;R1、R2、R3及R4係獨立地選自氫及C1至C4烷基;Y係選自-SO3R5、-CO2R5及-PO3R5 2,且R5係選自氫、C1-C4烷基及適合之相對離子。
若R5為適合之相對離子,則其可例如選自鹼金屬,如鈉及鉀或鎳及銨。若R5係選自由C1至C4烷基組成之群,則其較佳為甲基及乙基。
n=1或2之式(1)之化合物尤其較佳。X=O、NH或NCH3之式(1)之化合物尤其較佳。R1、R2、R3獨立地選自氫、CH3之式(1)之化合物尤其較佳。m=1、2、3或4之式(1)之化合物尤其較佳。Y選自-SO3H、-SO3Na、-SO3K、-CO2H、-CO2Na及-CO2K之式(1)之化合物尤其較佳。
舉例而言,下列化合物可用於本發明之鍍浴組合物:4-(丁-3-炔基氧基)-丁烷-1-磺酸鈉鹽、3-(丙-2-炔基氧基)-丙基-1-磺酸鈉鹽、3-(丙-2-炔基胺基)-丙烷-1-磺酸、2-(丙-2-炔基氧基)-乙酸鈉鹽、2-(丙-2-炔基氧基)-丙酸鈉鹽、4-(丙-2-炔基氧基)-丁烷-1-磺酸鈉鹽。
式(1)之穩定劑之濃度較佳在0.02至5.0mmol/l範圍內,更佳為0.05至3.0mmol/l,甚至更佳為0.1至2.0mmol/l,甚至更佳為0.1至5.0
mmol/l,甚至更佳為0.3至5.0mmol/l,且甚至更佳為0.5至5.0mmol/l。
本發明之穩定劑針對自發的不當鎳沈積及外電鍍為無電鎳沈積浴提供較高穩定性。本發明之穩定劑亦適於在長時間內提供較高鍍浴穩定性且即使加熱該浴亦可達成此作用。
另外,本發明之穩定劑對無電鎳沈積浴之沈積速率及經沈積之鎳或鎳合金層之耐腐蝕性無負面影響。
本發明之穩定劑具有另一優勢,其與含有碳碳參鍵且已知用於無電鎳沈積浴之其他化合物(如炔丙醇或炔丙醇乙氧基化物)相比毒性較小。
本發明之鍍浴中可包括其他物質,諸如pH值緩衝劑、潤濕劑、加速劑、增亮劑、其他穩定劑等。此等物質為此項技術中已知。
水性無電鍍浴可進一步包含合金金屬M之水溶性金屬鹽,該合金金屬M不為鎳。視情況選用之合金金屬M之金屬離子較佳選自由以下各者組成之群:鈦、釩、鉻、錳、鋯、鈮、鉬、鉿、鉭、鎢、銅、銀、金、鋁、鐵、鈷、鈀、釕、銠、鋨、銥、鉑、鋅、鎘、鎵、銦、錫、銻、鉈、鉛及鉍。
視情況選用之合金金屬M之金屬離子更佳選自由以下各者組成之群:鉬、鎢、銅、銀、金、鋁、鋅及錫。
視情況選用之合金金屬M之金屬離子之濃度較佳在10-4至0.2mol/l範圍內,更佳為10-2至0.1mol/l。
當向水性無電鍍浴中添加合金金屬M之金屬離子時(視所存在之還原劑之種類而定)沈積出三元或四元合金Ni-M-P、Ni-M-B及Ni-M-B-P。
在本發明之另一實施例中,向水性無電鍍浴中添加合金金屬M之水溶性鹽及第二合金金屬M*之水溶性鹽。在此情況下,獲得包含合
金金屬M及M*之鎳合金沈積物。
水性無電鍍浴可進一步包含粒子,該等粒子尺寸較佳在0.01至150μm範圍內,更佳為0.1至10μm。此等粒子在鍍浴中不溶或微溶。
粒子較佳在沈積製程期間懸浮在水性無電鍍浴中,且在電鍍期間與鎳合金共沈積。共沈積之粒子可提供諸如潤滑性、耐用性及耐磨性、腐蝕保護及其組合之功能性。
粒子係選自包含以下之群:諸如二氧化矽及氧化鋁之陶瓷,玻璃,滑石,諸如聚四氟乙烯(Teflon®)之塑膠,鑽石(多晶及單晶型),石墨,碳奈米管,各種金屬之氧化物,矽化物,碳酸鹽,碳化物(諸如碳化矽及碳化鎢),硫化物,磷酸鹽,硼化物,矽酸鹽,含氧酸鹽(oxylate),氮化物,氟化物,以及硼、鉭、不鏽鋼、鉻、鉬、釩、鋯、鈦及鎢之金屬及金屬合金。
視情況選用之粒子在水性無電鍍浴中之濃度較佳在0.01至0.5wt.-%範圍內。
本發明之無電鍍浴尤其適用於沈積鎳磷合金,例如上文定義之中及高NiP合金。將基於次磷酸鹽之還原劑應用於NiP合金之沈積。此類還原劑提供沈積之合金中磷之來源。
尤其較佳為高NiP合金。當以在4-14微米/小時之間、更佳為6-11微米/小時之電鍍速率進行電鍍製程時,獲得此類合金。熟悉此項技術者可藉由用常規實驗調整電鍍參數(溫度、濃度等)來確定電鍍參數以獲得該電鍍速率。
由本發明之無電鍍浴獲得之高NiP合金引起具有壓縮應力之合金。應力值例如在介於-10至-40N/mm2之間的範圍內。該等沈積物顯示較高耐腐蝕性及對上面電鍍該等沈積物之底層基板(例如銅基板)的良好黏著性。
無電鍍浴可進一步含有金屬穩定劑,諸如Pb離子、Cu離子、Se
離子、Bi離子或Sb離子。Pb離子通常由於其毒性而較少需要。金屬離子之濃度可變化且例如在介於1-50mg/l之間的範圍內,較佳在3-10mg/l之間。另外,可添加碘酸鹽作為額外穩定劑。
本發明進一步關於一種用於鎳及鎳合金之無電沈積之方法,該方法包含以下步驟:(i)提供基板,(ii)將基板浸沒在本發明之水性無電鍍浴中,(iii)及進而將鎳或鎳合金沈積至基板上。
在一個實施例中,本發明之方法利用本發明之無電鍍浴,該無電鍍浴含有次磷酸鹽作為至少一種還原劑。
在另一實施例中,本發明之方法之電鍍速率在4-14微米/小時範圍內,以獲得在10至15wt.%之間的磷含量。
清潔(預處理)待自本發明之鍍浴用鎳或鎳合金層塗佈之基板,隨後沈積金屬。預處理之類型視待塗佈之基板材料而定且為此項技術中已知。
用蝕刻清潔方法處理銅或銅合金表面,該方法通常在氧化性的酸性溶液(例如硫酸及過氧化氫溶液)中進行。此方法較佳與在蝕刻清潔之前或之後使用之酸性溶液(諸如硫酸溶液)中之另一清潔組合。
對於鋁及鋁合金之預處理,可利用滿足無氰化物之化學工業標準之不同鋅活化劑(zincation),例如Xenolyte®清潔劑ACA、Xenolyte® Etch MA、Xenolyte® CFA或Xenolyte® CF(均可自Atotech Deutschland GmbH獲得)。該等用於鋁及鋁合金之預處理方法例如揭示於US 7,223,299 B2中。
下列非限制性實例進一步說明本發明。
製備實例係關於本發明之鍍浴中使用之穩定劑之合成。
在氬氣下,將2.0g(49.9mmol)氫化鈉懸浮於85ml THF中。在環境溫度下向此反應混合物中逐滴添加3.5g(49.9mmol)丁-3-炔-1-醇。
析氫結束後,在環境溫度下逐滴添加溶解於20ml THF中之6.87g(49.9mmol)1,2-氧硫-2,2-二氧化物。添加之後,再攪拌反應混合物12小時且在真空下移除THF。
用乙酸乙酯萃取固體殘餘物且過濾。在真空下乾燥固體。
獲得10.2g(44.7mmol)淡黃色固體(89%產率)。
在氬氣下,將1.997g(49.9mmol)氫化鈉懸浮於70ml THF中。在環境溫度下向此反應混合物中逐滴添加2.830g(49.9mmol)丙-2-炔-1-醇。
析氫結束後,在環境溫度下逐滴添加溶解於15ml THF中之6.1g(49.9mmol)1,2-氧硫雜環戊烷-2,2-二氧化物。添加之後,再攪拌反應混合物12小時且在真空下移除THF。
用乙酸乙酯萃取固體殘餘物且過濾。在真空下乾燥固體。
獲得9.0g(44.9mmol)淡黃色固體(90%產率)。
將4g(71.2mmol)丙-2-炔-1-胺溶解於75ml THF中且冷卻至0℃。在0℃至5℃下向此混合物中逐滴添加溶解於25ml THF中之8.87g(71.2mmol)1,2-氧硫雜環戊烷2,2-二氧化物。添加之後,加熱反應混合物至室溫且攪拌12小時。
過濾出現之米色晶體且用10ml THF及10ml乙醇洗滌。在真空下
乾燥固體。
獲得10.2g(57.6mmol)米色固體(81%產率)。
在室溫下將1.8g(44mmol)氫化鈉懸浮於18.88g DMF中。在環境溫度下於10min內向此懸浮液中投與3.5g(37mmol)2-氯乙酸。
在第二燒瓶中將1.8g(44mmol)氫化鈉懸浮於56.6g DMF中。在室溫下向此懸浮液中給予2.08g(36.74mmol)丙-2-炔-1-醇。
析氫結束後,在室溫下於6分鐘內向丙-2-炔-1-醇鈉溶液中逐滴添加2-氯乙酸之鈉鹽溶液。添加之後,在室溫下再攪拌反應混合物25小時且加熱至50℃後再持續10小時。
將反應混合物冷卻至室溫,且用20ml水水解。移除溶劑,且將殘餘物溶解於50ml甲醇中且過濾。蒸發濾液,且用200ml二乙醚洗滌固體殘餘物。
在真空下乾燥所得固體。
獲得4.9g(36mmol)微棕色固體(98%產率)。
在室溫下將1.6g(39.11mmol)氫化鈉懸浮於18.88g DMF中。在環境溫度下於10min內向此懸浮液中投與3.8g(33mmol)2-氯丙酸。
在第二燒瓶中將1.6g(39.11mmol)氫化鈉懸浮於56.64g DMF中。在室溫下向此懸浮液中給予1.886g(363.33mmol)丙-2-炔-1-醇。
析氫結束後,在室溫下於6分鐘內向丙-2-炔-1-醇鈉溶液中逐滴添加2-氯乙酸之鈉鹽溶液。添加之後,在室溫下再攪拌反應混合物25小時且加熱至50℃後再持續10小時。
將反應混合物冷卻至室溫,且用20ml水水解。移除溶劑,且將
殘餘物溶解於50ml甲醇中且過濾。蒸發濾液,且用200ml二乙醚洗滌固體殘餘物。
在真空下乾燥所得固體。
獲得4.79g(32mmol)微棕色固體(96%產率)。
炔丙醇乙氧基化物可購自例如BASF AG(Golpanol PME)。
在氬氣下將1.999g(50mmol)氫化鈉懸浮於45mL THF中。在環境溫度下向此反應混合物中逐滴添加2.830g(50mmol)丙-2-炔-1-醇。
析氫結束後,在環境溫度下逐滴添加溶解於20mL THF中之6.87g(50mmol)1,2-氧硫-2,2-二氧化物。添加之後,再攪拌反應混合物12小時且在真空下移除THF。
用乙酸乙酯萃取固體殘餘物且過濾。在真空下乾燥固體。
獲得8.4g(39.2mmol)淡黃色固體(78%產率)。
向水性鍍浴儲備溶液中添加實例1至5(根據本發明)以及實例6(比較)中之相應穩定劑,該水性鍍浴儲備溶液包含
在200ml玻璃燒杯中將100ml研究中之鍍浴在攪拌的同時加熱至80±1℃。接著,向鍍浴中每60s添加0.2ml鈀測試溶液(125mg/l氯化鈀於去離子水中)。當在鍍浴中形成伴隨有氣泡之灰色沈澱(此表明鍍
浴之非所需分解)時,測試完成。
針對研究中之鍍浴達成之穩定數對應於在一分鐘時間間隔內以0.2ml之增量向鍍浴中添加鈀測試溶液直至形成灰色沈澱之次數。所給值對應於在80℃下120分鐘及240分鐘之後就在加熱至80℃之溫度之後新鮮製備的鍍浴。
針對樣品1之表列值17(表1,在穩定數/時間「0」欄中)例如對應於向加熱至80℃之鍍浴中添加0.2ml氯化鈀溶液17次。3.4ml(以一分鐘時間間隔添加0.2ml/l 17次)及17分鐘後,出現灰色沈澱。針對表1中表列值「120min」(在80℃下加熱120分鐘)及「240min」(在80℃下加熱240分鐘)之穩定數分別產生16及15之穩定數,表明浴甚至在延長加熱之後仍保持其較高穩定性。
如自表1及圖2而變得顯而易知,本發明之穩定劑適於在長時間內提供較高鍍浴穩定性。相比之下,炔丙醇乙氧基化物(與本發明之穩定劑結構類似(亦即,碳碳參鍵)之比較化合物)對無電鎳沈積浴具有較低穩定作用且無法充當持續較長時間之穩定劑。
表2顯示穩定劑並未消極影響電鍍速率。
在86℃(水浴)之溫度及4.8之pH值下,在一公升燒杯中,使用一公升下列物質之溶液進行表2之電鍍實驗:NiSO4.6H2O(26.3g/l)及作為錯合劑之三乙醇胺、單水合次磷酸鈉(30g/l)及不同濃度添加劑。
使用電鍍一小時之具有0.1mm厚度之不鏽鋼條帶測量沈積速率。使用測微器裝置進行測量。測定電鍍速率=0.5×(電鍍後之板厚度-電鍍前之板厚度(以μm計))。
利用應力條帶指測量塗層中之應力。測試條帶係由以化學方式蝕刻之鈹銅合金製成且具有彈簧樣性質。電鍍之後,將測試條帶安裝於測試架(Specialty Testing & Development Co.,York,PA,USA之沈積物應力分析器型號683)上,該測試架測量電鍍後測試條帶腿展開之距離。距離U包括於計算沈積物應力之公式中。
應力=U/3*T*K
U為展開增量數,T為沈積物厚度,且K為條帶校正常數。
沈積物厚度T係藉由增重法測定且根據下式測定:T=W/D*A,其中W=沈積物重量(以公克為單位),D=沈積金屬之比重(以公克/立方公分為單位),且A=表面積(以cm2為單位)。
應認識到所製造之各批次測試條帶當用於沈積物應力測試時將略有差異地回應。此差異程度將由供應商在校準各批次之測試條帶時測定。K值將與由Specialty Testing & Development Co.提供之各批次測試條帶一起提供。
亦測定應力為壓縮或拉伸本質。若測試條帶腿在已電鍍之側上向外展開,則沈積物應力本質上為拉伸。若測試條帶腿在已電鍍之側上向內展開,則沈積物應力本質上為壓縮。
表2:利用不同濃度之添加劑3-(丙-2-炔基氧基)-丙基-1-磺酸鈉鹽(實例2)之塗層中之沈積速率及應力
表2亦顯示藉由自本發明之浴組合物電鍍而獲得之沈積物展現出壓縮應力,該壓縮應力為所需的,因為其積極影響所沈積之鎳層之腐蝕保護。
進行進一步實驗以測試用於製造如半導體工業中所用之較小結構之本發明之鍍鎳浴。
水性鍍浴含有
藉由向上述浴基質中添加下列穩定劑而製備四種不同鍍浴組合物。
使用無添加劑之上述浴基質進行比較實例。
如圖1中所示,在測試基板之銅襯墊上沈積鎳。該等基板用於半導體工業中之電鍍實驗。圖1顯示數目為16之金屬化之銅襯墊。數字表示:
50(銅襯墊之直徑,以μm為單位),75(間距(兩個銅襯墊中心之間的距離),以μm為單位)。
藉由將基板浸沒至上述電鍍組合物(pH=4.9,T=85℃)中來進行電鍍。
施加含有本發明之穩定劑之鍍浴組合物可獲得極好的電鍍結果:觀測到沈積之鎳磷合金無過度電鍍且厚度分佈極其均一。
關於比較實例:自無穩定劑之鎳浴金屬化之襯墊顯示出不均一(就表面上之厚度分佈而言)之鎳沈積物及在襯墊邊緣處之小點。
向實例8之水性鍍浴儲備溶液中添加不同量之實例1至5及7(根據本發明)中之相應穩定劑,且保持在23℃之溫度下。在達至恆定溫度之後不久,如實例8中所描述測定穩定數。穩定劑之濃度及對應穩定數概述於表3中。
如自表3而變得顯而易知,本發明之穩定劑適於在廣泛濃度範圍內提供較高鍍浴穩定性。
向實例8之水性鍍浴儲備溶液中添加實例2、3及7(根據本發明)中之相應穩定劑,且加熱至86℃後持續該實驗之持續時間。在某些時間下,將100ml研究中之鍍浴之樣品轉移至200ml玻璃燒杯中,且在攪拌的同時加熱至80±1℃。如實例8中所描述測定穩定數。穩定劑之濃度、時間及相應穩定數概述於表4中。
如自表4而變得顯而易知,即使浴經加熱,本發明之穩定劑亦適於在長時間內提供較高鍍浴穩定性。
向實例8之水性鍍浴儲備溶液中添加不同量之實例2(根據本發明)中之穩定劑以及比較化合物炔丙基磺酸鈉鹽(樣品8)、3-己炔-2,5-二醇(樣品9)及2-丁炔-1-醇(樣品10),且保持在23℃之溫度下。在達至恆定溫度之後不久,如實例8中所描述測定穩定數。穩定劑、比較例化合物之濃度及相應穩定數概述於表5中。炔丙基磺酸鈉鹽可例如購自BASF AG(Golpanol PS)。3-己炔-2,5-二醇及2-丁炔-1-醇亦可購得。
如自表5而變得顯而易知,本發明之穩定劑適於在廣泛濃度範圍內提供較高鍍浴穩定性。相比之下,與本發明之穩定劑結構類似(亦即,碳碳參鍵)之比較化合物當以相同濃度添加至無電鎳沈積浴時展現明顯較低之穩定作用。
Claims (15)
- 一種用於鎳及鎳合金之無電沈積之水性鍍浴組合物,該鍍浴包含(i)鎳離子之來源,(ii)至少一種錯合劑,(iii)至少一種還原劑,(iv)式(1)之穩定劑:
- 如請求項1之水性無電鍍浴,其中R1、R2、R3及R4係選自氫、甲基及乙基。
- 如請求項1或2之水性無電鍍浴,其中R5係選自氫、甲基、乙基、鈉、鉀、鎳及銨。
- 如請求項1或2之水性無電鍍浴,其中Y為SO3R5。
- 如請求項1或2之水性無電鍍浴,其中該式(1)之穩定劑之濃度係在0.02至5.0mmol/l範圍內。
- 如請求項1或2之水性無電鍍浴,其進一步包含至少一種合金金屬離子來源,且其中該至少一種合金金屬離子係選自由以下組成之群:鈦、釩、鉻、錳、鋯、鈮、鉬、鉿、鉭、鎢、銅、 銀、金、鋁、鐵、鈷、鈀、釕、銠、鋨、銥、鉑、鋅、鎘、鎵、銦、錫、銻、鉈、鉛及鉍。
- 如請求項1或2之水性無電鍍浴,其中該鍍浴具有3.5至7之pH值。
- 如請求項1或2之水性無電鍍浴,其中該鎳離子之濃度係在0.1至60g/l範圍內。
- 如請求項1或2之水性無電鍍浴,其中該至少一種錯合劑係選自由以下組成之群:胺、羧酸、羥基羧酸、胺基羧酸及前述之鹽。
- 如請求項1或2之水性無電鍍浴,其中該至少一種錯合劑之濃度係在0.01至3.0mol/l範圍內。
- 如請求項1或2之水性無電鍍浴,其中該至少一種還原劑之濃度係在0.01至3.0mol/l範圍內。
- 如請求項1或2之水性無電鍍浴,其中該至少一種還原劑為次磷酸鹽。
- 一種用於鎳及鎳合金之無電沈積之方法,其包含以下步驟:(i)提供基板,(ii)將該基板浸沒在如請求項1至12中任一項之水性無電鍍浴中,(iii)及藉此將鎳或鎳合金沈積至該基板上。
- 如請求項13之方法,其中該無電鍍浴含有次磷酸鹽作為該至少一種還原劑。
- 如請求項13及14之方法,其中電鍍速率在4至14微米/小時之間變化,以獲得在10至15wt.%之間的磷含量。
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BR112014028715A2 (pt) | 2017-06-27 |
BR112014028715B1 (pt) | 2022-01-25 |
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US9175399B2 (en) | 2015-11-03 |
EP2855732A2 (en) | 2015-04-08 |
CA2875317C (en) | 2020-03-31 |
MY168645A (en) | 2018-11-27 |
KR101930585B1 (ko) | 2018-12-18 |
EP2671969A1 (en) | 2013-12-11 |
EP2855732B1 (en) | 2018-07-18 |
KR20150024317A (ko) | 2015-03-06 |
CA2875317A1 (en) | 2013-12-12 |
CN104321463A (zh) | 2015-01-28 |
ES2688547T3 (es) | 2018-11-05 |
US20150110965A1 (en) | 2015-04-23 |
JP2015524024A (ja) | 2015-08-20 |
WO2013182489A2 (en) | 2013-12-12 |
TWI560316B (en) | 2016-12-01 |
WO2013182489A3 (en) | 2014-07-17 |
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