JP2005171320A - Electrolytic peeling solution and electrolytic peeling method for copper - Google Patents
Electrolytic peeling solution and electrolytic peeling method for copper Download PDFInfo
- Publication number
- JP2005171320A JP2005171320A JP2003413387A JP2003413387A JP2005171320A JP 2005171320 A JP2005171320 A JP 2005171320A JP 2003413387 A JP2003413387 A JP 2003413387A JP 2003413387 A JP2003413387 A JP 2003413387A JP 2005171320 A JP2005171320 A JP 2005171320A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- electrolytic
- stripping solution
- electrolytic stripping
- silver
- 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.)
- Granted
Links
- 239000010949 copper Substances 0.000 title claims abstract description 122
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 100
- 239000004332 silver Substances 0.000 claims abstract description 100
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000007747 plating Methods 0.000 claims abstract description 81
- -1 cyanide compound Chemical class 0.000 claims abstract description 33
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000005749 Copper compound Substances 0.000 claims abstract description 9
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 8
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 7
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 6
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 6
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 235000003704 aspartic acid Nutrition 0.000 claims description 6
- 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 6
- 235000013922 glutamic acid Nutrition 0.000 claims description 6
- 239000004220 glutamic acid Substances 0.000 claims description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical group OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 3
- 229960002317 succinimide Drugs 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 1
- 239000005751 Copper oxide Substances 0.000 claims 1
- 229910000431 copper oxide Inorganic materials 0.000 claims 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 abstract 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- RQALKBLYTUKBFV-UHFFFAOYSA-N 1,4-dioxa-7-thiaspiro[4.4]nonane Chemical compound O1CCOC11CSCC1 RQALKBLYTUKBFV-UHFFFAOYSA-N 0.000 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 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 description 2
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 description 2
- BWKOZPVPARTQIV-UHFFFAOYSA-N azanium;hydron;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].OC(=O)CC(O)(C(O)=O)CC([O-])=O BWKOZPVPARTQIV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- CVOQYKPWIVSMDC-UHFFFAOYSA-L dipotassium;butanedioate Chemical compound [K+].[K+].[O-]C(=O)CCC([O-])=O CVOQYKPWIVSMDC-UHFFFAOYSA-L 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 239000001472 potassium tartrate Substances 0.000 description 2
- 229940111695 potassium tartrate Drugs 0.000 description 2
- 235000011005 potassium tartrates Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 2
- 239000001393 triammonium citrate Substances 0.000 description 2
- 235000011046 triammonium citrate Nutrition 0.000 description 2
- 235000015870 tripotassium citrate Nutrition 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- VCHSXYHBMFKRBK-UHFFFAOYSA-N 4771-47-5 Chemical compound OC(=O)C1=CC=CC(Cl)=C1[N+]([O-])=O VCHSXYHBMFKRBK-UHFFFAOYSA-N 0.000 description 1
- QAYNSPOKTRVZRC-UHFFFAOYSA-N 99-60-5 Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1Cl QAYNSPOKTRVZRC-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- YINMBLWEHNCLFF-UHFFFAOYSA-N benzenesulfonic acid;benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OS(=O)(=O)C1=CC=CC=C1 YINMBLWEHNCLFF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- PHWSCBWNPZDYRI-UHFFFAOYSA-N ethyl 4-nitrobenzoate Chemical compound CCOC(=O)C1=CC=C([N+]([O-])=O)C=C1 PHWSCBWNPZDYRI-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 235000006109 methionine Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 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
- 238000007788 roughening Methods 0.000 description 1
- 235000004400 serine Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000008521 threonine Nutrition 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract
Description
本発明は銅の電解剥離液及び銅の電解剥離方法に関し、更に詳細には、部材全面に形成した銅めっき皮膜を部分的に覆う銀めっき皮膜から露出する銅めっき皮膜を電解剥離によって剥離する銅の電解剥離液及び電解剥離方法に関する。 The present invention relates to a copper electrolytic stripping solution and a copper electrolytic stripping method. More specifically, the present invention relates to a copper that strips a copper plating film exposed from a silver plating film partially covering the copper plating film formed on the entire surface of the member by electrolytic stripping. The present invention relates to an electrolytic stripping solution and an electrolytic stripping method.
半導体装置に用いるリードフレームでは、図１に示す様に、鉄−ニッケル合金（４２合金）等の鉄系合金材から成るリードフレーム１０を構成するインナーリード１２，１２・・の各ダイパッド１４側の先端部（以下、単に先端部と称する）に、ダイパッド１４に搭載された半導体素子に一端部が接続された金ワイヤの他端部が接続されるボンディング部１２ａが形成される。
かかるボンディング部１２ａは、銀めっき皮膜が形成されており、金ワイヤの他端部が接続される。
In the lead frame used in the semiconductor device, as shown in FIG. 1, the
The bonding
図１に示す様に、鉄系合金から成るリードフレーム１０の各インナーリード１２の先端部に、銀めっき皮膜が形成されたボンディング部１２ａを形成する際には、リードフレーム１０の全周に電解銅めっきによって銅めっき皮膜を形成する。
かかる銅めっき皮膜が形成されたリードフレーム１０を、図２（ａ）に示す様に、インナーリード１２の先端部２０にボンディング部１２ａを形成する部分の銅めっき皮膜１６のみが露出するように、ゴム製のマスク板１８ａ，１８ｂの間に挟み込み、露出した銅めっき皮膜１６上に銀めっき皮膜を形成する電解銀めっきを施す。
次いで、電解銀めっきが終了した後、マスク板１８ａ，１８ｂを除去すると、図２（ｂ）に示す様に、インナーリード１２の先端部２０のボンディング部１２ａを形成する部分のみに、部分銀めっき皮膜２２が形成される。
その後、リードフレーム１０を電解剥離液に浸漬し、リードフレーム１０を陽極とする電解剥離によって、部分銀めっき皮膜２２で覆われることなく露出する銅めっき皮膜１６を除去することによって、図２（ｃ）に示す様に、インナーリード１２の先端部２０のボンディング部１２ａを形成する部分のみに、銅めっき皮膜１６と部分銀めっき皮膜２２とから成るボンディング部１２ａが形成される。
As shown in FIG. 1, when forming a
As shown in FIG. 2A, the
Next, after the electrolytic silver plating is completed, when the
Thereafter, the
ところで、マスク板１８ａ，１８ｂの間にリードフレーム１０を挟み込んで、露出した銅めっき皮膜１６上に銀めっき皮膜を形成する際に、マスク板１８ａ，１８ｂの歪み等によって、図２（ｂ）に示す様に、マスク板１８ａ，１８ｂで覆われていた部分にも、電解銀めっき液が洩れ込むことに因る薄い銀めっき皮膜２４（以下、洩れ銀２４と称することがある）が形成される。この洩れ銀２４も、銅めっき皮膜１６の電解剥離によって除去され、図２（ｃ）に示す様に、インナーリード１２の先端部２０のボンディング部１２ａを形成する部分のみに、部分銀めっき皮膜２２が形成される。
この様に、部分銀めっき皮膜２２を実質的に剥離せずに洩れ銀２４及び銅めっき皮膜１６を電解剥離する際には、下記特許文献１に記載されている様に、シアン系化合物を含有する電解剥離液が用いられている。
As described above, when the
特許文献１に記載されている様に、シアン系化合物を含有する電解剥離液に、インナーリード１２の先端部２０のみに、部分銀めっき皮膜２２が形成されているリードフレーム１０を浸漬し、このリードフレーム１０を陽極とすると共に、ステンレス板を陰極とする銅の電解剥離を施すことによって、部分銀めっき皮膜２２を実質的に剥離せずに洩れ銀２４及び銅めっき皮膜１６を電解剥離することができる。
しかし、シアン系化合物を含有する電解剥離液を継続して用い続けていると、比較的短時間で、洩れ銀２４及び銅めっき皮膜１６の電解剥離の際に、銅めっき皮膜１６及び洩れ銀２４の剥離速度が低下する。このため、かかる電解剥離液は、頻繁と交換することを要する。
また、シアン系化合物を含有する電解剥離液は、その安全性の面から、交換等の際に、特別の注意を要する。
そこで、本発明の課題は、シアン系化合物が無添加の電解剥離液であって、シアン系化合物を含有する電解剥離液に比較して、その寿命を大幅に延長し得る銅の電解剥離液及び電解剥離方法を提供することにある。
As described in
However, if the electrolytic stripping solution containing a cyanide compound is continuously used, the
In addition, the electrolytic stripping solution containing a cyanide compound requires special attention when it is replaced from the viewpoint of safety.
Therefore, an object of the present invention is an electrolytic stripping solution to which a cyanide compound is not added, and a copper electrolytic stripping solution that can greatly extend its life compared to an electrolytic stripping solution containing a cyanide compound and It is to provide an electrolytic stripping method.
本発明者等は、前記課題を達成すべく検討した結果、シアン系化合物が無添加の電解剥離液であって、銅の酸化剤として、芳香族ニトロ化合物を添加した銅の電解剥離液を用い、図２（ｂ）に示す、インナーリード１２の先端部２０のみに部分銀めっき皮膜２２が形成されているリードフレーム１０に電解剥離を施すことにより、部分銀めっき皮膜２２を実質的に剥離することなく洩れ銀２４及び銅めっき皮膜１６を電解剥離できることを見出した。
更に、この電解剥離液の寿命は、シアン系化合物を含有する電解剥離液に比較して長いことも見出し、本発明に到達した。
As a result of investigations to achieve the above-mentioned problems, the present inventors have used an electrolytic stripping solution containing no cyanide compound, and using a copper electrolytic stripping solution containing an aromatic nitro compound as an oxidizing agent for copper. The partial
Furthermore, it has been found that the lifetime of this electrolytic stripper is longer than that of an electrolytic stripper containing a cyanide compound, and has reached the present invention.
すなわち、本発明は、部材全面に形成した銅めっき皮膜を部分的に覆う銀めっき皮膜から露出する銅めっき皮膜を電解剥離によって剥離する銅の電解剥離液において、該電解剥離液は、シアン系化合物が無添加の電解剥離液であって、銅の酸化剤としての銅化合物又は芳香族ニトロ化合物が含有されていると共に、ｐＨが９〜１２に調整されていることを特徴とする銅の電解剥離液にある。
また、本発明は、部材全面に形成した銅めっき皮膜を部分的に覆う銀めっき皮膜から露出する銅めっき皮膜を電解剥離によって剥離する際に、該電解剥離に用いる銅の電解剥離液として、前述した銅の電解剥離液を用い、前記銅の電解剥離液中に浸漬した前記部材を陽極とすることを特徴とする銅の電解剥離方法でもある。
That is, the present invention relates to a copper electrolytic stripping solution for stripping a copper plating film exposed from a silver plating film partially covering the copper plating film formed on the entire surface of the member by electrolytic stripping, wherein the electrolytic stripping solution is a cyanide compound. Is an electrolytic stripping solution containing no additive, and contains a copper compound or aromatic nitro compound as an oxidizing agent for copper, and has a pH adjusted to 9 to 12 and is electrolytically stripped of copper In the liquid.
Further, the present invention provides the copper electrolytic stripping solution used for the electrolytic stripping as described above when stripping the copper plated coating exposed from the silver plated coating partially covering the copper plated coating formed on the entire surface of the member by electrolytic stripping. It is also a copper electrolytic stripping method characterized by using the copper electrolytic stripping solution thus obtained and using the member immersed in the copper electrolytic stripping solution as an anode.
かかる本発明において、電解剥離液中に含有している銅の酸化剤としては、銅アンモニウム錯体が好ましい。この銅アンモニウム錯体は、電解剥離液にアンモニウム源としてのアンモニア水又はアンモニウム塩と、銅源としての硫酸銅、炭酸銅、シュウ酸銅又は水酸化銅とを添加することによって形成できる。
この様な、銅の酸化剤としての銅化合物又は芳香族ニトロ化合物が含有されている電解剥離液に、リン酸及びその塩、クエン酸や酒石酸等の有機酸及びその塩、炭酸塩、炭酸水素塩、グルタミン酸やアスパラギン酸等のアミノカルボン酸及びその塩から成る群から選ばれた少なくとも一種の化合物を添加することによって、電解剥離液の電気伝導度の調整を図ることができる。
また、電解剥離液には、銀の剥離剤として、銀と反応して錯体を形成する化合物を添加することにより、洩れ銀等を迅速に剥離できる。この銀と反応して錯体を形成する化合物としては、ピリジンカルボン酸、チオシアン酸塩、ジメチルヒダントイン又はコハク酸イミドを用いることができる。
更に、電解剥離液には、界面活性剤を添加することによって、電解剥離を施す部材の電解剥離液に対する濡れ性を向上できる。かかる界面活性剤としては、ポリオキシエチレン鎖を有する界面活性剤又はフッ素系界面活性剤を好適に用いることができる。
かかる本発明に係る銅の電解剥離液を用いる部材としては、鉄系合金材から成るリードフレームを好適に用いることができ、電解剥離を施す際には、電解剥離中に金属が溶出することのない金属から成る電極を陰極に用いることが好ましい。
In the present invention, the copper oxidant contained in the electrolytic stripper is preferably a copper ammonium complex. This copper ammonium complex can be formed by adding ammonia water or an ammonium salt as an ammonium source and copper sulfate, copper carbonate, copper oxalate or copper hydroxide as a copper source to the electrolytic stripping solution.
In such an electrolytic stripping solution containing a copper compound or aromatic nitro compound as an oxidizing agent for copper, phosphoric acid and its salt, organic acid such as citric acid and tartaric acid and its salt, carbonate, hydrogen carbonate By adding at least one compound selected from the group consisting of salts, aminocarboxylic acids such as glutamic acid and aspartic acid, and salts thereof, the electrical conductivity of the electrolytic stripping solution can be adjusted.
Moreover, leakage silver etc. can be rapidly peeled by adding the compound which reacts with silver and forms a complex as a silver peeling agent to an electrolytic stripping solution. As a compound that reacts with silver to form a complex, pyridinecarboxylic acid, thiocyanate, dimethylhydantoin, or succinimide can be used.
Furthermore, the wettability with respect to the electrolytic stripping solution of the member to be electrolytically stripped can be improved by adding a surfactant to the electrolytic stripping solution. As such a surfactant, a surfactant having a polyoxyethylene chain or a fluorosurfactant can be suitably used.
As a member using the copper electrolytic stripping solution according to the present invention, a lead frame made of an iron-based alloy material can be suitably used. When electrolytic stripping is performed, metal is eluted during electrolytic stripping. It is preferable to use an electrode made of no metal for the cathode.
従来から用いられているシアン系化合物が添加された電解剥離液の寿命が短い原因は、次のように考えられる。
電解剥離液中のシアン系化合物は、電解剥離処理量に伴なって電解剥離液中の銀濃度が次第に上昇する。この電解剥離液中の銀濃度が上昇すると、電解剥離液中の銀イオンは剥離する銅めっき皮膜の銅と置換反応を惹起し、銅の剥離速度を低下させる。
更に、シアン系化合物は、銀とも容易に錯体を形成し易いため、銅めっき皮膜の剥離と共に、部分銀めっき皮膜も剥離する。このため、銅めっき皮膜の剥離を終了したとき、部分銀めっき皮膜の表面を粗面化して、外観を損ね易い。
The reason for the short life of the electrolytic stripping solution to which a cyan compound conventionally used is added is considered as follows.
In the cyan compound in the electrolytic stripping solution, the silver concentration in the electrolytic stripping solution gradually increases with the amount of electrolytic stripping treatment. When the silver concentration in the electrolytic stripping solution increases, the silver ions in the electrolytic stripping solution cause a substitution reaction with the copper of the copper plating film to be stripped, thereby reducing the copper stripping rate.
Furthermore, since a cyanide compound easily forms a complex with silver, the partial silver plating film peels off together with the peeling of the copper plating film. For this reason, when peeling of a copper plating film is complete | finished, the surface of a partial silver plating film is roughened and it is easy to impair an external appearance.
これに対し、本発明に係る電解剥離液は、シアン系化合物が無添加の電解剥離液であって、銅の酸化剤としての銅化合物又は芳香族ニトロ化合物が含有されている。
この様に、本発明に係る電解剥離液には、銀と錯体を形成し易いシアン系化合物が添加されていないため、その電解剥離の際に、部分銀めっき皮膜よりも銅めっき皮膜を選択的に剥離できる。
但し、本発明に係る電解剥離液でも、銅めっき皮膜の剥離速度に比較して遅いが、銅めっき皮膜上に形成された洩れ銀を剥離できる。
かかる部分銀めっき皮膜や洩れ銀等から本発明に係る電解剥離液中に溶出された銀イオンは、電解剥離液中に一定量は錯体として存在するものの、多くは陰極等に析出して電解剥離液中の銀濃度の高濃度化を抑制できる。
その結果、本発明に係る電解剥離液によれば、電解剥離液中の銀の蓄積に起因する銅めっき皮膜の剥離速度の低下や部分銀めっき皮膜の外観の粗面化を防止でき、シアン系化合物が添加された従来の電解剥離液に比較して、その寿命を大幅に延長できる。
On the other hand, the electrolytic stripping solution according to the present invention is an electrolytic stripping solution to which a cyanide compound is not added, and contains a copper compound or an aromatic nitro compound as an oxidizing agent for copper.
Thus, since the cyanide compound that easily forms a complex with silver is not added to the electrolytic stripping solution according to the present invention, a copper plating film is more selective than a partial silver plating film during the electrolytic stripping. Can be peeled off.
However, even with the electrolytic stripping solution according to the present invention, the leakage silver formed on the copper plating film can be stripped although it is slower than the stripping rate of the copper plating film.
Although a certain amount of silver ions eluted in the electrolytic stripping solution according to the present invention from such a partial silver plating film or leaked silver is present as a complex in the electrolytic stripping solution, many of them are deposited on the cathode or the like and electrolytic stripped. An increase in the silver concentration in the liquid can be suppressed.
As a result, according to the electrolytic stripping solution of the present invention, it is possible to prevent a decrease in the stripping rate of the copper plating film and roughening of the appearance of the partial silver plating film due to the accumulation of silver in the electrolytic stripping solution, Compared with the conventional electrolytic stripping solution to which the compound is added, the lifetime can be greatly extended.
本発明に係る電解剥離液は、シアン系化合物が無添加の電解剥離液であって、銅の酸化剤としての銅化合物又は芳香族ニトロ化合物を含有していることが肝要である。
この銅の酸化剤としての銅化合物は、銅アンモニウム錯体が好適である。かかる銅アンモニウム錯体は、アンモニウム源としてのアンモニア水又はアンモニウム塩と、銅源としての硫酸銅、炭酸銅、シュウ酸銅又は水酸化銅とを電解剥離液に添加することによって形成できる。
この様なアンモニウム源と銅源とを添加した電解剥離液中に形成される銅アンモニウム錯体は、［Ｃｕ（ＮＨ4）2］2+、［Ｃｕ（ＮＨ4）4］2+及び［Ｃｕ（ＮＨ4）6］2+の１種又は２種以上から成る。
また、芳香族ニトロ化合物としては、クロロニトロ安息香酸、２−クロロ−４−ニトロ安息香酸、オルトニトロ安息香酸、メタニトロ安息香酸、パラニトロ安息香酸、パラニトロ安息香酸エチル、パラニトロ安息香酸ナトリウムを好適に用いることができる。
ここで、銅の酸化剤としての銅化合物又は芳香族ニトロ化合物を含有しているものの、シアン系化合物が添加された電解剥離液では、部分銀めっきの外見が良好であっても、電解剥離液の寿命の延長を図ることができない。
The electrolytic stripping solution according to the present invention is an electrolytic stripping solution to which a cyanide compound is not added, and it is important that it contains a copper compound or an aromatic nitro compound as a copper oxidizing agent.
The copper compound as the copper oxidizing agent is preferably a copper ammonium complex. Such a copper ammonium complex can be formed by adding ammonia water or an ammonium salt as an ammonium source and copper sulfate, copper carbonate, copper oxalate or copper hydroxide as a copper source to the electrolytic stripping solution.
The copper ammonium complex formed in the electrolytic stripping solution to which such an ammonium source and a copper source are added is [Cu (NH 4 ) 2 ] 2+ , [Cu (NH 4 ) 4 ] 2+ and [Cu ( It consists of one or more of NH 4 ) 6 ] 2+ .
As the aromatic nitro compound, chloronitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, orthonitrobenzoic acid, metanitrobenzoic acid, paranitrobenzoic acid, ethyl paranitrobenzoate, sodium paranitrobenzoate are preferably used. it can.
Here, an electrolytic stripping solution containing a copper compound or an aromatic nitro compound as a copper oxidant, to which a cyanide compound is added, can be used even if the appearance of partial silver plating is good. It is not possible to extend the lifespan.
更に、本発明に係る電解剥離液では、ｐＨが９〜１２に調整されていることを要する。かかるｐＨの調整は、銅アンモニウム錯体を形成する化合物として添加する、アンモニウム源としてのアンモニア水によって調整してもよく、水酸化ナトリウム等のｐＨ調整剤を用いてもよい。
ここで、電解剥離液のｐＨが９未満の場合、或いは電解剥離液のｐＨが１２を越える場合には、銅めっき皮膜の剥離速度が低下する。
Furthermore, in the electrolytic stripping solution according to the present invention, the pH needs to be adjusted to 9-12. Such pH adjustment may be carried out with ammonia water as an ammonium source added as a compound that forms a copper ammonium complex, or a pH regulator such as sodium hydroxide may be used.
Here, when the pH of the electrolytic stripping solution is less than 9, or when the pH of the electrolytic stripping solution exceeds 12, the stripping rate of the copper plating film decreases.
かかる本発明に係る電解剥離液には、リン酸及びその塩、クエン酸や酒石酸等の有機酸及びその塩、炭酸塩、炭酸水素塩、グリシン、グルタミン酸及びアスパラギン酸から成る群から選ばれた少なくとも一種の化合物を添加することによって、電解剥離液の電気伝導度の調整を図ることができる。
ここで用いるリン酸及びその塩としては、電解剥離液の電気伝導度の調整に有効であり、リン酸、メタリン酸、オルトリン酸及びこれらのアンモニウム塩、カリウム塩、ナトリウム塩（具体的には、リン酸二水素アンモニウム、リン酸水素二アンモニウム、リン酸三アンモニウム、リン酸水素二カリウム、リン酸二水素一カリウム、リン酸水素二ナトリウム、リン酸二水素ナトリウム、ピロリン酸カリウムを挙げることができる）を用いることができる。かかる化合物のうち、リン酸、リン酸二水素アンモニウム、リン酸水素二アンモニウム、リン酸三アンモニウム、リン酸水素二カリウム、リン酸二水素一カリウム、リン酸水素二ナトリウム、リン酸二水素ナトリウムを好適に用いることができる。
The electrolytic stripping solution according to the present invention includes at least selected from the group consisting of phosphoric acid and salts thereof, organic acids such as citric acid and tartaric acid and salts thereof, carbonates, hydrogencarbonates, glycine, glutamic acid and aspartic acid. By adding a kind of compound, the electrical conductivity of the electrolytic stripping solution can be adjusted.
As phosphoric acid and its salt used here, it is effective in adjusting the electric conductivity of the electrolytic stripping solution, and phosphoric acid, metaphosphoric acid, orthophosphoric acid and their ammonium salts, potassium salts, sodium salts (specifically, Ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, dipotassium hydrogen phosphate, monopotassium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium pyrophosphate ) Can be used. Among such compounds, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, dipotassium hydrogen phosphate, monopotassium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate It can be used suitably.
また、有機酸及びその塩は、電解剥離液の電気伝導度の調整に有効であり、ギ酸、酢酸、シュウ酸、プロピオン酸、酪酸、吉草酸、クエン酸、乳酸、酒石酸、コハク酸、安息香酸、ベンゼンスルホン酸及びこれらのアンモニウム塩、カリウム塩、ナトリウム塩（具体的には、ギ酸アンモニウム、ギ酸カリウム、酢酸アンモニウム、酢酸カリウム、シュウ酸水素アンモニウム、クエン酸二水素アンモニウム、クエン酸水素二アンモニウム、クエン酸三アンモニウム、クエン酸二水素カリウム、クエン酸三カリウム、酒石酸アンモニウム、酒石酸カリウム、コハク酸アンモニウム、コハク酸カリウムを挙げることができる）を用いることができる。かかる有機酸及びその塩のうち、ギ酸、クエン酸、酒石酸、コハク酸、ギ酸アンモニウム、クエン酸二水素アンモニウム、クエン酸水素二アンモニウム、クエン酸三アンモニウム、クエン酸二水素カリウム、クエン酸三カリウム、酒石酸アンモニウム、酒石酸カリウム、コハク酸アンモニウム、コハク酸カリウムを好適に用いることができる。 In addition, organic acids and their salts are effective in adjusting the electrical conductivity of the electrolytic stripping solution. Formic acid, acetic acid, oxalic acid, propionic acid, butyric acid, valeric acid, citric acid, lactic acid, tartaric acid, succinic acid, benzoic acid Benzenesulfonic acid and ammonium salts, potassium salts and sodium salts thereof (specifically, ammonium formate, potassium formate, ammonium acetate, potassium acetate, ammonium hydrogen oxalate, ammonium dihydrogen citrate, diammonium hydrogen citrate, And triammonium citrate, potassium dihydrogen citrate, tripotassium citrate, ammonium tartrate, potassium tartrate, ammonium succinate, and potassium succinate). Among such organic acids and salts thereof, formic acid, citric acid, tartaric acid, succinic acid, ammonium formate, ammonium dihydrogen citrate, diammonium hydrogen citrate, triammonium citrate, potassium dihydrogen citrate, tripotassium citrate, Ammonium tartrate, potassium tartrate, ammonium succinate, and potassium succinate can be suitably used.
更に、炭酸塩、炭酸水素塩は、電解剥離液の電気伝導度の調整に有効であり、炭酸アンモニウム、炭酸水素アンモニウム、炭酸カリウム、炭酸水素カリウム、炭酸ナトリウム、炭酸水素ナトリウムを挙げることができる。かかる化合物のうち、炭酸アンモニウム、炭酸水素アンモニウム、炭酸カリウム、炭酸水素カリウムを好適に用いることができる。
また、グルタミン酸やアスパラギン酸等のアミノカルボン酸及びその塩も、電解剥離液の電気伝導度の調整に有効であり、グリシン、グルタミン酸、アスパラギン酸、システイン、メチオニン、スレオニン、セリン、アルギニン及びこれらのアンモニウム塩、カリウム塩、ナトリウム塩を挙げることができる。これらの化合物のうち、グリシン、グルタミン酸、アスパラギン酸を好適に用いることができる。
尚、剥離対象の銅めっき皮膜及び洩れ銀の各表面の電解剥離液に対する濡れ性を向上すべく、界面活性剤として、例えばポリオキシエチレン鎖を有する界面活性剤又はフッ素系界面活性剤を添加してもよい。
Furthermore, carbonates and hydrogen carbonates are effective in adjusting the electric conductivity of the electrolytic stripping solution, and examples thereof include ammonium carbonate, ammonium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, and sodium hydrogen carbonate. Of these compounds, ammonium carbonate, ammonium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate can be suitably used.
In addition, aminocarboxylic acids such as glutamic acid and aspartic acid and salts thereof are also effective in adjusting the electric conductivity of the electrolytic stripping solution, and are glycine, glutamic acid, aspartic acid, cysteine, methionine, threonine, serine, arginine and their ammonium. Examples thereof include salts, potassium salts, and sodium salts. Of these compounds, glycine, glutamic acid, and aspartic acid can be suitably used.
In addition, in order to improve the wettability with respect to the electrolytic stripping solution on each surface of the copper plating film and leakage silver to be peeled, for example, a surfactant having a polyoxyethylene chain or a fluorosurfactant is added. May be.
この様な、本発明に係る電解剥離液を用い、図２（ｂ）に示す洩れ銀２４が銅めっき皮膜１６上に形成されたリードフレーム１０を電解剥離する際に、図２（ｂ）に示す洩れ銀２４を剥離しつつ、銅めっき皮膜１６を剥離できる。
この際に、洩れ銀２４の剥離速度を更に向上したい場合には、銀の剥離剤として、銀と反応して錯体を形成する化合物、例えばピリジンカルボン酸、チオシアン酸塩、ジメチルヒダントイン又はコハク酸イミドを添加してもよい。
When electrolytic leakage of the
At this time, when it is desired to further improve the peeling rate of the leaked
以上、説明してきた本発明に係る電解剥離液を用いて、図２（ｂ）に示すリードフレーム１０の洩れ銀２４及び銅めっき皮膜１６を電解剥離する際には、電解剥離液が貯留された剥離槽内に浸漬した陽極としてのリードフレーム１０と陰極との間に直流電流を流すことによって、洩れ銀２４及び銅めっき皮膜１６を電解剥離できる。
かかる電解剥離の際に、陰極としては、電解剥離中に金属が溶出することのない金属から成る電極、例えば白金やステンレスから成る電極を好適に用いることができる。この様に、電解剥離中に金属が溶出することのない金属から成る電極を陰極に用いることによって、電解剥離液中に銀イオンを陰極に析出させることができ、電解剥離液中の銀濃度を低濃度に抑制でき且つ銀の回収を容易に行うことができる。
尚、この電解剥離では、電流密度を０．０１〜２０Ａ／ｄｍ2、好ましくは０．１〜１０Ａ／ｄｍ2程度とし、処理時間としては２〜３０秒程度とすることが好ましい。
As described above, the electrolytic stripper was stored when electrolytically stripping the leaked
In such electrolytic stripping, as the cathode, an electrode made of a metal that does not elute during electrolytic stripping, for example, an electrode made of platinum or stainless steel can be suitably used. Thus, by using an electrode made of a metal that does not elute during electrolytic stripping as a cathode, silver ions can be deposited on the cathode in the electrolytic stripper, and the silver concentration in the electrolytic stripper can be reduced. It can be suppressed to a low concentration and silver can be easily recovered.
In this electrolytic stripping, current density 0.01~20A / dm 2, preferably between 0.1 to 10 A / dm 2 about, preferably about 2 to 30 seconds treatment time.
鉄−ニッケル合金（４２合金）から成るリードフレーム１０の全面に電解銅めっきによって、厚さ０．１〜０．２μｍの銅めっき皮膜１６を形成した後、図２（ａ）に示す様に、インナーリード１２の先端部２０にボンディング部１２ａを形成する部分の銅めっき皮膜１６のみが露出するように、ゴム製のマスク板１８ａ，１８ｂの間に挟み込み、露出した銅めっき皮膜１６上に、電解銀めっきによって厚さ３〜６μｍの部分銀めっき皮膜２２形成した。
次いで、マスク板１８ａ，１８ｂを除去すると、図２（ｂ）に示す様に、インナーリード１２の先端部２０のボンディング部１２ａを形成する部分に、部分銀めっき皮膜２２が形成されていた。
唯、マスク板１８ａ，１８ｂで覆われていた部分にも、図２（ｂ）に示す様に、洩れ銀２４が所々に形成されていた。
After forming a
Next, when the
However, as shown in FIG. 2 (b), leaked
かかるリードフレーム１０を、下記表１に示す電解剥離液を貯留した剥離槽内に浸漬し、陽極としてのリードフレーム１０と白金電極から成る陰極との間に直流電流を流して、洩れ銀２４及び銅めっき皮膜１６に対して電解剥離を施した。
かかる電解剥離の際に、使用した電解剥離液、電流密度及び処理時間を下記表２に示す。また、電解剥離の結果についても下記表２に併せて示す。表２に示す各水準では、露出している銅めっき皮膜１６及び洩れ銀２４の残存、部分銀めっき皮膜２２の変色及びリードフレーム１０を形成する４２合金の腐食は認められなかった。
表１の電解剥離液５を用いて銅と銀とを所定量処理した後に銅及び銀の剥離速度を測定した。この剥離速度は、予め銅と銀とを等量づつ所定量処理した電解剥離液５に、陽極として浸漬した銅板又は銀板に対し、表２のNo.７の電解剥離条件下で電解剥離を施した後、銅板又は銀板の重量減を測定して得たものである。
電解剥離液５に予め処理する銅と銀との処理量を変更して測定した、銅及び銀の剥離速度についての結果を図３に示す。
図３から明らかな様に、銅及び銀の処理量が増加しても、銅及び銀の処理量がゼロ（建浴直後）における銅及び銀の剥離速度に比較して、銅の剥離速度はやや速くなる傾向にあり、銀の剥離速度はやや低下傾向にあるものの、略同一速度である。
この様に、電解剥離液５では、銅及び銀の処理量が増加しても、建浴直後の電解剥離液５と同程度の銅及び銀の剥離速度を維持でき、電解剥離液５の交換間隔を長くできる。
Copper and silver were treated with a predetermined amount using the electrolytic stripping solution 5 shown in Table 1, and then the stripping rate of copper and silver was measured. This stripping rate is obtained by subjecting the electrolytic stripping solution 5 in which copper and silver are treated in equal amounts in advance to a copper plate or silver plate immersed as an anode to electrolytic stripping under the electrolytic stripping conditions of No. 7 in Table 2. After the application, the weight loss of the copper plate or silver plate is measured.
The result about the peeling speed | rate of copper and silver which changed and measured the processing amount of the copper and silver previously processed to the electrolytic stripping solution 5 is shown in FIG.
As is clear from FIG. 3, even when the treatment amount of copper and silver is increased, the removal rate of copper is higher than the removal rate of copper and silver when the treatment amount of copper and silver is zero (immediately after the bath). Although it tends to be slightly faster and the silver peeling rate tends to decrease slightly, it is almost the same rate.
Thus, in the electrolytic stripping solution 5, even when the amount of copper and silver processed increases, the copper stripping rate and the silver stripping rate can be maintained at the same level as the electrolytic stripping solution 5 immediately after the bathing bath. The interval can be lengthened.
表１の電解剥離液９を用いて、実施例２と同様にして、表２のNo.１２※の電解剥離条件下での電解剥離における銅及び銀の剥離速度についての結果を図４に示す。
図４から明らかな様に、銅及び銀の処理量がゼロ（建浴直後）における銅及び銀の剥離速度は良好であるものの、銅及び銀の処理量の増加に伴なって銅の剥離速度は急激に低下し、その後は略一定値となる。
かかる現象は、シアン化合物が、銅及び銀の各々と錯体を形成し易いことに起因しているものと考えられる。つまり、シアン化合物を含有する電解剥離液は、当初は、銅のみならず、銀の剥離能力も非常に高いが、電解剥離液中の銀濃度が上昇すると、電解剥離液中の銀イオンは剥離する銅めっき皮膜の銅と置換反応を惹起し、銅の剥離速度を低下させることにあると考えられる。
かかる図４から明らかな様に、建浴直後の電解剥離液９が呈する銅及び銀の剥離速度を維持するには、電解剥離液９を頻繁に交換することを要する。
Using the electrolytic stripping
As is clear from FIG. 4, although the copper and silver stripping rates are zero (immediately after building bath), the copper and silver stripping rates are good, but the copper stripping rate increases as the copper and silver throughput increases. Decreases rapidly, and then becomes a substantially constant value.
Such a phenomenon is considered to be caused by the fact that the cyan compound easily forms a complex with each of copper and silver. In other words, the electrolytic stripping solution containing cyanide initially has a very high stripping ability not only for copper but also for silver, but when the silver concentration in the electrolytic stripping solution increases, the silver ions in the electrolytic stripping solution are stripped. It is thought that this causes the substitution reaction with copper of the copper plating film to be reduced, thereby reducing the copper peeling rate.
As is apparent from FIG. 4, it is necessary to frequently replace the electrolytic stripping
１０ リードフレーム
１２ インナーリード
１２ａ ボンディング部
１４ ダイパッド
１６ 銅めっき皮膜
２０ インナーリードの先端部
２２ 部分銀めっき皮膜
２４ 洩れ銀
DESCRIPTION OF
Claims (11)
該電解剥離液は、シアン系化合物が無添加の電解剥離液であって、銅の酸化剤としての銅化合物又は芳香族ニトロ化合物が含有されていると共に、ｐＨが９〜１２に調整されていることを特徴とする銅の電解剥離液。 In the copper electrolytic stripping solution for stripping the copper plating film exposed from the silver plating film partially covering the copper plating film formed on the entire surface of the member by electrolytic stripping,
The electrolytic stripper is an electrolytic stripper to which no cyanide compound is added, and contains a copper compound or an aromatic nitro compound as an oxidizing agent for copper, and the pH is adjusted to 9-12. An electrolytic stripping solution for copper.
該電解剥離に用いる銅の電解剥離液として、請求項１記載の銅の電解剥離液を用い、前記銅の電解剥離液中に浸漬した前記部材を陽極とすることを特徴とする銅の電解剥離方法。 When peeling the copper plating film exposed from the silver plating film partially covering the copper plating film formed on the entire surface of the member by electrolytic peeling,
A copper electrolytic stripping solution according to claim 1, wherein the member immersed in the copper electrolytic stripping solution is used as an anode. Method.
Priority Applications (5)
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| JP2003413387A JP4264338B2 (en) | 2003-12-11 | 2003-12-11 | Copper electrolytic stripping solution and electrolytic stripping method |
| KR1020040082415A KR20050058184A (en) | 2003-12-11 | 2004-10-15 | Electrolytic copper-stripping liquid and electrolytic stripping method |
| TW093132148A TWI385283B (en) | 2003-12-11 | 2004-10-22 | Electrolytic copper-stripping liquid and electrolytic stripping method |
| CNA2004100860305A CN1626703A (en) | 2003-12-11 | 2004-10-22 | Electrolytic copper-stripping liquid and electrolytic stripping method |
| US10/971,898 US20050126926A1 (en) | 2003-12-11 | 2004-10-22 | Electrolytic copper-stripping liquid and electrolytic stripping method |
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| JP2003413387A JP4264338B2 (en) | 2003-12-11 | 2003-12-11 | Copper electrolytic stripping solution and electrolytic stripping method |
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| JP (1) | JP4264338B2 (en) |
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| WO2009108922A1 (en) * | 2008-02-28 | 2009-09-03 | Aeromet Technologies, Inc. | Methods for removing precious metal-containing coatings and recovery of precious metals therefrom |
| US8506789B2 (en) | 2009-07-23 | 2013-08-13 | Ceramatec, Inc. | Method of producing coupled radical products |
| US9957622B2 (en) | 2009-07-23 | 2018-05-01 | Field Upgrading Limited | Device and method of obtaining diols and other chemicals using decarboxylation |
| CN103397373A (en) * | 2010-06-25 | 2013-11-20 | 张红雨 | Deplating solution |
| US9493882B2 (en) * | 2010-07-21 | 2016-11-15 | Ceramatec, Inc. | Custom ionic liquid electrolytes for electrolytic decarboxylation |
| ES2724528T3 (en) | 2011-01-25 | 2019-09-11 | Enlighten Innovations Inc | Production of fuel from chemical substances derived from biomass |
| DE102011005918A1 (en) * | 2011-03-22 | 2012-09-27 | Airbus Operations Gmbh | Peelable anodizing agent, especially for local anodic oxidation of metal surfaces |
| CN102168290B (en) * | 2011-04-08 | 2012-10-17 | 哈尔滨工业大学 | Cyanide-free silver plating electroplating solution and preparation method and electroplating method thereof |
| CN104404611B (en) * | 2014-11-28 | 2016-11-30 | 江门市瑞期精细化学工程有限公司 | A kind of release agent for electrolytic of copper alloy surface coating and preparation method thereof |
| JP6142408B2 (en) | 2015-03-13 | 2017-06-07 | 奥野製薬工業株式会社 | Electrolytic stripper for jigs |
| CN104882494B (en) * | 2015-04-27 | 2017-02-22 | 中国科学院光电技术研究所 | Film stripping technology for removing silver reflecting film using chromium-containing material as adhesive layer |
| CN105543948B (en) * | 2015-12-23 | 2017-10-31 | 苏州卓融新能源科技有限公司 | It is a kind of for PCB electroplate accompany plating plate/drag cylinder plate move back process for copper |
| KR102226075B1 (en) | 2017-04-05 | 2021-03-11 | 단국대학교 산학협력단 | A hydrogen gas filter using proton beam |
| CN109778299B (en) * | 2019-02-22 | 2021-05-04 | 江门市瑞期精细化学工程有限公司 | Electrolytic stripping agent for copper-plated layer on surface of iron base material, and preparation method and stripping process thereof |
| CN111487267B (en) * | 2020-04-09 | 2023-04-14 | 哈尔滨工业大学 | Method for stripping double-layer oxide film defect in aluminum bronze alloy |
| CN113122906B (en) * | 2021-03-23 | 2022-11-15 | 广州市睿承科技有限公司 | Electric release oil synergist |
| CN113652694A (en) * | 2021-06-24 | 2021-11-16 | 广东桐鸣环保科技有限公司 | Copper plating layer stripping liquid and stripping method |
| KR102534371B1 (en) * | 2021-08-30 | 2023-05-26 | 이강익 | Portable Electrolytic polisher Using Neutral Salt Electrolyte |
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| US2596307A (en) * | 1947-11-05 | 1952-05-13 | Charles Litzenberg | Process of electrostripping electrodeposited metals |
| US4264420A (en) * | 1979-10-29 | 1981-04-28 | Oxy Metal Industries Corporation | Electrolytic stripping bath and process |
| JPS6056800B2 (en) * | 1982-08-11 | 1985-12-11 | 新光電気工業株式会社 | Method for removing protruding parts of base copper plating in partial silver plating and method for finishing surface of silver plating |
| US7128825B2 (en) * | 2001-03-14 | 2006-10-31 | Applied Materials, Inc. | Method and composition for polishing a substrate |
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| TWI385283B (en) | 2013-02-11 |
| KR20050058184A (en) | 2005-06-16 |
| CN1626703A (en) | 2005-06-15 |
| TW200519238A (en) | 2005-06-16 |
| JP4264338B2 (en) | 2009-05-13 |
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