CN1147025A - 铜及铜合金的微蚀刻剂 - Google Patents
铜及铜合金的微蚀刻剂 Download PDFInfo
- Publication number
- CN1147025A CN1147025A CN96110803A CN96110803A CN1147025A CN 1147025 A CN1147025 A CN 1147025A CN 96110803 A CN96110803 A CN 96110803A CN 96110803 A CN96110803 A CN 96110803A CN 1147025 A CN1147025 A CN 1147025A
- Authority
- CN
- China
- Prior art keywords
- copper
- acid
- etching agent
- micro
- ion source
- 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 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 13
- 238000005530 etching Methods 0.000 title claims description 35
- 239000003795 chemical substances by application Substances 0.000 title claims description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 3
- -1 halide ion Chemical class 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010494 dissociation reaction Methods 0.000 abstract 1
- 230000005593 dissociations Effects 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 12
- 238000005476 soldering Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 6
- 229960003280 cupric chloride Drugs 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 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
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000005219 brazing Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 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
- 235000019253 formic acid Nutrition 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 1
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000006087 Brown hydroboration reaction Methods 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005538 encapsulation Methods 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
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000010808 liquid waste 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 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
- 239000012756 surface treatment agent Substances 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
-
- 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
- H05K2203/125—Inorganic compounds, e.g. silver salt
-
- 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
-
- 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
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Weting (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
一种由含有二价铜离子源、酸解离常数小于5的有机酸及卤离子源的水溶液组成的铜及铜合金表面的微蚀刻剂。所述微蚀刻剂可使铜及铜合金表面形成具有凹凸较深的粗化表面，使其具有与耐焊锡膜层等的优异的粘结性，且具有合适的锡焊性。
Description
本发明涉及一种可用于铜表面及铜合金表面处理的微蚀刻剂。已有技术
在印刷线路板的制作中，在对铜表面进行耐蚀刻剂和耐焊锡膜的表面覆层时，为了提高粘结性能，需对铜表面进行研磨。在该研磨方法中，有如抛光研磨、擦洗研磨等的机械研磨和微蚀刻(化学研磨)等，但对具有细线条图案的基片的表面处理来说，微蚀刻(研磨)更为合适。通常，在施以微蚀刻时，可在铜表面上蚀刻约1-5μm深度。
另外，在匀焊工序之前及电子元件封装之前，为了去除铜表面的氧化膜，提高锡焊性能，也常进行微蚀刻。在上述微蚀刻中，使用通常使用以硫酸和过氧化氢为主要成分的水溶液及以过硫酸盐为主要成分的水溶液。发明课题
可是，随着形成于印刷电路板上的电路图案的高密度化发展，所用的耐焊锡膜也正在从已往的热固化型转而使用可形成优异的细线条图案的紫外线固化型的耐焊锡涂膜。不过，由于所述的紫外线固化型耐焊锡膜比起以往的耐焊锡涂膜来，其与铜表面的粘结性能较差，在以往的微蚀刻法所得的铜表面上的粘结性能不够，在其后的电镀工序、匀焊工序、电子元件的封装过程中，会产生耐蚀(耐焊锡)覆膜的剥离和气泡等不良现象。
另一方面，在匀焊工序中，在印刷线路板上表面安装元件用的垫片增加，在以以往的微蚀刻法所得的表面上的焊接性能不理想，会产生锡焊不良现象。
本发明的目的是，提供一种微蚀刻剂，所述微蚀刻剂可使铜合金表面及铜表面形成具有较深的凹凸形状的粗糙面，使其具有与耐焊锡膜层等的优异的粘结性能，也可使该表面状态更适于焊锡性。
为达到上述目的，本发明者们经多次刻意研究，结果找到了一种由含有二价铜离子源、酸解离常数pKa为5以下的有机酸及卤离子源的水溶液组成的微蚀刻剂，从而完成了本发明。发明的实施形态
本发明中所用的二价铜离子源是用作用于氧化金属铜等的氧化剂的铜离子源。在本发明中，由于将二价铜离子源用作氧化剂，在用于微蚀刻剂时，可使其具有合适的蚀刻速度，且可在铜表面稳定地形成具有较深的凹凸形状。作为上述二价铜离子源，可举出如有机酸的铜盐和氯化铜(二价)、溴化铜(二价)、氢氧化铜(二价)等。形成所述铜盐的有机酸并无什么特别限制，但最好是如下所述的、pKa在5以下的有机酸。也可合并使用二种以上的上述二价铜离子源。
上述二价铜离子源的含量，换算为金属铜较理想的是0.01-20％(重量，以下同)，更好地是0.1-10％。如所述含量过少，则蚀刻速度变慢；另一方面，如所述含量过多，则溶解困难，会产生粉状物。
本发明中所用的pKa在5以下的有机酸，可掺用于因其二价铜离子源而氧化的铜的溶解，或掺用于pH的调节。但是，如上述有机酸的pKa超过5，则不能充分溶解氧化铜。作为pKa小于5的有机酸，可具体举例出，如甲酸、乙酸、丙酸、丁酸、戊酸、己酸等的饱和脂肪酸；如丙烯酸、巴豆酸、异巴豆酸等的不饱和脂肪酸；如草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸等的脂肪族饱和二羧酸；如马来酸等的脂肪族不饱和二羧酸；如苯甲酸、邻苯二甲酸、肉佳酸等的芳香族羧酸；如乙醇酸、乳酸、苹果酸、柠檬酸等的羟基羧酸；如氨基磺酸、β-氯丙酸、烟酸、抗坏血酸、羟基三甲基乙酸、乙酰丙酸等的带有取代基的羧酸；及其衍生物等。上述有机酸也可二种以上合并使用。
上述有机酸的含量以0.1-30％左右为理想。如该含量过少，则不能充分溶解氧化铜，残留有粉状物，不能得到稳定的蚀刻速度；而另一方面，如该含量过多，则铜的溶解稳定性降低，或在铜表面上发生再次氧化。
本发明中所用的卤离子源的掺用，是为了辅助铜的溶解，以形成具优异的粘结性能和钎焊性能的铜表面。作为所述的卤离子源，可举出氯离子、溴离子等的离子源，例如，盐酸、氢溴酸、氯化钠、氯化钾、氯化钙、氯化铵、溴化钾、氯化铜、溴化铜、氯化锌、氯化铁、溴化锡等，及其它可在溶液中解离卤离子的化合物。上述卤离子源可合并使用二种以上。另外，如氯化铜(二价)可作为即具有卤离子源，又具有二价离子源的离子源使用。
上述卤离子源最好含有0.01-20％左右的卤离子。上述含量过少及过多时，就不能得到具有优异的与树脂的粘结性及优异焊接性能的铜表面。
再者，在本发明的微蚀刻剂中，另减少在作微蚀刻处理时的pH值的变动，可添加有机酸的钠盐、钾盐及铵盐等；为了提高铜的溶解稳定性，也可添加如乙二胺、吡啶、苯胺、氨、一乙醇胺、二乙醇胺、三乙醇胺、N-甲基二乙醇胺等的配位剂；也可按需要，添加其它各种添加剂。
本发明的微蚀刻剂的使用方法并无特别限制，例如，对欲处理的铜或铜合金表面作喷雾处理、喷涂的方法，及将铜或铜合金浸渍于表面处理剂中的方法等。浸渍时，为由对铜和铜合金的蚀刻，将处理剂中生成的一价铜离子氧化为二价铜离子，可由鼓泡法鼓入空气。又，本发明的微蚀刻剂使用后，其废液处理也方便，例如，可用通常的，使用中和、高分子凝聚剂等的、简便方法进行处理。
在用本发明的微蚀刻处理剂处理后，为了进一步提高其与树脂的密着性能，也可用如偶氮类的水溶液和醇溶液进行处理，如同美国专利说明书3645772号所揭示的。另外，在用本发明的微蚀刻剂处理之后，还可作被称为棕色氧化和黑色氧化的氧化处理。
本发明的微蚀刻剂可广泛使用于铜及铜合金的化学研磨等研磨中。特别是，由该处理，可在处理的铜等的表面上形成较深的凹凸状，使其与预浸渍膜、耐焊锡膜层、耐干膜膜层、耐电镀涂层等的树脂层具有良好的密着性能，而且，该表面具优异的钎焊性，特别有用于如包括脉冲信号引线阵列(PGA)和压块引线阵列(BGA)等用的各种印刷线路板的制作。此外，本发明的蚀刻剂也可用于对引线框架的表面处理。
例如，在印刷电路板用的镀铜层合板的制作中，用本发明的微蚀刻剂对铜膜进行处理，使之表面粗化，则该表面与预浸渍片的粘结强度增大，且在形成图案时具有优异的蚀刻性。又，在制造多层印刷线路板时，将本发明的微蚀刻剂用于其内层基片的铜表面的粗化处理时，则可制得与预浸渍片的粘结强度优异、且具优异的耐引线冷却性能的表面。再有，用本发明的微蚀刻剂处理的表面，与以往用硫酸、过氧化氢系的蚀刻剂等处理的表面比较，其光泽度较低，因此，在涂敷或层合感光性树脂时，不但可得到提高其与树脂的密着性的效果，而且，曝光时的光散射也减少，还可得到提高感光性树脂分辨率的效果。实施例实施例1-4
混合表1所述的各成分，配制本发明的微蚀刻剂。其次，以所述的微蚀刻剂，在40℃、60秒的条件下，对印刷线路板用镀铜层合板(FR-4)作喷雾处理。然后，涂敷耐锡焊涂膜(PSR-4000，太阳印墨制造株式会社制)，使其曝光，显象、固化(后固化)，形成各种图案。接着，涂敷以无洗净型的后焊剂(AP-4626、美克株式会社制)，用喷流式的自动钎焊装置进行钎焊，观察其后的耐焊锡膜的状态。另外，缩短耐锡焊涂膜的后固化时间至少于标准时间内，使耐锡焊涂膜易于剥离，提高后焊剂的浓度达3倍。其结果示于表2。
又，用表1所示的微蚀刻剂，在40℃、60秒的条件下，对带有多个直径1mm的圆形垫片、其余部分覆有耐焊锡膜的印刷线路板用的镀铜膜叠层板(FR-4)作喷雾处理后，涂敷以匀焊用焊剂(W-2556，美克株式会社制)，以水平型匀焊机作钎焊，调查钎焊合格率(焊上焊锡的垫片比率)。其结果示于表2。比较例1-4
与实施例1同样，调节表1所示的微蚀刻剂，并作评价。其结果示于表2。
表1
表2
| 实施例编号 | 组成(％) |
| 1 | 氯化铜(二价)·二水合物 4醋酸)(kPa＝4.56) 5离子交换水 余 |
| 2 | 甲酸铜(二价) 5甲酸(kPa＝3.55) 2氯化铵 8离子交换水 余 |
| 3 | 醋酸铜(二价) 5丙烯酸(kPa＝4.26) 20氯化钠 4乙二胺 1离子交换水 余 |
| 4 | 溴化铜(二价) 2乙醇酸(kPa＝3.63) 10离子交换水 余 |
| 比较例1 | 硫酸 1035％过氧化氢水溶液 5离子交换水 余 |
| 比较例2 | 过硫酸钠 10硫酸 1离子交换水 余 |
| 比较例3 | 氯化铜(二价) 4盐酸 5离子交换水 余 |
| 比较例4 | 氯化铜(二价) 4尿酸(kPa＝5.61) 0.5离子交换水 余 |
| 实施例编号 | 锡焊合格率(％) | 耐锡焊膜的剥离、起泡 |
| 1 | 100 | 完全无 |
| 2 | 97.4 | 完全无 |
| 3 | 96.6 | 完全无 |
| 4 | 95.3 | 完全无 |
| 比较例1 | 60.2 | 有 |
| 比较例2 | 54.3 | 有 |
| 比较例3 | 80.8 | 稍有 |
| 比较例4 | 50.0 | 有 |
(注)比较例3的微蚀刻剂在重复多次对镀铜叠层板进行处理后，其蚀刻
性能(蚀刻速度)不稳定，很难作均匀的处理。
比较例4的微蚀刻剂处理的铜表面上产生了结晶态粉状物。另外，锡焊后的焊锡表面光泽度变差。发明效果
用本发明的微蚀刻剂处理铜或铜合金，由此可使铜表面与预浸渍涂膜及耐蚀膜层等的树脂的粘结性良好，也可形成具优异的软钎焊性能的表面。而且，如此所得的表面与以往的微蚀刻方法所得的表面比较，由于其光泽度小，因此当将该铜表面用作感光性树脂的衬底材料时可以得到提高分辨率的效果，在以自动光学检测仪(AOI)对印刷线路板的电路作检测时，也可减少误动作。因而，本发明的微蚀刻剂是一种完全可适用于今后图案日益线条细化和高强度化的印刷线路板的制造。
Claims (1)
1.一种铜及铜合金的微蚀刻剂，其特征在于，所述微蚀刻剂由含有二价铜离子源酸解离常数pKa小于5的有机酸及卤离子源的水溶液组成。
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| JP7196637A JP2923524B2 (ja) | 1995-08-01 | 1995-08-01 | 銅および銅合金のマイクロエッチング剤並びにマイクロエッチング方法 |
| JP196637/95 | 1995-08-01 |
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- 1996-07-22 EP EP96111792A patent/EP0757118B1/en not_active Expired - Lifetime
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| CN101331595B (zh) * | 2005-12-21 | 2010-08-11 | 麦克德米德有限公司 | 微蚀刻组合物及使用它的方法 |
| CN102985596A (zh) * | 2010-06-18 | 2013-03-20 | 三菱瓦斯化学株式会社 | 用于包含铜层和钼层的多层结构膜的蚀刻液 |
| CN102985596B (zh) * | 2010-06-18 | 2016-08-10 | 三菱瓦斯化学株式会社 | 用于包含铜层和钼层的多层结构膜的蚀刻液 |
| US9580818B2 (en) | 2010-06-18 | 2017-02-28 | Mitsubishi Gas Chemical Company, Inc. | Etching liquid for film of multilayer structure containing copper layer and molybdenum layer |
| CN103781941A (zh) * | 2012-07-24 | 2014-05-07 | Mec股份有限公司 | 铜微蚀刻液及其补充液、以及配线基板的制造方法 |
| CN103781941B (zh) * | 2012-07-24 | 2015-04-08 | Mec股份有限公司 | 铜微蚀刻液及其补充液、以及配线基板的制造方法 |
| CN104694909A (zh) * | 2014-07-03 | 2015-06-10 | 广东丹邦科技有限公司 | 一种铜表面粗化剂 |
| CN104694909B (zh) * | 2014-07-03 | 2017-01-25 | 广东丹邦科技有限公司 | 一种铜表面粗化剂 |
| CN107488856A (zh) * | 2016-06-10 | 2017-12-19 | 三星显示有限公司 | 蚀刻液组合物及使用它的薄膜晶体管显示面板的制造方法 |
| CN108930038A (zh) * | 2017-05-22 | 2018-12-04 | 东友精细化工有限公司 | 银薄膜蚀刻液组合物、蚀刻方法和金属图案的形成方法 |
| CN108930038B (zh) * | 2017-05-22 | 2021-03-16 | 东友精细化工有限公司 | 银薄膜蚀刻液组合物、蚀刻方法和金属图案的形成方法 |
| CN111094628A (zh) * | 2017-09-22 | 2020-05-01 | Mec股份有限公司 | 铜的微蚀刻剂、铜表面的粗化方法以及配线基板的制造方法 |
| CN111094628B (zh) * | 2017-09-22 | 2021-06-04 | Mec股份有限公司 | 微蚀刻剂、铜表面的粗化方法以及配线基板的制造方法 |
| US11208726B2 (en) | 2017-09-22 | 2021-12-28 | Mec Company Ltd. | Microetching agent for copper, copper surface roughening method and wiring board production method |
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| CN115110085A (zh) * | 2021-10-23 | 2022-09-27 | 赵晓峰 | 一种铜及合金过氧化氢化学抛光体系中改进脱膜工序的新方法 |
| CN114457335A (zh) * | 2022-02-15 | 2022-05-10 | 江西省科学院应用物理研究所 | 一种铜铁碳合金金相浸蚀剂及其使用方法 |
| CN114457335B (zh) * | 2022-02-15 | 2023-10-27 | 江西省科学院应用物理研究所 | 一种铜铁碳合金金相浸蚀剂及其使用方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0757118B1 (en) | 2001-04-04 |
| DE69612336D1 (de) | 2001-05-10 |
| JP2923524B2 (ja) | 1999-07-26 |
| JPH0941163A (ja) | 1997-02-10 |
| TW366368B (en) | 1999-08-11 |
| EP0757118A1 (en) | 1997-02-05 |
| DE69612336T2 (de) | 2001-09-20 |
| KR970011017A (ko) | 1997-03-27 |
| CN1090686C (zh) | 2002-09-11 |
| US5807493A (en) | 1998-09-15 |
| KR100409189B1 (ko) | 2004-06-04 |
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