CN101029397B - 表面处理剂和使用了该表面处理剂的皮膜形成方法 - Google Patents
表面处理剂和使用了该表面处理剂的皮膜形成方法 Download PDFInfo
- Publication number
- CN101029397B CN101029397B CN2007100844607A CN200710084460A CN101029397B CN 101029397 B CN101029397 B CN 101029397B CN 2007100844607 A CN2007100844607 A CN 2007100844607A CN 200710084460 A CN200710084460 A CN 200710084460A CN 101029397 B CN101029397 B CN 101029397B
- Authority
- CN
- China
- Prior art keywords
- surface treatment
- treatment agent
- copper
- epithelium
- quality
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 title abstract description 7
- 239000011248 coating agent Substances 0.000 title abstract 2
- 238000000576 coating method Methods 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 150000005846 sugar alcohols Chemical class 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 11
- 239000012756 surface treatment agent Substances 0.000 claims description 76
- 210000000981 epithelium Anatomy 0.000 claims description 59
- 239000002253 acid Substances 0.000 claims description 19
- 150000004693 imidazolium salts Chemical class 0.000 claims description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000000811 xylitol Substances 0.000 claims description 7
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 7
- 235000010447 xylitol Nutrition 0.000 claims description 7
- 229960002675 xylitol Drugs 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 229910001020 Au alloy Inorganic materials 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001431 copper ion Inorganic materials 0.000 abstract description 7
- -1 imidazole compound Chemical class 0.000 abstract description 7
- 239000010808 liquid waste Substances 0.000 abstract description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000463 material Substances 0.000 description 19
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000005476 soldering Methods 0.000 description 12
- 239000011135 tin Substances 0.000 description 12
- 229910052737 gold Inorganic materials 0.000 description 11
- 229910052718 tin Inorganic materials 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 6
- 239000005017 polysaccharide Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 150000002500 ions Chemical group 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 229960002920 sorbitol Drugs 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000003352 sequestering agent Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- FHHCKYIBYRNHOZ-UHFFFAOYSA-N 2,5-diphenyl-1h-imidazole Chemical compound C=1N=C(C=2C=CC=CC=2)NC=1C1=CC=CC=C1 FHHCKYIBYRNHOZ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NAPDOWNULRULLI-UHFFFAOYSA-N 2-benzyl-1h-imidazole Chemical compound C=1C=CC=CC=1CC1=NC=CN1 NAPDOWNULRULLI-UHFFFAOYSA-N 0.000 description 1
- JDLHQBAZAFNBPQ-UHFFFAOYSA-N 2-benzyl-5-methyl-1h-imidazole Chemical compound CC1=CNC(CC=2C=CC=CC=2)=N1 JDLHQBAZAFNBPQ-UHFFFAOYSA-N 0.000 description 1
- ZUKYCLYMFNPDCT-UHFFFAOYSA-N 2-cyclohexyl-1h-benzimidazole Chemical class C1CCCCC1C1=NC2=CC=CC=C2N1 ZUKYCLYMFNPDCT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- JQEVCCUJHLRAEY-UHFFFAOYSA-N 5-methyl-2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=C(C)N1 JQEVCCUJHLRAEY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-DCSYEGIMSA-N Beta-Lactose Chemical compound OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-DCSYEGIMSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 102000004377 Thiopurine S-methyltransferases Human genes 0.000 description 1
- 108090000958 Thiopurine S-methyltransferases Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- YTLQFZVCLXFFRK-UHFFFAOYSA-N bendazol Chemical compound N=1C2=CC=CC=C2NC=1CC1=CC=CC=C1 YTLQFZVCLXFFRK-UHFFFAOYSA-N 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- KDPAWGWELVVRCH-UHFFFAOYSA-N bromoacetic acid Chemical compound OC(=O)CBr KDPAWGWELVVRCH-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
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000012538 light obscuration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000009997 thermal pre-treatment Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009736 wetting Methods 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of 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
- C23C20/00—Chemical coating by decomposition of either solid compounds or suspensions of the coating forming compounds, without leaving reaction products of surface material in the coating
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
- C23F11/122—Alcohols; Aldehydes; Ketones
-
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
本发明提供的表面处理剂是铜或铜合金的表面处理剂,其含有咪唑化合物和糖醇。根据本发明的表面处理剂,因为溶解在表面处理剂中的铜离子和糖醇结合,所以可以抑制向异种金属上形成皮膜。另外,因为使用糖醇,所以废液处理变得容易,并且可以减轻环境负荷。
Description
技术领域
本发明涉及铜或铜合金的表面处理剂和使用了该表面处理剂的皮膜形成方法。
背景技术
一直以来,作为为了由铜或铜合金(以下也简单称为“铜”)构成的电路布线的防锈和锡焊焊接性的提高而形成皮膜的表面处理剂,已知的有含有苯并咪唑等咪唑化合物的OSP(水溶性预焊剂,preflux)(例如,参照特开平7-54169号公报、特开平5-237688号公报、特开平5-163585号公报、特开平11-177218号公报)。
另一方面,对于印刷线路板来说,有时在铜配线上共存有金、银、铝、锡、焊锡等铜以外的金属(以下也称为“异种金属”)。若以含有上述那样的咪唑化合物的水溶性预焊剂处理,则有在异种金属上也形成皮膜、产生变色等不良情况的担心。
作为在异种金属上形成皮膜的原因,据认为是,在以上述水溶性预焊剂处理时,从铜表面溶解在水溶性预焊剂液中的铜离子以氧化物和氢氧化物的形式附着在异种金属上,该附着在异种金属上的铜和咪唑化合物结合而形成皮膜。
为了解决上述问题,提出了将从基板溶解在表面处理剂中的铜离子螯合化、从而防止铜离子附着到异种金属上的技术方案(例如,参照特开昭52-72342号公报、特开平6-81161号公报、特开平9-291372号公报)。
但是,对于在特开昭52-72342号公报、特开平6-81161号公报、特开平9-291372号公报中记载的方法来说,因为使用了在废液处理时处理方法繁杂的螯合剂,所以有环境负荷变高的可能性。另外,在上述公报中记载的螯合剂因为阻碍在铜上形成皮膜,所以对于上述公报中记载的方法来说,有锡焊焊接性下降的担心。
发明内容
本发明提供一种表面处理剂和使用了该表面处理剂的皮膜形成方法,该表面处理剂可以在不阻碍向铜上形成皮膜的情况下抑制向异种金属上形成皮膜,并且可以降低环境负荷。
本发明的表面处理剂是铜或铜合金的表面处理剂,其含有咪唑化合物和糖醇。
本发明的皮膜形成方法是使有铜或铜合金和铜以外的金属共存的基板表面与表面处理剂接触,从而在上述铜或铜合金上形成皮膜的皮膜形成方法,其中上述表面处理剂是上述本发明的表面处理剂。
具体实施方式
本发明的表面处理剂例如以为了防锈和锡焊焊接性的提高等而在形成配线的铜表面上形成皮膜的目的而加以使用。上述表面处理剂含有成为所形成的皮膜的主要成分的咪唑化合物、和与溶解在上述表面处理剂中的铜离子结合的糖醇。由此,可以抑制向异种金属上形成皮膜,而且因为使用了糖醇,所以与使用以往的螯合剂的表面处理剂相比,废液处理变得容易,并且可以降低环境负荷。另外,当将上述表面处理剂作为水溶性预焊剂使用时,即使在回流(reflow)等高温处理工序后、锡焊焊接性也不降低,可以形成耐热性高的皮膜。
上述表面处理剂例如可以通过使咪唑化合物和糖醇溶解在溶剂中而配制。作为溶剂,可以使用离子交换水、纯水、超纯水等水;有机酸、无机酸等酸;和水溶性有机溶剂等。在使用酸或水溶性有机溶剂作为溶剂时,可以促进咪唑化合物的溶解。
上述咪唑化合物没有特别的限定,例如可以使用2-丙基苯并咪唑、2-环己基苯并咪唑、2-苯基苯并咪唑、2-苄基苯并咪唑、2-(3-苯丙基)-5-甲基苯并咪唑、2-(巯甲基)苯并咪唑、2-(1-萘甲基)苯并咪唑、2-(5’-苯基)戊基苯并咪唑、2-苯乙基苯并咪唑等苯并咪唑化合物;2,4-二苯基-5-甲基咪唑、2-戊基咪唑、2-十一烷基-4-甲基咪唑、2,4-二甲基咪唑、2,4-二苯基咪唑、2,4,5-三苯基咪唑、2-苄基咪唑、2-苄基-4-甲基咪唑等咪唑化合物等。另外,本发明的表面处理剂可以含有2种以上的这些咪唑化合物。
上述表面处理剂中的咪唑化合物的浓度优选是0.01~5质量%、更优选是0.05~1质量%。咪唑化合物的浓度小于0.01质量%时,有皮膜不能形成的可能性。另一方面,咪唑化合物的浓度大于5质量%时,有时产生咪唑化合物的沉淀物。
关于上述糖醇也没有特别的限定,可以使用甘露糖醇、山梨糖醇、木糖醇、赤藓醇、麦芽糖醇、乳糖醇等单糖醇,蔗糖等二糖醇、低聚糖醇等多糖醇等。其中,甘露糖醇、山梨糖醇和木糖醇因为价格低、容易得到而是优选的。另外,本发明的表面处理剂可以含有2种以上的这些糖醇。
上述表面处理剂中的糖醇浓度优选是0.01~7质量%,更优选是0.05~4质量%,最优选是0.1~1质量%。糖醇的浓度小于0.01质量%时,有抑制向异种金属上形成皮膜的效果降低的担心。另一方面,糖醇的浓度大于7质量%时,看不到更高的效果从而有变得不经济的可能性。
本发明的表面处理剂含有有机酸时,作为可以使用的有机酸的具体例子,可以列举出甲酸、乙酸、丙酸、羟基乙酸、正丁酸、异丁酸、丙烯酸、丁烯酸、异丁烯酸、乙二酸、丙二酸、丁二酸、己二酸、马来酸、乙炔二羧酸、一氯醋酸、三氯醋酸、一溴醋酸、乳酸、羟基丁酸,甘油酸、酒石酸、苹果酸、柠檬酸、庚酸、己酸以及将它们之中2种以上混合而得到的酸。从经济性的观点出发,优选选自甲酸和乙酸之中的至少之一。上述表面处理剂中的有机酸浓度优选是1~80质量%,更优选是1.5~45质量%,最优选是3~30质量%。有机酸的浓度小于1质量%时,有时产生咪唑化合物的沉淀物。另一方面,有机酸的浓度大于80质量%时,有变得难以形成皮膜的可能性。
本发明的表面处理剂含有无机酸时,作为可以使用的无机酸的具体例子,可以列举出盐酸、硫酸、硝酸、磷酸和将它们之中的2种以上混合而得到的酸等。上述表面处理剂中的无机酸的浓度优选是1~80质量%,更优选是1.5~30质量%,最优选是3~15质量%。无机酸的浓度小于1质量%时,有时产生咪唑化合物的沉淀物。另一方面,无机酸的浓度大于80质量%时,有变得难以形成皮膜的可能性。
本发明的表面处理剂含有水溶性有机溶剂时,作为可以使用的水溶性有机溶剂的具体例子,可以列举出甲醇、乙醇、2-丙醇、乙二醇单甲醚、乙二醇单乙醚等。上述表面处理剂中的水溶性有机溶剂的浓度优选是1~80质量%,更优选是1.5~30质量%,最优选是3~15质量%。水溶性有机溶剂的浓度小于1质量%时,有时产生咪唑化合物的沉淀物。另一方面,无机酸的浓度大于80质量%时,有变得难以形成皮膜的可能性。
本发明的表面处理剂的使用方法没有特别的限定,例如可以通过浸渍法、喷雾法等使用。特别是当使用浸渍法时,因为可以更均匀地形成皮膜而是优选的。当通过浸渍法使用时,从皮膜形成性的观点出发,优选将浸渍时间设定为15~120秒,更优选设定为30~90秒。另外,从皮膜形成性的观点出发,上述表面处理剂的使用温度优选为10~45℃的范围,更优选为25~35℃的范围。另外,在本发明的表面处理剂中,除了上述例示的成分以外,根据需要还可以配合皮膜形成用辅助剂、溶解稳定剂等添加剂。
在利用装置使用本发明的表面处理剂时,例如,既可以将上述表面处理剂的全部成分配制成预定的组成后供给装置,或者也可以将各成分单独地供给装置、在装置内混合上述各成分、从而配制成为预定的组成。另外,在将上述表面处理剂的各成分供给装置时,上述各成分的浓度没有特别的限定,例如,可以将高浓度的上述各成分供给装置,在装置内用酸或水稀释,从而配制为预定的浓度。
另外,在用于在铜上形成防锈皮膜的表面处理剂中,为了易于形成皮膜的目的而有时添加铜离子,但是在有异种金属共存的印刷线路板的情况下,当添加铜离子时,在异种金属上也能形成皮膜,所以不能添加铜离子而使得有可能变得在铜表面难以形成皮膜。在本发明的表面处理剂中,由于糖醇的作用,即使不添加铜离子,也不会降低铜表面的皮膜形成性。
本发明的皮膜形成方法是使有铜或铜合金和铜以外的金属共存的基板表面与表面处理剂接触,从而在上述铜或铜合金上形成皮膜的皮膜形成方法,其中上述表面处理剂是上述的本发明的表面处理剂。根据本发明的皮膜形成方法,因为如上述那样,溶解在表面处理剂中的铜离子和糖醇结合,所以可以在不阻碍向铜上形成皮膜的情况下抑制向铜以外的金属(异种金属)上形成皮膜。特别是在异种金属为金或金合金时,可以使本发明的功能有效地发挥。另外,因为使用了糖醇,所以废液处理变得容易,并且可以减轻环境负荷。另外,使基板表面与表面处理剂接触的具体方法,与上述的本发明的表面处理剂的使用方法相同。
(实施例)
以下,就本发明的表面处理剂的实施例连同比较例一并进行说明。另外,本发明不限于下述的实施例。
实验1(在异种金属上形成的皮膜量的评价)
首先,在离子交换水中加入0.1质量%的2-(1-萘甲基)苯并咪唑和5.25质量%的甲酸、和表1中所示的浓度的木糖醇,从而配制成实施例1~12的表面处理剂。另外,作为比较例1,除了不加入木糖醇以外,制备与实施例1~12同样地配制的表面处理剂。
接着,制备在玻璃环氧基材(日立化成工业生产、GEA-67N、厚度:1.6mm)的两面贴附了厚度为18μm的铜箔而得到的两面铜箔叠层板(4cm×4cm),在两面铜箔上形成厚度为0.5μm的镀镍膜,再在该镀镍膜上形成厚度为0.05μm的镀金膜,从而制作成被处理材料。接着,将该被处理材料分别在实施例1~12和比较例1的表面处理剂中浸渍各1片,浸渍60秒钟后,进行水洗、干燥。此时,分如下两种情况进行:在各表面处理剂中以铜离子浓度计添加30mg/L的醋酸铜;和不添加醋酸铜。另外,表面处理剂的温度都设定为30℃。接着,在35质量%盐酸和甲醇的混合液(质量比是盐酸∶甲醇=0.5∶99.5)中将干燥后的被处理材料浸渍5分钟,使在金上附着的皮膜成分溶解在上述混合液中。然后,对溶解了皮膜成分的上述混合液进行抽样,以紫外可见吸光分光光度计测定2-(1-萘甲基)苯并咪唑的吸收峰(277nm)的吸光度。然后,以比较例1的不添加铜离子时的吸光度为1,算出使用其它表面处理剂时的吸光度的相对值,从该值评价金上的皮膜量。将结果示于表1中。
表1
实施例1~12不但没有目测观察的外观不良,而且如表1所示,与比较例1相比,吸光度小(即金上的皮膜量少),由此可知,可以抑制向金上形成皮膜。特别是在木糖醇浓度为0.05~4质量%的实施例3~10中,由目测观察的外观良好,即使在添加30mg/L铜离子时,也可以有效地抑制向金上形成皮膜。
实验2(表面处理剂中的铜离子浓度和皮膜量的关系)
首先,在离子交换水中加入0.3质量%的2-甲基苯并咪唑和4.5质量%的醋酸及0.5质量%的D-山梨糖醇,再添加醋酸铜以达到在表2中所示的铜离子浓度,从而配制成实施例13~20的表面处理剂。另外,作为比较例,分别制备除了不添加D-山梨糖醇以外、其它分别与实施例13~20同样地配制的比较例2~9的表面处理剂。然后,分别针对实施例13~20和比较例2~9,与上述实验1同样地处理被处理材料,以与上述实验1同样的方法评价金上的皮膜量。将结果示于表2中。
表2
铜离子浓度(mg/L) | 吸光度(相对值) | |
实施例13 | 0 | 0.44 |
实施例14 | 5 | 0.48 |
实施例15 | 10 | 0.44 |
实施例16 | 20 | 0.56 |
实施例17 | 30 | 0.52 |
实施例18 | 50 | 0.76 |
实施例19 | 75 | 1.12 |
实施例20 | 100 | 1.60 |
比较例2 | 0 | 1.00 |
比较例3 | 5 | 1.24 |
比较例4 | 10 | 1.40 |
比较例5 | 20 | 1.56 |
比较例6 | 30 | 1.60 |
比较例7 | 50 | 1.84 |
比较例8 | 75 | 2.08 |
比较例9 | 100 | 1.80 |
如表2所示,实施例13~20分别与对应的比较例2~9相比,即使铜离子浓度变高,金上的皮膜量也少,由此可知,可以抑制向金上形成皮膜。
从以上的结果可知,根据本发明的表面处理剂、可以抑制向异种金属上形成皮膜。另外,如变更咪唑化合物并同样地评价金上的皮膜量的表3中所示,和如变更糖醇并同样地评价金上的皮膜量的表4中所示,在本发明的表面处理剂中,不论咪唑化合物的种类和糖醇的种类如何,均可以使上述效果得以发挥。另外,在表3中都对以铜离子浓度计添加了30mg/L的醋酸铜的情况测定吸光度,将不添加糖醇的情况作为空白(吸光度:1)而评价皮膜量。另外,在表4中,针对使用0.1质量%的2-(5’-苯基)戊基苯并咪唑和4.5质量%的醋酸的体系,改变糖醇的种类而评价皮膜量。
表3
使用的咪唑化合物 | 使用的酸 | 吸光度(相对值) | |
实施例21 | 2-(1-萘甲基)苯并咪唑(0.3质量%) | 甲酸(5.25质量%) | 0.29 |
实施例22 | 2-(5’-苯基)戊基苯并咪唑(0.3质量%) | 乙酸(4.5质量%) | 0.30 |
实施例23 | 2,4-二苯基-5-甲基咪唑(0.3质量%) | 乙酸(4.5质量%) | 0.50 |
实施例24 | 2-苯乙基苯并咪唑(0.3质量%) | 乙酸(4.5质量%) | 0.48 |
表4
实验3(锡焊焊接性提高效果的确认)
首先,在离子交换水中加入0.3质量%的2-(5’-苯基)戊基苯并咪唑和4.5质量%的醋酸以及在表5中所示的糖醇,从而配制成实施例35~44的表面处理剂。另外,作为比较例11,制备除了不添加糖醇以外、与实施例35~44同样地配制的表面处理剂。
接着,制备在玻璃环氧基材(日立化成工业生产、GEA-67N、厚度:1.6mm)的两面贴附了厚度为18μm的铜箔的两面铜箔叠层板(7.8cm×4.8cm),在其上形成160个直径为0.8mm的贯通孔,从而制作成被处理材料。接着,将该被处理材料在MECBRITE CB-801(MEC株式会社生产、微蚀剂)中浸渍,将铜箔表面蚀刻仅1μm,并进行水洗后,分别在实施例35~44和比较例11的表面处理剂中浸渍各1片,浸渍60秒钟后,进行水洗、干燥。另外,表面处理剂的温度都设定为30℃。接着,针对干燥后的各被处理材料,分别进行1~4次回流处理。在回流处理中使用热风循环型回流炉,在1次回流处理时,以被处理材料的表面温度达到240~245℃的温度加热40秒。接着,通过喷雾器对被处理材料进行后焊剂(post-flux)处理。作为后焊剂,使用株式会社朝日化学研究所生产的AGF-880。此后,进行流动处理。在流动处理中,首先,以被处理材料的表面温度达到100℃的温度加热80秒作为预热处理后,以焊锡温度成为255℃的条件进行双波处理(double-wave process)。此时,使用的焊锡的质量比(Sn∶Ag∶Cu)是96.5∶3∶0.5。另外,在本实验中的双波处理中,使被处理材料和焊锡接触2.5秒后,间隔2.5秒、再次进行使被处理材料和焊锡接触3秒的处理。然后,分别对上述被处理材料确认锡焊焊接不良率。将结果示于表5中。表5的锡焊焊接不良率是160个贯通孔中发生锡焊焊接不良的贯通孔比例。另外,所谓本实验中的锡焊焊接不良,是指通过目测观察可以确认焊锡在贯通孔内没有完全填充的情况。
表5
如在表5中所示,对于实施例35~44来说,相比于比较例11,可以降低锡焊焊接不良率。从以上的结果可知,根据本发明的表面处理剂,可以形成耐热性高的皮膜。
实验4(焊锡润湿性提高效果的确认)
首先,在离子交换水中加入0.3质量%的2-(5’-苯基)戊基苯并咪唑和4.5质量%的醋酸及在表6中所示的糖醇,从而配制成实施例45~54的表面处理剂。另外,作为比较例12,制备除了不添加糖醇以外、与实施例45~54同样地配制的表面处理剂。
接着,制备在玻璃环氧基材(日立化成工业生产、GEA-67N、厚度:1.6mm)的单面贴附了厚度为18μm的铜箔的单面铜箔叠层板,在其上形成40个0.3mm×8mm的矩形状的导体图案的贯通孔,从而制作成被处理材料。接着,将该被处理材料在MECBRITE CB-801(MEC株式会社生产、微蚀剂)中浸渍,将铜箔表面蚀刻仅1μm,并进行水洗后,分别在实施例45~54和比较例12的表面处理剂中浸渍各1片,浸渍60秒钟后,进行水洗、干燥。另外,表面处理剂的温度都设定为30℃。此后,在上述导体图案上的中央部分印刷焊膏(SOLDER COAT公司生产、TAS650S10/011/M9.5)。此时,使印刷图案为圆形状。另外各印刷图案的直径是0.4mm、厚度是100μm。印刷后,使用与上述实验3同样的回流炉,以被处理材料的表面温度达到225~230℃的温度加热40秒。然后,对通过该回流处理而蔓延的焊锡区域(40个),以显微镜分别测量最长直径的长度,算出其平均值。结果示于表6中。
表6
使用的糖醇 | 焊锡蔓延的区域的直径平均值(mm) | |
实施例45 | D-山梨糖醇(0.3质量%) | 2.20 |
实施例46 | 木糖醇(0.3质量%) | 2.13 |
实施例47 | D-甘露糖醇(0.3质量%) | 2.05 |
实施例48 | Amarutei MR20(东和化成工业公司生产、二糖醇、0.3质量%) | 2.00 |
实施例49 | Resisu(东和化成工业公司生产、二糖醇、0.3质量%) | 1.99 |
实施例50 | PO-10(东和化成工业公司生产、多糖醇、0.3质量%) | 2.08 |
实施例51 | PO-20(东和化成工业公司生产、多糖醇、0.3质量%) | 1.89 |
实施例52 | PO-40(东和化成工业公司生产、多糖醇、0.3质量%) | 1.95 |
实施例53 | PO-300(东和化成工业公司生产、多糖醇、0.3质量%) | 2.11 |
实施例54 | Amamiru(东和化成工业公司生产、多糖醇、0.3质量%) | 1.91 |
比较例12 | 无 | 1.63 |
如表6所示,与比较例12相比,实施例45~54之中的任意一个焊锡浸润性都提高了。
Claims (9)
1.一种铜或铜合金的表面处理剂,其含有咪唑化合物和糖醇,还含有选自无机酸和有机酸之中的至少之一。
2.如权利要求1所述的表面处理剂,所述糖醇的含量为0.01~7质量%的范围。
3.如权利要求1或2所述的表面处理剂,所述糖醇是选自甘露糖醇、山梨糖醇和木糖醇之中的至少之一。
4.如权利要求1所述的表面处理剂,所述选自无机酸和有机酸之中的至少之一的浓度是1~80质量%。
5.如权利要求1、2或4所述的表面处理剂,所述有机酸是选自甲酸和乙酸之中的至少之一。
6.一种皮膜形成方法,其是使有铜或铜合金和铜以外的金属共存的基板表面与表面处理剂接触,从而在所述铜或铜合金上形成皮膜,其中所述表面处理剂是权利要求1~5的任一项所述的表面处理剂。
7.如权利要求6所述的皮膜形成方法,其中所述铜以外的金属是金或金合金。
8.如权利要求6所述的皮膜形成方法,其中使所述基板表面与所述表面处理剂接触的方法是将所述基板表面浸渍在所述表面处理剂中。
9.如权利要求8所述的皮膜形成方法,所述浸渍的时间是15~120秒,所述浸渍所用的所述表面处理剂的温度是10~45℃。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006058108 | 2006-03-03 | ||
JP058108/2006 | 2006-03-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101029397A CN101029397A (zh) | 2007-09-05 |
CN101029397B true CN101029397B (zh) | 2011-04-13 |
Family
ID=38090310
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2007100844607A Expired - Fee Related CN101029397B (zh) | 2006-03-03 | 2007-03-02 | 表面处理剂和使用了该表面处理剂的皮膜形成方法 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1829987A3 (zh) |
KR (1) | KR20070090808A (zh) |
CN (1) | CN101029397B (zh) |
TW (1) | TW200741031A (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101008373B1 (ko) * | 2009-11-26 | 2011-01-13 | 주식회사 엘지화학 | 포토레지스트 스트리퍼 조성물 및 이를 이용한 포토레지스트 박리방법 |
KR101679030B1 (ko) * | 2009-12-16 | 2016-11-23 | 주식회사 동진쎄미켐 | 레지스트 제거용 조성물 |
CN101982288B (zh) * | 2010-09-30 | 2013-04-24 | 深圳市成功科技有限公司 | 一种具有选择性成膜的有机铜保焊剂及其使用方法 |
CN103698442B (zh) * | 2013-12-30 | 2015-04-08 | 上海微谱化工技术服务有限公司 | 金属表面处理剂中丙二酸的定量方法 |
CN104060260B (zh) * | 2014-05-29 | 2016-09-21 | 合肥奥福表面处理科技有限公司 | 一种增强铜质水龙头耐磨性的方法 |
CN109082667B (zh) * | 2016-12-25 | 2021-09-21 | 吴彬 | 一种金属缓蚀剂 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4772645A (en) * | 1986-05-07 | 1988-09-20 | Minnesota Mining And Manufacturing Company | Epoxy resin composition |
JP2005208329A (ja) * | 2004-01-22 | 2005-08-04 | Parker Corp | レジスト現像液および当該レジスト現像液を用いた半導体装置の製造方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6036477B2 (ja) * | 1977-06-27 | 1985-08-20 | デイツプソ−ル株式会社 | 銅および銅合金のアルカリ脱脂液 |
JP2906590B2 (ja) * | 1990-06-14 | 1999-06-21 | 三菱瓦斯化学株式会社 | アルミニウム配線半導体基板の表面処理剤 |
JP3277025B2 (ja) * | 1993-05-10 | 2002-04-22 | 四国化成工業株式会社 | 銅及び銅合金の表面処理剤 |
JP3547028B2 (ja) * | 1996-02-26 | 2004-07-28 | 四国化成工業株式会社 | 銅及び銅合金の表面処理剤 |
US6720264B2 (en) * | 1999-11-04 | 2004-04-13 | Advanced Micro Devices, Inc. | Prevention of precipitation defects on copper interconnects during CMP by use of solutions containing organic compounds with silica adsorption and copper corrosion inhibiting properties |
TWI295076B (en) * | 2002-09-19 | 2008-03-21 | Dongwoo Fine Chem Co Ltd | Washing liquid for semiconductor substrate and method of producing semiconductor device |
TW200428512A (en) * | 2003-05-02 | 2004-12-16 | Ekc Technology Inc | Reducing oxide loss when using fluoride chemistries to remove post-etch residues in semiconductor processing |
US20050077502A1 (en) * | 2003-10-09 | 2005-04-14 | Munie Gregory C. | Surface reactive preservative for use with solder preforms |
US20050089489A1 (en) * | 2003-10-22 | 2005-04-28 | Carter Melvin K. | Composition for exfoliation agent effective in removing resist residues |
US20050230354A1 (en) * | 2004-04-14 | 2005-10-20 | Hardikar Vishwas V | Method and composition of post-CMP wetting of thin films |
JP2006016438A (ja) * | 2004-06-30 | 2006-01-19 | Dongwoo Fine-Chem Co Ltd | 電子部品洗浄液 |
EP1628336B1 (en) * | 2004-08-18 | 2012-01-04 | Mitsubishi Gas Chemical Company, Inc. | Cleaning liquid and cleaning method |
-
2007
- 2007-03-02 KR KR1020070020833A patent/KR20070090808A/ko not_active Application Discontinuation
- 2007-03-02 CN CN2007100844607A patent/CN101029397B/zh not_active Expired - Fee Related
- 2007-03-02 TW TW096107148A patent/TW200741031A/zh unknown
- 2007-03-05 EP EP07004489A patent/EP1829987A3/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4772645A (en) * | 1986-05-07 | 1988-09-20 | Minnesota Mining And Manufacturing Company | Epoxy resin composition |
JP2005208329A (ja) * | 2004-01-22 | 2005-08-04 | Parker Corp | レジスト現像液および当該レジスト現像液を用いた半導体装置の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1829987A3 (en) | 2009-04-22 |
EP1829987A2 (en) | 2007-09-05 |
CN101029397A (zh) | 2007-09-05 |
KR20070090808A (ko) | 2007-09-06 |
TW200741031A (en) | 2007-11-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101029397B (zh) | 表面处理剂和使用了该表面处理剂的皮膜形成方法 | |
JPH08255968A (ja) | プリント回路板の製造 | |
CN101962776A (zh) | 退锡剂及其制备方法 | |
CN108396325B (zh) | 一种水溶性可焊镍保护剂 | |
KR20020040788A (ko) | 구리 기판의 선택적 침착방법 | |
CN101697662B (zh) | 一种高抗热性有机保焊剂 | |
KR101366938B1 (ko) | 에칭액 및 이를 이용한 인쇄 배선 기판의 제조방법 | |
DE10066028C2 (de) | Kupfersubstrat mit aufgerauhten Oberflächen | |
KR101616731B1 (ko) | 금속 표면 처리 수용액 및 금속 표면상의 휘스커 억제방법 | |
CN107971655B (zh) | 一种高抗热性有机保焊剂及其应用 | |
JP4242915B2 (ja) | 銅表面処理剤及び表面処理方法 | |
CN101348913B (zh) | 表面处理剂 | |
US4964920A (en) | Method of removing deposits of tin, lead or tin/lead alloys from copper substrates and compositions for use therein | |
CN101780614B (zh) | 可作有机保焊剂的咪唑衍生物溶液 | |
US20080200360A1 (en) | Aqueous Solution and Method for Removing Ionic Contaminants from the Surface of a Workpiece | |
CA2326049A1 (en) | Method for coating surfaces of copper or of a copper alloy with a tin or tin alloy layer | |
DE10226328B3 (de) | Saure Lösung zur Silberabscheidung und Verfahren zum Abscheiden von Silberschichten auf Metalloberflächen | |
JP4395148B2 (ja) | レジスト剥離剤 | |
JP5985368B2 (ja) | 銅または銅合金の表面処理液及びその利用 | |
KR101494618B1 (ko) | 인쇄회로기판용 화성처리 조성물 및 이를 이용한 화성처리 방법 | |
JP4065110B2 (ja) | 銅または銅合金の表面処理法およびプリント配線板の製造法 | |
JPH04231473A (ja) | スズ−鉛浸漬メッキ用の予備処理組成物と方法 | |
JP4968909B2 (ja) | 表面処理剤 | |
JPS61261484A (ja) | 過酸化水素−硫酸系エツチングにおける後処理方法 | |
KR19990014550A (ko) | 동 및 동합금의 표면처리 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110413 Termination date: 20130302 |