EP3224388B1 - Plating bath and method for electroless deposition of nickel layers - Google Patents
Plating bath and method for electroless deposition of nickel layers Download PDFInfo
- Publication number
- EP3224388B1 EP3224388B1 EP15797992.3A EP15797992A EP3224388B1 EP 3224388 B1 EP3224388 B1 EP 3224388B1 EP 15797992 A EP15797992 A EP 15797992A EP 3224388 B1 EP3224388 B1 EP 3224388B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nickel
- plating bath
- bath composition
- ion
- aqueous plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 222
- 238000007747 plating Methods 0.000 title claims description 131
- 229910052759 nickel Inorganic materials 0.000 title claims description 111
- 230000008021 deposition Effects 0.000 title claims description 59
- 238000000034 method Methods 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 claims description 127
- 239000003381 stabilizer Substances 0.000 claims description 103
- 238000000151 deposition Methods 0.000 claims description 64
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 63
- 239000000758 substrate Substances 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000007772 electroless plating Methods 0.000 claims description 29
- 229910021645 metal ion Inorganic materials 0.000 claims description 29
- 239000003638 chemical reducing agent Substances 0.000 claims description 26
- 239000008139 complexing agent Substances 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- 239000011574 phosphorus Substances 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 238000005275 alloying Methods 0.000 claims description 15
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 claims description 14
- 229910001449 indium ion Inorganic materials 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 12
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001453 nickel ion Inorganic materials 0.000 claims description 11
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 10
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 9
- 229940006461 iodide ion Drugs 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 230000000087 stabilizing effect Effects 0.000 claims description 9
- 229940005633 iodate ion Drugs 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- KHIWWQKSHDUIBK-UHFFFAOYSA-M periodate Chemical compound [O-]I(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-M 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- RJMMFJHMVBOLGY-UHFFFAOYSA-N indium(3+) Chemical compound [In+3] RJMMFJHMVBOLGY-UHFFFAOYSA-N 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001450 In3+ Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 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
- 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
- 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
- CXIHYTLHIDQMGN-UHFFFAOYSA-L methanesulfonate;nickel(2+) Chemical compound [Ni+2].CS([O-])(=O)=O.CS([O-])(=O)=O CXIHYTLHIDQMGN-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 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
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 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
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 45
- 229910052751 metal Inorganic materials 0.000 description 35
- 239000002184 metal Substances 0.000 description 35
- 230000035882 stress Effects 0.000 description 30
- 238000000576 coating method Methods 0.000 description 23
- -1 organic acid salts Chemical class 0.000 description 21
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 17
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000000956 alloy Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 229910001096 P alloy Inorganic materials 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 150000004677 hydrates Chemical class 0.000 description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 6
- 230000005291 magnetic effect Effects 0.000 description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 230000002269 spontaneous effect Effects 0.000 description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 5
- 239000001230 potassium iodate Substances 0.000 description 5
- 235000006666 potassium iodate Nutrition 0.000 description 5
- 229940093930 potassium iodate Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004876 x-ray fluorescence Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910000085 borane Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 4
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 4
- KLRHPHDUDFIRKB-UHFFFAOYSA-M indium(i) bromide Chemical compound [Br-].[In+] KLRHPHDUDFIRKB-UHFFFAOYSA-M 0.000 description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 4
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- JKNHZOAONLKYQL-UHFFFAOYSA-K tribromoindigane Chemical compound Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- UXLRWZBQRAWBQA-UHFFFAOYSA-H digallium;trisulfate Chemical compound [Ga+3].[Ga+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O UXLRWZBQRAWBQA-UHFFFAOYSA-H 0.000 description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 3
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229960002449 glycine Drugs 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 3
- 230000007306 turnover Effects 0.000 description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 2
- WBPWDGRYHFQTRC-UHFFFAOYSA-N 2-ethoxycyclohexan-1-one Chemical compound CCOC1CCCCC1=O WBPWDGRYHFQTRC-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N Alanine Chemical compound CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 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
- 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 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- 229910021620 Indium(III) fluoride Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VUAQKPWIIMBHEK-UHFFFAOYSA-K bis(methylsulfonyloxy)indiganyl methanesulfonate Chemical compound [In+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O VUAQKPWIIMBHEK-UHFFFAOYSA-K 0.000 description 2
- KKAXNAVSOBXHTE-UHFFFAOYSA-N boranamine Chemical class NB KKAXNAVSOBXHTE-UHFFFAOYSA-N 0.000 description 2
- 239000008364 bulk solution Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 150000002258 gallium Chemical class 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 description 2
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 2
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 2
- ZMFWDTJZHRDHNW-UHFFFAOYSA-N indium;trihydrate Chemical compound O.O.O.[In] ZMFWDTJZHRDHNW-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 2
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011697 sodium iodate Substances 0.000 description 2
- 235000015281 sodium iodate Nutrition 0.000 description 2
- 229940032753 sodium iodate Drugs 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- JNLSTWIBJFIVHZ-UHFFFAOYSA-K trifluoroindigane Chemical compound F[In](F)F JNLSTWIBJFIVHZ-UHFFFAOYSA-K 0.000 description 2
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- 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
- 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920006942 ABS/PC Polymers 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004151 Calcium iodate Substances 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910005258 GaBr3 Inorganic materials 0.000 description 1
- 229910005267 GaCl3 Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical group [S-2] UCKMPCXJQFINFW-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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- GASILTKHXWGKMG-UHFFFAOYSA-L barium iodate Chemical compound [Ba+2].[O-]I(=O)=O.[O-]I(=O)=O GASILTKHXWGKMG-UHFFFAOYSA-L 0.000 description 1
- 229940054259 barium iodate Drugs 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- UHWJJLGTKIWIJO-UHFFFAOYSA-L calcium iodate Chemical compound [Ca+2].[O-]I(=O)=O.[O-]I(=O)=O UHWJJLGTKIWIJO-UHFFFAOYSA-L 0.000 description 1
- 235000019390 calcium iodate Nutrition 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- LKRFCKCBYVZXTC-UHFFFAOYSA-N dinitrooxyindiganyl nitrate Chemical compound [In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LKRFCKCBYVZXTC-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- YVFORYDECCQDAW-UHFFFAOYSA-N gallium;trinitrate;hydrate Chemical compound O.[Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YVFORYDECCQDAW-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- LIOSZQDAIGKTBU-UHFFFAOYSA-N hexanedioic acid;octanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCCCC(O)=O LIOSZQDAIGKTBU-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229940116298 l- malic acid Drugs 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- UYNRPXVNKVAGAN-UHFFFAOYSA-L magnesium;diiodate Chemical compound [Mg+2].[O-]I(=O)=O.[O-]I(=O)=O UYNRPXVNKVAGAN-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- RAJUJHHGBPSUAC-UHFFFAOYSA-I pentasodium pentaoxido(oxo)-lambda7-iodane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-][I]([O-])([O-])([O-])([O-])=O RAJUJHHGBPSUAC-UHFFFAOYSA-I 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- FJVZDOGVDJCCCR-UHFFFAOYSA-M potassium periodate Chemical compound [K+].[O-]I(=O)(=O)=O FJVZDOGVDJCCCR-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HJSRRUNWOFLQRG-UHFFFAOYSA-N propanedioic acid Chemical compound OC(=O)CC(O)=O.OC(=O)CC(O)=O HJSRRUNWOFLQRG-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229940083599 sodium iodide Drugs 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
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 229910052717 sulfur Chemical group 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
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 1
- 239000011787 zinc oxide 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- 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
Definitions
- the present invention relates to aqueous plating bath compositions for electroless deposition of nickel and nickel alloys.
- the present invention relates further to a method utilizing the aqueous plating bath compositions for electrolessly depositing nickel and nickel alloys.
- the aqueous plating bath compositions have high stability against undesired decomposition.
- the nickel and nickel alloy coatings obtained by the invention show high corrosion resistance and adhesion to the subjacent substrate.
- Such coatings are suitable as a functional coating in aerospace, automotive, electronics and chemical industries.
- the metal layers deposited from such aqueous plating bath compositions are also useful as barrier and cap layers in semiconducting devices, printed circuit boards, IC substrates and the like.
- the metal layers deposited are also suitable as overcoat for hard disks or rigid memory disks (RMD).
- Barrier layers are used in electronic devices such as semiconducting devices, printed circuit boards, IC substrates and the like to separate layers of different composition, e.g.substrate layers and further layers, and thereby prevent undesired diffusion between such layers of different composition.
- barrier layer materials in electronic devices is as a cap layer which is e.g. deposited onto copper to prevent corrosion of copper.
- Rigid memory disks are used as magnetic data storage media in hard disk drives.
- the disks are basically composed of a substrate, made of aluminum, glass or ceramics.
- An overcoat is deposited onto the substrate by a vacuum deposition process or an electroless metal plating process.
- the overcoat may consist of various metallic, mostly non-magnetic, alloys one of which may be a nickel phosphorus alloy layer.
- the overcoat provides e.g. a smooth surface onto which the magnetic recording layers are deposited. Further protective layers are coated onto the recording layers.
- compositions for electroless nickel plating solutions are known in the art.
- US Patent 2,658,841 teaches the use of soluble organic acid salts as buffers for electroless nickel plating solutions.
- US Patent 2,658,842 teaches the use of short chain, dicarboxylic acids as exaltants to electroless nickel baths.
- US Patent 2,762,723 teaches the use of sulfide and sulfur bearing additives to an electroless nickel plating bath for improved bath stability.
- Patent application JP 2005-194562 discloses an electroless nickel plating bath containing indium compounds as bath stabilizers.
- EP2194156 discloses a bath for electroless deposition of nickel which contains a source of Ni ions and two stabilisers, namely iron metal ion and iodide.
- US Patent 4,189,324 describes an electroless nickel plating solution including of a source of gallium that improves stability of the solution. None of the prior art documents teaches a specific mixture of stabilizing agents having a particular good stabilizing effect in electroless nickel plating compositions.
- the invention further relates to a method for deposition of nickel and nickel alloys by contacting the substrate to be plated with above described composition.
- aqueous plating bath composition for electroless deposition of nickel and nickel alloys is also abbreviated as “composition” herein.
- the invention relates to a method for stabilizing any electroless plating bath for deposition of nickel and nickel alloys by adding a mixture of stabilizing agents to the electroless plating bath.
- Electroless nickel plating compositions for applying nickel coatings are well known in the art and plating processes and compositions are described in numerous publications such as U.S. Patents Nos. 2,935,425 ; 3,338,726 ; 3,597,266 ; 3,915,716 and 4,780,342 .
- Electroless plating generally describes methods without using external current sources for reduction of metal ions. Plating processes using external current sources are commonly described as electrolytic or galvanic plating methods.
- chemical reducing agents like hypophosphite, boranes or formaldehyde are used to reduce the metal ions to their metallic form and thereby forming a deposit on the substrate.
- NiP deposition solutions comprise at least three ingredients dissolved in a solvent, typically water. They are (1) a source of the nickel ions, (2) a reducing agent and (3) a complexing agent for metal ions sufficient to prevent their precipitation in solution. A large number of suitable complexing agents for NiP solutions are described in the above noted publications. If hypophosphite is used as the reducing agent, the deposit will contain nickel and phosphorus. Similarly, if an aminoborane is employed, the deposit will contain nickel and boron as shown in U.S. Pat. No. 3,953,654 .
- the aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention comprises a source of nickel ions.
- the source of nickel ions may be provided by the use of any soluble salt such as nickel sulfate, nickel chloride, nickel acetate, nickel methyl sulfonate, nickel sulfamate and mixtures thereof.
- the concentration of the nickel ions in the composition may vary widely and preferably ranges from 0.01 mol/l to 1 mol/l, more preferably from 0.03 mol/l to 0.8 mol/l, even more preferably from 0.06 mol/l to 0.3 mol/l.
- the aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention further comprises at least one reducing agent.
- the at least one reducing agent is preferably a chemical reducing agent. Reducing agents provide the electrons needed to reduce metal ions to their metallic form and thereby form a metal deposit on a substrate.
- the at least one reducing agent is preferably a hypophosphite salt or hypophosphorous acid, more preferably a hypophosphite salt.
- the hypophosphite salt is supplied to the composition by any suitable source such as sodium, potassium, ammonium and nickel hypophosphite.
- Other reducing agents such as aminoboranes, borohydrides, hydrazine and derivatives thereof and formaldehyde may also suitably be employed.
- Two or more reducing agents may be employed as a mixture in the composition.
- the concentration of the at least one reducing agent is generally in molar excess of the amount sufficient to reduce the nickel ions in the composition.
- the concentration of the reducing agent preferably ranges from 0.01 mol/l to 3.0 mol/l, more preferably from 0.1 mol/l to 1 mol/l.
- a hypophosphite compound is used as the reducing agent
- a Ni-P alloy deposit is obtained.
- Such reducing agents provide the source of phosphorus in the deposited alloy.
- a borane-based compound as reducing agent leads to a NiB alloy deposit and a mixture of hypophosphite and borane-based compounds as the reducing agents leads to a ternary Ni-B-P alloy deposit.
- a nitrogen-based reducing agent such as hydrazine and derivatives thereof as well as formaldehyde as reducing agent lead to nickel deposits.
- the aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention may be acidic, neutral or alkaline.
- An acidic or an alkaline pH adjustor may be selected from a wide range of materials such as ammonium hydroxide, sodium hydroxide, hydrochloric acid, sulfuric acid and the like.
- the pH of the composition may range from about 2 to 12.
- the compositions are preferably acidic. More preferably, the pH of the acidic compositions ranges from 3.5 to 7, even more preferably from 3.5 to 6.5, most preferably from 3.5 to 5.5.
- the compositions are preferably alkaline. More preferably the pH of the alkaline compositions ranges from 7.5 to 12, even more preferably from 8 to 10, most preferably from 8 to 9.
- the aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention further comprises at least one complexing agent.
- a complexing agent (sometimes also referred to as chelating agent) or mixture of complexing agents is included in the composition for nickel and nickel alloy plating.
- a complexing agent keeps metal ions dissolved and prevents their undesired precipitation in solution.
- the at least one complexing agent is preferably selected from complexing agents for nickel ions and complexing agents for alloying metal ions, more preferably from complexing agents for nickel ions.
- the at least one complexing agent is preferably selected from the group comprising alkyl amines, ammonia, carboxylic acids, hydroxyl carboxylic acids, aminocarboxylic acids, salts of the aforementioned and mixtures thereof.
- carboxylic acids, hydroxylcarboxylic acids, aminocarboxylic acids and salts of the aforementioned or mixtures thereof may be employed as the at least one complexing agent.
- Useful carboxylic acids include the mono-, di-, tri- and tetra-carboxylic acids.
- the carboxylic acids may be substituted with various substituent moieties such as hydroxy or amino groups and the acids may be introduced into the composition as their sodium, potassium or ammonium salts.
- Some complexing agents such as acetic acid, for example, may also act as a pH buffering agent, and the appropriate concentration of such additive components can be optimised for any composition in consideration of their dual functionality.
- monocarboxylic acids such as acetic acid, hydroxyacetic acid (glycolic acid), aminoacetic acid
- Preferred carboxylic acids are acetic acid, aminoacetic acid, propanoic acid, 2-hydroxy propanoic acid, succinic acid, hydroxy succinic acid, adipic acid or 2-hydroxy-1,2,3-propane-tricarboxylic acid.
- mixtures of two or more of the above complexing/chelating agents are utilised in the composition according to the present invention.
- Alkyl amines may also be used as the at least one complexing agent, for example mono-, di- and trialkylamines.
- C 1 - C 3 alkyl amines, for example triethanolamine are preferred.
- Ammonia may also be used as the at least one complexing agent.
- the concentration of the at least one complexing agent or, in case more than one complexing agent is used, the concentration of all complexing agents in total preferably ranges from 0.01 mol/l to 3.0 mol/l, more preferably from 0.1 mol/l to 1.0 mol/l and even more preferably from 0.2 mol/l - 0.6 mol/l.
- the aqueous plating bath composition for electroless deposition of nickel and nickel alloys comprises a mixture of stabilizing agents according to (ii) comprising
- Stabilizing agents are compounds that stabilize an electroless metal plating solution against undesired plate out in the bulk solution and spontaneous decomposition.
- plate out means undesired and/or uncontrolled deposition of the metal on surfaces other than substrate surfaces.
- the indium ion may be selected from any indium ions, preferably from the group comprising indium(III) ions and indium(I) ions and mixtures thereof. More preferably, the indium ion is an indium(III) ion.
- the gallium ion may be selected from any gallium ions, preferably from the group comprising gallium(III) ions, gallium(I) ions and mixtures thereof. More preferably, the gallium ion is a gallium(III) ion.
- the indium ion or the gallium ion may be in the form of their salts.
- the salts of indium ions or gallium ions are preferably selected from the group comprising indium(III) sulfate (In 2 (SO 4 ) 3 ), indium(III) hydroxide (In(OH) 3 ), indium(III) oxide (In 2 O 3 ), indium(III) methane sulfonate (In(CH 3 -SO 3 ) 3 ), indium(III) nitrate (In(NO 3 ) 3 ), indium(III) chloride (InCl 3 ), indium(III) bromide (InBr 3 ), indium(III) fluoride (InF 3 ), indium(III) acetate (In(CH 3 -COO) 3 ), indium(I) chloride (InCI), indium(I) bromide (InBr), gallium(III) sulfate (Ga 2 (SO 4 ) 3 ), gallium(III) hydroxide (Ga(OH) 3 ), gallium(III) methane
- the concentration of the at least one metal ion according to (ii)a) preferably ranges from 0.01 mmol/l to 0.5 mmol/l, more preferably from 0.01 mmol/l to 0.1 mmol/l, even more preferably from 0.02 mmol/l to 0.08 mmol/l.
- Higher concentrations of the at least one metal ion according to (ii)a) result in deposition of nickel or nickel alloy layers of dull appearance and skip plating.
- Skip plating is a plating defect in which the coating undesirably does not cover all areas of the plated substrate.
- the mixture i.e.
- the combination, of metal ions according to (ii)a) with stabilizing agents according to (ii)b) allows to shift the lower concentration limit of metal ions according to (ii)a) to the lower values as described above, without impairing stability of the composition.
- concentration range of metal ions according to (ii)a) suitable for stabilizing the composition and any electroless plating bath for deposition of nickel and nickel alloys, and suitable for depositing nickel or nickel alloy layers of good quality is widened.
- the wider process window improves process control for plating.
- the at least one stabilizing agent according to (ii)b) is preferably selected from the group comprising iodide ion containing compounds and iodate ion containing compounds; more preferably iodide ion containing compounds.
- the iodide ion containing compounds are preferably selected from the group comprising potassium iodide, sodium iodide, ammonium iodide, calcium iodide, barium iodide, magnesium iodide, lithium iodide, zinc iodide, and hydrates of the aforementioned; more preferably potassium iodide, sodium iodide, ammonium iodide, and hydrates of the aforementioned; even more preferably potassium iodide and hydrates thereof.
- the iodate ion containing compounds are preferably selected from water soluble iodate salts.
- the water soluble iodate salts are preferably iodate salts of alkali metals or earth alkali metals.
- the iodate salt is preferably selected from the group comprising potassium iodate, sodium iodate, ammonium iodate, calcium iodate, barium iodate, magnesium iodate, lithium iodate and hydrates of the aforementioned; more preferably potassium iodate, sodium iodate, ammonium iodate, lithium iodate and hydrates of the aforementioned; even more preferably potassium iodate and hydrates thereof.
- the periodate ion containing compounds may be selected from the group comprising preferably metaperiodate ion containing compounds (IO 4 - ), and orthoperiodate ion containing compounds (IO 6 5- ).
- the periodate ion containing compounds are preferably selected from the group comprising potassium metaperiodate (KIO 4 ), sodium metaperiodate (NaIO 4 ) and sodium ortho periodate (Na 3 H 2 IO 6 ).
- the concentration of the at least one stabilizing agent according to (ii)b) preferably ranges from 0.05 to 50.0 mmol/l, more preferably from 0.1 to 30.0 mmol/l, even more preferably from 0.5 to 10.0 mmol/l, and even more preferred from 1.0 mmol/l to 5.0 mmol/l.
- Higher concentrations of the at least one stabilizing agent according to (ii)b) result in lower deposition rates, in difficulties to initiate deposition on the substrate surface, in deposition of nickel or nickel alloy layers having low adhesion to the subjacent substrate, e.g. blistering, and less compressive stress.
- Lower concentrations of the at least one stabilizing agent according to (ii)b) do not show the desired enhanced bath stability against undesired, spontaneous decomposition.
- the stabilizing agents of the present invention are suitable to enhance the stability of the aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention against undesired, spontaneous decomposition.
- Undesired, spontaneous decomposition means undesired formation of a black precipitate, undesired plate out of nickel in the bulk solution or undesired and/or uncontrolled deposition of nickel, for example on the bottom of a plating tank or on other surfaces different from the substrate.
- the stabilizing effect is particularly pronounced when the stabilizing agents are used as a mixture, i.e. in combination.
- the combination of metal ions according to (ii)a) with stabilizing agents according to (ii)b) provides in particular a long life to the composition of the present invention.
- the bath stability imparted by the combination of stabilizing agents is much higher than the stabilizing effect of one of the stabilizing agents alone.
- the combination of stabilizing agents of the present invention has a synergistic effect on the bath stability.
- the combination of stabilizing agents of the present invention also imparts an improved resistance of the composition against contamination with catalytic metals.
- Contamination with catalytic metals may be caused by metal ions dissolving from the substrate material while in contact with the composition, or metal ions are dragged into the composition from pre-treatment or activation steps.
- Catalytic metals may be palladium, platinum, rhodium, ruthenium or mixtures thereof, preferably palladium.
- composition of the present invention containing a combination of stabilizing agents, namely metal ions according to (ii)a) and stabilizing agents according to (ii)b), are suitable for plating on electrically non-conductive substrates, on electrically conductive substrates, and on electrically semi-conductive substrates.
- the combination of stabilizing agents according to the invention has a synergistic effect on the bath stability and the composition containing the combination of stabilizing agents is much less prone to contamination with catalytic metals.
- the combination of stabilizing agents according to the invention has only a low effect on the deposition rate, i.e. increasing the concentration of the stabilizing agents does not alter the deposition rate and the combination of stabilizing agents does not decrease the deposition rate of the composition of the present invention.
- the deposited nickel or nickel alloy layers are of good quality, i.e. the quality of the nickel or nickel alloy layers are not influenced disadvantageously by the combination of stabilizing agents according to the invention.
- the deposited nickel or nickel alloy layers completely cover the substrate surface; no skip plating is obtained.
- the deposited nickel or nickel alloy layers are of uniform thickness, adhere well to the substrate surface and have a good appearance.
- the combination of stabilizing agents according to the present invention has no negative effect on the plating bath performance and no negative effect on the coating quality.
- the aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention further shows a high stability during idle periods.
- Idle periods are defined as time periods in which the operating parameters, like temperature or pH value, of a plating bath are adjusted to its desired value for plating operation, but no substrate is immersed in the plating bath.
- the combination of stabilizing agents according to the invention also keeps the composition stable against undesired, spontaneous decomposition during prolonged periods at high temperature while not plating. This effect is better than with stabilizing agents known in the art, e.g. tin ions, bismuth ions or antimony ions.
- compositions according to the present invention may include pH buffers, wetting agents, accelerators, brighteners, additional stabilizing agents etc.
- the composition may contain further organic stabilizing agents and/or further inorganic stabilizing agents. These materials are known in the art.
- the composition may contain further metal stabilizing agents such as Cu-, Se-, Sn-, Bi- or Sb-ions.
- concentration of the metal ions can vary and e.g. range between 0.1 - 100 mg/l, preferably between 0.1 - 50 mg/l, more preferably between 0.1 - 10 mg/l.
- the composition does not contain toxic heavy metals.
- the composition does preferably not contain lead, cadmium, antimony, bismuth, arsenic or mercury.
- the aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention may further comprise at least one alloying element.
- nickel alloy layers containing the alloying element are deposited from the composition.
- the at least one alloying element may be selected from phosphorus, boron, and a metal which is not nickel.
- the alloying elements phosphorus or boron may be comprised in the composition in the form of a hypophosphite salt, hypophosphorous acid or a borane-based compound, such as aminoboranes or borohydrides, as mentioned above as reducing agents.
- the metal which is not nickel may be comprised in the composition in the form of a water-soluble metal salt containing the ions of the alloying metal M.
- the optional alloying metal M is preferably selected from the group consisting of titanium, vanadium, chromium, manganese, zirconium, niobium, molybdenum, hafnium, tantalum, tungsten, copper, silver, gold, aluminum, iron, cobalt, palladium, ruthenium, rhodium, osmium, iridium, platinum, zinc, cadmium, gallium, indium, tin, antimony, thallium, lead, and bismuth. More preferably, the optional alloying metal M is selected from the group consisting of molybdenum, tungsten, copper, silver, gold, aluminum, zinc and tin.
- the concentration of the optional alloying metal M preferably ranges from 10 -5 to 0.2 mol/l, more preferably from 10 -4 to 0.2 mol/l, even more preferably from 10 -2 to 0.1 mol/l.
- Ni-M-P, Ni-M-B, and Ni-M-B-P are deposited.
- a water-soluble salt of an alloying metal M and a water-soluble salt of a second alloying metal M* are added to the composition.
- nickel alloy deposits comprising alloying metals M and M* are obtained.
- a suitable composition may be formed by dissolving the ingredients in water and adjusting the pH to the desired range.
- the indium or gallium salts may be dissolved in an acid prior to adding them to the composition.
- the present invention further relates to a method for electroless deposition of nickel and nickel alloys by contacting the substrate to be plated with the above described aqueous plating bath composition for electroless deposition of nickel and nickel alloys.
- the deposition method comprises the steps of
- the substrate to be nickel or nickel alloy plated may be plated to the desired thickness and deposit quantity by contacting the substrate with the composition.
- the inventive composition may be maintained over a temperature range of 20 °C to 100 °C, preferably 70 °C to 95 °C, more preferably 85 °C to 95 °C during deposition.
- a deposit thickness of up to 100 ⁇ m, or higher may be employed.
- the thickness of the nickel or nickel phosphorus (NiP) deposits varies between 1 - 60 ⁇ m. The thickness depends on the technical application and can be higher or lower for some applications. For example, if the nickel or NiP layer is deposited to provide a corrosion resistant coating, a thickness of between 30 - 60 ⁇ m is desired, while for electronics applications a thickness of between 1 - 15 ⁇ m is applied.
- the thickness of the nickel or nickel-phosphorus deposits preferably ranges from 9 to 13 ⁇ m.
- the thickness of the nickel or nickel-phosphorus deposits preferably ranges from 1 to 5 ⁇ m. Thicknesses of nickel or nickel alloy layers may be measured with x-ray fluorescence (XRF) which is known in the art.
- XRF x-ray fluorescence
- the present invention further relates to a method for stabilizing any electroless plating bath for deposition of nickel and nickel alloys, the method comprises the steps of
- the mixture of stabilizing agents comprises
- the electroless plating bath may be any electroless plating bath for deposition of nickel and nickel alloys.
- the electroless plating bath is the aqueous plating bath composition for electroless deposition of nickel and nickel alloys according to the present invention.
- the electroless plating bath may be a freshly prepared electroless plating bath.
- the electroless plating bath may be already used for some time for plating.
- the electroless plating bath may be stored for some time without plating. During storage the electroless plating bath may be kept at a temperature ranging from 15 to 100 °C.
- the concentrations of the stabilizing agents of the inventive mixture may be determined during plating or storage and replenished if below a threshold value. Replenishment is performed by adding the stabilizing agents of the inventive mixture or combination to the electroless plating baths.
- the mixture of stabilizing agents of the present invention keeps the electroless plating bath stable against undesired, spontaneous decomposition during prolonged periods of plating, during prolonged storage times and during prolonged periods at high temperature while not plating, e.g. idle periods.
- the overall consumption of metal ions according to (ii)a) as stabilizing agents is lower during plating if the inventive mixture of stabilizing agents is used. Therefore, the amount of metal ions according to (ii)a) which has to be replenished per metal turnover (MTO) is decreased in comparison to electroless plating baths that include only metal ions according to (ii)a) as stabilizing agents.
- MTO metal turnover
- a further advantage is that the metal ions according to (ii)a) can be employed in lower concentration ranges, thus preventing dull appearance of nickel or nickel alloy layers and skip plating while still ensuring stability of the composition.
- the stabilizing agents of the inventive mixture may be added as a solid or a powder or may be dissolved in a solvent prior to adding to the electroless plating baths.
- the indium or gallium salts may be dissolved in an acid prior to adding them to the electroless plating bath.
- the aqueous plating bath composition for electroless deposition of nickel and nickel alloys and the methods of the present invention are suitable to provide nickel and nickel alloy coatings having an attractive bright or semi-bright appearance.
- the compressive stress of the deposited nickel or nickel alloy layers is maintained.
- the mixture of stabilizing agents of the present invention does not shift the internal stress to neutral or tensile stress.
- the advantages of nickel or nickel alloy layers having compressive stress are high corrosion resistance and good adhesion to the substrate surface.
- a high phosphorus NiP alloy is herein defined as a metallic coating containing less than 91 wt.% Ni and more than 9 wt.% P, e.g. 10.5 wt.%. Generally, high phosphorus alloys contain up to 15 wt.% P.
- a nickel-phosphorus (NiP) alloy containing more than about 10.5% phosphorus is known as a high phosphorus NiP coating and is paramagnetic (non-magnetic) as plated.
- a mid phosphorus NiP alloy is herein defined as a metallic coating containing between 5 - 9 wt.% P.
- a low-phosphorus NiP alloy is herein defined as a metallic coating containing between 1 - 5 wt.% P.
- the aqueous plating bath composition for electroless deposition of nickel and nickel alloys and the methods of the present invention are suitable to provide nickel phosphorus alloy coatings with a wide range of P content of between 1 - 15 wt.% P.
- the composition and the methods of the present invention are particularly suitable for depositing nickel phosphorus alloys, e.g. high NiP alloys as defined above.
- the combination of stabilizing agents according to the present invention does not change the phosphorus content of the deposited nickel alloy layers compared to electroless nickel-phosphorus baths containing no stabilizer or single stabilizing agents according to (ii)a) or (ii)b).
- the combination of stabilizing agents according to the present invention has no negative effect on the bath performance and no negative effect on the coating quality.
- the phosphorus content of nickel alloy layers and the thickness of nickel or nickel alloy layers were measured by x-ray fluorescence (XRF) which is well known to persons skilled in the art.
- XRF x-ray fluorescence
- the XRF measurements make use of the characteristic fluorescence radiation emitted from a sample (substrate, deposit) being excited with x-rays.
- phosphorus content and layer thicknesses can be calculated.
- High NiP alloys are obtained when the plating process is performed at a plating rate of preferably between 5 - 14 ⁇ m / hour, more preferred 6 - 12 ⁇ m / hour, even more preferred 6 - 10 ⁇ m / hour.
- Such plating rate can be obtained by adjusting the plating parameters, like pH or temperature.
- High NiP alloys obtained by the composition according to the present invention contribute to generating alloys having high compressive stress.
- the stress values for example range between 0 to -70 N/mm 2 , preferably between 0 to -50 N/mm 2 , more preferably between -30 to -50 N/mm 2 .
- Such deposits show high corrosion resistance and excellent adhesion to the underlying substrate they are plated on.
- the combination of stabilizing agents according to the present invention does also not change the stress of the deposited nickel-phosphorus layer compared to electroless nickel-phosphorus baths containing no stabilizer or only a single stabilizing agent.
- the combination of stabilizing agents according to the present invention has also no negative effect on the coating quality in terms of stress.
- the combination of stabilizing agents imparts a significantly higher stability to nickel and nickel alloy baths at comparable bath performance and coating quality.
- substrates can be metal plated with an aqueous plating bath composition for electroless deposition of nickel and nickel alloys and the methods of the present invention.
- the substrates to be metal plated can be selected from the group comprised of electrical non-conductive substrates, electrical conductive substrates, and electrical semi-conductive substrates.
- the electrical non-conductive substrates to be metal plated can be selected from the group comprising glass, ceramics, and plastics.
- Plastics can be selected from the group comprising acrylnitrile-butadiene-styrol-copolymer (ABS copolymer); polyamide; a mixture of an ABS copolymer and at least one other polymer which is different to the ABS copolymer; polycarbonate (PC); ABS/PC blends; epoxy resin; bismaleimide-triazine resin (BT); cyanate ester resin; polyimide; polyethylene terephthalate (PET); polybutylene terephthalate (PBT); polylactic acid (PLA); polypropylene (PP); and polyester.
- ABS copolymer acrylnitrile-butadiene-styrol-copolymer
- PC polycarbonate
- ABS/PC blends ABS/PC blends
- epoxy resin bismaleimide-triazine resin
- BT bismaleimide-triazine resin
- PBT polycyanate ester resin
- polyimide polyethylene terephthalate
- PET polybutylene tere
- the electrical conductive substrates to be metal plated can be selected from the group comprised of metallic substrates, and conductive metal oxides.
- the metallic substrates to be metal plated can be selected from the group comprised of copper, zinc, silver, gold, platinum, palladium, iron, iridium, tin, aluminum and nickel.
- the conductive metal oxides to be metal plated can be selected from indium tin oxide (ITO), antimony tin oxide (ATO) and aluminum doped zinc oxide (AZO).
- ITO indium tin oxide
- ATO antimony tin oxide
- AZO aluminum doped zinc oxide
- the electrical semi-conductive substrates to be metal plated can be selected from the group comprised of silicon, germanium, gallium, arsenide and silicon carbide.
- a stock solution of an electroless nickel plating bath comprising: Nickel sulfate hexahydrate 22.4 g/l Sodium orthophosphite (pre-aging salt) 60.0 g/l Lactic acid (90%) (complexing agent/chelating agent) 14.4 g/l Malic acid (complexing agent/chelating agent) 19.8 g/l Succinic acid (complexing agent/chelating agent) 6.1 g/l Sodium hypophosphite monohydrate (reducing agent) 24.0 g/l
- composition of the stock solution corresponds to the composition of the electroless nickel bath disclosed in patent application WO 2010/045559 A1 (Example 4 therein) with the exception that the present stock solution does not contain lead nitrate as a stabilizer.
- Sodium orthophosphite was contained in the stock solution as a pre-aging salt.
- Orthophosphite salts are by-products of the chemical reduction process when hypophosphite is used as the reducing agent. The amount of this by-product in an electroless nickel plating bath depends on how long the bath has been used. This bath age is referred to in the plating industry as the number of metal turnovers or MTOs of the bath.
- nickel salt and a reducing agent When an electroless nickel plating bath is used, nickel salt and a reducing agent must be replenished as nickel is plated, so as to continue the effective use (or life) of the bath.
- the bath When the amount of the replenished nickel salt is equal to the initial amount of nickel contained in the original plating bath, the bath is said to have plated one metal turnover (MTO).
- MTO metal turnover
- the amount of orthophosphite used herein corresponds to 2.5 MTO level.
- the stock solution did not contain any stabilizers.
- Indium ions and iodide ions were added as stabilizers. Indium ions were added in the form of indium(III) hydroxide and iodide ions were added in the form of potassium iodide. Concentrations of the stabilizers in the electroless nickel plating bath were as outlined in Table 2. One batch of the electroless nickel plating bath was used without any stabilizer as comparison. The electroless nickel plating bath had a pH value of 4.4.
- Stability of the electroless nickel plating baths containing the respective concentrations of stabilizers was measured by determining the stability number and by visual inspection.
- the stability number achieved for the investigated plating bath corresponds to the number of palladium test solution additions (each 0.2 ml) within a one minute interval to the plating bath until formation of a gray precipitate.
- the stability test was done twice for each plating bath sample. The average stability number is given in Table 2.
- the entry "5" for an electroless plating bath solely containing iodide ions as stabilizers corresponds to an addition of 5 times 0.2 ml of a palladium chloride solution to the plating bath. After 1 ml (5 times 0.2 ml/l added in one minute intervals) and 5 minutes, a gray precipitate occurs.
- Stability was further evaluated visually in a separate plating experiment.
- the plating conditions were as described in Example 2 below. In contrast to Example 2, the plating time was 90 minutes.
- the result of the test is the total number of substrates plated without stability issues. Excessive plating in the heating surface area of the beaker, i.e. the bottom of the beaker, was observed as a sign of instability. Prior to plating, the beaker and the magnetic stirrer were stripped in 50% (v/v) nitric acid for 30 minutes.
- the test for determining the stability number does not only show improved stability of electroless nickel plating baths containing the combination of stabilizing agents, but also an improved resistance of such electroless nickel plating baths against contamination with catalytic metals, like Pd.
- Aluminum plates were used as substrates for deposition of nickel-phosphorus alloy layers.
- the substrates were pre-treated as summarized in Table 1 in order to clean and double zincate the substrate surface prior to nickel deposition.
- Table 1 Pre-treatment of substrates Pre-treatment step Atotech Product Concentration Temp.
- the substrates were immersed in electroless nickel plating baths of compositions as described in Example 1. Deposition was done in 2L-beakers. Each beaker was placed on a heater and temperature was maintained at 89.5 °C. Mechanical agitation with 175 RPM was applied by a magnetic stirrer. Bath loading was 1.4 dm 2 /l corresponding to two substrates per bath volume. Deposition time was 60 minutes.
- the phosphorus content and deposit thickness were measured at 5 points of each substrate by XRF using the XRF instrument Fischerscope XDV-SDD (Helmut Fischer GmbH, Germany).
- the deposition rate was calculated by using the deposition time and the measured deposit thickness. Results are summarized in Table 2.
- the deposited nickel-phosphorus alloy layers completely covered the substrate surface; no skip plating was obtained.
- the deposited nickel-phosphorus alloy layers were of uniform thickness, adhered well to the substrate surface and had a good appearance with technical brightness and a typical gray color.
- the combination of stabilizing agents according to the present invention did neither decrease the deposition rate nor changed the phosphorus content of the deposited nickel alloy layers compared to electroless nickel plating baths containing no stabilizer or a single stabilizing agent.
- the combination of stabilizing agents according to the present invention had no negative effect on the bath performance and no negative effect on the coating quality.
- U is the number of increments spread
- T is the deposit thickness
- K is the strip calibration constant.
- the deposit thickness T was determined by XRF as described in Example 2.
- Stress was also determined to be of compressive or tensile nature. If the test strip legs were spread outward on the side that has been plated, the deposit stress was tensile in nature. If the test strip legs were spread inward on the side that has been plated, the deposit stress was compressive in nature.
- the stress of the deposited nickel-phosphorus alloy layer was measured to be between -35 and -45 N/mm 2 and thus, was compressive. Results are summarized in Table 2.
- Table 2 also shows that the combination of stabilizing agents according to the present invention did not change the stress of the deposited nickel-phosphorus layer compared to electroless nickel plating baths containing no stabilizer or only a single stabilizing agent. Thus, the combination of stabilizing agents according to the present invention had also no negative effect on the coating quality in terms of stress. In summary, the combination of stabilizing agents imparted a significantly higher stability to electroless plating baths for deposition of nickel and nickel alloys at comparable bath performance and coating quality.
- the combination of stabilizing agents according to the present invention is suitable to provide high plating bath stability against undesired decomposition.
- the plating bath stability imparted by the combination of stabilizing agents is much higher than would be expected from the stabilizing effects of each single stabilizing agent.
- the combination of stabilizing agents has a synergistic effect on the stability of the electroless plating bath.
- the test for determining the stability number does also show an improved resistance of such electroless nickel plating baths against contamination with catalytic metals, like Pd.
- Deposition rates of electroless nickel plating baths according to the invention and phosphorus contents of nickel layers deposited therefrom were measured as described in Example 2. Internal stress of the nickel layers deposited was measured as described in Example 3.
- Gallium ions were added in the form of gallium(III) sulfate to the stock solution of an electroless nickel plating bath.
- Iodate ions were added in the form of potassium iodate and iodide ions in the form of potassium iodide. Concentrations of stabilizing agents in the plating baths and results are summarized in Table 5.
- Table 5 Deposition rate, phosphorus content and internal stress Ga(III) [ ⁇ mol/l] iodide [mmol/l] Iodate [mmol/l] deposition rate [ ⁇ m/h] P content [wt.%] Stress [N/mm 2 ] 10 3.0 0 6.6 12.1 -45.4 40 3.0 0 6.1 12.1 -48.0 80 3.0 0 6.1 11.8 -44.9 80 0 0.47 5.8 11.9 -48.6
- the deposited nickel-phosphorus alloy layers completely covered the substrate surface; no skip plating was obtained.
- the deposited nickel-phosphorus alloy layers were of uniform thickness, adhered well to the substrate surface and had a good appearance with technical brightness and a typical gray color.
- the combination of stabilizing agents according to the present invention did neither decrease the deposition rate nor changed the phosphorus content of the deposited nickel alloy layers compared to electroless nickel plating baths containing no stabilizer (see Table 2).
- the combination of stabilizing agents according to the present invention had no negative effect on the bath performance and no negative effect on the coating quality.
- Table 5 also shows that nickel-phosphorus alloy layers were deposited from the inventive nickel plating baths having compressive stress ranging from -45 to -49 N/mm 2 .
- the combination of stabilizing agents according to the present invention did not change the stress of the deposited nickel-phosphorus layer or did advantageously increase the compressive stress.
- the combination of stabilizing agents according to the present invention had also no negative effect on the coating quality in terms of stress.
Description
- The present invention relates to aqueous plating bath compositions for electroless deposition of nickel and nickel alloys. The present invention relates further to a method utilizing the aqueous plating bath compositions for electrolessly depositing nickel and nickel alloys. The aqueous plating bath compositions have high stability against undesired decomposition. The nickel and nickel alloy coatings obtained by the invention show high corrosion resistance and adhesion to the subjacent substrate.
- Such coatings are suitable as a functional coating in aerospace, automotive, electronics and chemical industries. The metal layers deposited from such aqueous plating bath compositions are also useful as barrier and cap layers in semiconducting devices, printed circuit boards, IC substrates and the like. The metal layers deposited are also suitable as overcoat for hard disks or rigid memory disks (RMD).
- Barrier layers are used in electronic devices such as semiconducting devices, printed circuit boards, IC substrates and the like to separate layers of different composition, e.g.substrate layers and further layers, and thereby prevent undesired diffusion between such layers of different composition.
- Another application of barrier layer materials in electronic devices is as a cap layer which is e.g. deposited onto copper to prevent corrosion of copper.
- Rigid memory disks are used as magnetic data storage media in hard disk drives. The disks are basically composed of a substrate, made of aluminum, glass or ceramics. An overcoat is deposited onto the substrate by a vacuum deposition process or an electroless metal plating process. The overcoat may consist of various metallic, mostly non-magnetic, alloys one of which may be a nickel phosphorus alloy layer. The overcoat provides e.g. a smooth surface onto which the magnetic recording layers are deposited. Further protective layers are coated onto the recording layers.
- Another application of nickel and nickel alloy deposits is corrosion protection for various substrates.
- Compositions for electroless nickel plating solutions are known in the art. For example,
US Patent 2,658,841 teaches the use of soluble organic acid salts as buffers for electroless nickel plating solutions.US Patent 2,658,842 teaches the use of short chain, dicarboxylic acids as exaltants to electroless nickel baths.US Patent 2,762,723 teaches the use of sulfide and sulfur bearing additives to an electroless nickel plating bath for improved bath stability. - Patent application
JP 2005-194562 EP2194156 discloses a bath for electroless deposition of nickel which contains a source of Ni ions and two stabilisers, namely iron metal ion and iodide.US Patent 4,189,324 describes an electroless nickel plating solution including of a source of gallium that improves stability of the solution. None of the prior art documents teaches a specific mixture of stabilizing agents having a particular good stabilizing effect in electroless nickel plating compositions. - It is the objective of the present invention to provide an electroless plating bath for deposition of nickel and nickel alloys which has a high stability against undesired decomposition. It is a further objective of the present invention to provide electroless nickel and nickel alloy plating baths having high stability during use and during storage. Furthermore, it is an objective of the present invention to provide an electroless plating bath for deposition of nickel and nickel alloys which has a good plating performance and generates coatings of good quality.
- This objective is solved by providing an aqueous plating bath composition for electroless deposition of nickel and nickel alloys, the composition comprising
- (i) a source of nickel ions,
characterized in that the aqueous plating bath composition further comprises - (ii) a mixture of stabilizing agents comprising
- a) at least one metal ion selected from indium ion and gallium ion, and
- b) at least one selected from elementary iodine, iodide ion containing compounds, iodate ion containing compounds and periodate ion containing compounds.
- The invention further relates to a method for deposition of nickel and nickel alloys by contacting the substrate to be plated with above described composition. The term "aqueous plating bath composition for electroless deposition of nickel and nickel alloys" is also abbreviated as "composition" herein. In addition, the invention relates to a method for stabilizing any electroless plating bath for deposition of nickel and nickel alloys by adding a mixture of stabilizing agents to the electroless plating bath.
- Electroless nickel plating compositions for applying nickel coatings are well known in the art and plating processes and compositions are described in numerous publications such as
U.S. Patents Nos. 2,935,425 ;3,338,726 ;3,597,266 ;3,915,716 and4,780,342 . Electroless plating generally describes methods without using external current sources for reduction of metal ions. Plating processes using external current sources are commonly described as electrolytic or galvanic plating methods. In the electroless plating solutions chemical reducing agents like hypophosphite, boranes or formaldehyde are used to reduce the metal ions to their metallic form and thereby forming a deposit on the substrate. - One commonly used nickel alloy deposit is nickel phosphorus (NiP) alloy. In general, NiP deposition solutions comprise at least three ingredients dissolved in a solvent, typically water. They are (1) a source of the nickel ions, (2) a reducing agent and (3) a complexing agent for metal ions sufficient to prevent their precipitation in solution. A large number of suitable complexing agents for NiP solutions are described in the above noted publications. If hypophosphite is used as the reducing agent, the deposit will contain nickel and phosphorus. Similarly, if an aminoborane is employed, the deposit will contain nickel and boron as shown in
U.S. Pat. No. 3,953,654 . - The aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention comprises a source of nickel ions. The source of nickel ions may be provided by the use of any soluble salt such as nickel sulfate, nickel chloride, nickel acetate, nickel methyl sulfonate, nickel sulfamate and mixtures thereof. The concentration of the nickel ions in the composition may vary widely and preferably ranges from 0.01 mol/l to 1 mol/l, more preferably from 0.03 mol/l to 0.8 mol/l, even more preferably from 0.06 mol/l to 0.3 mol/l.
- The aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention further comprises at least one reducing agent. The at least one reducing agent is preferably a chemical reducing agent. Reducing agents provide the electrons needed to reduce metal ions to their metallic form and thereby form a metal deposit on a substrate. The at least one reducing agent is preferably a hypophosphite salt or hypophosphorous acid, more preferably a hypophosphite salt. The hypophosphite salt is supplied to the composition by any suitable source such as sodium, potassium, ammonium and nickel hypophosphite. Other reducing agents such as aminoboranes, borohydrides, hydrazine and derivatives thereof and formaldehyde may also suitably be employed. Two or more reducing agents may be employed as a mixture in the composition. The concentration of the at least one reducing agent is generally in molar excess of the amount sufficient to reduce the nickel ions in the composition. The concentration of the reducing agent preferably ranges from 0.01 mol/l to 3.0 mol/l, more preferably from 0.1 mol/l to 1 mol/l.
- In case a hypophosphite compound is used as the reducing agent, a Ni-P alloy deposit is obtained. Such reducing agents provide the source of phosphorus in the deposited alloy. A borane-based compound as reducing agent leads to a NiB alloy deposit and a mixture of hypophosphite and borane-based compounds as the reducing agents leads to a ternary Ni-B-P alloy deposit. A nitrogen-based reducing agent such as hydrazine and derivatives thereof as well as formaldehyde as reducing agent lead to nickel deposits.
- The aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention may be acidic, neutral or alkaline. An acidic or an alkaline pH adjustor may be selected from a wide range of materials such as ammonium hydroxide, sodium hydroxide, hydrochloric acid, sulfuric acid and the like. The pH of the composition may range from about 2 to 12. In one embodiment, the compositions are preferably acidic. More preferably, the pH of the acidic compositions ranges from 3.5 to 7, even more preferably from 3.5 to 6.5, most preferably from 3.5 to 5.5. In another embodiment, the compositions are preferably alkaline. More preferably the pH of the alkaline compositions ranges from 7.5 to 12, even more preferably from 8 to 10, most preferably from 8 to 9.
- The aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention further comprises at least one complexing agent. A complexing agent (sometimes also referred to as chelating agent) or mixture of complexing agents is included in the composition for nickel and nickel alloy plating. A complexing agent keeps metal ions dissolved and prevents their undesired precipitation in solution. The at least one complexing agent is preferably selected from complexing agents for nickel ions and complexing agents for alloying metal ions, more preferably from complexing agents for nickel ions.
- The at least one complexing agent is preferably selected from the group comprising alkyl amines, ammonia, carboxylic acids, hydroxyl carboxylic acids, aminocarboxylic acids, salts of the aforementioned and mixtures thereof.
- In one embodiment, carboxylic acids, hydroxylcarboxylic acids, aminocarboxylic acids and salts of the aforementioned or mixtures thereof may be employed as the at least one complexing agent. Useful carboxylic acids include the mono-, di-, tri- and tetra-carboxylic acids. The carboxylic acids may be substituted with various substituent moieties such as hydroxy or amino groups and the acids may be introduced into the composition as their sodium, potassium or ammonium salts. Some complexing agents such as acetic acid, for example, may also act as a pH buffering agent, and the appropriate concentration of such additive components can be optimised for any composition in consideration of their dual functionality.
- Examples of such carboxylic acids which are useful as complexing or chelating agents in the composition of the present invention include: monocarboxylic acids such as acetic acid, hydroxyacetic acid (glycolic acid), aminoacetic acid (glycine), propanoic acid, 2-amino propanoic acid (alanine); 2-hydroxy propanoic acid (lactic acid); dicarboxylic acids such as succinic acid, amino succinic acid (aspartic acid), hydroxy succinic acid (malic acid), propanedioic acid (malonic acid), tartaric acid, hexane-1,6-dicarboxylic acid (adipic acid); tricarboxylic acids such as 2-hydroxy-1,2,3-propane tricarboxylic acid (citric acid); and tetracarboxylic acids such as ethylene diamine tetra acetic acid (EDTA). Preferred carboxylic acids are acetic acid, aminoacetic acid, propanoic acid, 2-hydroxy propanoic acid, succinic acid, hydroxy succinic acid, adipic acid or 2-hydroxy-1,2,3-propane-tricarboxylic acid. In one embodiment, mixtures of two or more of the above complexing/chelating agents are utilised in the composition according to the present invention.
- Alkyl amines may also be used as the at least one complexing agent, for example mono-, di- and trialkylamines. C1 - C3 alkyl amines, for example triethanolamine are preferred. Ammonia may also be used as the at least one complexing agent.
- The concentration of the at least one complexing agent or, in case more than one complexing agent is used, the concentration of all complexing agents in total preferably ranges from 0.01 mol/l to 3.0 mol/l, more preferably from 0.1 mol/l to 1.0 mol/l and even more preferably from 0.2 mol/l - 0.6 mol/l.
- Furthermore, the aqueous plating bath composition for electroless deposition of nickel and nickel alloys comprises a mixture of stabilizing agents according to (ii) comprising
- a) at least one metal ion selected from indium ion and gallium ion, and
- b) at least one selected from elementary iodine (I2), iodide ion containing compounds, iodate ion containing compounds (IO3 -) and periodate ion containing compounds.
- Stabilizing agents, also referred to as stabilizers, are compounds that stabilize an electroless metal plating solution against undesired plate out in the bulk solution and spontaneous decomposition. The term "plate out" means undesired and/or uncontrolled deposition of the metal on surfaces other than substrate surfaces.
- The indium ion may be selected from any indium ions, preferably from the group comprising indium(III) ions and indium(I) ions and mixtures thereof. More preferably, the indium ion is an indium(III) ion. The gallium ion may be selected from any gallium ions, preferably from the group comprising gallium(III) ions, gallium(I) ions and mixtures thereof. More preferably, the gallium ion is a gallium(III) ion. The indium ion or the gallium ion may be in the form of their salts. The salts of indium ions or gallium ions are preferably selected from the group comprising indium(III) sulfate (In2(SO4)3), indium(III) hydroxide (In(OH)3), indium(III) oxide (In2O3), indium(III) methane sulfonate (In(CH3-SO3)3), indium(III) nitrate (In(NO3)3), indium(III) chloride (InCl3), indium(III) bromide (InBr3), indium(III) fluoride (InF3), indium(III) acetate (In(CH3-COO)3), indium(I) chloride (InCI), indium(I) bromide (InBr), gallium(III) sulfate (Ga2(SO4)3), gallium(III) hydroxide (Ga(OH)3), gallium(III) methane sulfonate (Ga(CH3-SO3)3), gallium(III) nitrate (Ga(NO3)3), gallium(III) chloride ((GaCl3)2), gallium(III) bromide ((GaBr3)2), gallium(III) acetate (Ga(CH3-COO)3), gallium chloride (Ga(I)Ga(III)Cl4), gallium bromide (Ga(I)Ga(III)Br4), and hydrates of the aforementioned; more preferably indium(III) sulfate (In2(SO4)3), indium(III) hydroxide (In(OH)3), indium(III) methane sulfonate (In(CH3-SO3)3), gallium(III) sulfate (Ga2(SO4)3), gallium(III) hydroxide (Ga(OH)3), gallium(III) methane sulfonate (Ga(CH3-SO3)3), and hydrates of the aforementioned.
- The concentration of the at least one metal ion according to (ii)a) preferably ranges from 0.01 mmol/l to 0.5 mmol/l, more preferably from 0.01 mmol/l to 0.1 mmol/l, even more preferably from 0.02 mmol/l to 0.08 mmol/l. Higher concentrations of the at least one metal ion according to (ii)a) result in deposition of nickel or nickel alloy layers of dull appearance and skip plating. Skip plating is a plating defect in which the coating undesirably does not cover all areas of the plated substrate. The mixture, i.e. the combination, of metal ions according to (ii)a) with stabilizing agents according to (ii)b) allows to shift the lower concentration limit of metal ions according to (ii)a) to the lower values as described above, without impairing stability of the composition. Thus, the concentration range of metal ions according to (ii)a) suitable for stabilizing the composition and any electroless plating bath for deposition of nickel and nickel alloys, and suitable for depositing nickel or nickel alloy layers of good quality is widened. The wider process window improves process control for plating.
- The at least one stabilizing agent according to (ii)b) is preferably selected from the group comprising iodide ion containing compounds and iodate ion containing compounds; more preferably iodide ion containing compounds.
- The iodide ion containing compounds are preferably selected from the group comprising potassium iodide, sodium iodide, ammonium iodide, calcium iodide, barium iodide, magnesium iodide, lithium iodide, zinc iodide, and hydrates of the aforementioned; more preferably potassium iodide, sodium iodide, ammonium iodide, and hydrates of the aforementioned; even more preferably potassium iodide and hydrates thereof.
- The iodate ion containing compounds are preferably selected from water soluble iodate salts. The water soluble iodate salts are preferably iodate salts of alkali metals or earth alkali metals. The iodate salt is preferably selected from the group comprising potassium iodate, sodium iodate, ammonium iodate, calcium iodate, barium iodate, magnesium iodate, lithium iodate and hydrates of the aforementioned; more preferably potassium iodate, sodium iodate, ammonium iodate, lithium iodate and hydrates of the aforementioned; even more preferably potassium iodate and hydrates thereof.
- The periodate ion containing compounds may be selected from the group comprising preferably metaperiodate ion containing compounds (IO4 -), and orthoperiodate ion containing compounds (IO6 5-).
- The periodate ion containing compounds are preferably selected from the group comprising potassium metaperiodate (KIO4), sodium metaperiodate (NaIO4) and sodium ortho periodate (Na3H2IO6).
- The concentration of the at least one stabilizing agent according to (ii)b) preferably ranges from 0.05 to 50.0 mmol/l, more preferably from 0.1 to 30.0 mmol/l, even more preferably from 0.5 to 10.0 mmol/l, and even more preferred from 1.0 mmol/l to 5.0 mmol/l. Higher concentrations of the at least one stabilizing agent according to (ii)b) result in lower deposition rates, in difficulties to initiate deposition on the substrate surface, in deposition of nickel or nickel alloy layers having low adhesion to the subjacent substrate, e.g. blistering, and less compressive stress. Lower concentrations of the at least one stabilizing agent according to (ii)b) do not show the desired enhanced bath stability against undesired, spontaneous decomposition.
- The stabilizing agents of the present invention, metal ions according to (ii)a) and stabilizing agents according to (ii)b), are suitable to enhance the stability of the aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention against undesired, spontaneous decomposition. Undesired, spontaneous decomposition means undesired formation of a black precipitate, undesired plate out of nickel in the bulk solution or undesired and/or uncontrolled deposition of nickel, for example on the bottom of a plating tank or on other surfaces different from the substrate.
- The stabilizing effect is particularly pronounced when the stabilizing agents are used as a mixture, i.e. in combination. The combination of metal ions according to (ii)a) with stabilizing agents according to (ii)b) provides in particular a long life to the composition of the present invention. The bath stability imparted by the combination of stabilizing agents is much higher than the stabilizing effect of one of the stabilizing agents alone. The combination of stabilizing agents of the present invention has a synergistic effect on the bath stability.
- The combination of stabilizing agents of the present invention also imparts an improved resistance of the composition against contamination with catalytic metals. Contamination with catalytic metals may be caused by metal ions dissolving from the substrate material while in contact with the composition, or metal ions are dragged into the composition from pre-treatment or activation steps. Catalytic metals may be palladium, platinum, rhodium, ruthenium or mixtures thereof, preferably palladium.
- For example, palladium is used for plating methods in which surface activation is needed. This causes consequently contamination of the subsequent plating bath with palladium ions. An example is electroless plating on non-conductive substrates. Thus, the composition of the present invention containing a combination of stabilizing agents, namely metal ions according to (ii)a) and stabilizing agents according to (ii)b), are suitable for plating on electrically non-conductive substrates, on electrically conductive substrates, and on electrically semi-conductive substrates.
- The combination of stabilizing agents according to the invention has a synergistic effect on the bath stability and the composition containing the combination of stabilizing agents is much less prone to contamination with catalytic metals.
- Simultaneously, the combination of stabilizing agents according to the invention has only a low effect on the deposition rate, i.e. increasing the concentration of the stabilizing agents does not alter the deposition rate and the combination of stabilizing agents does not decrease the deposition rate of the composition of the present invention. In addition, the deposited nickel or nickel alloy layers are of good quality, i.e. the quality of the nickel or nickel alloy layers are not influenced disadvantageously by the combination of stabilizing agents according to the invention. The deposited nickel or nickel alloy layers completely cover the substrate surface; no skip plating is obtained. The deposited nickel or nickel alloy layers are of uniform thickness, adhere well to the substrate surface and have a good appearance. Good appearance means herein, that the nickel or nickel alloy layers have no pitting, no blistering, no increased nodular structure and no unusual color. Thus, the combination of stabilizing agents according to the present invention has no negative effect on the plating bath performance and no negative effect on the coating quality.
- The aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention further shows a high stability during idle periods. Idle periods are defined as time periods in which the operating parameters, like temperature or pH value, of a plating bath are adjusted to its desired value for plating operation, but no substrate is immersed in the plating bath. Thus, the combination of stabilizing agents according to the invention also keeps the composition stable against undesired, spontaneous decomposition during prolonged periods at high temperature while not plating. This effect is better than with stabilizing agents known in the art, e.g. tin ions, bismuth ions or antimony ions.
- Other materials may be included in the composition according to the present invention such as pH buffers, wetting agents, accelerators, brighteners, additional stabilizing agents etc. The composition may contain further organic stabilizing agents and/or further inorganic stabilizing agents. These materials are known in the art.
- The composition may contain further metal stabilizing agents such as Cu-, Se-, Sn-, Bi- or Sb-ions. The concentration of the metal ions can vary and e.g. range between 0.1 - 100 mg/l, preferably between 0.1 - 50 mg/l, more preferably between 0.1 - 10 mg/l. In one embodiment, the composition does not contain toxic heavy metals. In this embodiment, the composition does preferably not contain lead, cadmium, antimony, bismuth, arsenic or mercury.
- The aqueous plating bath composition for electroless deposition of nickel and nickel alloys of the present invention may further comprise at least one alloying element. In this embodiment, nickel alloy layers containing the alloying element are deposited from the composition. The at least one alloying element may be selected from phosphorus, boron, and a metal which is not nickel.
- The alloying elements phosphorus or boron may be comprised in the composition in the form of a hypophosphite salt, hypophosphorous acid or a borane-based compound, such as aminoboranes or borohydrides, as mentioned above as reducing agents.
- The metal which is not nickel (abbreviated as M herein) may be comprised in the composition in the form of a water-soluble metal salt containing the ions of the alloying metal M. The optional alloying metal M is preferably selected from the group consisting of titanium, vanadium, chromium, manganese, zirconium, niobium, molybdenum, hafnium, tantalum, tungsten, copper, silver, gold, aluminum, iron, cobalt, palladium, ruthenium, rhodium, osmium, iridium, platinum, zinc, cadmium, gallium, indium, tin, antimony, thallium, lead, and bismuth. More preferably, the optional alloying metal M is selected from the group consisting of molybdenum, tungsten, copper, silver, gold, aluminum, zinc and tin.
- The concentration of the optional alloying metal M preferably ranges from 10-5 to 0.2 mol/l, more preferably from 10-4 to 0.2 mol/l, even more preferably from 10-2 to 0.1 mol/l.
- In case additional metal salts or metal ions are present in the composition the respective nickel alloy is obtained as deposit.
- When adding an alloying metal M to the composition (depending on the kind of reducing agent present) ternary or quaternary alloys Ni-M-P, Ni-M-B, and Ni-M-B-P are deposited.
- In another embodiment of the present invention, a water-soluble salt of an alloying metal M and a water-soluble salt of a second alloying metal M* are added to the composition. In this case, nickel alloy deposits comprising alloying metals M and M* are obtained.
- A suitable composition may be formed by dissolving the ingredients in water and adjusting the pH to the desired range. The indium or gallium salts may be dissolved in an acid prior to adding them to the composition.
- The present invention further relates to a method for electroless deposition of nickel and nickel alloys by contacting the substrate to be plated with the above described aqueous plating bath composition for electroless deposition of nickel and nickel alloys.
- The deposition method comprises the steps of
- (A) providing a substrate,
- (B) contacting the substrate with the aqueous plating bath composition for electroless deposition of nickel and nickel alloys according to the invention as described above,
- (C) and thereby depositing a nickel or nickel alloy onto the substrate.
- The substrate to be nickel or nickel alloy plated may be plated to the desired thickness and deposit quantity by contacting the substrate with the composition.
- The inventive composition may be maintained over a temperature range of 20 °C to 100 °C, preferably 70 °C to 95 °C, more preferably 85 °C to 95 °C during deposition.
- A deposit thickness of up to 100 µm, or higher may be employed. Preferably, the thickness of the nickel or nickel phosphorus (NiP) deposits varies between 1 - 60 µm. The thickness depends on the technical application and can be higher or lower for some applications. For example, if the nickel or NiP layer is deposited to provide a corrosion resistant coating, a thickness of between 30 - 60 µm is desired, while for electronics applications a thickness of between 1 - 15 µm is applied. In the technical area of rigid memory disks, the thickness of the nickel or nickel-phosphorus deposits preferably ranges from 9 to 13 µm. In the technical area of semi-conductors, the thickness of the nickel or nickel-phosphorus deposits preferably ranges from 1 to 5 µm. Thicknesses of nickel or nickel alloy layers may be measured with x-ray fluorescence (XRF) which is known in the art.
- The present invention further relates to a method for stabilizing any electroless plating bath for deposition of nickel and nickel alloys, the method comprises the steps of
- (D) providing any electroless plating bath for deposition of nickel and nickel alloys, and
- (E) adding a mixture of stabilizing agents, wherein the stabilizing agents are the stabilizing agents according to the invention as described above.
- Thus, the mixture of stabilizing agents comprises
- (ii)a) at least one metal ion selected from indium ion and gallium ion, and
- (ii)b) at least one selected from elementary iodine, iodide ion containing compounds, iodate ion containing compounds and periodate ion containing compounds.
- The electroless plating bath may be any electroless plating bath for deposition of nickel and nickel alloys. In one embodiment, the electroless plating bath is the aqueous plating bath composition for electroless deposition of nickel and nickel alloys according to the present invention.
- In one embodiment of the present invention, the electroless plating bath may be a freshly prepared electroless plating bath.
- In another embodiment, the electroless plating bath may be already used for some time for plating.
- In a further embodiment, the electroless plating bath may be stored for some time without plating. During storage the electroless plating bath may be kept at a temperature ranging from 15 to 100 °C.
- In the two latter embodiments, the concentrations of the stabilizing agents of the inventive mixture may be determined during plating or storage and replenished if below a threshold value. Replenishment is performed by adding the stabilizing agents of the inventive mixture or combination to the electroless plating baths.
- The mixture of stabilizing agents of the present invention keeps the electroless plating bath stable against undesired, spontaneous decomposition during prolonged periods of plating, during prolonged storage times and during prolonged periods at high temperature while not plating, e.g. idle periods.
- The overall consumption of metal ions according to (ii)a) as stabilizing agents is lower during plating if the inventive mixture of stabilizing agents is used. Therefore, the amount of metal ions according to (ii)a) which has to be replenished per metal turnover (MTO) is decreased in comparison to electroless plating baths that include only metal ions according to (ii)a) as stabilizing agents. This is of advantage, as costs for expensive metallic stabilizers are reduced. A further advantage is that the metal ions according to (ii)a) can be employed in lower concentration ranges, thus preventing dull appearance of nickel or nickel alloy layers and skip plating while still ensuring stability of the composition.
- The stabilizing agents of the inventive mixture may be added as a solid or a powder or may be dissolved in a solvent prior to adding to the electroless plating baths. Preferably, the indium or gallium salts may be dissolved in an acid prior to adding them to the electroless plating bath.
- The aqueous plating bath composition for electroless deposition of nickel and nickel alloys and the methods of the present invention are suitable to provide nickel and nickel alloy coatings having an attractive bright or semi-bright appearance. Advantageously, the compressive stress of the deposited nickel or nickel alloy layers is maintained. In contrast to stabilizing agents known in the art, the mixture of stabilizing agents of the present invention does not shift the internal stress to neutral or tensile stress. The advantages of nickel or nickel alloy layers having compressive stress are high corrosion resistance and good adhesion to the substrate surface.
- The above parameters of the aqueous plating bath composition for electroless deposition of nickel and nickel alloys and methods of the present invention are only provided to give general guidance for practicing the invention.
- A high phosphorus NiP alloy is herein defined as a metallic coating containing less than 91 wt.% Ni and more than 9 wt.% P, e.g. 10.5 wt.%. Generally, high phosphorus alloys contain up to 15 wt.% P. A nickel-phosphorus (NiP) alloy containing more than about 10.5% phosphorus is known as a high phosphorus NiP coating and is paramagnetic (non-magnetic) as plated.
- A mid phosphorus NiP alloy is herein defined as a metallic coating containing between 5 - 9 wt.% P. A low-phosphorus NiP alloy is herein defined as a metallic coating containing between 1 - 5 wt.% P.
- The aqueous plating bath composition for electroless deposition of nickel and nickel alloys and the methods of the present invention are suitable to provide nickel phosphorus alloy coatings with a wide range of P content of between 1 - 15 wt.% P. The composition and the methods of the present invention are particularly suitable for depositing nickel phosphorus alloys, e.g. high NiP alloys as defined above.
- The combination of stabilizing agents according to the present invention does not change the phosphorus content of the deposited nickel alloy layers compared to electroless nickel-phosphorus baths containing no stabilizer or single stabilizing agents according to (ii)a) or (ii)b). Thus, the combination of stabilizing agents according to the present invention has no negative effect on the bath performance and no negative effect on the coating quality.
- The phosphorus content of nickel alloy layers and the thickness of nickel or nickel alloy layers were measured by x-ray fluorescence (XRF) which is well known to persons skilled in the art. The XRF measurements make use of the characteristic fluorescence radiation emitted from a sample (substrate, deposit) being excited with x-rays. By evaluating the wavelength and intensities and assuming a layered structure of the sample, phosphorus content and layer thicknesses can be calculated.
- High NiP alloys are obtained when the plating process is performed at a plating rate of preferably between 5 - 14 µm / hour, more preferred 6 - 12 µm / hour, even more preferred 6 - 10 µm / hour. Such plating rate can be obtained by adjusting the plating parameters, like pH or temperature.
- High NiP alloys obtained by the composition according to the present invention contribute to generating alloys having high compressive stress. The stress values for example range between 0 to -70 N/mm2, preferably between 0 to -50 N/mm2, more preferably between -30 to -50 N/mm2. Such deposits show high corrosion resistance and excellent adhesion to the underlying substrate they are plated on.
- The combination of stabilizing agents according to the present invention does also not change the stress of the deposited nickel-phosphorus layer compared to electroless nickel-phosphorus baths containing no stabilizer or only a single stabilizing agent. Thus, the combination of stabilizing agents according to the present invention has also no negative effect on the coating quality in terms of stress. Thus, the combination of stabilizing agents imparts a significantly higher stability to nickel and nickel alloy baths at comparable bath performance and coating quality.
- Various kinds of substrates can be metal plated with an aqueous plating bath composition for electroless deposition of nickel and nickel alloys and the methods of the present invention. The substrates to be metal plated can be selected from the group comprised of electrical non-conductive substrates, electrical conductive substrates, and electrical semi-conductive substrates.
- The electrical non-conductive substrates to be metal plated can be selected from the group comprising glass, ceramics, and plastics.
- Plastics can be selected from the group comprising acrylnitrile-butadiene-styrol-copolymer (ABS copolymer); polyamide; a mixture of an ABS copolymer and at least one other polymer which is different to the ABS copolymer; polycarbonate (PC); ABS/PC blends; epoxy resin; bismaleimide-triazine resin (BT); cyanate ester resin; polyimide; polyethylene terephthalate (PET); polybutylene terephthalate (PBT); polylactic acid (PLA); polypropylene (PP); and polyester.
- The electrical conductive substrates to be metal plated can be selected from the group comprised of metallic substrates, and conductive metal oxides.
- The metallic substrates to be metal plated can be selected from the group comprised of copper, zinc, silver, gold, platinum, palladium, iron, iridium, tin, aluminum and nickel.
- The conductive metal oxides to be metal plated can be selected from indium tin oxide (ITO), antimony tin oxide (ATO) and aluminum doped zinc oxide (AZO).
- The electrical semi-conductive substrates to be metal plated can be selected from the group comprised of silicon, germanium, gallium, arsenide and silicon carbide.
- The following non-limiting examples further illustrate the present invention.
- For stability determination, a stock solution of an electroless nickel plating bath was used, comprising:
Nickel sulfate hexahydrate 22.4 g/l Sodium orthophosphite (pre-aging salt) 60.0 g/l Lactic acid (90%) (complexing agent/chelating agent) 14.4 g/l Malic acid (complexing agent/chelating agent) 19.8 g/l Succinic acid (complexing agent/chelating agent) 6.1 g/l Sodium hypophosphite monohydrate (reducing agent) 24.0 g/l - The composition of the stock solution corresponds to the composition of the electroless nickel bath disclosed in patent application
WO 2010/045559 A1 (Example 4 therein) with the exception that the present stock solution does not contain lead nitrate as a stabilizer. Sodium orthophosphite was contained in the stock solution as a pre-aging salt. Orthophosphite salts are by-products of the chemical reduction process when hypophosphite is used as the reducing agent. The amount of this by-product in an electroless nickel plating bath depends on how long the bath has been used. This bath age is referred to in the plating industry as the number of metal turnovers or MTOs of the bath. When an electroless nickel plating bath is used, nickel salt and a reducing agent must be replenished as nickel is plated, so as to continue the effective use (or life) of the bath. When the amount of the replenished nickel salt is equal to the initial amount of nickel contained in the original plating bath, the bath is said to have plated one metal turnover (MTO). The amount of orthophosphite used herein corresponds to 2.5 MTO level. The stock solution did not contain any stabilizers. - Indium ions and iodide ions were added as stabilizers. Indium ions were added in the form of indium(III) hydroxide and iodide ions were added in the form of potassium iodide. Concentrations of the stabilizers in the electroless nickel plating bath were as outlined in Table 2. One batch of the electroless nickel plating bath was used without any stabilizer as comparison. The electroless nickel plating bath had a pH value of 4.4.
- Stability of the electroless nickel plating baths containing the respective concentrations of stabilizers was measured by determining the stability number and by visual inspection.
- 100 ml of the investigated plating bath were heated to 80 ±1 °C in a 200 ml glass beaker while stirring. Next, 0.2 ml of a palladium test solution (125 mg/l palladium chloride in deionized water) was added every 60 s to the plating bath. The test was finished when a gray precipitate associated with gas bubbles was formed in the plating bath which indicated the undesired decomposition and thus instability of the plating bath.
- The stability number achieved for the investigated plating bath corresponds to the number of palladium test solution additions (each 0.2 ml) within a one minute interval to the plating bath until formation of a gray precipitate. The stability test was done twice for each plating bath sample. The average stability number is given in Table 2.
- For example, the entry "5" for an electroless plating bath solely containing iodide ions as stabilizers (Table 2 in column "Stability Number") corresponds to an addition of 5 times 0.2 ml of a palladium chloride solution to the plating bath. After 1 ml (5 times 0.2 ml/l added in one minute intervals) and 5 minutes, a gray precipitate occurs.
- Stability was further evaluated visually in a separate plating experiment. The plating conditions were as described in Example 2 below. In contrast to Example 2, the plating time was 90 minutes. The result of the test is the total number of substrates plated without stability issues. Excessive plating in the heating surface area of the beaker, i.e. the bottom of the beaker, was observed as a sign of instability. Prior to plating, the beaker and the magnetic stirrer were stripped in 50% (v/v) nitric acid for 30 minutes.
- Results of stability determinations are summarized in Table 2. As becomes apparent from Table 2 the combination of stabilizing agents according to the present invention is suitable to provide high plating bath stability against undesired decomposition. The plating bath stability imparted by the combination of stabilizing agents is much higher than would be expected from the stabilizing effects of each single stabilizing agent. Thus, the combination of stabilizing agents has a synergistic effect on the stability of the electroless plating bath.
- The test for determining the stability number does not only show improved stability of electroless nickel plating baths containing the combination of stabilizing agents, but also an improved resistance of such electroless nickel plating baths against contamination with catalytic metals, like Pd.
- Aluminum plates were used as substrates for deposition of nickel-phosphorus alloy layers. The substrates were pre-treated as summarized in Table 1 in order to clean and double zincate the substrate surface prior to nickel deposition.
Table 1: Pre-treatment of substrates Pre-treatment step Atotech Product Concentration Temp. (°C) Time Soak Cleaner Uniclean 190 50g/l 50 5 min Rinse Dip rinse 20 s Etch ALKLEAN AC-2 50ml/l RT 1min Rinse Dip rinse 20 s Desmut HNO3 35%(w/w) (350ml/l) RT 1min Rinse Dip rinse 20 s Zincate 1 Zincate M RT 30s Rinse Dip rinse 20 s Zincate Strip HNO3 35%(w/w) (350ml/l) RT 1min Rinse Dip rinse 20 s Zincate 2 EDEN Zincate M RT 15s Rinse Dip rinse 20 sec - Afterwards, the substrates were immersed in electroless nickel plating baths of compositions as described in Example 1. Deposition was done in 2L-beakers. Each beaker was placed on a heater and temperature was maintained at 89.5 °C. Mechanical agitation with 175 RPM was applied by a magnetic stirrer. Bath loading was 1.4 dm2/l corresponding to two substrates per bath volume. Deposition time was 60 minutes.
- The phosphorus content and deposit thickness were measured at 5 points of each substrate by XRF using the XRF instrument Fischerscope XDV-SDD (Helmut Fischer GmbH, Germany).
- The deposition rate was calculated by using the deposition time and the measured deposit thickness. Results are summarized in Table 2.
- The deposited nickel-phosphorus alloy layers completely covered the substrate surface; no skip plating was obtained. The deposited nickel-phosphorus alloy layers were of uniform thickness, adhered well to the substrate surface and had a good appearance with technical brightness and a typical gray color.
- As becomes apparent from Table 2 the combination of stabilizing agents according to the present invention did neither decrease the deposition rate nor changed the phosphorus content of the deposited nickel alloy layers compared to electroless nickel plating baths containing no stabilizer or a single stabilizing agent. Thus, the combination of stabilizing agents according to the present invention had no negative effect on the bath performance and no negative effect on the coating quality.
- Stress in the nickel-phosphorus coating was measured using a stress-strip finger. The test strips were made of copper and had spring like properties. After plating as described in Example 2, the test strip was mounted on the Testing Stand (Deposit stress analyzer Model No. 683 of Specialty Testing & Development Co., York, PA, USA) which measured the distance which the test strip legs had spread after plating. The distance U is included in the following formula which allows for the deposit stress to be calculated.
- U is the number of increments spread, T is the deposit thickness and K is the strip calibration constant.
- The deposit thickness T was determined by XRF as described in Example 2.
- Each lot of test strips manufactured will respond with slight differences when used for deposit stress test. This degree of difference was determined by the supplier when each lot of test strips was calibrated. The value for K was supplied with each lot of test strips provided by Specialty Testing & Development Co.
- Stress was also determined to be of compressive or tensile nature. If the test strip legs were spread outward on the side that has been plated, the deposit stress was tensile in nature. If the test strip legs were spread inward on the side that has been plated, the deposit stress was compressive in nature.
- The stress of the deposited nickel-phosphorus alloy layer was measured to be between -35 and -45 N/mm2 and thus, was compressive. Results are summarized in Table 2.
- Table 2 also shows that the combination of stabilizing agents according to the present invention did not change the stress of the deposited nickel-phosphorus layer compared to electroless nickel plating baths containing no stabilizer or only a single stabilizing agent. Thus, the combination of stabilizing agents according to the present invention had also no negative effect on the coating quality in terms of stress. In summary, the combination of stabilizing agents imparted a significantly higher stability to electroless plating baths for deposition of nickel and nickel alloys at comparable bath performance and coating quality.
Table 2: Results of Examples 1 to 3 Stabilizer In(III) [µmol/l] iodide [mmol/l] deposition rate [µm/h] P content [wt.%] stability visually Stability number [minutes] Stress [N/mm2] No stabilizer (comparative) 0 0 6.6 11.8 0 0.5 -40.2 Only Iodide (comparative) 0 3.0 6.4 12.0 0 4.5 -45.3 0 12.0 3.7 11.9 1 5.0 -33.5 0 24.1 3.7 12.1 2 5.0 -31.8 0 48.2 3.5 12.1 3 5.0 -32.6 Only Indium(III) (comparative) 60.3 0 6.3 12.0 1 3.5 -46.8 75.3 0 5.9 11.7 1 4.5 -35.0 90.4 0 6.1 11.9 1.5 8.0 -36.1 Indium(III) + Iodide (according to invention) 60.3 3.0 6.0 12.0 4 12.5 -44.7 75.3 3.0 5.9 12.0 5 14.5 -38.3 90.4 3.0 6.0 12.0 5 15.5 -36.7 - Stability of electroless nickel plating baths containing In(III) ions and iodide ions as mixtures of stabilizing agents were measured by determining the stability number as described in Example 1. Concentrations of the stabilizers in the electroless nickel plating baths and resulting stability numbers are summarized in Table 3.
Table 3: Concentrations of stabilizing agents and stability numbers In(III) [µmol/l] iodide [mmol/l] Stability number [minutes] comparative 0 12.0 5 0 24.1 5 0 48.2 5 60.3 0 3.5 according to invention 60.3 12.0 13 60.3 24.1 16 60.3 48.2 18 - Stability of electroless nickel plating baths containing In(III) ions and iodate ions as mixtures of stabilizing agents were measured by determining the stability number as described in Example 1.
- Indium ions were added in the form of indium(III) hydroxide to the stock solution of an electroless nickel plating bath. Iodate ions were added in the form of potassium iodate. Concentrations of the stabilizers in the electroless nickel plating bath and resulting stability numbers are summarized in Table 4.
Table 4: Concentrations of stabilizing agents and stability numbers In(III) [µmol/l] Iodate [mmol/l] Stability number [minutes] comparative 0 0.47 21 60.3 0 3.5 according to invention 60.3 0.47 28 - As becomes apparent from Tables 3 and 4, the combination of stabilizing agents according to the present invention is suitable to provide high plating bath stability against undesired decomposition. The plating bath stability imparted by the combination of stabilizing agents is much higher than would be expected from the stabilizing effects of each single stabilizing agent. Thus, the combination of stabilizing agents has a synergistic effect on the stability of the electroless plating bath. The test for determining the stability number does also show an improved resistance of such electroless nickel plating baths against contamination with catalytic metals, like Pd.
- Deposition rates of electroless nickel plating baths according to the invention and phosphorus contents of nickel layers deposited therefrom were measured as described in Example 2. Internal stress of the nickel layers deposited was measured as described in Example 3. Gallium ions were added in the form of gallium(III) sulfate to the stock solution of an electroless nickel plating bath. Iodate ions were added in the form of potassium iodate and iodide ions in the form of potassium iodide. Concentrations of stabilizing agents in the plating baths and results are summarized in Table 5.
Table 5: Deposition rate, phosphorus content and internal stress Ga(III) [µmol/l] iodide [mmol/l] Iodate [mmol/l] deposition rate [µm/h] P content [wt.%] Stress [N/mm2] 10 3.0 0 6.6 12.1 -45.4 40 3.0 0 6.1 12.1 -48.0 80 3.0 0 6.1 11.8 -44.9 80 0 0.47 5.8 11.9 -48.6 - The deposited nickel-phosphorus alloy layers completely covered the substrate surface; no skip plating was obtained. The deposited nickel-phosphorus alloy layers were of uniform thickness, adhered well to the substrate surface and had a good appearance with technical brightness and a typical gray color.
- As becomes apparent from Table 5, the combination of stabilizing agents according to the present invention did neither decrease the deposition rate nor changed the phosphorus content of the deposited nickel alloy layers compared to electroless nickel plating baths containing no stabilizer (see Table 2). Thus, the combination of stabilizing agents according to the present invention had no negative effect on the bath performance and no negative effect on the coating quality.
- Table 5 also shows that nickel-phosphorus alloy layers were deposited from the inventive nickel plating baths having compressive stress ranging from -45 to -49 N/mm2. Thus, the combination of stabilizing agents according to the present invention did not change the stress of the deposited nickel-phosphorus layer or did advantageously increase the compressive stress. Thus, the combination of stabilizing agents according to the present invention had also no negative effect on the coating quality in terms of stress.
Claims (15)
- An aqueous plating bath composition for electroless deposition of nickel and nickel alloys, the composition comprising(i) a source of nickel ions,
characterized in that the aqueous plating bath composition further comprises(ii) a mixture of stabilizing agents comprisinga) at least one metal ion selected from indium ion and gallium ion, andb) at least one selected from elementary iodine, iodide ion containing compounds, iodate ion containing compounds and periodate ion containing compounds. - The aqueous plating bath composition according to claim 1 wherein the indium ion is an indium(III) ion.
- The aqueous plating bath composition according to any of the foregoing claims wherein the gallium ion is a gallium(III) ion.
- The aqueous plating bath composition according to any of the foregoing claims wherein the stabilizing agent according to (ii)b) is selected from iodide ion containing compounds and iodate ion containing compounds.
- The aqueous plating bath composition according to any of the foregoing claims wherein the concentration of the at least one metal ion according to (ii)a) ranges from 0.01 to 0.5 mmol/l.
- The aqueous plating bath composition according to any of the foregoing claims wherein the concentration of the stabilizing agent according to (ii)b) ranges from 0.05 to 50.0 mmol/l.
- The aqueous plating bath composition according to any of the foregoing claims wherein the source of nickel ions is selected from nickel sulfate, nickel chloride, nickel acetate, nickel methyl sulfonate, nickel sulfamate and mixtures thereof.
- The aqueous plating bath composition according to any of the foregoing claims wherein the concentration of nickel ions ranges from 0.01 to 1 mol/l.
- The aqueous plating bath composition according to any of the foregoing claims wherein the aqueous plating bath composition further comprises at least one complexing agent.
- The aqueous plating bath composition according to claim 9 wherein the concentration of the at least one complexing agent ranges from 0.01 to 3.0 mol/l.
- The aqueous plating bath composition according to any of the foregoing claims wherein the aqueous plating bath composition further comprises at least one reducing agent.
- The aqueous plating bath composition according to claim 11 wherein the concentration of the at least one reducing agent ranges from 0.01 to 3.0 mol/l.
- The aqueous plating bath composition according to any of the foregoing claims wherein the aqueous plating bath composition further comprises at least one alloying element wherein the at least one alloying element is selected from phosphorus, boron, titanium, vanadium, chromium, manganese, zirconium, niobium, molybdenum, hafnium, tantalum, tungsten, copper, silver, gold, aluminum, iron, cobalt, palladium, ruthenium, rhodium, osmium, iridium, platinum, zinc, cadmium, gallium, indium, tin, antimony, thallium, lead, and bismuth.
- A method for electroless deposition of nickel and nickel alloys comprising the steps of(A) providing a substrate,(B) contacting the substrate with the aqueous plating bath composition according to any of claims 1 to 13,(C) and thereby depositing a nickel or nickel alloy onto the substrate.
- A method for stabilizing any electroless plating bath for deposition of nickel and nickel alloys, the method comprises the steps of(D) providing any electroless plating bath for deposition of nickel and nickel alloys, and characterised by(E) adding a mixture of stabilizing agents, wherein the mixture of stabilizing agents comprises(ii)a) at least one metal ion selected from indium ion and gallium ion, and(ii)b) at least one selected from elementary iodine, iodide ion containing compounds, iodate ion containing compounds and periodate ion containing compounds.
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EP14194890.1A EP3026143A1 (en) | 2014-11-26 | 2014-11-26 | Plating bath and method for electroless deposition of nickel layers |
PCT/EP2015/076822 WO2016083195A1 (en) | 2014-11-26 | 2015-11-17 | Plating bath and method for electroless deposition of nickel layers |
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EP15797992.3A Active EP3224388B1 (en) | 2014-11-26 | 2015-11-17 | Plating bath and method for electroless deposition of nickel layers |
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EP (2) | EP3026143A1 (en) |
JP (1) | JP6667525B2 (en) |
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MY185286A (en) * | 2015-07-17 | 2021-04-30 | Coventya Inc | Electroless nickel-phosphorous plating baths with reduced ion concentration and methods of use |
DE102019112883A1 (en) * | 2019-05-16 | 2020-11-19 | Pac Tech - Packaging Technologies Gmbh | Coating bath for electroless coating of a substrate |
JP2022185929A (en) * | 2021-06-03 | 2022-12-15 | 東洋鋼鈑株式会社 | Nickel phosphorus alloy coated substrate, solution for electroless plating nickel phosphorus alloy film, and method for manufacturing nickel phosphorus alloy coated substrate |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2658841A (en) | 1950-11-08 | 1953-11-10 | Gen Am Transport | Process of chemical nickel plating and bath therefor |
US2658842A (en) | 1951-01-04 | 1953-11-10 | Gen Am Transport | Process of chemical nickel plating and bath therefor |
US2762723A (en) | 1953-06-03 | 1956-09-11 | Gen American Transporation Cor | Processes of chemical nickel plating and baths therefor |
US2935425A (en) | 1954-12-29 | 1960-05-03 | Gen Am Transport | Chemical nickel plating processes and baths therefor |
US3338726A (en) | 1958-10-01 | 1967-08-29 | Du Pont | Chemical reduction plating process and bath |
US3597266A (en) | 1968-09-23 | 1971-08-03 | Enthone | Electroless nickel plating |
US3915716A (en) | 1969-04-17 | 1975-10-28 | Schering Ag | Chemical nickel plating bath |
US3719508A (en) * | 1971-11-16 | 1973-03-06 | Shipley Co | Electroless nickel solution |
US3953654A (en) | 1973-08-13 | 1976-04-27 | Rca Corporation | Temperature-stable non-magnetic alloy |
US4189324A (en) | 1978-06-02 | 1980-02-19 | Michael Gulla | Stabilized electroless plating solutions |
US4780342A (en) | 1987-07-20 | 1988-10-25 | General Electric Company | Electroless nickel plating composition and method for its preparation and use |
JP3455709B2 (en) * | 1999-04-06 | 2003-10-14 | 株式会社大和化成研究所 | Plating method and plating solution precursor used for it |
CN1132963C (en) * | 2000-03-03 | 2003-12-31 | 北京航空航天大学 | Formula for chemical plating nickel and application thereof |
US6800121B2 (en) * | 2002-06-18 | 2004-10-05 | Atotech Deutschland Gmbh | Electroless nickel plating solutions |
JP2005194562A (en) | 2004-01-06 | 2005-07-21 | Murata Mfg Co Ltd | Electroless nickel plating liquid, and method for producing ceramic electronic component |
CN100476026C (en) * | 2005-07-11 | 2009-04-08 | 佛山市顺德区汉达精密电子科技有限公司 | Copper-alloy chemical nickeling process |
JP2012505970A (en) | 2008-10-16 | 2012-03-08 | アトテック・ドイチュラント・ゲーエムベーハー | Metal plating additive, substrate plating method and product obtained by this method |
JP5297171B2 (en) * | 2008-12-03 | 2013-09-25 | 上村工業株式会社 | Electroless nickel plating bath and electroless nickel plating method |
US8404369B2 (en) * | 2010-08-03 | 2013-03-26 | WD Media, LLC | Electroless coated disks for high temperature applications and methods of making the same |
KR101365457B1 (en) * | 2012-03-15 | 2014-02-21 | 한국기계연구원 | Method of Manufacturing Ni-coated Nano- carbons |
EP2671969A1 (en) * | 2012-06-04 | 2013-12-11 | ATOTECH Deutschland GmbH | Plating bath for electroless deposition of nickel layers |
CN103952687B (en) * | 2014-05-05 | 2017-02-15 | 广东东硕科技有限公司 | Plating penetration prevention method for chemical nickel-plating of printed circuit board |
CN104103433B (en) * | 2014-07-21 | 2016-02-17 | 南通万德科技有限公司 | Switch contact of a kind of arc ablation resistance and preparation method thereof |
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EP3224388A1 (en) | 2017-10-04 |
CN107109654B (en) | 2019-08-27 |
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