CN104321463B - 用于镍层无电沉积的镀浴 - Google Patents
用于镍层无电沉积的镀浴 Download PDFInfo
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- CN104321463B CN104321463B CN201380026312.3A CN201380026312A CN104321463B CN 104321463 B CN104321463 B CN 104321463B CN 201380026312 A CN201380026312 A CN 201380026312A CN 104321463 B CN104321463 B CN 104321463B
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- Prior art keywords
- aqueous bath
- nickel
- bath compositions
- plating bath
- range
- Prior art date
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 51
- 230000008021 deposition Effects 0.000 title claims description 26
- 238000007747 plating Methods 0.000 title description 53
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims description 32
- 238000000151 deposition Methods 0.000 claims description 27
- 239000003638 chemical reducing agent Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 17
- 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 15
- 239000002738 chelating agent Substances 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 238000005275 alloying Methods 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 150000002431 hydrogen Chemical group 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 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
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 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
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910010277 boron hydride Inorganic materials 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 compound 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 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
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 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
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract 1
- 238000007772 electroless plating Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 14
- 239000000956 alloy Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 238000009713 electroplating Methods 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000376 reactant 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
- YGTZTXICKXYYBD-UHFFFAOYSA-N 3-(prop-2-ynylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCNCC#C YGTZTXICKXYYBD-UHFFFAOYSA-N 0.000 description 6
- 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
- 230000000052 comparative 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
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- 239000007788 liquid Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 3
- 210000003141 lower extremity Anatomy 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical group [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 3
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- 238000004062 sedimentation Methods 0.000 description 3
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 229910018536 Ni—P Inorganic materials 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 238000001704 evaporation Methods 0.000 description 2
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- 239000000706 filtrate Substances 0.000 description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 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
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 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
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- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
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- 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
- 241000534944 Thia Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- PAMVFMLMCGDWGU-UHFFFAOYSA-N [K].O[PH2]=O Chemical compound [K].O[PH2]=O PAMVFMLMCGDWGU-UHFFFAOYSA-N 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
- 239000012190 activator Substances 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
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- 125000000217 alkyl group Chemical group 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 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
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
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- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- RPOHBMAQTOJHKM-UHFFFAOYSA-M sodium;2-chloropropanoate Chemical compound [Na+].CC(Cl)C([O-])=O RPOHBMAQTOJHKM-UHFFFAOYSA-M 0.000 description 1
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 1
- LDHXNOAOCJXPAH-UHFFFAOYSA-M sodium;prop-2-yne-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC#C LDHXNOAOCJXPAH-UHFFFAOYSA-M 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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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
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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
- C23C18/48—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
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- 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
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Abstract
本发明涉及用于镍和镍合金沉积的水性镀浴组合物,其利用具有碳碳三键和官能团的新颖稳定剂来增强所述浴性能。
Description
技术领域
本发明涉及用于镍和镍合金的无电沉积的水性镀浴组合物。由本发明获得的镍涂层展示出高均一性和高硬度、良好的耐磨性和耐腐蚀性。此类涂层适合在航空、汽车、电力和化学工业中作为功能性涂层。从此类镀浴沉积的金属层也适合在半导体装置、印刷电路板、IC衬底等中作为阻挡和顶盖层。
背景技术
阻挡层用于如半导体装置、印刷电路板、IC衬底等的电子装置中,以分隔不同组合物层,且进而防止在所述不同组合物层之间的非所需扩散。
典型的阻挡层材料为二元镍合金,如Ni-P合金,其通常通过无电电镀而沉积到第一组合物的第一层上,随后将第二组合物的第二层沉积到阻挡层上。所述第一层可由铜或铝组成。
阻挡层材料在电子装置中的另一应用为作为顶盖层,例如将其沉积到铜上以防止铜腐蚀。
镍和镍合金沉积物的另一应用为针对各种衬底的腐蚀保护。
用于无电镀镍溶液的组合物为此项技术中已知。举例来说,美国专利2,658,841教示可溶性有机酸盐作为用于无电镀镍溶液的缓冲剂的用途。美国专利2,658,842教示短链二羧酸作为EN浴的激发剂的用途。美国专利2,762,723教示将硫化物和含硫添加剂用于无电镀镍浴以用于改良浴稳定性。
美国专利2,847,327已介绍稳定无电镀镍溶液的其它手段。这些手段包括使用较高纯度的起始物质;来自如Pb、Sb、Bi、Cu和Se的重金属类别的较有效的稳定剂;无机化合物,如碘酸盐,和硫代化合物;有机化合物,如不饱和烯烃与炔烃和其它。
本发明的目标
本发明的目标为提供用于镍和镍合金沉积的无电镀浴,其具有对抗非所需分解的高稳定性且提供均一涂层。
发明内容
此目标通过提供一种用于镍和镍合金的无电沉积的水性镀浴组合物而得以解决,所述镀浴包含
(i)镍离子的来源,
(ii)至少一种络合剂,
(iii)至少一种还原剂,
(iv)式(1)的稳定剂:
其中X是选自O和NR4,n在1到6范围内,m在1到8范围内;R1、R2、R3和R4是独立地选自氢和C1到C4烷基;Y是选自-SO3R5、-CO2R5和-PO3R5 2,且R5是选自氢、C1-C4烷基和适合的反离子。
本发明进一步关于一种通过将待电镀的衬底浸没到上述电镀液中来沉积镍和镍合金的方法。
附图说明
图1展示具有用于无电镍沉积的铜衬垫的测试衬底。
图2展示在储存时间(也称为闲置时间)期间,含有本发明稳定剂(样品1到3)或比较化合物(样品6)的无电镍沉积浴的稳定性。
具体实施方式
用于施加镍涂层的无电镀镍组合物为此项技术中所熟知,且电镀方法和组合物描述于大量公开案中,如美国专利第2,935,425号;第3,338,726号;第3,597,266号;第3,717,482号;第3,915,716号;第4,467,067号;第4,466,233号和第4,780,342号。无电电镀通常描述不使用外部电流源来还原金属离子的方法。通常将后者描述为电解或电化电镀法。在无电电镀溶液中,使用如次磷酸盐、硼烷或甲醛的化学还原剂将金属离子还原成其金属形式,且进而在衬底上形成沉积物。
一种常用的镍合金沉积物为镍磷(NiP)合金。一般来说,NiP沉积溶液包含溶解于溶剂(通常为水)中的至少四种成分。所述成分为(1)镍离子的来源,(2)还原剂,(3)提供需要的pH的酸或氢氧化物pH调节剂,和(4)足以防止金属离子在溶液中沉淀的金属离子的络合剂。用于NiP溶液的大量适合的络合剂描述于以上提到的公开案中。如果使用次磷酸盐作为还原剂,那么沉积物将含有镍和磷。类似地,如果采用胺硼烷,那么沉积物将含有镍和硼,如美国专利第3,953,654号中所示。
镍离子可通过使用任何可溶性盐来提供,如硫酸镍、氯化镍、乙酸镍、甲基磺酸镍和其混合物。溶液中镍的浓度可广泛变化,且为约0.1g/l到60g/l,优选为约2g/l到50g/l,例如4g/l到10g/l。
还原剂通常且优选为次磷酸根离子,其通过任何适合的来源(如次磷酸钠、次磷酸钾、次磷酸铵和次磷酸镍)提供到浴中。也可适当采用其它还原剂,如胺硼烷、硼氢化物、肼和其衍生物和甲醛。还原剂的浓度通常摩尔浓度超过足以还原浴中的镍的量。还原剂的浓度通常在0.05mol/l到0.35mol/l范围内。
浴可为酸性、中性或碱性,且酸性或碱性pH调节剂可选自广泛范围的物质,如氢氧化铵、氢氧化钠、盐酸等。浴的pH可在约2到12范围内,且优选为酸性浴。建议优选3.5到7、更优选4到6.5的弱酸性pH范围。
用于镍和镍合金电镀的镀浴组合物中包括络合剂(有时也称为螯合剂)或络合剂的混合物。
在一个实施例中,羧酸、羟基羧酸、氨基羧酸和前述的盐或其混合物可用作络合剂。适用的羧酸包括单-、双-、三-和四-羧酸。羧酸可经各种取代基部分(如羟基或氨基)取代,且所述酸可以其钠盐、钾盐或铵盐形式引入镀浴中。举例来说,某些络合剂,如乙酸也可充当pH值缓冲剂,且考虑到所述添加剂组分的双重功能性,所述组分的适合浓度可经优化以用于任何镀浴。
适用作本发明镀浴中的络合剂或螯合剂的此类羧酸的实例包括:单羧酸,如乙酸、羟基乙酸(乙醇酸)、氨基乙酸(甘氨基)、2-氨基丙酸(丙氨基);2-羟基丙酸(乳酸);二羧酸,如丁二酸、氨基丁二酸(天冬氨基)、羟基丁二酸(苹果酸)、丙二酸(propanedioic acid、malonic acid)、酒石酸;三羧酸,如2-羟基-1,2,3丙烷三羧酸(柠檬酸);和四羧酸,如乙二胺四乙酸(EDTA)。在一个实施例中,在本发明的镀浴中使用上述络合剂/螯合剂中的两者或两者以上的混合物。
烷基胺也可用作为络合剂,例如单-、双-和三烷基胺。优选为C1-C3烷基胺,例如三乙醇胺。
络合剂的浓度,或在使用超过一种络合剂的情况下所有络合剂一起的浓度优选在0.01到3.0mol/l范围内,更优选为0.1到1.0mol/l,且甚至更优选为0.2-0.6mol/l。
在次磷酸盐化合物用作还原剂的情况下,获得Ni-P合金沉积物。基于硼烷的化合物作为还原剂产生Ni-B合金沉积物,且次磷酸盐与基于硼烷的化合物的混合物作为还原剂产生三元Ni-B-P合金沉积物。基于氮的还原剂(如肼和其衍生物)以及甲醛作为还原剂产生镍沉积物。
其它金属离子可存在于镀镍溶液中,在此情况下相应镍合金以沉积物形式获得。
适合的电镀组合物可通过将成分溶解于水中且将pH值调整到所需范围而形成。
待镀镍或镍合金的部件可通过将所述部件浸没于镀镍浴中而电镀到所需厚度和沉积物量,所述镀镍浴维持在约20℃到100℃、优选70℃到95℃或90℃的温度范围内。视应用而定,可采用高达60μm或60μm以上的沉积物厚度。
对于耐腐蚀涂层,通常需要在30-60μm之间的较高厚度,而对于电子应用,通常施加在5-14μm之间的厚度。
所属领域的技术人员应了解,电镀速率可受许多因素影响,所述因素包括(1)电镀液的pH值,(2)还原剂的浓度,(3)镀浴的温度,(4)可溶性镍的浓度,(5)浴的体积与所电镀的表面积的比率,和(6)溶液搅拌的方法与设计,且上述参数仅为给出用于实践本发明的一般导引而提供。
高磷NiP合金在本文中定义为含有低于90重量%Ni和等于或超过10重量%P(例如10.5重量%)的金属涂层。高磷合金通常含有高达15重量%P。已知含有超过约10.5%磷的镍磷(NiP)合金为高磷NiP涂层且当电镀时其为顺磁性的(非磁性的)。
中磷NiP合金在本文中定义为含有5-9重量%P的金属涂层。
本发明的无电镀浴适于提供具有在5-15重量%P之间的广泛P含量范围的镍磷合金涂层。
NiP沉积物的厚度通常可在5-60μm之间变化。厚度视技术应用而定,且对于某些应用可较高或较低。举例来说,如果沉积NiP层以提供耐腐蚀涂层,那么通常需要在30-60μm之间的厚度。
此外,镀浴组合物含有式(1)的稳定剂:
其中X是选自O和NR4,n在1到6范围内,m在1到8范围内;R1、R2、R3和R4是独立地选自氢和C1到C4烷基;Y是选自-SO3R5、-CO2R5和-PO3R5 2,且R5是选自氢、C1-C4烷基和适合的反离子。
如果R5为适合的反离子,那么其可例如选自碱金属,如钠和钾或镍和铵。如果R5是选自由C1到C4烷基组成的群组,那么其优选为甲基和乙基。
n=1或2的式(1)的化合物尤其优选。X=O、NH或NCH3的式(1)的化合物尤其优选。R1、R2、R3独立地选自氢CH3的式(1)的化合物尤其优选。m=1、2、3或4的式(1)的化合物尤其优选。Y选自-SO3H、-SO3Na、-SO3K、-CO2H、-CO2Na和-CO2K的式(1)的化合物尤其优选。
举例来说,下列化合物可用于本发明的镀浴组合物:
4-(丁-3-炔基氧基)-丁烷-1-磺酸钠盐、3-(丙-2-炔基氧基)-丙基-1-磺酸钠盐、3-(丙-2-炔基氨基)-丙烷-1-磺酸、2-(丙-2-炔基氧基)-乙酸钠盐、2-(丙-2-炔基氧基)-丙酸钠盐、4-(丙-2-炔基氧基)-丁烷-1-磺酸钠盐。
式(1)的稳定剂的浓度优选在0.02到5.0mmol/l范围内,更优选为0.05到3.0mmol/l,甚至更优选为0.1到2.0mmol/l,甚至更优选为0.1到5.0mmol/l,甚至更优选为0.3到5.0mmol/l,且甚至更优选为0.5到5.0mmol/l。
本发明的稳定剂针对自发的不当镍沉积和外电镀为无电镍沉积浴提供高稳定性。本发明的稳定剂也适于在长时间内提供高镀浴稳定性且即使加热所述浴也可实现此作用。
另外,本发明的稳定剂对无电镍沉积浴的沉积速率和经沉积的镍或镍合金层的耐腐蚀性无负面影响。
本发明的稳定剂具有另一优势,其与含有碳碳三键且已知用于无电镍沉积浴的其它化合物(如炔丙醇或炔丙醇乙氧基化物)相比毒性较小。
本发明的镀浴中可包括其它物质,如pH值缓冲剂、润湿剂、加速剂、增亮剂、其它稳定剂等。这些物质为此项技术中已知。
水性无电镀浴可进一步包含合金金属M的水溶性金属盐,所述合金金属M不为镍。任选的合金金属M的金属离子优选地选自由以下各者组成的群组:钛、钒、铬、锰、锆、铌、钼、铪、钽、钨、铜、银、金、铝、铁、钴、钯、钌、铑、锇、铱、铂、锌、镉、镓、铟、锡、锑、铊、铅和铋。
任选的合金金属M的金属离子更优选地选自由以下各者组成的群组:钼、钨、铜、银、金、铝、锌和锡。
任选的合金金属M的金属离子的浓度优选在10-4到0.2mol/l范围内,更优选为10-2到0.1mol/l。
当向水性无电镀浴中添加合金金属M的金属离子时(视所存在的还原剂的种类而定)沉积出三元或四元合金Ni-M-P、Ni-M-B和Ni-M-B-P。
在本发明的另一实施例中,向水性无电镀浴中添加合金金属M的水溶性盐和第二合金金属M*的水溶性盐。在此情况下,获得包含合金金属M和M*的镍合金沉积物。
水性无电镀浴可进一步包含粒子,所述粒子尺寸优选在0.01μm到150μm范围内,更优选为0.1μm到10μm。这些粒子在镀浴中不溶或微溶。
粒子优选在沉积工艺期间悬浮在水性无电镀浴中,且在电镀期间与镍合金共沉积。共沉积的粒子可提供如润滑性、耐用性和耐磨性、腐蚀保护和其组合的功能性。
粒子是选自包含以下的群组:如二氧化硅和氧化铝的陶瓷、玻璃、滑石、如聚四氟乙烯的塑料、金刚石(多晶和单晶型)、石墨、碳纳米管、各种金属的氧化物、硅化物、碳酸盐、碳化物(如碳化硅和碳化钨)、硫化物、磷酸盐、硼化物、硅酸盐、含氧酸盐(oxylate)、氮化物、氟化物,以及硼、钽、不锈钢、铬、钼、钒、锆、钛和钨的金属和金属合金。
任选的粒子在水性无电镀浴中的浓度优选在0.01重量%到0.5重量%范围内。
本发明的无电镀浴尤其适用于沉积镍磷合金,例如上文定义的中和高NiP合金。将基于次磷酸盐的还原剂应用于NiP合金的沉积。此类还原剂提供沉积的合金中磷的来源。
尤其优选为高NiP合金。当以在4-14微米/小时之间、更优选为6-11微米/小时的电镀速率进行电镀工艺时,获得此类合金。所属领域的技术人员可通过用常规实验调整电镀参数(温度、浓度等)来确定电镀参数以获得所述电镀速率。
由本发明的无电镀浴获得的高NiP合金引起具有压缩应力的合金。应力值例如在介于-10到-40N/mm2之间的范围内。所述沉积物显示高耐腐蚀性和对上面电镀所述沉积物的底层衬底(例如铜衬底)的良好粘着性。
无电镀浴可进一步含有金属稳定剂,如Pb离子、Cu离子、Se离子、Bi离子或Sb离子。Pb离子通常由于其毒性而较少需要。金属离子的浓度可变化且例如在介于1-50mg/l之间的范围内,优选在3-10mg/l之间。另外,可添加碘酸盐作为额外稳定剂。
本发明进一步关于一种用于镍和镍合金的无电沉积的方法,所述方法包含以下步骤:
(i)提供衬底,
(ii)将衬底浸没在本发明的水性无电镀浴中,
(iii)和由此将镍或镍合金沉积到衬底上。
在一个实施例中,本发明的方法利用本发明的无电镀浴,所述无电镀浴含有次磷酸盐作为至少一种还原剂。
在另一实施例中,本发明的方法的电镀速率在4-14微米/小时范围内,以获得在10到15重量%之间的磷含量。
清洁(预处理)待从本发明的镀浴用镍或镍合金层涂布的衬底,随后沉积金属。预处理的类型视待涂布的衬底材料而定且为此项技术中已知。
用蚀刻清洁方法处理铜或铜合金表面,所述方法通常在氧化性的酸性溶液(例如硫酸和过氧化氢溶液)中进行。此方法优选与在蚀刻清洁之前或之后使用的酸性溶液(如硫酸溶液)中的另一清洁组合。
对于铝和铝合金的预处理,可利用满足无氰化物化学的工业标准的不同锌活化剂(zincation),例如清洁剂ACA、Etch MA、CFA或CF(均可从安美特德国有限公司(Atotech Deutschland GmbH)获得)。所述用于铝和铝合金的预处理方法例如公开于US 7,223,299 B2中。
下列非限制性实例进一步说明本发明。
实例
制备实例涉及本发明的镀浴中使用的稳定剂的合成。
制备实例1
4-(丁-3-炔基氧基)-丁烷-1-磺酸钠盐的制备
在氩气下,将2.0g(49.9mmol)氢化钠悬浮于85ml THF中。在环境温度下向此反应混合物中逐滴添加3.5g(49.9mmol)丁-3-炔-1-醇。
析氢结束后,在环境温度下逐滴添加溶解于20ml THF中的6.87g(49.9mmol)1,2-氧硫杂环己烷-2,2-二氧化物。添加之后,再搅拌反应混合物12小时且在真空下移除THF。
用乙酸乙酯萃取固体残余物且过滤。在真空下干燥固体。
获得10.2g(44.7mmol)淡黄色固体(89%产率)。
制备实例2
3-(丙-2-炔基氧基)-丙基-1-磺酸钠盐的制备
在氩气下,将1.997g(49.9mmol)氢化钠悬浮于70ml THF中。在环境温度下向此反应混合物中逐滴添加2.830g(49.9mmol)丙-2-炔-1-醇。
析氢结束后,在环境温度下逐滴添加溶解于15ml THF中的6.1g(49.9mmol)1,2-氧硫杂环戊烷-2,2-二氧化物。添加之后,再搅拌反应混合物12小时且在真空下移除THF。
用乙酸乙酯萃取固体残余物且过滤。在真空下干燥固体。
获得9.0g(44.9mmol)淡黄色固体(90%产率)。
制备实例3
3-(丙-2-炔基氨基)-丙烷-1-磺酸的制备
将4g(71.2mmol)丙-2-炔-1-胺溶解于75ml THF中且冷却到0℃。在0℃到5℃下向此混合物中逐滴添加溶解于25ml THF中的8.87g(71.2mmol)1,2-氧硫杂环戊烷2,2-二氧化物。添加之后,加热反应混合物到室温且搅拌12小时。
过滤出现的米色晶体且用10ml THF和10ml乙醇洗涤。在真空下干燥固体。
获得10.2g(57.6mmol)米色固体(81%产率)。
制备实例4
2-(丙-2-炔基氧基)-乙酸钠盐的制备
在室温下将1.8g(44mmol)氢化钠悬浮于18.88g DMF中。在环境温度下于10分钟内向此悬浮液中投与3.5g(37mmol)2-氯乙酸。
在第二烧瓶中将1.8g(44mmol)氢化钠悬浮于56.6g DMF中。在室温下向此悬浮液中给予2.08g(36.74mmol)丙-2-炔-1-醇。
析氢结束后,在室温下于6分钟内向丙-2-炔-1-醇钠溶液中逐滴添加2-氯乙酸的钠盐溶液。添加之后,在室温下再搅拌反应混合物25小时且加热到50℃后再持续10小时。
将反应混合物冷却到室温,且用20ml水水解。移除溶剂,且将残余物溶解于50ml甲醇中且过滤。蒸发滤液,且用200ml二乙醚洗涤固体残余物。
在真空下干燥所得固体。
获得4.9g(36mmol)微棕色固体(98%产率)。
制备实例5
2-(丙-2-炔基氧基)-丙酸钠盐的制备
在室温下将1.6g(39.11mmol)氢化钠悬浮于18.88g DMF中。在环境温度下于10分钟内向此悬浮液中投与3.8g(33mmol)2-氯丙酸。
在第二烧瓶中将1.6g(39.11mmol)氢化钠悬浮于56.64g DMF中。在室温下向此悬浮液中给予1.886g(363.33mmol)丙-2-炔-1-醇。
析氢结束后,在室温下于6分钟内向丙-2-炔-1-醇钠溶液中逐滴添加2-氯丙酸的钠盐溶液。添加之后,在室温下再搅拌反应混合物25小时且加热到50℃后再持续10小时。
将反应混合物冷却到室温,且用20ml水水解。移除溶剂,且将残余物溶解于50ml甲醇中且过滤。蒸发滤液,且用200ml二乙醚洗涤固体残余物。
在真空下干燥所得固体。
获得4.79g(32mmol)微棕色固体(96%产率)。
实例6
炔丙醇乙氧基化物可购自例如BASF AG(Golpanol PME)。
制备实例7
4-(丙-2-炔基氧基)-丁烷-1-磺酸钠盐的制备
在氩气下将1.999g(50mmol)氢化钠悬浮于45mL THF中。在环境温度下向此反应混合物中逐滴添加2.830g(50mmol)丙-2-炔-1-醇。
析氢结束后,在环境温度下逐滴添加溶解于20mL THF中的6.87g(50mmol)1,2-氧硫杂环己烷-2,2-二氧化物。添加之后,再搅拌反应混合物12小时且在真空下移除THF。
用乙酸乙酯萃取固体残余物且过滤。在真空下干燥固体。
获得8.4g(39.2mmol)淡黄色固体(78%产率)。
实例8:
无电镀浴的稳定数的测定:
向水性镀浴储备溶液中添加实例1到5(根据本发明)以及实例6(比较)中的相应稳定剂,所述水性镀浴储备溶液包含
在200ml玻璃烧杯中将100ml研究中的镀浴在搅拌的同时加热到80±1℃。接着,向镀浴中每60秒添加0.2ml钯测试溶液(125mg/l氯化钯于去离子水中)。当在镀浴中形成伴随有气泡的灰色沉淀(此表明镀浴的非所需分解)时,测试完成。
针对研究中的镀浴实现的稳定数对应于在一分钟时间间隔内以0.2ml的增量向镀浴中添加钯测试溶液直到形成灰色沉淀的次数。所给值对应于在80℃下120分钟和240分钟之后就在加热到80℃的温度之后新鲜制备的镀浴。
针对样品1的表列值17(表1,在稳定数/时间“0”列中)例如对应于向加热到80℃的镀浴中添加0.2ml氯化钯溶液17次。3.4ml(以一分钟时间间隔添加0.2ml/l 17次)和17分钟后,出现灰色沉淀。针对表1中表列值“120分钟”(在80℃下加热120分钟)和“240分钟”(在80℃下加热240分钟)的稳定数分别产生16和15的稳定数,表明浴甚至在延长加热之后仍保持其高稳定性。
表1:各种浴组合物的稳定数
如从表1和图2而变得显而易知,本发明的稳定剂适于在长时间内提供高镀浴稳定性。相比之下,炔丙醇乙氧基化物(与本发明的稳定剂结构类似(即,碳碳三键)的比较化合物)对无电镍沉积浴具有较低稳定作用且无法充当持续较长时间的稳定剂。
实例9:
表2显示稳定剂并未消极影响电镀速率。
在86℃(水浴)的温度和4.8的pH值下,在一公升烧杯中,使用一公升下列物质的溶液进行表2的电镀实验:NiSO4·6H2O(26.3g/l)和作为络合剂的三乙醇胺、单水合次磷酸钠(30g/l)和不同浓度添加剂。
使用电镀一小时的具有0.1mm厚度的不锈钢条带测量沉积速率。使用测微器装置进行测量。测定电镀速率=0.5×(电镀后的板厚度-电镀前的板厚度(以μm计))。
利用应力条带指测量涂层中的应力。测试条带是由以化学方式蚀刻的铍铜合金制成且具有弹簧样性质。电镀之后,将测试条带安装于测试架(美国宾夕法尼亚州约克的专业测试与开发公司(Specialty Testing&Development Co.,York,PA,USA)的沉积物应力分析器型号683)上,所述测试架测量电镀后测试条带腿展开的距离。距离U包括于计算沉积物应力的公式中。
应力=U/3*T*K
U为展开增量数,T为沉积物厚度,且K为条带校正常数。
沉积物厚度T是通过增重法测定且根据下式测定:T=W/D*A,其中W=沉积物重量(以克为单位),D=沉积金属的比重(以克/立方厘米为单位),且A=表面积(以cm2为单位)。
应认识到所制造的每一批次测试条带当用于沉积物应力测试时将略有差异地回应。此差异程度将由供应商在校准每一批次的测试条带时测定。K值将与由专业测试与开发公司提供的每一批次测试条带一起提供。
还测定应力为压缩或拉伸本质。如果测试条带腿在已电镀的侧上向外展开,那么沉积物应力本质上为拉伸。如果测试条带腿在已电镀的侧上向内展开,那么沉积物应力本质上为压缩。
表2:利用不同浓度的添加剂3-(丙-2-炔基氧基)-丙基-1-磺酸钠盐(实例2)的涂层中的沉积速率和应力
表2还显示通过从本发明的浴组合物电镀而获得的沉积物展现出压缩应力,所述压缩应力为所需的,因为其积极影响所沉积的镍层的腐蚀保护。
实例10:
进行进一步实验以测试用于制造如半导体工业中所用的较小结构的本发明的镀镍浴。
水性镀浴含有
通过向上述浴基质中添加下列稳定剂而制备四种不同镀浴组合物。
3-(丙-2-炔基氨基)-丙烷-1-磺酸(实例3) 35mg/l
4-(丙-2-炔基氧基)-丁烷-1-磺酸钠盐(实例7) 100mg/l
4-(丁-3-炔基氧基)-丁烷-1-磺酸钠盐(实例1) 150mg/l
3-(丙-2-炔基氧基)-丙基-1-磺酸钠盐(实例2) 120mg/l。
使用无添加剂的上述浴基质进行比较实例。
如图1中所示,在测试衬底的铜衬垫上沉积镍。所述衬底用于半导体工业中的电镀实验。图1显示数目为16的金属化的铜衬垫。数字表示:
50(铜衬垫的直径,以μm为单位),
75(间距(两个铜衬垫中心之间的距离),以μm为单位)。
通过将衬底浸没到上述电镀组合物(pH=4.9,T=85℃)中来进行电镀。
施加含有本发明的稳定剂的镀浴组合物可获得极好的电镀结果:观测到沉积的镍磷合金无过度电镀且厚度分布极其均一。
关于比较实例:从无稳定剂的镍浴金属化的衬垫显示出不均一(就表面上的厚度分布来说)的镍沉积物和在衬垫边缘处的小点。
实例11:根据本发明
针对不同浓度的稳定剂测定无电镀浴的稳定数:
向实例8的水性镀浴储备溶液中添加不同量的实例1到5和7(根据本发明)中的相应稳定剂,且保持在23℃的温度下。在达到恒定温度之后不久,如实例8中所描述测定稳定数。稳定剂的浓度和对应稳定数概述于表3中。
表3:多种浓度的稳定剂的稳定数
如从表3而变得显而易知,本发明的稳定剂适于在广泛浓度范围内提供高镀浴稳定性。
实例12:根据本发明
在延长时间期间测定无电镀浴的稳定数:
向实例8的水性镀浴储备溶液中添加实例2、3和7(根据本发明)中的相应稳定剂,且加热到86℃后持续所述实验的持续时间。在某些时间下,将100ml研究中的镀浴的样品转移到200ml玻璃烧杯中,且在搅拌的同时加热到80±1℃。如实例8中所描述测定稳定数。稳定剂的浓度、时间和相应稳定数概述于表4中。
表4:在延长时间期间各种浴组合物的稳定数
如从表4而变得显而易知,即使浴经加热,本发明的稳定剂也适于在长时间内提供高镀浴稳定性。
实例13:比较实例
针对不同浓度的稳定剂测定无电镀浴的稳定数:
向实例8的水性镀浴储备溶液中添加不同量的实例2(根据本发明)中的稳定剂以及比较化合物炔丙基磺酸钠盐(样品8)、3-己炔-2,5-二醇(样品9)和2-丁炔-1-醇(样品10),且保持在23℃的温度下。在达到恒定温度之后不久,如实例8中所描述测定稳定数。稳定剂、比较化合物的浓度和相应稳定数概述于表5中。炔丙基磺酸钠盐可例如购自巴斯夫集团(BASF AG)(Golpanol PS)。3-己炔-2,5-二醇和2-丁炔-1-醇也可购得。
表5:针对多种浓度的稳定剂和比较化合物的稳定数
如从表5而变得显而易知,本发明的稳定剂适于在广泛浓度范围内提供高镀浴稳定性。相比之下,与本发明的稳定剂结构类似(即,碳碳三键)的比较化合物当以相同浓度添加到无电镍沉积浴时展现明显较低的稳定作用。
Claims (17)
1.一种用于镍和镍合金的无电沉积的水性镀浴组合物,所述水性镀浴组合物包含
(i)镍离子的来源,
(ii)至少一种络合剂,
(iii)至少一种还原剂,
(iv)式(1)的稳定剂:
其中X是选自O和NR4,n在1到6范围内,m在1到8范围内;R1、R2、R3和R4是独立地选自氢和C1到C4烷基;Y是选自-SO3R5、-CO2R5和-PO3R5 2,且R5是选自氢、C1-C4烷基和适合的反离子。
2.根据权利要求1所述的水性镀浴组合物,其中R1、R2、R3和R4是选自氢、甲基和乙基。
3.根据前述权利要求中任一权利要求所述的水性镀浴组合物,其中R5选自氢、甲基、乙基、钠、钾、镍和铵。
4.根据权利要求1或2所述的水性镀浴组合物,其中Y为SO3R5。
5.根据权利要求3所述的水性镀浴组合物,其中Y为SO3R5。
6.根据权利要求1或2所述的水性镀浴组合物,其中所述式(1)的稳定剂的浓度在0.02mmol/l到5.0mmol/l范围内。
7.根据权利要求1或2所述的水性镀浴组合物,其进一步包含至少一种合金金属离子来源,且其中所述至少一种合金金属离子是选自由以下组成的群组:钛、钒、铬、锰、锆、铌、钼、铪、钽、钨、铜、银、金、铝、铁、钴、钯、钌、铑、锇、铱、铂、锌、镉、镓、铟、锡、锑、铊、铅和铋。
8.根据权利要求1或2所述的水性镀浴组合物,其中所述水性镀浴组合物具有3.5到7的pH值。
9.根据权利要求1或2所述的水性镀浴组合物,其中所述镍离子的浓度在0.1g/l到60g/l范围内。
10.根据权利要求1或2所述的水性镀浴组合物,其中所述至少一种络合剂是选自由以下组成的群组:胺、羧酸、羟基羧酸、氨基羧酸和前述的盐。
11.根据权利要求1或2所述的水性镀浴组合物,其中所述至少一种络合剂的浓度在0.01mol/l到3.0mol/l范围内。
12.根据权利要求1或2所述的水性镀浴组合物,其中所述至少一种还原剂的浓度在0.01mol/l到3.0mol/l范围内。
13.根据权利要求1或2所述的水性镀浴组合物,其中所述至少一种还原剂选自次磷酸盐、胺硼烷、硼氢化物、肼和甲醛。
14.根据权利要求1或2所述的水性镀浴组合物,其中所述至少一种还原剂为次磷酸盐。
15.一种用于镍和镍合金的无电沉积的方法,其包含以下步骤:
(i)提供衬底,
(ii)将所述衬底浸没在根据权利要求1到14中任一权利要求所述的水性镀浴组合物中,
(iii)和由此将镍或镍合金沉积到所述衬底上。
16.根据权利要求15所述的方法,其中所述水性镀浴组合物含有次磷酸盐作为所述至少一种还原剂。
17.根据权利要求15或16所述的方法,其中电镀速率在4微米/小时到14微米/小时之间变化,以获得在10重量%到15重量%之间的磷含量。
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EP20120170693 EP2671969A1 (en) | 2012-06-04 | 2012-06-04 | Plating bath for electroless deposition of nickel layers |
EP12170693.1 | 2012-06-04 | ||
PCT/EP2013/061280 WO2013182489A2 (en) | 2012-06-04 | 2013-05-31 | Plating bath for electroless deposition of nickel layers |
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EP (2) | EP2671969A1 (zh) |
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CA (1) | CA2875317C (zh) |
ES (1) | ES2688547T3 (zh) |
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US9175399B2 (en) | 2015-11-03 |
ES2688547T3 (es) | 2018-11-05 |
BR112014028715B1 (pt) | 2022-01-25 |
WO2013182489A2 (en) | 2013-12-12 |
US20150110965A1 (en) | 2015-04-23 |
JP2015524024A (ja) | 2015-08-20 |
JP6161691B2 (ja) | 2017-07-12 |
EP2855732B1 (en) | 2018-07-18 |
CN104321463A (zh) | 2015-01-28 |
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MY168645A (en) | 2018-11-27 |
EP2855732A2 (en) | 2015-04-08 |
CA2875317C (en) | 2020-03-31 |
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