CN1053233C - 铜及铜合金的表面处理剂 - Google Patents
铜及铜合金的表面处理剂 Download PDFInfo
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- CN1053233C CN1053233C CN94104029A CN94104029A CN1053233C CN 1053233 C CN1053233 C CN 1053233C CN 94104029 A CN94104029 A CN 94104029A CN 94104029 A CN94104029 A CN 94104029A CN 1053233 C CN1053233 C CN 1053233C
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- acid
- copper
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- treatment agent
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- Expired - Fee Related
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 title claims abstract description 20
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 30
- 239000012756 surface treatment agent Substances 0.000 claims description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 229940015043 glyoxal Drugs 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- QLPKTAFPRRIFQX-UHFFFAOYSA-N 2-thiophen-2-ylpyridine Chemical compound C1=CSC(C=2N=CC=CC=2)=C1 QLPKTAFPRRIFQX-UHFFFAOYSA-N 0.000 claims description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004475 Arginine Substances 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- UBORTCNDUKBEOP-UHFFFAOYSA-N L-xanthosine Natural products OC1C(O)C(CO)OC1N1C(NC(=O)NC2=O)=C2N=C1 UBORTCNDUKBEOP-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- XJWPISBUKWZALE-UHFFFAOYSA-N N-acetylhistamine Chemical compound CC(=O)NCCC1=CN=CN1 XJWPISBUKWZALE-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- UBORTCNDUKBEOP-HAVMAKPUSA-N Xanthosine Natural products O[C@@H]1[C@H](O)[C@H](CO)O[C@H]1N1C(NC(=O)NC2=O)=C2N=C1 UBORTCNDUKBEOP-HAVMAKPUSA-N 0.000 claims description 2
- -1 Yi Bingchunan Chemical compound 0.000 claims description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 2
- 235000003704 aspartic acid Nutrition 0.000 claims description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 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 claims description 2
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- UBORTCNDUKBEOP-UUOKFMHZSA-N xanthosine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C(NC(=O)NC2=O)=C2N=C1 UBORTCNDUKBEOP-UUOKFMHZSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims 1
- 229940125904 compound 1 Drugs 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 abstract description 6
- 238000007788 roughening Methods 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 238000003466 welding Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229940043237 diethanolamine Drugs 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000003628 erosive effect Effects 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
- B23K35/3618—Carboxylic acids or salts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/383—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by microetching
-
- 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
- H05K2203/121—Metallo-organic 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
- 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, thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
-
- 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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/064—Photoresists
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- ing And Chemical Polishing (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
本发明提供了一种可用于铜及铜合金的除锈、表面粗糙化等处理时用的表面处理剂，该处理剂可形成焊接性良好的表面，不会腐蚀处理后的铜，且其操作环境良好。本发明的表面处理剂由配合唑类的二价铜配合物作为氧化剂，沸点或分解温度在230℃以下的有机酸作溶解氧化铜的酸，难挥发性配位剂及比上述唑类络合能力弱的配位剂作为配位剂配制而成。
Description
本发明涉及一种可用于铜及铜合金的除锈、表面粗糙化处理等的表面处理剂。
现时，在制造印刷电路板时，对铜表面进行通常称作微蚀刻的化学研磨的处理，其目的是提高防蚀涂层，或防焊涂层的粘结性，或者是提高电子零件安装时对焊锡结合性。在该微蚀刻中，通常使用以硫酸和过氧化氢为主成分的水溶液或以过硫酸盐为主成分的水溶液。
然而，在使用以硫酸及过氧化氢，或过硫酸盐为主成分的蚀刻剂进行处理时，若其后的水洗不充分，蚀刻剂会残留于印刷电路基板上，使电路被腐蚀；最严重时，会导致电路断线。另外，由于这些蚀刻剂在使用时会产生烟雾，从操作环境的观点来说，上述蚀刻剂也不理想。
本发明的目的在于提供一种表面处理剂，即使处理后的水洗不充分，也不会腐蚀电路，消除了电路断线之忧；而且可抑止烟雾，或有害气体的发生，改善操作环境。
因此，本发明者为达到上述目的而反复进行了刻意研究，研制出一种表面处理剂，该表面处理剂系由含有唑(azole)类的二价铜配位化合物，沸点或分解点在230C之下的有机酸及难挥发性配位剂，并添加其络合能力弱于上述唑类配位剂的水溶液所组成，从而达到了本发明。
在本发明所用的唑类铜配位化合物之作用为氧化金属铜等的氧化剂。在本发明中，在具氧化作用的各种二价铜配位化合物中，唑类二价铜配位化合物作为表面处理剂，其蚀刻率适中。上述之唑类配合剂可包括二唑、三唑、四唑及其衍生物，但其中，咪唑、2-甲基咪唑、2-乙基-4甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、苯并咪唑等比较便宜。
上述唑类的二价铜配位化合物的含量可根据其对氧化力的需要而适当设定，通常为1-5％((重量％)以下同)。上述之含量过少，则氧化力不足，无法得到充分的蚀刻效果。
上述唑类的二价铜配位化合物既可以铜配位化合物的形式添加，也可分别添加二价铜离子源和唑类配位剂，使在液体中形成为铜配位化合物。作为上述二价铜离子源，有氢氧化铜或下述的有机酸的铜盐之类的物质。
本发明中所用的沸点或分解温度在230℃以下的有机酸，是为了溶解唑类二价铜配位化合物氧化的铜，且在所制造的印刷电路板上安装电子零件时，在焊接过程中(通常为200°-260℃)蒸发或分解而被除去，对产品之可靠性不产生不利影响。上述有机酸的具体例子有：甲酸、乙酸、丙酸、丁酸、戊酸、己酸等饱和脂肪酸；丙烯酸、巴豆酸(丁烯酸)、异丁烯酸等不饱和脂肪酸；草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸等脂肪族饱和二羧酸；马来酸等脂肪族不饱和二羧酸；苯甲酸、邻苯二甲酸等芳香族羧酸等。
上述有机酸的含量宜在5-30％之间。如其含量过少，则不能充分溶解氧化铜，使铜表面状态恶化；而它们的含量过多时，则铜的溶解稳定性降低。
本发明所用难挥发性配位剂，其目的在于保持被有机酸溶解的铜的稳定性，且由于其难挥发性，便不会恶化操作环境。上述难挥发性配位剂的具体例子有：丁胺、戊胺、己胺、二丙胺、二异丙胺、二丁胺、三乙胺、三丙胺等脂肪胺类；苯胺等芳香胺类；乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺等醇胺类；甘胺酸、丙胺酸、精氨酸、天冬氨酸等氨基酸类等。其中，在以本发明的表面处理剂处理的印刷电路板上焊接时，醇胺类可提高焊接效果，因此可优先使用。
上述难挥发性配位剂的含量，为保持溶解铜的稳定，宜在1％以上，通常在20％以下。又，在表面处理的实施中，难挥发性配位剂会随铜等的溶解而消耗，所以，为使表面处理顺利地进行，难挥发性配位剂的含量要满足上述规定要求。
考虑到铜的溶解稳定性，难挥发性配位剂应比唑类更强些，然而，仅用这样的配位剂，则会使唑配合物的氧化能力下降，无法得到充分的蚀刻率，因此，在本发明中，还要添加配位能力较唑类弱的配位剂以调节至所希望的蚀刻率。作为配位能力较唑类弱的配位剂，可依所使用的唑的种类而定，例如，氨、吡啶、乙酰组胺、黄苷、2-(2-噻嗯基)吡啶等。
配位力较上述唑类弱的配位剂的添加量无法依其它成分的种类、成本等作硬性的规定，通常其在表面处理剂中的含量为0.5-10％。
由如上所述成分所形成的本发明表面处理剂，可藉氢氧化钠、氨及上述有机酸的再添加，使其pH调节至6-8(在40℃时测定)后使用。又，在再添加氨或上述有机酸时，添加量应在上述范围内。如上述pH不到6，则无法进行氧化，蚀刻率降低；而当pH超过8时，则氧化速度过快，其表面状态变差。
本以明的表面处理剂的使用方法，有喷雾于被处理金属的喷洒法；将被处理金属浸渍于表面处理剂中的浸渍方法等。在采用浸渍方法时，为使由铜或铜合金的蚀刻将生成于处理剂中的一价铜离子氧化成二价铜离子，可以鼓泡形式吹入空气。
本发明的表面处理剂可厂泛使用于铜或铜合金的化学研磨，由于处理后铜等的表面形成了适度的凹凸状，与各种保护涂层具良好的粘合性，而且，焊接性能也有提高，所以在印刷电路板的制造中特别适用。
实施例实施例1-4
混合表1所示的成份，调整pH值成6，5而制得本发明的表面处理剂。
其次，准备两面镀铜之长150mm，宽70mm，厚1.6mm，具有1000个直径0.3mm的通孔的印刷电路板用镀膜层合板(FR-4)。使该基板之一面涂覆以防焊涂层后，在25℃浸渍于上述表面处理剂1分钟后，取出。此时的臭味、未被基板的防焊涂层所覆盖的面的表面状态及蚀刻量示于表1。其次，使该基板在不经水洗直接在230℃加热3分钟，再放置于80℃，90％RH之恒温恒湿器中30天，由通孔内电阻的测定而测得通孔断线的发生率。其结果示于表1。比较例1-3
与实施例1相同，制备表2所示的表面处理剂，加以评价。其结果示于表2。
使用本发明之表面处理剂，即使在处理后水洗不充分，也不会腐蚀线路。而且，也不易发出烟雾等有害气体，从而能改善作业环境，并能形成焊接性能良好的表面。
表1
| 组成及配合量 | 断线发生率(％) | 完成状态 | 气 味 | 蚀刻量(μm) | |
| 实施例1 | 2-甲基咪唑二价铜配合物 3％醋 酸 5％苯 胺 3％吡 啶 1％离子交换水 88％ | 0 | 产生适于层合及焊接之凹凸表面 | 仅有些微醋酸气味，并不构成问题 | 0.28 |
| 实施例2 | 2-甲基咪唑二价铜配合物 3％醋 酸 5％苯 胺 3％吡 啶 1％离子交换水 88％ | 0 | 产生适于层合及焊接之凹凸表面 | 无气味 | 0.42 |
| 实施例3 | 2-甲基咪唑二价铜配合物 3％醋 酸 5％二乙醇胺 3％吡 啶 1％离子交换水 88％ | 0 | 产生适于层合及焊接之凹凸表面 | 仅有些微醋酸气味，并不构成问题 | 0.33 |
| 实施例4 | 基咪唑二价铜配合物 3％醋 酸 5％苯 胺 3％吡 啶 1％离子交换水 88％ | 0 | 产生适于层合及焊接之凹凸表面 | 仅有些微醋酸气味，并不构成问题 | 0.56 |
注：断线发生率系将通孔内电阻在1Ω以上时作为断线，求得其比率。
表2
| 组成及配合量 | 断线发生率(％) | 完成状态 | 气 味 | 蚀刻量(μm) | |
| 比较例1 | 硫 酸 10％过氧化氢 5％离子交换水 85％ | 32.4 | 产生适合于层合及焊接之凹凸表面 | 刺鼻臭味 | 0.82 |
| 比较例2 | 过硫酸钠 10％硫 酸 1％离子交换水 89％ | 21.4 | 产生适合于层合及焊接之凹凸表面 | 刺鼻臭味 | 0.63 |
| 比较例3 | 硫 酸 10％离子交换水 90％ | 29.7 | 仅有除锈效果，表面平滑如故。 | 无气味 | 0.011 |
注：断线发生率系将通孔内电阻在1Ω以上时作为断线，求得其比率。
Claims (3)
1.一种铜及铜合金表面的处理剂，其特征在于，所述表面处理剂由含有：选自为咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、及苯并咪唑的二唑、三唑、四唑及其衍生物的唑类的二价铜配位化合物1～5％(重量)，其沸点或分解温度在230℃以下的有机酸5～30％(重量)，选自丁胺、戊胺、己胺、二丙胺、二异丙胺、二丁胺、三乙胺、三丙胺、苯胺、乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、甘氨酸、丙氨酸、精氨酸及天冬氨酸的难挥发性配位剂1～20％(重量)及再添加有其配位能力较所述唑类弱的配位剂0.5～10％(重量)的水溶液。
2.如权利要求1所述的表面处理剂，其特征在于，所述其沸点或其分解温度在230℃以下的有机酸为甲酸、乙酸、丙酸、丁酸、戊酸、己酸、丙烯酸、丁烯酸、异丁烯酸、草酸、琥珀酸、戊二酸、己二酸、庚二酸、马来酸、苯甲酸及邻苯二甲酸。
3.如权利要求1所述的表面处理剂，其特征在于，所述配位能力较所述唑类弱的配位剂为氨、吡啶、乙酰组胺、黄苷、2-(2-噻吩基)吡啶。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP100121/93 | 1993-04-05 | ||
| JP5100121A JPH06287774A (ja) | 1993-04-05 | 1993-04-05 | 銅および銅合金の表面処理剤 |
| JP100121/1993 | 1993-04-05 |
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| Publication Number | Publication Date |
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| CN1120077A CN1120077A (zh) | 1996-04-10 |
| CN1053233C true CN1053233C (zh) | 2000-06-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94104029A Expired - Fee Related CN1053233C (zh) | 1993-04-05 | 1994-04-04 | 铜及铜合金的表面处理剂 |
Country Status (7)
| Country | Link |
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| US (1) | US5439783A (zh) |
| EP (1) | EP0620293B1 (zh) |
| JP (1) | JPH06287774A (zh) |
| CN (1) | CN1053233C (zh) |
| DE (1) | DE69401453T2 (zh) |
| SG (1) | SG47858A1 (zh) |
| TW (1) | TW256856B (zh) |
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| US6524644B1 (en) | 1999-08-26 | 2003-02-25 | Enthone Inc. | Process for selective deposition of OSP coating on copper, excluding deposition on gold |
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| WO2009036215A2 (en) * | 2007-09-14 | 2009-03-19 | Qualcomm Mems Technologies, Inc. | Etching processes used in mems production |
| JP5363377B2 (ja) * | 2010-02-19 | 2013-12-11 | 新光電気工業株式会社 | 配線基板及びその製造方法 |
| WO2013005631A1 (ja) * | 2011-07-04 | 2013-01-10 | 三菱瓦斯化学株式会社 | 銅または銅を主成分とする化合物のエッチング液 |
| JP5382892B2 (ja) * | 2012-12-27 | 2014-01-08 | メック株式会社 | エッチング方法 |
| KR101318733B1 (ko) * | 2013-06-13 | 2013-10-18 | 주식회사 에이씨엠 | 구리 유기 착물을 이용한 에칭제 조성물 |
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| JP6710402B2 (ja) * | 2017-10-23 | 2020-06-17 | メック株式会社 | 膜形成基材の製造方法及び表面処理剤 |
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- 1994-03-25 US US08/217,638 patent/US5439783A/en not_active Expired - Fee Related
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- 1994-03-30 DE DE69401453T patent/DE69401453T2/de not_active Expired - Fee Related
- 1994-03-30 EP EP94105065A patent/EP0620293B1/en not_active Expired - Lifetime
- 1994-04-04 CN CN94104029A patent/CN1053233C/zh not_active Expired - Fee Related
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| CN102717161A (zh) * | 2011-05-10 | 2012-10-10 | 中国科学院金属研究所 | 一种通过表面多孔结构实现钎焊性可调的工艺 |
| CN102717161B (zh) * | 2011-05-10 | 2014-09-03 | 中国科学院金属研究所 | 一种通过表面多孔结构实现钎焊性可调的工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69401453T2 (de) | 1997-04-30 |
| EP0620293A1 (en) | 1994-10-19 |
| JPH06287774A (ja) | 1994-10-11 |
| CN1120077A (zh) | 1996-04-10 |
| EP0620293B1 (en) | 1997-01-15 |
| US5439783A (en) | 1995-08-08 |
| SG47858A1 (en) | 1998-04-17 |
| DE69401453D1 (de) | 1997-02-27 |
| TW256856B (zh) | 1995-09-11 |
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