TW202336272A - 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
- TW202336272A TW202336272A TW111140222A TW111140222A TW202336272A TW 202336272 A TW202336272 A TW 202336272A TW 111140222 A TW111140222 A TW 111140222A TW 111140222 A TW111140222 A TW 111140222A TW 202336272 A TW202336272 A TW 202336272A
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- TW
- Taiwan
- Prior art keywords
- aluminum
- metal
- treatment liquid
- replacement treatment
- film
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 151
- 239000002184 metal Substances 0.000 title claims abstract description 151
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 111
- 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 52
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004381 surface treatment Methods 0.000 title claims abstract description 16
- 238000006073 displacement reaction Methods 0.000 title abstract description 5
- 238000007747 plating Methods 0.000 claims abstract description 50
- 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
- 238000011282 treatment Methods 0.000 claims description 113
- 239000007788 liquid Substances 0.000 claims description 75
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 70
- 239000011701 zinc Substances 0.000 claims description 42
- 229910052759 nickel Inorganic materials 0.000 claims description 33
- 229910052725 zinc Inorganic materials 0.000 claims description 27
- 229910052732 germanium Inorganic materials 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 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
- 238000010979 pH adjustment Methods 0.000 description 43
- 239000000758 substrate Substances 0.000 description 25
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- 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 6
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 239000011698 potassium fluoride Substances 0.000 description 6
- 235000003270 potassium fluoride Nutrition 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000011775 sodium fluoride Substances 0.000 description 6
- 235000013024 sodium fluoride Nutrition 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- -1 aluminum-manganese Chemical compound 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000001384 succinic acid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000005554 pickling Methods 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
- 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
- 238000005452 bending Methods 0.000 description 3
- 239000000872 buffer Substances 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 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
- 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
- 239000002245 particle Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000006467 substitution reaction Methods 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
- 101100133719 Caenorhabditis elegans npr-18 gene Proteins 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 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
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 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
- 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 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
- 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
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000011160 research 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
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-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
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 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
- 150000001242 acetic acid derivatives Chemical class 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
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy 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
- 239000012298 atmosphere Substances 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
- 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
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 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
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940116232 nickel gluconate Drugs 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
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method 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
- 238000005507 spraying Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- VDNSGQQAZRMTCI-UHFFFAOYSA-N sulfanylidenegermanium Chemical compound [Ge]=S VDNSGQQAZRMTCI-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 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
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
- C23C18/18—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
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
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- C—CHEMISTRY; METALLURGY
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- 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
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—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
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—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
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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- 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
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- 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
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- 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
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- 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
Abstract
Description
本發明涉及金屬置換處理液、鋁或鋁合金的表面處理方法。The present invention relates to a metal replacement treatment liquid and a surface treatment method for aluminum or aluminum alloys.
鋁在大氣中、水中容易形成氧化膜。已知由於該氧化膜，在鋁或鋁合金上實施鍍敷處理時，鍍敷膜的附著性低。因此，鍍敷處理之前，為了去除鋁或鋁合金表面的氧化覆膜，確保與鋁上形成的鍍敷膜的附著性的目的，進行鋅置換處理（鋅酸鹽處理）步驟（例如專利文獻1～3、非專利文獻1～3）。 [先前技術文獻] [專利文獻] Aluminum easily forms an oxide film in the atmosphere and water. It is known that due to this oxide film, when plating is performed on aluminum or an aluminum alloy, the adhesion of the plating film is low. Therefore, before the plating treatment, a zinc replacement treatment (zincate treatment) step is performed (for example, Patent Document 1) for the purpose of removing the oxide film on the surface of the aluminum or aluminum alloy and ensuring adhesion to the plated film formed on the aluminum. ~3, non-patent literature 1~3). [Prior technical literature] [Patent Document]
[專利文獻1] 日本專利特開2000-256864號公報 [專利文獻2] 日本專利特開2020-196914號公報 [專利文獻3] 日本專利特開2009-127101號公報 [非專利文獻] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-256864 [Patent Document 2] Japanese Patent Application Laid-Open No. 2020-196914 [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-127101 [Non-patent literature]
[非專利文獻1] 表面技術Vol.64(2013), No.12, p.645-649 [非專利文獻2] 表面技術Vol.66(2015), No.12, p.658-665 [非專利文獻3] 表面技術Vol.47(1996), No.9, p.802-807 [Non-patent document 1] Surface Technology Vol.64(2013), No.12, p.645-649 [Non-patent document 2] Surface Technology Vol.66(2015), No.12, p.658-665 [Non-patent document 3] Surface Technology Vol.47(1996), No.9, p.802-807
[發明所要解決的課題][Problem to be solved by the invention]
本發明人專心研究的結果，已弄清楚：先前技術中，關於與鍍敷膜的附著性，還有改善餘地。As a result of intensive research by the present inventors, it has been clarified that there is room for improvement in the adhesion to the plating film in the conventional technology.
本發明的目的在於，解決本發明人新發現的上述課題，提供能夠賦予與鍍敷膜（金屬膜）的良好附著性的金屬置換處理液、使用該金屬置換處理液的鋁或鋁合金的表面處理方法。 [用以解決課題的手段] An object of the present invention is to provide a metal replacement treatment liquid capable of imparting good adhesion to a plating film (metal film) and a surface of aluminum or aluminum alloy using the metal replacement treatment liquid to solve the above-mentioned problems newly discovered by the present inventors. Processing methods. [Means used to solve problems]
本發明人專心研究的結果，發現通過使用特定組成的金屬置換處理液，能夠賦予與鍍敷膜（金屬膜）的良好附著性，完成了本發明。即，本發明涉及含有鋅化合物、鎳化合物、鍺化合物、氟化合物的金屬置換處理液。As a result of intensive research, the inventor found that good adhesion to a plating film (metal film) can be imparted by using a metal replacement treatment liquid of a specific composition, and completed the present invention. That is, the present invention relates to a metal replacement treatment liquid containing a zinc compound, a nickel compound, a germanium compound, and a fluorine compound.
所述金屬置換處理液較佳含有以鋅濃度計為0.2～5.0g/L的鋅化合物。The metal replacement treatment liquid preferably contains a zinc compound with a zinc concentration of 0.2 to 5.0 g/L.
所述金屬置換處理液較佳含有以鎳濃度計為0.2～10g/L的鎳化合物。The metal replacement treatment liquid preferably contains a nickel compound with a nickel concentration of 0.2 to 10 g/L.
所述金屬置換處理液較佳含有以鍺濃度計為0.2～5.0g/L的鍺化合物。The metal replacement treatment liquid preferably contains a germanium compound with a germanium concentration of 0.2 to 5.0 g/L.
所述金屬置換處理液較佳含有以氟濃度計為5.0～50g/L的氟化合物。The metal replacement treatment liquid preferably contains a fluorine compound with a fluorine concentration of 5.0 to 50 g/L.
所述金屬置換處理液較佳鋅濃度、鍺濃度的比率為1：5～5：1。The preferred ratio of zinc concentration and germanium concentration in the metal replacement treatment liquid is 1:5 to 5:1.
所述金屬置換處理液較佳pH為4.0～6.5。The preferred pH of the metal replacement treatment liquid is 4.0-6.5.
所述金屬置換處理液較佳用於鋁或鋁合金。The metal replacement treatment liquid is preferably used for aluminum or aluminum alloys.
此外，本發明涉及鋁或鋁合金的表面處理方法，該方法中，進行以下的金屬置換處理，在被處理物的表面上形成含有金屬的置換金屬膜。所述金屬置換處理為，使表面上具有鋁或鋁合金的被處理物與所述金屬置換處理液接觸，去除所述鋁或鋁合金上的氧化膜，使所述鋁被所述金屬置換處理液所含的金屬置換。Furthermore, the present invention relates to a surface treatment method of aluminum or aluminum alloy, in which the following metal replacement treatment is performed to form a replacement metal film containing metal on the surface of the object to be treated. The metal replacement treatment is to contact the object to be treated with aluminum or aluminum alloy on the surface with the metal replacement treatment liquid, remove the oxide film on the aluminum or aluminum alloy, and cause the aluminum to be replaced by the metal replacement treatment. The metal contained in the liquid is replaced.
形成所述置換金屬膜後，較佳在該置換金屬膜表面形成鍍敷膜。 [發明的效果] After the replacement metal film is formed, a plating film is preferably formed on the surface of the replacement metal film. [Effects of the invention]
根據本發明，由於是含有鋅化合物、鎳化合物、鍺化合物、氟化合物的金屬置換處理液，因此能夠賦予與鍍敷膜（金屬膜）的良好附著性。According to the present invention, since it is a metal replacement treatment liquid containing a zinc compound, a nickel compound, a germanium compound, and a fluorine compound, it is possible to provide good adhesion to a plating film (metal film).
本發明的金屬置換處理液含有鋅化合物、鎳化合物、鍺化合物、氟化合物。由此，可賦予與鍍敷膜（金屬膜）的良好附著性。The metal replacement treatment liquid of the present invention contains a zinc compound, a nickel compound, a germanium compound, and a fluorine compound. This can provide good adhesion to the plating film (metal film).
通過所述金屬置換處理液得到前述效果的理由推測為如下。 使表面具有鋁或鋁合金的被處理物與所述金屬置換處理液接觸，去除所述鋁或鋁合金上的氧化膜，使所述鋁被所述金屬置換處理液所含的金屬置換，通過進行該金屬置換處理，鎳（Ni）、鍺（Ge）與鋅（Zn）一同共析，可在鋁或鋁合金表面形成含有Zn、Ni、Ge的置換金屬膜。 在表面具有這樣的有Zn、Ni、Ge的置換金屬膜的鋁或鋁合金上進行鍍敷處理，形成鍍敷膜（金屬膜，例如鎳膜）時，在鋁或鋁合金與鍍敷膜（金屬膜，例如鎳膜）之間，置換金屬膜中存在的Zn、Ni、Ge協同地發揮作用，可對鋁或鋁合金賦予與鍍敷膜（金屬膜）的良好附著性。 Zn、Ni、Ge協同地發揮作用從以下情況很清楚：在Zn、Ni、Ge單獨的情況時，Zn、Ni組合（無Ge）的情況時，Zn、Ge組合（無Ni）的情況時，Ni、Ge組合（無Zn）的情況時，不能賦予與鍍敷膜（金屬膜）的良好附著性。 The reason why the above-described effects are obtained by the metal replacement treatment liquid is presumed to be as follows. The object to be treated with aluminum or aluminum alloy on the surface is brought into contact with the metal replacement treatment liquid, the oxide film on the aluminum or aluminum alloy is removed, and the aluminum is replaced by the metal contained in the metal replacement treatment liquid. During this metal replacement treatment, nickel (Ni), germanium (Ge) and zinc (Zn) eutectoid together, and a replacement metal film containing Zn, Ni, and Ge can be formed on the surface of aluminum or aluminum alloy. When plating is performed on aluminum or an aluminum alloy having such a substitution metal film containing Zn, Ni, or Ge on its surface to form a plated film (metal film, such as a nickel film), the aluminum or aluminum alloy and the plated film ( Metal films, such as nickel films), replace Zn, Ni, and Ge present in the metal film and act synergistically to impart good adhesion to the plated film (metal film) to aluminum or aluminum alloys. It is clear from the following that Zn, Ni, and Ge act synergistically: when Zn, Ni, and Ge are alone, when Zn and Ni are combined (without Ge), when Zn and Ge are combined (without Ni), In the case of a combination of Ni and Ge (without Zn), good adhesion to the plating film (metal film) cannot be provided.
＜金屬置換處理液＞ 本發明的金屬置換處理液含有鋅化合物、鎳化合物、鍺化合物、氟化合物。 ＜Metal replacement treatment liquid＞ The metal replacement treatment liquid of the present invention contains a zinc compound, a nickel compound, a germanium compound, and a fluorine compound.
＜＜鋅化合物＞＞ 鋅化合物若是水溶性的鋅化合物，則沒有特別限定。作為其具體例子，例如可例示硫酸鋅、硝酸鋅、氯化鋅、醋酸鋅、氧化鋅、葡萄糖酸鋅等。這些可以單獨使用，也可以將2種以上並用。其中，較佳硫酸鋅。 ＜＜Zinc compounds＞＞ The zinc compound is not particularly limited as long as it is a water-soluble zinc compound. Specific examples thereof include zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, zinc oxide, zinc gluconate, and the like. These may be used individually or in combination of 2 or more types. Among them, zinc sulfate is preferred.
金屬置換處理液較佳含有以鋅（金屬鋅（Zn））濃度計為0.1～7.0g/L的鋅化合物，更佳含有0.2～5.0g/L，進一步較佳含有0.2～4.0g/L。小於0.1g/L時，有Zn析出量少、不能確保充分的附著性的傾向。超過7.0g/L時，有Zn析出量過剩、不能確保充分的附著性的傾向。The metal replacement treatment liquid preferably contains a zinc compound with a zinc (metal zinc (Zn)) concentration of 0.1 to 7.0 g/L, more preferably 0.2 to 5.0 g/L, and further preferably 0.2 to 4.0 g/L. When it is less than 0.1 g/L, the amount of Zn precipitated is small, and sufficient adhesion tends not to be ensured. When it exceeds 7.0 g/L, the amount of Zn precipitated will tend to be excessive and sufficient adhesion will not be ensured.
＜＜鎳化合物＞＞ 鎳化合物若是水溶性的鎳化合物，則沒有特別限定。作為其具體例子，例如可例示硫酸鎳、硝酸鎳、氯化鎳、醋酸鎳、葡萄糖酸鎳等。這些可以單獨使用，也可以將2種以上並用。其中較佳硫酸鎳。 ＜＜Nickel compounds＞＞ The nickel compound is not particularly limited as long as it is a water-soluble nickel compound. Specific examples thereof include nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, nickel gluconate, and the like. These may be used individually or in combination of 2 or more types. Among them, nickel sulfate is preferred.
金屬置換處理液較佳含有以鎳（金屬鎳（Ni））濃度計為0.1～12g/L的鎳化合物，更佳含有0.2～10g/L。小於0.1g/L時，有與Zn的共析量降低、不能確保充分的附著性的傾向。超過12g/L時，有與Zn的共析量過剩、不能確保充分的附著性的傾向。The metal replacement treatment liquid preferably contains a nickel compound with a nickel (metal nickel (Ni)) concentration of 0.1 to 12 g/L, more preferably 0.2 to 10 g/L. When it is less than 0.1 g/L, the eutectoid amount with Zn tends to decrease, and sufficient adhesion tends not to be ensured. When it exceeds 12 g/L, the eutectoid amount with Zn tends to be excessive, and sufficient adhesion tends not to be ensured.
＜＜鍺化合物＞＞ 鍺化合物若是水溶性的鍺化合物，則沒有特別限定。作為其具體例子，例如可例示二氧化鍺、硫酸鍺、硫化鍺、氟化鍺、氯化鍺、碘化鍺等。這些可以單獨使用，也可以將2種以上並用。其中較佳二氧化鍺。 此外，本說明書中，當氟化鍺等既能當鍺化合物也能當氟化合物時，視為鍺化合物。關於鋅化合物、鎳化合物也是同樣的情況，同樣視為鋅化合物、鎳化合物。 ＜＜Germanium Compounds＞＞ The germanium compound is not particularly limited as long as it is a water-soluble germanium compound. Specific examples thereof include germanium dioxide, germanium sulfate, germanium sulfide, germanium fluoride, germanium chloride, germanium iodide, and the like. These may be used individually or in combination of 2 or more types. Among them, germanium dioxide is preferred. In addition, in this specification, when germanium fluoride or the like can serve as both a germanium compound and a fluorine compound, it is regarded as a germanium compound. The same is true for zinc compounds and nickel compounds, which are also regarded as zinc compounds and nickel compounds.
金屬置換處理液較佳含有以鍺（金屬鍺（Ge））濃度計為0.1～7.0g/L的鍺化合物，更佳含有0.2～5.0g/L。若小於0.1g/L時，有與Zn的共析量降低、不能確保充分的附著性的傾向。超過7.0g/L時，有與Zn的共析量過剩、不能確保充分的附著性的傾向。The metal replacement treatment liquid preferably contains a germanium compound with a germanium (metal germanium (Ge)) concentration of 0.1 to 7.0 g/L, more preferably 0.2 to 5.0 g/L. If it is less than 0.1 g/L, the amount of eutectoid with Zn will decrease, and sufficient adhesion will tend to be unable to be ensured. If it exceeds 7.0 g/L, the amount of eutectoid with Zn will be excessive, and sufficient adhesion will tend to be unable to be ensured.
鋅濃度、鍺濃度的比率（鋅濃度：鍺濃度）較佳為1：5～5：1。The ratio of zinc concentration to germanium concentration (zinc concentration: germanium concentration) is preferably 1:5 to 5:1.
＜＜氟化合物＞＞ 氟化合物溶解鋁或鋁合金表面的氧化覆膜中的鋁，使鋅等金屬的置換順利地進行。 作為氟化合物的具體例子，例如可例示氟硼酸、氟化鈉、氟化鉀、氟化氫銨、氟化銨、氟化氫、氟化鋰等。這些可以單獨使用，也可以將2種以上並用。其中，較佳氟硼酸、氟化鈉、氟化鉀、氟化氫銨、氟化銨、氟化氫，更佳氟硼酸、氟化鈉、氟化鉀、氟化氫銨、氟化銨。 ＜＜Fluorine compounds＞＞ Fluorine compounds dissolve aluminum in the oxide film on the surface of aluminum or aluminum alloys, allowing smooth replacement of metals such as zinc. Specific examples of the fluorine compound include fluoroboric acid, sodium fluoride, potassium fluoride, ammonium bifluoride, ammonium fluoride, hydrogen fluoride, lithium fluoride, and the like. These may be used individually or in combination of 2 or more types. Among them, fluoboric acid, sodium fluoride, potassium fluoride, ammonium bifluoride, ammonium fluoride, and hydrogen fluoride are preferred, and fluoboric acid, sodium fluoride, potassium fluoride, ammonium bifluoride, and ammonium fluoride are more preferred.
金屬置換處理液較佳含有以氟（F）濃度為1.0～100g/L的氟化合物，更佳含有5.0～50g/L。小於1.0g/L時，有使鋁溶解的作用變弱、不能確保充分附著性的傾向。超過100g/L時，有鋁過多溶解、不能確保充分附著性的傾向。 此外，本說明書中，金屬置換處理液中的鋅（金屬鋅（Zn））濃度、鎳（金屬鎳（Ni））濃度、鍺（金屬鍺（Ge））濃度通過ICP（株式會社堀場製作所製）測定。 此外，本說明書中，金屬置換處理液中的氟（F）濃度使用氟離子電極測定。 The metal replacement treatment liquid preferably contains a fluorine compound with a fluorine (F) concentration of 1.0 to 100 g/L, more preferably 5.0 to 50 g/L. If it is less than 1.0 g/L, the effect of dissolving aluminum will be weakened, and sufficient adhesion will tend to be unable to be ensured. When it exceeds 100 g/L, aluminum tends to dissolve too much and sufficient adhesion may not be ensured. In addition, in this specification, the zinc (metal zinc (Zn)) concentration, nickel (metal nickel (Ni)) concentration, and germanium (metal germanium (Ge)) concentration in the metal replacement treatment liquid are determined by ICP (manufactured by Horiba Manufacturing Co., Ltd.) Determination. In addition, in this specification, the fluorine (F) concentration in the metal replacement treatment liquid is measured using a fluorine ion electrode.
＜＜pH＞＞ 金屬置換處理液的pH較佳為1.0～12.0，更佳為2.0～10.0。即，本發明的金屬置換處理液可使用鹼性、酸性中的任意種。這裡，在通常的鋅酸鹽處理中，鹼性情況時有鋁過多溶出（例如非專利文獻3的圖9）的情況，有產生鋁尖刺的傾向，酸性情況時，鋁不會過多溶出，但有不能確保充分的附著性的傾向。 另一方面，本發明的金屬置換處理液，在酸性情況時也能確保充分的附著性，因而通過採用酸性，得到更顯著的附著性改善效果。進一步地，酸性情況時，鋁不會過多溶出，也可減少鋁尖刺。不過，pH小於3.5時，有鋁過多溶出的擔憂。 因此，金屬置換處理液的pH更佳為3.5～6.5，特佳為4.0～6.5，最佳為4.5～6.5。由此，在如上所述地得到更顯著的附著性改善效果的同時，鋁不會過多溶出，也可減少鋁尖刺。這裡，鋁被過多溶出，產生鋁尖刺時，鋁表面上會產生大量的楔狀凹陷，在之後的鍍敷膜形成步驟中，例如鍍鎳進入其凹陷，形成缺乏平滑性的鍍敷膜，給導通性也帶來影響，對外觀也大有損傷。因此，通過鋁尖刺的減少，可形成平滑性高、鍍敷外觀優異的鍍敷膜。 此外，本說明書中，金屬置換處理液的pH是在25℃下測定的值。 ＜＜pH＞＞ The pH of the metal replacement treatment liquid is preferably 1.0 to 12.0, more preferably 2.0 to 10.0. That is, any of alkaline and acidic liquids can be used for the metal replacement treatment liquid of the present invention. Here, in normal zincate treatment, in alkaline conditions, aluminum may be eluted too much (for example, Figure 9 of Non-Patent Document 3), and aluminum spikes tend to be generated. In acidic conditions, aluminum will not be eluted too much. However, sufficient adhesion tends not to be ensured. On the other hand, the metal replacement treatment liquid of the present invention can ensure sufficient adhesion even in acidic conditions. Therefore, by using acidity, a more significant adhesion improvement effect can be obtained. Furthermore, in acidic conditions, aluminum will not dissolve too much, and aluminum spikes can also be reduced. However, when the pH is less than 3.5, there is a concern that aluminum may be eluted excessively. Therefore, the pH of the metal replacement treatment liquid is more preferably 3.5 to 6.5, particularly preferably 4.0 to 6.5, and most preferably 4.5 to 6.5. Accordingly, while achieving a more significant adhesion improvement effect as described above, excessive aluminum elution is prevented and aluminum spikes can be reduced. Here, when aluminum is excessively eluted and aluminum spikes are generated, a large number of wedge-shaped depressions are generated on the aluminum surface. In the subsequent plating film formation step, for example, nickel plating enters the depressions, forming a plating film that lacks smoothness. It also affects the conductivity and greatly damages the appearance. Therefore, by reducing the aluminum spikes, a plated film with high smoothness and excellent plated appearance can be formed. In this specification, the pH of the metal replacement treatment liquid is a value measured at 25°C.
金屬置換處理液的pH調整可通過鋅化合物、鎳化合物、鍺化合物、氟化合物的種類的選擇而進行。另外，根據需要，也可添加鹼成分、酸成分。 鹼成分沒有特別限定，例如可舉出氫氧化鈉，銨等。酸成分沒有特別限定，例如可舉出硫酸、磷酸等。這些鹼成分、酸成分可單獨使用，也可以將2種以上並用。 The pH of the metal replacement treatment liquid can be adjusted by selecting the type of zinc compound, nickel compound, germanium compound, or fluorine compound. In addition, alkali components and acid components may be added as necessary. The alkali component is not particularly limited, and examples thereof include sodium hydroxide, ammonium, and the like. The acid component is not particularly limited, and examples thereof include sulfuric acid, phosphoric acid, and the like. These alkali components and acid components may be used alone, or two or more types may be used in combination.
為了提高pH緩衝性，金屬置換處理液也可含有緩衝劑。 作為緩衝劑，若有緩衝性，則沒有特別限定，例如，作為在pH4.0～6.5附近具有緩衝性的化合物，例如可舉出醋酸、蘋果酸、琥珀酸、檸檬酸、丙二酸、乳酸、草酸、戊二酸、己二酸、甲酸等。這些可以單獨使用，也可以將2種以上並用。 金屬置換處理液中的緩衝劑濃度較佳為1.0～50g/L，更佳為5.0～30g/L。 In order to improve the pH buffering property, the metal replacement treatment liquid may also contain a buffering agent. The buffering agent is not particularly limited as long as it has buffering properties. For example, examples of compounds that have buffering properties around pH 4.0 to 6.5 include acetic acid, malic acid, succinic acid, citric acid, malonic acid, and lactic acid. , oxalic acid, glutaric acid, adipic acid, formic acid, etc. These may be used individually or in combination of 2 or more types. The buffer concentration in the metal replacement treatment liquid is preferably 1.0 to 50 g/L, more preferably 5.0 to 30 g/L.
＜＜其他＞＞ 金屬置換處理液可以在含有所述成分的同時含有金屬置換處理液中通用的成分，例如表面活性劑、光澤劑等。此外，還可含有上述以外的金屬，例如鐵、銅、銀、鈀、鉛、鉍、鉈等金屬的水溶性鹽類。這些可以單獨使用，也可以將2種以上並用。 ＜＜Others＞＞ The metal replacement treatment liquid may contain the above-mentioned components as well as common components in metal replacement treatment liquids, such as surfactants, gloss agents, and the like. In addition, metals other than those mentioned above, such as water-soluble salts of metals such as iron, copper, silver, palladium, lead, bismuth, and thallium, may be included. These may be used individually or in combination of 2 or more types.
金屬置換處理液可通過用溶劑（較佳水）將各成分適當混合來製造。基於操作安全性的觀點，金屬置換處理液較佳作為水溶液配製，但也可使用其他溶劑，例如甲醇、乙醇、乙二醇、二乙二醇、三乙二醇、甘油、IPA(異丙醇(isopropanol))等，或也可作為與水的混合溶劑。此外，這些溶劑可單獨使用，也可以將2種以上並用。The metal replacement treatment liquid can be produced by appropriately mixing the ingredients with a solvent (preferably water). From the viewpoint of operational safety, the metal replacement treatment solution is preferably formulated as an aqueous solution, but other solvents may also be used, such as methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, IPA (isopropyl alcohol (isopropanol)), etc., or can also be used as a mixed solvent with water. In addition, these solvents may be used individually or in combination of 2 or more types.
金屬置換處理液可作為鋁或鋁合金用的金屬置換處理液適當使用。The metal replacement treatment liquid can be suitably used as a metal replacement treatment liquid for aluminum or aluminum alloys.
＜鋁或鋁合金的表面處理方法＞ 接下來，關於使用本發明的金屬置換處理液的、本發明的鋁或鋁合金的表面處理方法進行說明。 本發明的鋁或鋁合金的表面處理方法中，進行金屬置換處理（使表面具有鋁或鋁合金的被處理物與本發明的金屬置換處理液接觸，去除所述鋁或鋁合金上的氧化膜，使所述鋁被所述金屬置換處理液所含的金屬置換），在所述被處理物的表面形成含有所述金屬的置換金屬膜。 該表面處理方法是用於對被處理物實施鍍敷膜、例如鎳鍍敷膜或鈀鍍敷膜的前處理方法，使至少在表面具有鋁或鋁合金的被處理物與本發明的金屬置換處理液接觸，去除表面附著的氧化膜，形成置換金屬膜，由此提高之後處理的鎳鍍敷膜等的附著性。 ＜Surface treatment methods for aluminum or aluminum alloys＞ Next, the surface treatment method of the aluminum or aluminum alloy of the present invention using the metal replacement treatment liquid of the present invention will be described. In the surface treatment method of aluminum or aluminum alloy of the present invention, a metal replacement treatment is performed (the object to be treated having aluminum or aluminum alloy on the surface is brought into contact with the metal replacement treatment liquid of the present invention to remove the oxide film on the aluminum or aluminum alloy , the aluminum is replaced by the metal contained in the metal replacement treatment liquid), and a replacement metal film containing the metal is formed on the surface of the object to be treated. This surface treatment method is a pretreatment method for applying a plating film, such as a nickel plating film or a palladium plating film, to an object to be treated, and replaces the object to be treated with aluminum or aluminum alloy at least on the surface with the metal of the present invention. Contact with the treatment liquid removes the oxide film attached to the surface and forms a replacement metal film, thereby improving the adhesion of the nickel plating film and the like that are processed later.
本發明的鋁或鋁合金的表面處理方法中，通過本發明的金屬置換處理液，至少在表面具有鋁或鋁合金的被處理物（以下也記作鋁基板）上附著的氧化膜被去除，通過鋅等金屬與鋁的電極電位差引起的置換反應，鋅粒子、鎳粒子、鍺粒子在被處理物的表面析出。In the surface treatment method of aluminum or aluminum alloy of the present invention, the oxide film attached to at least the object to be treated (hereinafter also referred to as aluminum substrate) having aluminum or aluminum alloy on the surface is removed by the metal replacement treatment liquid of the present invention, Due to the substitution reaction caused by the electrode potential difference between metals such as zinc and aluminum, zinc particles, nickel particles, and germanium particles are precipitated on the surface of the object to be processed.
一般，使用鋅酸鹽處理液的、對鋁基板進行的鍍前處理中，進行實施2次鋅置換處理的二次鋅酸鹽處理製程。即，是（1）對鋁基板實施第1鋅置換處理，（2）酸洗後，（3）接下來實施第2鋅置換處理這樣的製程，在該二次鋅酸鹽處理後，（4）進行無電解鍍鎳等鍍敷處理。 另一方面，使用本發明的金屬置換處理液的、本發明的鋁或鋁合金的表面處理方法中，由於能得到非常良好的附著性，因此無需進行二次鋅酸鹽處理，能通過鋅酸鹽處理而賦予良好的附著性。因此，本發明的鋁或鋁合金的表面處理方法中，較佳（1）對鋁基板實施金屬置換處理，在該單次鋅酸鹽處理後，（4）進行無電解鍍鎳等鍍敷處理。即，較佳在金屬置換處理和鍍敷處理之間不進行（2）酸洗處理、（3）酸洗處理後的第2金屬置換處理。 Generally, in the pre-plating treatment of an aluminum substrate using a zincate treatment liquid, a secondary zincate treatment process in which zinc replacement treatment is performed twice is performed. That is, it is a process in which (1) the aluminum substrate is subjected to the first zinc replacement treatment, (2) after pickling, (3) then the second zinc replacement treatment is carried out, and after the second zincate treatment, (4 ) for electroless nickel plating and other plating treatments. On the other hand, in the surface treatment method of aluminum or aluminum alloy of the present invention using the metal replacement treatment liquid of the present invention, very good adhesion can be obtained, so there is no need to perform secondary zincate treatment, and zincate treatment can be performed Salt treatment imparts good adhesion. Therefore, in the surface treatment method of aluminum or aluminum alloy of the present invention, it is preferable to (1) perform a metal replacement treatment on the aluminum substrate, and after this single zincate treatment, (4) perform a plating treatment such as electroless nickel plating . That is, it is preferable not to perform (2) the pickling process and (3) the second metal replacement process after the pickling process between the metal replacement process and the plating process.
＜＜（1）金屬置換處理＞＞ 鍍敷被處理物即鋁基板，只要至少在其表面具有鋁或鋁合金即可。鋁基板例如除了以鋁或鋁合金為材質的各種物品之外，可使用在非鋁材（例如陶瓷、晶圓等各種基材）上形成鋁或鋁合金膜而成的物品，實施了熔融鋁鍍敷處理的物品、鑄件、壓鑄物等。鋁基板的形狀也沒有特別限定，可以是成形為通常的板狀物（包括膜、片等薄膜狀物）、各種形狀的成型品中的任意種。此外，上述板狀物不限於單獨鋁或鋁合金的板狀物，也包括例如在陶瓷、晶圓等基板上通過濺射法、真空蒸鍍法、離子鍍法等通常方法成形的鋁膜（與基板一體化的膜）。 ＜＜(1) Metal replacement treatment＞＞ The object to be plated, that is, the aluminum substrate, only needs to have aluminum or an aluminum alloy at least on its surface. For example, the aluminum substrate can be used in addition to various products made of aluminum or aluminum alloys, as well as products in which aluminum or aluminum alloy films are formed on non-aluminum materials (such as various base materials such as ceramics and wafers). Plated items, castings, die-castings, etc. The shape of the aluminum substrate is not particularly limited, and it may be any of a general plate-shaped object (including thin-film-shaped objects such as films and sheets) and various shapes of molded products. In addition, the above-mentioned plate-shaped object is not limited to plate-shaped objects of aluminum or aluminum alloy alone, but also includes aluminum films formed on substrates such as ceramics and wafers by common methods such as sputtering, vacuum evaporation, and ion plating ( membrane integrated with the substrate).
作為鋁合金沒有特別限定，例如可使用以鋁為主要金屬成分的各種合金。例如，可將A1000系的准鋁、A2000系的含有銅和錳的鋁合金、A3000系的鋁-錳合金、A4000系的鋁-矽合金、A5000系的鋁-鎂合金、A6000系的鋁-鎂-矽合金、A7000系的鋁-鋅-鎂合金、A8000系的鋁-鋰系合金等作為適用對象。The aluminum alloy is not particularly limited, and for example, various alloys containing aluminum as a main metal component can be used. For example, A1000 series quasi-aluminum, A2000 series aluminum alloy containing copper and manganese, A3000 series aluminum-manganese alloy, A4000 series aluminum-silicon alloy, A5000 series aluminum-magnesium alloy, A6000 series aluminum- Magnesium-silicon alloys, A7000 series aluminum-zinc-magnesium alloys, A8000 series aluminum-lithium alloys, etc. are applicable.
基於鍍敷平滑性的觀點，鋁或鋁合金的鋁純度較佳為98％以上，更佳為98.5％以上，進一步較佳為99％以上。From the viewpoint of plating smoothness, the aluminum purity of aluminum or aluminum alloy is preferably 98% or more, more preferably 98.5% or more, and further preferably 99% or more.
鍍敷被處理物即鋁基板可通過公知的方法例如濺射法等在非鋁材、例如矽板上包覆鋁層而製作。鋁層的包覆可以是對非鋁材全部的包覆，也可以是僅對其一部分的包覆，通常包覆具有0.5μm以上、較佳1μm以上的厚度的鋁層。此外，該鋁基板的形成方法也不限於濺射法，可使用真空蒸鍍法、離子鍍法等製作。The aluminum substrate that is the object to be plated can be produced by coating a non-aluminum material, such as a silicon plate, with an aluminum layer by a known method such as sputtering. The coating of the aluminum layer may cover the entire non-aluminum material or may cover only a part of the non-aluminum material. Generally, the aluminum layer has a thickness of 0.5 μm or more, preferably 1 μm or more. In addition, the formation method of the aluminum substrate is not limited to the sputtering method, and can be produced using a vacuum evaporation method, an ion plating method, or the like.
首先，將該鋁基板用公知方法實施脫脂處理等清潔處理，適當水洗後，通過鹼或酸，實施公知的蝕刻處理。具體地，脫脂處理是通過在鋁用脫脂液中浸漬，或進行電解脫脂來進行的。此外，蝕刻處理是通過用例如約1～10％鹼溶液，或者約1～20％的酸性溶液，在約25～75℃的液溫下，在溶液中浸漬約1～15分鐘來進行的。First, the aluminum substrate is cleaned by a known method such as a degreasing process, washed appropriately with water, and then subjected to a known etching process using an alkali or an acid. Specifically, the degreasing treatment is performed by immersing in an aluminum degreasing liquid or performing electrolytic degreasing. In addition, the etching treatment is performed by immersing in an alkali solution of about 1 to 10% or an acidic solution of about 1 to 20% at a liquid temperature of about 25 to 75° C. for about 1 to 15 minutes.
接下來，以去除鹼或酸帶來的蝕刻殘渣（污物）為目的，在酸性溶液中浸漬規定時間。具體地，例如，在具有約10～800ml/L、較佳約100～600ml/L的濃度範圍，液溫為約15～35℃的硝酸水溶液中，將實施了蝕刻的鋁基板浸漬約30秒～2分鐘，去除污物。Next, in order to remove etching residue (contamination) caused by alkali or acid, it is immersed in an acidic solution for a predetermined time. Specifically, for example, the etched aluminum substrate is immersed in a nitric acid aqueous solution having a concentration 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. ~2 minutes to remove dirt.
然後，將如此實施污物處理等的鋁基板在水洗後，在本發明的金屬置換處理液（鋅酸鹽處理液）中浸漬，實施金屬置換處理。具體地，例如，在具有上述組成的、液溫為10～50℃、較佳15～30℃的鋅酸鹽處理液中浸漬鋁基板。鋅酸鹽處理液的溫度若為10℃以上，則置換反應不會太慢，不會產生斑，能夠形成金屬膜，另外，若為50℃以下，則置換反應不會過於增大，也可防止置換金屬膜表面變粗，因而較佳上述溫度。Then, the aluminum substrate subjected to the dirt treatment and the like is washed with water and then immersed in the metal replacement treatment liquid (zincate treatment liquid) of the present invention to perform the metal replacement treatment. Specifically, for example, the aluminum substrate is immersed in a zincate treatment liquid having the above composition and a liquid temperature of 10 to 50°C, preferably 15 to 30°C. If the temperature of the zincate treatment solution is 10°C or higher, the replacement reaction will not be too slow and spots will not occur, and a metal film can be formed. In addition, if the temperature is 50°C or lower, the replacement reaction will not increase too much, and it is also possible The above temperature is preferred to prevent the surface of the replacement metal film from becoming rough.
與浸漬時間有關的條件也沒有特別限定，可根據需要去除的鋁氧化膜的厚度等而適當設定，例如，通常為約5秒以上，較佳10秒以上，作為上限為5分鐘以下。浸漬時間若過短，則置換不進行，氧化膜的去除變得不充分，另一方面，浸漬時間若過長，則處理液從置換金屬層的小孔進入，有鋁或鋁合金溶出的擔憂，因而需要考慮這幾點而設定條件。The conditions related to the immersion time are not particularly limited and can be appropriately set according to the thickness of the aluminum oxide film to be removed. For example, it is usually about 5 seconds or more, preferably 10 seconds or more, and the upper limit is 5 minutes or less. If the immersion time is too short, replacement will not proceed and the removal of the oxide film will become insufficient. On the other hand, if the immersion time is too long, the treatment liquid will enter through the small holes of the replacement metal layer, and there is a concern that aluminum or aluminum alloys may dissolve. , so it is necessary to consider these points when setting conditions.
通過如此地在鋅酸鹽處理液中讓鋁基板浸漬，由此可去除其基板表面附著的氧化膜，同時進一步包覆含有Zn、Ni、Ge的置換金屬膜，使鋁表面活性化，由此，對於被處理物，可形成具有良好附著性的鍍敷膜。By immersing the aluminum substrate in the zincate treatment solution in this way, the oxide film attached to the substrate surface can be removed, and at the same time, the substitution metal film containing Zn, Ni, and Ge can be further coated to activate the aluminum surface. , can form a plating film with good adhesion to the object to be processed.
金屬置換處理中，只要是本發明的金屬置換處理液可接觸鋁基板表面的方式，就沒有特別限制。作為該接觸方法，除了浸漬外，例如可採用塗佈、噴塗等方法。In the metal replacement treatment, there is no particular limitation as long as the metal replacement treatment liquid of the present invention can contact the surface of the aluminum substrate. As the contacting method, in addition to dipping, methods such as coating and spraying can be used.
＜＜（4）鍍敷處理＞＞ 該鍍敷處理是對實施了鋅酸鹽處理的鋁基板，通過無電解鍍敷或者電解鍍敷進行的。例如，用無電解鎳、無電解鈀或銅鍍浴那樣的適合的金屬鍍敷液鍍敷為期望的最終膜厚。 ＜＜(4) Plating treatment＞＞ This plating treatment is performed by electroless plating or electrolytic plating on the zincate-treated aluminum substrate. For example, a suitable metal plating solution such as electroless nickel, electroless palladium or copper plating bath is used to achieve the desired final film thickness.
具體地，作為一例，關於無電解鍍鎳進行說明。無電解鎳鍍敷液是：例如通過使用硫酸鎳、氯化鎳、醋酸鎳等水溶性鎳鹽來提供鎳離子，作為該鎳離子的濃度，例如約為1～10g/L。此外，無電解鎳鍍敷液中，例如含有具有約20～80g/L的濃度範圍的醋酸鹽、琥珀酸鹽、檸檬酸鹽等有機酸鹽、銨鹽、胺鹽等鎳的絡合劑，還作為還原劑含有具有約10～40g/L的濃度範圍的次亞磷酸或次亞磷酸鈉等次亞磷酸鹽。通過作為還原劑含有次亞磷酸鹽等，鍍敷液的穩定性得以提高，可形成成本廉價的鎳-磷的合金膜。而且，由這些化合物構成的鍍敷液被配製成pH為約4～7而使用，還將該鍍敷液配製為60～95℃的液溫，作為鍍敷處理液中鋁基板的浸漬時間，浸漬約15秒～120分鐘，由此進行鍍敷處理。此外，通過適當地改變該鍍敷處理時間，可改變鍍敷膜的厚度。Specifically, electroless nickel plating will be described as an example. The electroless nickel plating solution uses water-soluble nickel salts such as nickel sulfate, nickel chloride, and nickel acetate to provide nickel ions, and the concentration of the nickel ions is, for example, about 1 to 10 g/L. In addition, the electroless nickel plating solution contains, for example, organic acid salts such as acetates, succinates, and citrates, and nickel complexing agents such as ammonium salts and amine salts with a concentration range of about 20 to 80 g/L. Hypophosphite such as hypophosphite or sodium hypophosphite having a concentration range of approximately 10 to 40 g/L is contained as the reducing agent. By containing hypophosphite or the like as a reducing agent, the stability of the plating solution is improved, and a low-cost nickel-phosphorus alloy film can be formed. Furthermore, a plating solution composed of these compounds is prepared and used with a pH of about 4 to 7, and the plating solution is also prepared to a liquid temperature of 60 to 95° C. as the immersion time of the aluminum substrate in the plating treatment solution. , immerse for about 15 seconds to 120 minutes, thereby performing plating treatment. In addition, by appropriately changing the plating treatment time, the thickness of the plated film can be changed.
此外，如上所述，作為鍍敷處理，不限於無電解鍍敷處理限，也可通過電解鍍敷進行。此外，鍍敷金屬的種類在以上示例之外，可使用Cu、Au等鍍敷金屬進行，還可通過置換鍍敷法等，以形成2層以上的層的方式進行鍍敷處理。In addition, as mentioned above, the plating treatment is not limited to electroless plating, and may also be performed by electrolytic plating. In addition, the type of plating metal may be other than the above examples, and plating metals such as Cu and Au may be used. The plating process may also be performed to form two or more layers by a displacement plating method or the like.
顯然，關於以上說明的鋅酸鹽處理及鍍敷處理中的處理條件，各種濃度設定，不限於以上那樣的條件，可根據形成的膜厚度等適當變更。Obviously, the treatment conditions and various concentration settings in the zincate treatment and plating treatment described above are not limited to the above conditions, and can be appropriately changed according to the thickness of the film to be formed, and the like.
本發明的鋁或鋁合金的表面處理方法中，通過進行金屬置換處理（使表面具有鋁或鋁合金的被處理物與本發明的金屬置換處理液接觸，去除所述鋁或鋁合金上的氧化膜，使所述鋁被所述金屬置換處理液所含的金屬置換），Ni、Ge與Zn一同共析，可在鋁或鋁合金表面形成含有Zn、Ni、Ge的置換金屬膜。 對表面具有含有這樣的Zn、Ni、Ge的置換金屬膜的鋁或鋁合金進行鍍敷處理，在形成鍍敷膜（金屬膜，例如鎳膜）時，在鋁或鋁合金和鍍敷膜（金屬膜，例如鎳膜）間，置換金屬膜中存在的Zn、Ni、Ge協同地發揮作用，可對鋁或鋁合金賦予與鍍敷膜（金屬膜）的良好附著性。 In the surface treatment method of aluminum or aluminum alloy of the present invention, the oxidation on the aluminum or aluminum alloy is removed by performing metal replacement treatment (making the object to be treated having aluminum or aluminum alloy on the surface come into contact with the metal replacement treatment liquid of the present invention). film, so that the aluminum is replaced by the metal contained in the metal replacement treatment liquid), Ni, Ge and Zn are eutectoided together, and a replacement metal film containing Zn, Ni, and Ge can be formed on the surface of the aluminum or aluminum alloy. When aluminum or an aluminum alloy having a replacement metal film containing Zn, Ni, or Ge on its surface is plated, and a plated film (metal film, such as a nickel film) is formed, the aluminum or aluminum alloy and the plated film ( Between metal films, such as nickel films), Zn, Ni, and Ge present in the replacement metal film work synergistically to provide aluminum or aluminum alloys with good adhesion to the plated film (metal film).
實施有通過本發明得到的鍍敷膜（金屬膜）的鋁或鋁合金，可用於各種電子部件。作為電子部件，例如可舉出用於家電機器、車載機器、供電系統、輸送機器、通信機器等的電子部件，具體可舉出空調、電梯、電動汽車、混合動力汽車、電車、發電裝置用的電源控制單元等電源模組、一般家電、個人電腦等。 本發明中，通過使金屬置換處理液的pH為4.0～6.5，可實施用於形成鋁尖刺也減少、平滑性高、鍍敷外觀優異的鍍敷膜的鍍敷前表面處理，因此，可適合用於半導體用途，較佳適合用於晶圓用途，特別地，適合作為對於在晶圓上形成凸點下金屬或凸點時的前處理有效的鋁或鋁合金上的金屬置換處理液，及使用該金屬置換處理液的鋁或鋁合金的表面處理方法。 [實施例] Aluminum or aluminum alloy coated with the plating film (metal film) obtained by the present invention can be used for various electronic components. Examples of electronic components include electronic components used in home appliances, vehicle-mounted equipment, power supply systems, transportation equipment, communication equipment, etc. Specific examples include those for air conditioners, elevators, electric vehicles, hybrid vehicles, electric trains, and power generation devices. Power modules such as power control units, general home appliances, personal computers, etc. In the present invention, by setting the pH of the metal replacement treatment liquid to 4.0 to 6.5, pre-plating surface treatment can be performed to form a plated film with reduced aluminum spikes, high smoothness, and excellent plated appearance. Therefore, it is possible to It is suitable for use in semiconductors, preferably for wafers, and is particularly suitable as a metal replacement treatment liquid on aluminum or aluminum alloys that is effective in pre-processing when forming under-bump metal or bumps on wafers. And a surface treatment method of aluminum or aluminum alloy using the metal replacement treatment liquid. [Example]
基於實施例，具體說明本發明，但本發明不僅限於這些。The present invention will be specifically described based on examples, but the present invention is not limited to these.
按照表1～3所示的條件，對鋁基板實施各處理，形成鍍敷膜。這裡，作為鋁基板，使用了1cm×2cm的Al-Cu TEG晶圓。關於得到的鍍敷膜，設有鍍敷膜的基板，用下述方法評價。評價結果如表2、3所示。 此外，表2、3中，表中的數值（濃度）是除去琥珀酸的換算為氟（F）或各金屬元素的濃度（g/L）。 According to the conditions shown in Tables 1 to 3, each treatment was performed on the aluminum substrate to form a plated film. Here, as the aluminum substrate, a 1 cm × 2 cm Al-Cu TEG wafer was used. The obtained plated film was evaluated by the following method on a substrate provided with the plated film. The evaluation results are shown in Tables 2 and 3. In addition, in Tables 2 and 3, the numerical values (concentrations) in the tables are converted into fluorine (F) or the concentration (g/L) of each metal element excluding succinic acid.
＜附著性評價：彎折切割試驗＞ 關於設有得到的鍍敷膜的基板，進行氣流乾燥，在鍍敷面貼透明膠帶。然後，在貼膠帶的晶圓中央部劃上刻痕，切割為兩半。從切割的中央部剝離膠帶，將Al基底與Ni膜間剝離的量作為100分率求出。此外，彎折切割試驗的概要如圖1所示。 0％是指剝離膠帶時鍍敷膜完全沒有剝離，100％是指剝離膠帶時鍍敷膜整面剝離。 ＜Adhesion evaluation: bending and cutting test＞ The substrate provided with the obtained plated film was air-dried, and a transparent tape was attached to the plated surface. Then, a score is scored in the center of the taped wafer and cut into two halves. The tape was peeled off from the cut center part, and the amount of peeling between the Al base and the Ni film was calculated as a fraction of 100. In addition, the outline of the bending and cutting test is shown in Figure 1. 0% means that the plated film is not peeled off at all when the tape is peeled off, and 100% means that the entire surface of the plated film is peeled off when the tape is peeled off.
＜鋁（Al）尖刺評價＞ 對於得到的鍍敷膜，用日立高新技術公司製的XVision 210DB，進行FIB（集束離子束）截面觀察。圖2（a）顯示未見Al尖刺時的一例，圖2（b）顯示可見Al尖刺時的一例。如圖2（a），未見Al尖刺時，判斷為良好。 ＜Aluminum (Al) Spike Evaluation＞ The obtained plated film was subjected to FIB (clustered ion beam) cross-sectional observation using XVision 210DB manufactured by Hitachi High-Technology Corporation. Figure 2(a) shows an example when Al spikes are not seen, and Figure 2(b) shows an example when Al spikes are visible. As shown in Figure 2(a), when no Al spikes are seen, it is judged to be good.
[表1]
[表2]
從表2、3可知，含有鋅化合物、鎳化合物、鍺化合物、氟化合物的實施例的金屬置換處理液可賦予與鍍敷膜（金屬膜）的良好附著性。此外可知，通過使金屬置換處理液的pH為3.5～6.5，鋁尖刺也可減少。此外，表2、3雖然是作為鋁基板使用Al-Cu TEG晶圓時的結果，但作為鋁基板使用．Al-Si TEG晶圓時也是同樣的結果。As can be seen from Tables 2 and 3, the metal replacement treatment liquid of the Example containing a zinc compound, a nickel compound, a germanium compound, and a fluorine compound can provide good adhesion to a plating film (metal film). Furthermore, it was found that aluminum spikes can also be reduced by setting the pH of the metal replacement treatment liquid to 3.5 to 6.5. In addition, Tables 2 and 3 are the results when Al-Cu TEG wafer is used as the aluminum substrate. The same results are obtained for Al-Si TEG wafers.
無without
[圖1] 是顯示彎折切割試驗的概要的模式圖。 [圖2] （a）是表示未見Al尖刺的情況的一例的照片。（b）是表示可見Al尖刺的情況的一例的照片。 [Fig. 1] is a schematic diagram showing an outline of the bending and cutting test. [Fig. 2] (a) is a photograph showing an example in which Al spikes are not seen. (b) is a photograph showing an example in which Al spikes are visible.
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