US20230151493A1 - Metal displacement solution, method for surface treatment of aluminum or aluminum alloy - Google Patents
Metal displacement solution, method for surface treatment of aluminum or aluminum alloy Download PDFInfo
- Publication number
- US20230151493A1 US20230151493A1 US18/052,569 US202218052569A US2023151493A1 US 20230151493 A1 US20230151493 A1 US 20230151493A1 US 202218052569 A US202218052569 A US 202218052569A US 2023151493 A1 US2023151493 A1 US 2023151493A1
- Authority
- US
- United States
- Prior art keywords
- aluminum
- metal
- displacement solution
- compound
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 140
- 239000002184 metal Substances 0.000 title claims abstract description 139
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 110
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 108
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004381 surface treatment Methods 0.000 title claims abstract description 16
- 238000007747 plating Methods 0.000 claims abstract description 72
- 150000002291 germanium compounds Chemical class 0.000 claims abstract description 16
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 16
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 16
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 65
- 239000011701 zinc Substances 0.000 claims description 38
- 229910052759 nickel Inorganic materials 0.000 claims description 32
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- 229910052732 germanium Inorganic materials 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 150000002739 metals Chemical class 0.000 claims description 14
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000010408 film Substances 0.000 description 85
- 239000000243 solution Substances 0.000 description 74
- 239000000758 substrate Substances 0.000 description 31
- 238000010979 pH adjustment Methods 0.000 description 26
- 238000011282 treatment Methods 0.000 description 22
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- -1 e.g. Substances 0.000 description 10
- 238000007654 immersion Methods 0.000 description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- 235000003270 potassium fluoride Nutrition 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910018182 Al—Cu Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000221561 Ustilaginales Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- GGJOARIBACGTDV-UHFFFAOYSA-N germanium difluoride Chemical compound F[Ge]F GGJOARIBACGTDV-UHFFFAOYSA-N 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 101100133719 Caenorhabditis elegans npr-18 gene Proteins 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- VXXCTRXMBKNRII-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Ge+2] Chemical compound S(=O)(=O)([O-])[O-].[Ge+2] VXXCTRXMBKNRII-UHFFFAOYSA-L 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 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 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940116232 nickel gluconate Drugs 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- DVQYNXRSNFYQRW-IYEMJOQQSA-L nickel(2+);(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ni+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O DVQYNXRSNFYQRW-IYEMJOQQSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 101150017560 npp-18 gene Proteins 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002203 pretreatment Methods 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- VDNSGQQAZRMTCI-UHFFFAOYSA-N sulfanylidenegermanium Chemical compound [Ge]=S VDNSGQQAZRMTCI-UHFFFAOYSA-N 0.000 description 1
- RVUXIPACAZKWHU-UHFFFAOYSA-N sulfuric acid;heptahydrate Chemical compound O.O.O.O.O.O.O.OS(O)(=O)=O RVUXIPACAZKWHU-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- CUDGTZJYMWAJFV-UHFFFAOYSA-N tetraiodogermane Chemical compound I[Ge](I)(I)I CUDGTZJYMWAJFV-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Images
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
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
-
- 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
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
-
- 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
- C23C18/02—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 thermal decomposition
- C23C18/08—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 thermal decomposition characterised by the deposition of metallic material
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1841—Multistep pretreatment with use of metal first
-
- 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
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
- C25D5/44—Aluminium
Definitions
- the present invention relates to a metal displacement solution and a method for surface treatment of aluminum or an aluminum alloy.
- Aluminum readily forms an oxide film in the air or water. It is known that when aluminum or an aluminum alloy is subjected to plating, the plating film has low adhesion due to such an oxide film. Hence, zinc displacement (zincate treatment) has been performed prior to plating in order to remove the oxide film on the aluminum or aluminum alloy surface and thereby ensure adhesion to a plating film to be formed on the aluminum (e.g., Patent Literatures 1 to 3 and Non-Patent Literatures 1 to 3).
- the present invention aims to solve the problem newly found by the present inventors and provide a metal displacement solution that can provide good adhesion to a plating film (metal film), and a method for surface treatment of aluminum or an aluminum alloy using the metal displacement solution.
- the present invention relates to a metal displacement solution, containing:
- the metal displacement solution contains the zinc compound in an amount corresponding to a zinc concentration of 0.2 to 5.0 g/L.
- the metal displacement solution contains the nickel compound in an amount corresponding to a nickel concentration of 0.2 to 10 g/L.
- the metal displacement solution contains the germanium compound in an amount corresponding to a germanium concentration of 0.2 to 5.0 g/L.
- the metal displacement solution contains the fluorine compound in an amount corresponding to a fluorine concentration of 5.0 to 50 g/L.
- the metal displacement solution has a ratio of zinc concentration to germanium concentration of 1:5 to 5:1.
- the metal displacement solution has a pH of 4.0 to 6.5.
- the metal displacement solution is for treating aluminum or an aluminum alloy.
- the present invention also relates to a method for surface treatment of aluminum or an aluminum alloy, the method including:
- the method includes, after forming the displacement metal film, forming a plating film on a surface of the displacement metal film.
- the metal displacement solution according to the present invention contains a zinc compound, a nickel compound, a germanium compound, and a fluorine compound and thus can provide good adhesion to a plating film (metal film).
- FIG. 1 is a view schematically showing a cutting and breaking test.
- FIG. 2 shows (a) a photograph showing an exemplary case where no Al spikes are observed, and (b) a photograph showing an exemplary case where Al spikes are observed.
- the metal displacement solution of the present invention contains a zinc compound, a nickel compound, a germanium compound, and a fluorine compound. This can provide good adhesion to a plating film (metal film).
- zinc (Zn) may co-deposit with nickel (Ni) and germanium (Ge) to form a displacement metal film containing Zn, Ni, and Ge on a surface of the aluminum or aluminum alloy.
- the Zn, Ni, and Ge present in the displacement metal film may act synergistically between the aluminum or aluminum alloy and the plating film (metal film, e.g., nickel film), thereby providing good adhesion to the plating film (metal film) to the aluminum or aluminum alloy.
- the metal displacement solution of the present invention contains a zinc compound, a nickel compound, a germanium compound, and a fluorine compound.
- the zinc compound is not limited as long as it is a water-soluble zinc compound. Specific examples include zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, zinc oxide, and zinc gluconate. These may be used alone or in combinations of two or more. Preferred among these is zinc sulfate.
- the metal displacement solution preferably contains at least one zinc compound in an amount corresponding to a zinc (metallic zinc (Zn)) concentration of 0.1 to 7.0 g/L, more preferably 0.2 to 5.0 g/L, still more preferably 0.2 to 4.0 g/L.
- Zn metal zinc
- the nickel compound is not limited as long as it is a water-soluble nickel compound. Specific examples include nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, and nickel gluconate. These may be used alone or in combinations of two or more. Preferred among these is nickel sulfate.
- the metal displacement solution preferably contains at least one nickel compound in an amount corresponding to a nickel (metallic nickel (Ni)) concentration of 0.1 to 12 g/L, more preferably 0.2 to 10 g/L.
- Ni nickel
- concentration of lower than 0.1 g/L the co-deposition with Zn tends to be reduced, failing to ensure sufficient adhesion.
- concentration of higher than 12 g/L the co-deposition with Zn tends to be excessive, failing to ensure sufficient adhesion.
- the germanium compound is not limited as long as it is a water-soluble germanium compound. Specific examples include germanium dioxide, germanium sulfate, germanium sulfide, germanium fluoride, germanium chloride, and germanium iodide. These may be used alone or in combinations of two or more. Preferred among these is germanium dioxide.
- a compound that corresponds to both a germanium compound and a fluorine compound, such as germanium fluoride is regarded as a germanium compound.
- a zinc compound and a nickel compound are also regarded as a zinc compound and a nickel compound, respectively.
- the metal displacement solution preferably contains at least one germanium compound in an amount corresponding to a germanium (metallic germanium (Ge)) concentration of 0.1 to 7.0 g/L, more preferably 0.2 to 5.0 g/L.
- a germanium (metallic germanium (Ge)) concentration of 0.1 to 7.0 g/L, more preferably 0.2 to 5.0 g/L.
- the ratio of the zinc concentration to the germanium concentration is preferably 1:5 to 5:1.
- the fluorine compound dissolves aluminum from the oxide film on the aluminum or aluminum alloy surface to allow it to be smoothly displaced with the metals such as zinc.
- fluorine compound examples include hydrofluoboric acid, sodium fluoride, potassium fluoride, ammonium hydrogen fluoride, ammonium fluoride, hydrogen fluoride, and lithium fluoride. These may be used alone or in combinations of two or more. Preferred among these are hydrofluoboric acid, sodium fluoride, potassium fluoride, ammonium hydrogen fluoride, ammonium fluoride, and hydrogen fluoride, with hydrofluoboric acid, sodium fluoride, potassium fluoride, ammonium hydrogen fluoride, and ammonium fluoride being more preferred.
- the metal displacement solution preferably contains at least one fluorine compound in an amount corresponding to a fluorine (F) concentration of 1.0 to 100 g/L, more preferably 5.0 to 50 g/L.
- F fluorine
- concentration of lower than 1.0 g/L the aluminum-dissolving action tends to be lowered, failing to ensure sufficient adhesion.
- concentration of higher than 100 g/L excess aluminum tends to be dissolved, failing to ensure sufficient adhesion.
- the zinc (metallic zinc (Zn)) concentration, nickel (metallic nickel (Ni)) concentration, and germanium (metallic germanium (Ge)) concentration in the metal displacement solution are measured by ICP (HORIBA, Ltd.).
- the fluorine (F) concentration in the metal displacement solution is measured using a fluorine ion electrode.
- the pH of the metal displacement solution is preferably 1.0 to 12.0, more preferably 2.0 to 10.0.
- the metal displacement solution of the present invention may be used under either alkaline or acidic conditions.
- excess aluminum may be eluted under alkaline conditions (e.g., FIG. 9 of Non-Patent Literature 3), which tends to form aluminum spikes, while under acidic conditions, no elution of excess aluminum occurs, but sufficient adhesion tends not to be ensured.
- the metal displacement solution of the present invention even under acidic conditions, can ensure sufficient adhesion, and a more significant effect on improving adhesion is obtained when it is used under acidic conditions. Further, as no elution of excess aluminum occurs under acidic conditions, it is also possible to reduce aluminum spikes. However, when the pH is lower than 3.5, excess aluminum may be eluted.
- the pH of the metal displacement solution is still more preferably 3.5 to 6.5, particularly preferably 4.0 to 6.5, most preferably 4.5 to 6.5.
- a more significant effect on improving adhesion is obtained as described above, and it is also possible to reduce aluminum spikes as no elution of excess aluminum occurs.
- excess aluminum is eluted to form aluminum spikes, many wedge-shaped depressions are formed on the aluminum surface, and in the subsequent plating film formation step, for example, a nickel plating may enter the depressions so that a plating film having poor smoothness is formed, which also affects the conductivity and greatly impairs the appearance.
- the reduction of aluminum spikes enables the formation of a plating film having high smoothness and excellent plating appearance.
- the pH of the metal displacement solution is measured at 25° C.
- the pH of the metal displacement solution may be adjusted by selecting the type of the zinc compound, nickel compound, germanium compound, or fluorine compound.
- An alkaline component or an acid component may also be added as necessary.
- Non-limiting examples of the alkaline component include sodium hydroxide and ammonium.
- Non-limiting examples of the acid component include sulfuric acid and phosphoric acid. These alkaline or acid components may be used alone or in combinations of two or more.
- the metal displacement solution may contain a buffer to enhance the pH buffering capacity.
- the buffer may be any compound having a buffering capacity, and examples of compounds having a buffering capacity around a pH of 4.0 to 6.5 include acetic acid, malic acid, succinic acid, citric acid, malonic acid, lactic acid, oxalic acid, glutaric acid, adipic acid, and formic acid. These may be used alone or in combinations of two or more.
- the buffer concentration in the metal displacement solution is preferably 1.0 to 50 g/L, more preferably 5.0 to 30 g/L.
- the metal displacement solution may contain, in addition to the above-described components, components that are generally used in metal displacement solutions, such as surfactants and brightening agents.
- the metal displacement solution may also contain water-soluble salts of metals other than the above-described metals, such as iron, copper, silver, palladium, lead, bismuth, and thallium. These may be used alone or in combinations of two or more.
- the metal displacement solution can be prepared by appropriately mixing the components using a solvent, preferably water.
- a solvent preferably water.
- other solvents such as methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, or IPA may be used, or they may be used as a solvent mixture with water.
- these solvents may be used alone or in combinations of two or more.
- the metal displacement solution can be suitably used as a metal displacement solution for treating aluminum or an aluminum alloy.
- the following describes a method for surface treatment of aluminum or an aluminum alloy of the present invention using the metal displacement solution of the present invention.
- the method for surface treatment of aluminum or an aluminum alloy of the present invention includes bringing a workpiece having aluminum or an aluminum alloy on its surface into contact with the metal displacement solution of the present invention to remove the oxide film on the aluminum or aluminum alloy and displace the aluminum with the metals in the metal displacement solution to form a displacement metal film containing the metals on the surface of the workpiece.
- the surface treatment method includes a pretreatment method prior to forming a plating film such as a nickel or palladium plating film on a workpiece.
- This method brings a workpiece having aluminum or an aluminum alloy at least on its surface into contact with the metal displacement solution of the present invention to remove the oxide film adhered to the surface and form a displacement metal film, thereby increasing adhesion to a nickel plating film or other plating film to be formed in the subsequent treatment.
- the metal displacement solution of the present invention removes the oxide film adhered to a workpiece (hereinafter also referred to as “aluminum substrate”) having aluminum or an aluminum alloy at least on its surface, and allows the zinc, nickel, and germanium particles to deposit on the surface of the workpiece via a displacement reaction between the metals such as zinc and the aluminum which have different electrode potentials.
- a double zincate process is performed in which zinc displacement is performed twice.
- the process includes: ( 1 ) a first zinc displacement of an aluminum substrate, ( 2 ) pickling, and then ( 3 ) a second zinc displacement.
- the double zincate treatment is followed by ( 4 ) plating such as electroless nickel plating.
- the method for surface treatment of aluminum or an aluminum alloy of the present invention using the metal displacement solution of the present invention requires no double zincate treatment and can provide good adhesion by a single zincate treatment.
- ( 1 ) metal displacement of an aluminum substrate is performed, and this single zincate treatment is followed by ( 4 ) plating such as electroless nickel plating.
- ( 2 ) pickling followed by ( 3 ) a second metal displacement are not performed between the metal displacement and the plating.
- the aluminum substrate which is a workpiece to be plated, may be any substrate that has aluminum or an aluminum alloy at least on its surface.
- Examples of such aluminum substrates include various articles made of aluminum or aluminum alloys, articles in which an aluminum or aluminum alloy film is formed on a non-aluminum material (e.g., various substrates such as ceramic substrates and wafers), hot-dip aluminized articles, castings, and die castings.
- the aluminum substrate may also have any shape and may be in the form of a typical plate (including a film, a sheet, or other thin film) or in the form of any formed article of any of various shapes.
- the plate is not limited to a plate made of aluminum or an aluminum alloy alone, and may include, for example, an aluminum film that is formed on (integrated with) a substrate such as a ceramic substrate or a wafer by sputtering, vacuum deposition, ion plating, or other conventional techniques.
- the aluminum alloy may be, but is not limited to, for example, any of various alloys containing aluminum as a main metal component.
- applicable alloys include A1000 series quasi-aluminum, A2000 series aluminum alloys containing copper and manganese, A3000 series aluminum-manganese alloys, A4000 series aluminum-silicon alloys, A5000 series aluminum-magnesium alloys, A6000 series aluminum-magnesium-silicon alloys, A7000 series aluminum-zinc-magnesium alloys, and A8000 series aluminum-lithium alloys.
- the aluminum purity of the aluminum or aluminum alloy is preferably 98% or higher, more preferably 98.5% or higher, still more preferably 99% or higher, from the standpoint of plating smoothness.
- the aluminum substrate which is a workpiece to be plated, can be prepared by coating a non-aluminum material such as a silicon plate with an aluminum layer using well-known techniques such as sputtering.
- the aluminum layer may fully or partially coat the non-aluminum material, and the coated aluminum layer usually has a thickness of 0.5 ⁇ m or more, preferably 1 ⁇ m or more.
- the method for preparing the aluminum substrate is not limited to sputtering and may include vacuum deposition, ion plating, or other techniques.
- the thus-prepared aluminum substrate may be cleaned in a well-known manner, for example, by degreasing, rinsed with water as appropriate, and then subjected to a well-known etching process using alkali or acid.
- the degreasing process may be carried out by immersion in a degreasing solution for aluminum or by electrolytic degreasing.
- the etching process may be carried out, for example, by immersion in an about 1-10% alkaline solution or an about 1-20% acidic solution having a liquid temperature of about 25 to 75° C. for about 1 to 15 minutes.
- the aluminum substrate may be immersed in an acidic solution for a predetermined period of time in order to remove the residues (smuts) produced by etching using alkali or acid.
- the aluminum substrate after etching may be immersed in an aqueous nitric acid solution having a concentration in the range of about 10 to 800 ml/L, preferably about 100 to 600 ml/L and a liquid temperature of about 15 to 35° C. for about 30 seconds to 2 minutes to remove the smuts.
- the thus-treated (e.g., desmutted) aluminum substrate may be rinsed with water and then immersed in the metal displacement solution of the present invention (zincate treatment solution) to perform metal displacement.
- the aluminum substrate may be immersed in a zincate treatment solution having the composition described above and a liquid temperature of 10 to 50° C., preferably 15 to 30° C. This liquid temperature is preferred because when the temperature of the zincate treatment solution is 10° C. or higher, the displacement reaction does not become too slow and a metal film without irregularities can be formed, while when the temperature is 50° C. or lower, the displacement reaction is not excessively enhanced and the surface of the displacement metal film can be prevented from becoming rough.
- the conditions of the immersion period are not limited and can be set appropriately in consideration of, for example, the thickness of the aluminum oxide film to be removed.
- the immersion period is usually about five seconds or longer, preferably 10 seconds or longer, and the upper limit thereof is five minutes or shorter. With too short an immersion period, the displacement does not proceed enough to cause sufficient removal of the oxide film, while with too long an immersion period, the treatment solution may penetrate through the small holes in the displacement metal layer to cause elution of the aluminum or aluminum alloy. Thus, the conditions need to be set in consideration of these points.
- Such immersion of the aluminum substrate in the zincate treatment solution makes it possible to remove the oxide film adhered to the substrate surface and also to further coat the surface with a displacement metal film containing Zn, Ni, and Ge to activate the aluminum surface, thereby enabling the formation of a plating film having good adhesion to the workpiece.
- the metal displacement process is not limited as long as it is an embodiment in which the surface of the aluminum substrate can be brought into contact with the metal displacement solution of the present invention.
- Examples of such contact methods include, in addition to immersion, application and spraying.
- the plating process may be carried out by electroless plating or electrolytic plating on the zincated aluminum substrate.
- an appropriate metal plating solution such as an electroless nickel plating, electroless palladium plating, or copper plating bath may be used to form a plating having a desired final film thickness.
- an electroless nickel plating solution contains a water-soluble nickel salt such as nickel sulfate, nickel chloride, or nickel acetate, which provides nickel ions at a concentration of, for example, about 1 to 10 g/L.
- the electroless nickel plating solution may further contain, for example: a nickel complexing agent such as an organic acid salt (e.g., acetate, succinate, or citrate), an ammonium salt, or an amine salt at a concentration in the range of about 20 to 80 g/L; and hypophosphorous acid or a hypophosphite such as sodium hypophosphite as a reducing agent at a concentration in the range of about 10 to 40 g/L.
- a nickel complexing agent such as an organic acid salt (e.g., acetate, succinate, or citrate), an ammonium salt, or an amine salt at a concentration in the range of about 20 to 80 g/L
- hypophosphorous acid or a hypophosphite such as sodium hypopho
- the plating solution containing these compounds may be prepared to have a pH of about 4 to 7 before use. Further, this plating solution may be prepared to have a liquid temperature of 60 to 95° C., and the aluminum substrate may be immersed in the plating solution for about 15 seconds to 120 minutes to perform plating. Moreover, the thickness of the plating film can be varied by changing this plating period as appropriate.
- the plating process is not limited to electroless plating and may be carried out by electrolytic plating, as described above. Besides the above-mentioned types of metals, other plating metals such as Cu and Au may also be used. Moreover, the plating process may be performed by displacement plating or other techniques to form two or more layers.
- a workpiece having aluminum or an aluminum alloy on its surface is brought into contact with the metal displacement solution of the present invention to remove the oxide film on the aluminum or aluminum alloy and displace the aluminum with the metals in the metal displacement solution.
- Zn may co-deposit with Ni and Ge to form a displacement metal film containing Zn, Ni, and Ge on a surface of the aluminum or aluminum alloy.
- the Zn, Ni, and Ge present in the displacement metal film may act synergistically between the aluminum or aluminum alloy and the plating film (metal film, e.g., nickel film), thereby providing good adhesion to the plating film (metal film) to the aluminum or aluminum alloy.
- the aluminum or aluminum alloy provided with a plating film (metal film) according to the present invention can be used in various electronic components.
- the electronic components include electronic components used in home appliances, in-vehicle equipment, power transmission systems, transportation equipment, and communication equipment.
- Specific examples include power modules such as power control units for air conditioners, elevators, electric vehicles, hybrid vehicles, trains, and power generation equipment, general home appliances, and personal computers.
- the present invention when the metal displacement solution has a pH of 4.0 to 6.5, pre-plating treatment can be performed to also reduce aluminum spikes and form a plating film having high smoothness and excellent plating appearance.
- the present invention is suitable for semiconductor applications, preferably for wafer applications.
- the present invention is suitable as a metal displacement solution for treating aluminum or an aluminum alloy which is effective for pretreatment prior to forming an under-bump metal or bump on a wafer, or as a method for surface treatment of aluminum or an aluminum alloy using the metal displacement solution.
- An aluminum substrate was subjected to the treatments according to the conditions shown in Tables 1 to 3 to form a plating film.
- a 1 cm ⁇ 2 cm Al—Cu TEG wafer was used as the aluminum substrate.
- the thus-prepared plating films and substrates provided with the plating films were evaluated as described below. The evaluation results are shown in Tables 2 and 3.
- Each of the substrates provided with the plating films was dried by air-blowing, and cellophane tape was put on the plated surface. Then, the center of the wafer with the tape was cut and broken into two pieces. The tape was peeled off from the broken center, and the amount of removal between the Al substrate and the Ni film was determined in percentage.
- the cutting and breaking test is schematically illustrated in FIG. 1 .
- FIG. 2 ( a ) shows an exemplary case where no Al spikes are observed
- FIG. 2 ( b ) shows an exemplary case where Al spikes are observed.
- a case where no Al spikes are observed as shown in FIG. 2 ( a ) is considered good.
- Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10
- Example 11 Example 12
- Example 13 Example 14
- Tables 2 and 3 show that the metal displacement solutions of the examples containing a zinc compound, a nickel compound, a germanium compound, and a fluorine compound provided good adhesion to a plating film (metal film). It is also shown that the metal displacement solutions having a pH of 3.5 to 6.5 also reduced aluminum spikes.
- Tables 2 and 3 show the results when an Al-Cu TEG wafer was used as the aluminum substrate, similar results were also obtained when an Al-Si TEG wafer was used as the aluminum substrate.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-182009 | 2021-11-08 | ||
JP2021182009A JP2023069841A (ja) | 2021-11-08 | 2021-11-08 | 金属置換処理液、アルミニウム又はアルミニウム合金の表面処理方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
US20230151493A1 true US20230151493A1 (en) | 2023-05-18 |
Family
ID=82512418
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/052,569 Pending US20230151493A1 (en) | 2021-11-08 | 2022-11-03 | Metal displacement solution, method for surface treatment of aluminum or aluminum alloy |
Country Status (6)
Country | Link |
---|---|
US (1) | US20230151493A1 (zh) |
EP (1) | EP4177376A1 (zh) |
JP (1) | JP2023069841A (zh) |
KR (1) | KR20230067550A (zh) |
CN (1) | CN114807918A (zh) |
TW (1) | TW202336272A (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW202407151A (zh) * | 2022-06-16 | 2024-02-16 | 日商上村工業股份有限公司 | 蝕刻處理液、鋁或鋁合金的表面處理方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2354911A1 (de) * | 1972-11-06 | 1974-05-16 | Metallgesellschaft Ag | Verfahren zur oberflaechenbehandlung von zink oder zinklegierungen |
JPH07188971A (ja) * | 1993-12-28 | 1995-07-25 | Nkk Corp | アルミニウムおよびアルミニウム合金板の亜鉛系めっき 方法 |
JP2000256864A (ja) | 1999-03-05 | 2000-09-19 | Okuno Chem Ind Co Ltd | アルミニウム又はアルミニウム合金表面の亜鉛置換方法、そのための置換液及び亜鉛置換皮膜を有するアルミニウム又はアルミニウム合金 |
JP2001026896A (ja) * | 1999-07-16 | 2001-01-30 | Nisshin Steel Co Ltd | 表面処理金属板 |
US7407689B2 (en) * | 2003-06-26 | 2008-08-05 | Atotech Deutschland Gmbh | Aqueous acidic immersion plating solutions and methods for plating on aluminum and aluminum alloys |
JP5136746B2 (ja) * | 2007-01-12 | 2013-02-06 | 上村工業株式会社 | アルミニウム又はアルミニウム合金の表面処理方法 |
JP4538490B2 (ja) | 2007-11-26 | 2010-09-08 | 上村工業株式会社 | アルミニウム又はアルミニウム合金上の金属置換処理液及びこれを用いた表面処理方法 |
JP4605409B2 (ja) * | 2008-08-21 | 2011-01-05 | 上村工業株式会社 | アルミニウム又はアルミニウム合金の表面処理方法 |
JP5643484B2 (ja) * | 2009-01-13 | 2014-12-17 | 日本パーカライジング株式会社 | 金属表面処理用処理液、金属表面処理方法および金属材料 |
JP2020196914A (ja) | 2019-05-31 | 2020-12-10 | 奥野製薬工業株式会社 | めっき前処理方法 |
-
2021
- 2021-11-08 JP JP2021182009A patent/JP2023069841A/ja active Pending
-
2022
- 2022-04-28 CN CN202210500745.9A patent/CN114807918A/zh active Pending
- 2022-10-24 TW TW111140222A patent/TW202336272A/zh unknown
- 2022-10-28 EP EP22204326.7A patent/EP4177376A1/en active Pending
- 2022-11-03 US US18/052,569 patent/US20230151493A1/en active Pending
- 2022-11-08 KR KR1020220147573A patent/KR20230067550A/ko unknown
Also Published As
Publication number | Publication date |
---|---|
CN114807918A (zh) | 2022-07-29 |
TW202336272A (zh) | 2023-09-16 |
KR20230067550A (ko) | 2023-05-16 |
EP4177376A1 (en) | 2023-05-10 |
JP2023069841A (ja) | 2023-05-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8414711B2 (en) | Method of surface treatment for aluminum or aluminum alloy | |
US9139915B2 (en) | Solution for removing aluminum oxide film and method for surface treatment of aluminum or aluminum alloy | |
US20050121330A1 (en) | Chromium-free antitarnish adhesion promoting treatment composition | |
US20060237097A1 (en) | Immersion method | |
WO2014207975A1 (ja) | めっき材の製造方法及びめっき材 | |
US20230151493A1 (en) | Metal displacement solution, method for surface treatment of aluminum or aluminum alloy | |
TWI480421B (zh) | 用於錫及錫合金之無電電鍍之方法 | |
KR102280838B1 (ko) | 추가 금속의 존재 하에 구리를 선택적으로 처리하는 방법 | |
US20160108254A1 (en) | Zinc immersion coating solutions, double-zincate method, method of forming a metal plating film, and semiconductor device | |
EP4293136A1 (en) | Etchant and method of surface treatment of aluminum or aluminum alloy | |
CN117248215A (zh) | 蚀刻处理液、铝或铝合金的表面处理方法 | |
JP2023184437A (ja) | エッチング処理液、アルミニウム又はアルミニウム合金の表面処理方法 | |
TWI790062B (zh) | 具備Ni電鍍皮膜之鍍敷結構體及含有該鍍敷結構體之引線框 | |
US20230304137A1 (en) | Surface modifying method for galvanized steel sheet and surface modified galvanized steel sheet by thereof | |
KR20090102464A (ko) | 무전해 도금용액 및 이를 이용한 도금 방법 | |
JP2001262390A (ja) | パラジウムめっき液 | |
EP2491163B1 (en) | Composition and process for improved zincating of magnesium and magnesium alloy substrates | |
TW201432089A (zh) | 以金屬鍍覆基材的方法 | |
US20130216721A1 (en) | Process for Electroless Deposition on Magnesium Using a Nickel Hydrate Plating Bath | |
JP2022183021A (ja) | 無電解Co-Wめっき皮膜、および無電解Co-Wめっき液 | |
KR20060067454A (ko) | 무전해 도금을 이용한 패턴 내 금속배선 형성방법 | |
TW202033827A (zh) | 置換金鍍覆液及置換金鍍覆方法 | |
JPH0715149B2 (ja) | 耐糸▲錆▼性に優れたアルミニウム板 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: C. UYEMURA & CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MAEKAWA, TAKUMA;TANABE, KATSUHISA;TANAKA, SAYURI;AND OTHERS;SIGNING DATES FROM 20220921 TO 20220922;REEL/FRAME:062489/0549 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE AFTER FINAL ACTION FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: ADVISORY ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |