CN1924091B - 用于金属表面处理的水溶液和防止金属表面变色的方法 - Google Patents
用于金属表面处理的水溶液和防止金属表面变色的方法 Download PDFInfo
- Publication number
- CN1924091B CN1924091B CN200610126251XA CN200610126251A CN1924091B CN 1924091 B CN1924091 B CN 1924091B CN 200610126251X A CN200610126251X A CN 200610126251XA CN 200610126251 A CN200610126251 A CN 200610126251A CN 1924091 B CN1924091 B CN 1924091B
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- tin
- value
- acid
- film
- 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.)
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Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002845 discoloration Methods 0.000 title abstract 2
- 238000004381 surface treatment Methods 0.000 title description 7
- 239000010408 film Substances 0.000 claims description 62
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 42
- 239000004471 Glycine Substances 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- 239000010409 thin film Substances 0.000 claims description 18
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 17
- 150000003863 ammonium salts Chemical class 0.000 claims description 15
- 229920000388 Polyphosphate Polymers 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 239000001205 polyphosphate Substances 0.000 claims description 13
- 235000011176 polyphosphates Nutrition 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 abstract description 25
- 150000001875 compounds Chemical class 0.000 abstract description 20
- 229910000679 solder Inorganic materials 0.000 abstract description 11
- 238000007747 plating Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 235000019830 sodium polyphosphate Nutrition 0.000 description 12
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 description 9
- 229930064664 L-arginine Natural products 0.000 description 9
- 235000014852 L-arginine Nutrition 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229910001128 Sn alloy Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- -1 phospho Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000013339 cereals Nutrition 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
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-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
- 238000005299 abrasion Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 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
- 238000003287 bathing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 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
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- MSXHSNHNTORCAW-GGLLEASOSA-M sodium;(2s,3s,4s,5r,6s)-3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].O[C@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O MSXHSNHNTORCAW-GGLLEASOSA-M 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 1
- GUEGQOBGTVZOIM-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;potassium Chemical compound [K].[K].OC(=O)CC(O)(C(O)=O)CC(O)=O GUEGQOBGTVZOIM-UHFFFAOYSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- GPSAAQWVJOVCBK-UHFFFAOYSA-N [K].[K].[K].OC(=O)CC(O)(C(O)=O)CC(O)=O Chemical compound [K].[K].[K].OC(=O)CC(O)(C(O)=O)CC(O)=O GPSAAQWVJOVCBK-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 229960005261 aspartic acid Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 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
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- NFIYTPYOYDDLGO-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].OP(O)(O)=O NFIYTPYOYDDLGO-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/58—Treatment of other metallic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/495—Lead-frames or other flat leads
- H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
- H01L23/49582—Metallic layers on lead frames
-
- 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
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
- H05K3/3473—Plating of solder
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
- H01L2224/818—Bonding techniques
- H01L2224/81801—Soldering or alloying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
提供了一种焊料镀膜,该镀膜具有良好的焊料润湿性,防止了锡薄膜加热之后的变色和翘曲。揭示了一种用来对锡薄膜进行表面处理的方法和溶液。该水溶液包含某些化合物,在对锡薄膜进行软熔处理之前,使该水溶液与镀锡薄膜接触。
Description
技术领域
本发明涉及用于金属、具体来说是锡镀膜的表面处理的溶液;还涉及对锡镀膜进行表面处理的方法。更具体来说,本发明涉及一种方法,该方法是在使用镀锡法形成锡薄膜的时候,在进行软熔处理之前,对所述锡镀膜的表面施加用于表面处理的溶液;本发明还涉及所述方法所用的处理溶液。
背景技术
锡和锡合金薄膜具有极佳的粘着性质、低廉的成本、电性质和可焊性;因此被广泛地用于芯片、晶体振荡器、引线框、印刷电路和其他电子元件之类的需要电接触的部件中,还在半导体和印刷基片制造的步骤中广泛地用作抗蚀剂。
随着时间的流逝,未处理的镀锡和镀锡合金的表面上会形成被称为须晶的毛发状金属沉淀物。当形成在用于电子元件等的基片表面上的锡或锡合金薄膜的表面上生成须晶时,可能会发生电短路。众所周知,在锡或锡合金薄膜形成之后,进行高温处理(即软熔处理),以防形成这种须晶或并借此形成有光泽的锡或锡合金薄膜表面。但是软熔处理的一个问题在于,尽管可以观察到防止须晶生成的效果,但是薄膜表面在加热时容易发生变色和氧化。薄膜表面的氧化被认为是镀膜表面变色的一个因素;随着氧化膜变得越来越厚,薄膜发生变色;镀膜的氧化还会降低焊料润湿性。锡是一种容易氧化的金属,过去已使用锡铅合金来应对锡薄膜的这些问题。铅具有控制锡的氧化和须晶生长的效果。然而,由于近来人们所关注的铅的毒性,铅在电子元件中的应用受到了限制。因此,人们需要无铅的锡或锡合金镀敷,还需要用来防止其镀膜氧化和形成须晶的方法。
另一方面,已知锡镀膜与镀锡-铅合金的薄膜不同,软熔处理容易凿成锡镀膜表面翘曲(twisting)。在这里,术语“翘曲”表示锡薄膜中出现的起伏凸起,在一些情况下,这种翘曲会形成木纹图案。薄膜表面上的这种翘曲所导致的问题是,锡薄膜的厚度不均匀,而且根据情况,基材(例如镍)会暴露出来,使得难以保证可焊性。因此,需要防止镀膜翘曲。
多年来,已有种锡薄膜表面处理的方案和方法用于镀锡钢板的表面处理。例如JP(Kokai)52-53739号揭示了一种镀锡钢板的表面处理方法,该方法使用加入了5-50克/升游离酸形式的磷酸或磷酸与亚磷酸的混合物或连二磷酸的水溶液。另外,根据该专利,将处理浴的pH值调节至等于或小于4。该专利未揭示在软熔处理之前使用本发明的化合物或溶液进行表面处理。
JP(Kokoku)58-1085号揭示了一种用来防止镀锡表面上形成木纹图案的方法,在此方法中,在对电镀了锡的钢带进行软熔处理之前,对该刚带的表面施用有机酸或其盐的水溶液,所述有机酸或其盐的熔点为170-300℃,而且能够在软熔的时候分解。该专利中列举的所述有机酸或其盐为葡糖酸钠、谷氨酸单钠盐、乙二胺四乙酸钠(EDTA)等。另外,根据该专利,施用磷酸钠并不能消除镀锡表面上的木纹图案,这种化合物不适合。该专利未揭示用于本发明的或用于电子元件的化合物的优良性质。
JP(Kokai)7-286285号揭示了一种用来进行化学转化处理的水溶液,该水溶液的pH值等于或小于5.0,包含磷酸离子、有机膦酸和锡离子;该水溶液被用于镀锡钢板的表面。该专利揭示了一种化学转化水溶液,其主要组分是有机膦酸化合物,该专利未揭示本发明的化合物或其有益的性能。
本发明的目的是提供具有良好的焊料润湿性的镀膜,以及用来形成该镀膜的方法,通过该方法,即使在对用于电子元件的锡或锡合金镀膜进行软熔处理之后,仍然能够使得镀膜无翘曲,而且变色得到控制。
为完成上述目的,本发明人对用来在软熔处理镀膜之前对锡镀膜进行表面处理的水溶液进行了详细的研究,结果发现了磷酸铵盐之类的某些化合物相对于包含具有类似结构的其他化合物的水溶液而言具有选择效用,从而完成了本发明。本发明用于表面处理的水溶液可以制得不会发生变色、而且具有良好的焊料润湿性的镀膜,使用该水溶液还可防止镀膜翘曲。
发明内容
本发明第一方面涉及:用来对锡镀膜进行表面处理的水溶液,该水溶液是pH值为3-5的包含磷酸的铵盐的溶液;用来对锡镀膜进行表面处理的水溶液是pH值为2-10的包含多磷酸盐的溶液;用来对锡镀膜进行表面处理的水溶液是pH值为4.5-8.5的包含马来酸盐的溶液;用来对锡镀膜进行表面处理的水溶液是pH值为7-12的包含L-精氨酸的溶液;用来对锡镀膜进行表面处理的水溶液是pH值为4-7的包含甘氨酸的溶液;或者用来对锡镀膜进行表面处理的水溶液,该溶液由磷酸的铵盐和多磷酸盐的混合物、甘氨酸和磷酸的铵盐的混合物、或者甘氨酸和多磷酸铵盐的混合物组成。
本发明第二方面涉及一种对锡镀膜进行表面处理的方法,其中使用上述用来对锡镀膜进行表面处理的水溶液处理锡薄膜。
本发明第三方面涉及一种对锡镀膜进行表面处理的方法,在此方法中,在基片表面上进行镀锡,形成锡薄膜,然后用上述用来对锡镀膜进行表面处理的水溶液处理锡薄膜的表面。
本发明第四方面涉及一种在金属上形成锡镀膜的方法,该方法包括以下步骤:制备表面上具有金属的基片;用酸活化该基片;在活化后的基片上镀锡;使用用于表面处理的水溶液处理所述锡镀膜;对锡薄膜进行软熔处理,所述用来进行表面处理的水溶液是上述用来对锡镀膜进行表面处理的水溶液。
本发明第五方面涉及一种用来制造具有锡薄膜的电子部件的方法,该方法包括以下步骤:在对基片镀锡和对具有锡薄膜的基片进行软熔处理的步骤之间,用上述用于锡镀膜表面处理的水溶液处理所述锡薄膜的表面。
具体实施方式
除非另外说明,本说明书中所用缩写的含义如下:g=克,mg=毫克;℃=摄氏度;V=伏特,A=安培,m=米;cm=厘米;μm=微米,L=升;mL=毫升;dm2=立方分米。所有的数据范围均包括端值,而且可以任意顺序组合。
在本说明书中,术语“镀液”和“镀浴”含义相同,可以互换使用。
所述用来对锡镀膜进行表面处理的水溶液包含水和选自以下的一种或多种化合物:磷酸的铵盐,多磷酸盐,以及甘氨酸、L-精氨酸和马来酸的盐。
本发明的多磷酸盐和马来酸盐的例子是铵盐以及钠盐、钾盐和其他碱金属盐,但是并不限于此。
所述选自磷酸的铵盐,多磷酸盐,以及甘氨酸、L-精氨酸和马来酸的盐的一种或多种化合物以化合物的形式存在于所述用于表面处理的水溶液中,其含量为5-100克/升、优选10-80克/升,特别优选30-60克/升。
本发明用来对锡镀膜进行表面处理的水溶液具有根据其组分预先确定的最佳pH范围。例如,当该溶液包含磷酸的铵盐的时候,其pH值为3-5,优选大于4至4.5;当使用L-精氨酸时,pH值为7-12;当使用马来酸时,pH值为6-9;当使用多磷酸盐时,其pH值为2-10,优选6-10;当使用甘氨酸时,pH值为4-7。另外,当该水溶液包含磷酸的铵盐和多磷酸盐的混合物时,其pH值为4-7,优选为5-6;当该溶液包含磷酸的铵盐和甘氨酸时,其pH值为4-6,优选4-5;当该水溶液包含多磷酸盐和甘氨酸的混合物的时候,其pH值优选为7-9,特别优选为7-8。可使用常规的pH调节剂来调节pH值。例如,可使用磷酸或乙酸来降低pH值,加入氨水、氢氧化钠或氢氧化钾来提高pH值。在优选的实施方式中,使用构成溶液中所含组分的酸或碱来调节该水溶液的pH值。例如,优选的是,当所述水溶液包含磷酸的铵盐的时候,用磷酸或氨来调节溶液的pH值。另外,优选的是当该溶液包含多磷酸盐时,用多磷酸或构成所述盐的碱组分调节水溶液的pH值。另外,当溶液包含马来酸盐时,优选用马来酸或构成所述的盐的碱组分调节水溶液的pH值。
使用本发明用来进行表面处理的水溶液的浴温通常为10-100℃、优选室温(25℃)至70℃、最佳为40-70℃。
可以根据需要向本发明加入常规的添加剂,例如表面活性剂、抗菌剂和溶剂,但是基本上是不需要的。
可通过浸渍处理或喷雾处理之类的常规方法将本发明的用于锡镀膜表面处理的试剂施用在基片上。通常用水洗涤锡薄膜的表面,然后通过浸渍或喷雾施用本发明的用来对锡镀膜进行表面处理的溶液。处理时间通常为5-120秒,优选为10-60秒。然后通常依次对产品进行淋洗、纯水洗涤和干燥。
本发明的处理溶液对电子元件等的锡镀膜的表面处理是理想之选。这些元件包括片状电阻器、片状电容器和其他片状元件;插头;缓冲器;印刷电路板;引线框;和其他电子元件。
通过以下操作实施例可以清楚地看出,本发明所用的化合物;具体来说是磷酸,多磷酸盐,以及甘氨酸、L-精氨酸和马来酸的盐相对于其他类似的化合物具有显著的功效。也即是说,通过在软熔处理之前施用本发明的用于表面处理的溶液对锡镀膜进行表面处理,可以控制薄膜表面的变色和翘曲,可以形成即使在软熔处理之后也仍具有良好的焊料润湿性的锡镀膜。
下面将通过操作实施例和比较例详细描述本发明。
在操作实施例和比较例中依照如下标准来评价外观、变色和翘曲。
(1)外观
对使用用于表面处理的溶液处理过的锡镀膜进行软熔处理并干燥。然后目视观察锡镀膜表面的有光泽和镀敷外观均匀性(外观中的不规则结构),根据以下四个等级对进行评价。
1:有光泽而均匀:有光泽、均匀的薄膜
2:有光泽、不规则:有光泽、但不规则的薄膜
3:无光泽,均匀:无光泽、但均匀的薄膜
4:无光泽,不规则:无光泽、不规则的薄膜
(2)变色
对使用用于表面处理的溶液处理过的锡镀膜进行软熔处理并干燥。然后目视观察锡镀膜表面变色,根据以下四个等级进行评价。
优秀:无变色
良好:基本无变色(非常有光泽)
一般:轻微变白、变灰、变黄或其他变色。
差:变棕色或变紫色。
(3)翘曲
对使用用于表面处理的溶液处理过的锡镀膜进行软熔处理并干燥。目视观察锡镀膜表面的翘曲,根据以下四个等级进行评价。
优秀:无翘曲
良好:基本无翘曲
一般:轻微翘曲
差:翘曲
操作实施例1-4和比较例0-38
在4伏的电压下,在浴温60℃的碱性电解脱脂剂(Cleaner 160P,Meltex Inc.)溶液中对铜引线框进行1分钟的阴极电解脱脂;用水淋洗产品;通过在室温下将其在过硫酸盐化学磨蚀剂(Actronal 55)中浸渍30分钟,进行化学磨蚀;产物用水淋洗,在10%的硫酸溶液中用酸洗涤,然后用水洗涤;在55℃的不含添加剂的瓦兹镀槽中,在3安/立方分米的电流密度下镀镍2分钟,形成1微米厚的镍膜;产品用水淋洗;使用常规的甲磺酸镀锡浴(SOLDERONTM TMBT-280镀锡)形成3微米厚的锡镀膜;产品用水淋洗,在具有表1所示组成和pH值的25℃的水溶液中浸渍30秒,用水淋洗,然后干燥。多磷酸钠由Kanto Chemical Co.,Inc制造。干燥之后,使用软熔装置(Japan Pulse Laboratories,Inc.生产,型号为RF-330)在260℃下进行1分钟的软熔处理,评价各个部件上锡膜的外观、变色和翘曲。评价结果列于表1。
表1
比较例 | 化合物 | 含量 | pH值 | 外观 | 变色 | 翘曲 |
1 | 磷酸二氢铵 | 50 | 4.21 | 1 | 良好 | 良好 |
2 | 多磷酸钠 | 50 | 7.95 | 1 | 一般 | 良好 |
3 | L-精氨酸 | 50 | 11.67 | 1 | 一般 | 良好 |
4 | 甘氨酸 | 50 | 6.17 | 1 | 一般 | 良好 |
比较例 | ||||||
0 | 未处理 | n/a | 1 | 差 | 差 | |
1 | 磷酸氢二胺 | 50 | 7.95 | 4 | 一般 | 一般 |
2 | 磷酸三铵 | 50 | 9.68 | 1 | 一般 | 差 |
3 | 四水合磷酸二钠铵 | 50 | 8.13 | 1 | 一般 | 一般 |
4 | 磷酸氢钾 | 50 | 4.63 | 4 | 一般 | 差 |
5 | 磷酸氢二钾 | 50 | 9.18 | 4 | 一般 | 一般 |
6 | 磷酸三钠 | 50 | ≥12 | 1 | 一般 | 一般 |
7 | 磷酸 | 50 | 1.07 | 4 | 一般 | 一般 |
8 | 甲磺酸 | 50 | 1 | 1 | 一般 | 差 |
9 | 三聚磷酸钠 | 50 | 9.28 | 4 | 一般 | 一般 |
10 | 次膦酸 | 50 | 1.04 | 4 | 差 | 差 |
11 | 焦磷酸钠 | 50 | 10.95 | 1 | 一般 | 一般 |
12 | 偏磷酸钠 | 50 | 6.06 | 1 | 一般 | 一般 |
13 | 六偏磷酸钠 | 50 | 5.96 | 1 | 差 | 差 |
14 | 乳酸 | 50 | 2 | 1 | 差 | 差 |
表1(续)
比较例 | 化合物 | 含量 | pH值 | 外观 | 变色 | 翘曲 | |
15 | 柠檬酸 | 50 | 1.82 | 4 | 差 | 差 | |
16 | 一水合柠檬酸 | 50 | 1.81 | 4 | 一般 | 一般 | |
17 | 柠檬酸二钾 | 50 | 4.94 | 1 | 差 | 差 | |
18 | 柠檬酸三钾 | 50 | 8.25 | 1 | 差 | 差 | |
19 | 柠檬酸铵 | 50 | 4.89 | 4 | 一般 | 差 | |
20 | 丙二酸 | 50 | 2.27 | 4 | 一般 | 一般 | |
21 | 衣康酸 | 50 | 2.27 | 4 | 一般 | 一般 | |
22 | 丙氨酸 | 50 | 6.17 | 1 | 一般 | 差 | |
23 | L-天冬氨酸 | 50 | ≥12 | 1 | 差 | 一般 | |
24 | 烟酸 | 50 | 5.89 | 1 | 一般 | 差 | |
25 | 苹果酸 | 50 | 1.18 | 4 | 差 | 差 | |
26 | 次氮基三乙酸 | 50 | 3.89 | 1 | 差 | 差 | |
27 | 酒石酸 | 50 | 1.67 | 1 | 差 | 差 | |
28 | 亚氨基二乙酸 | 50 | 3.06 | 1 | 差 | 差 | |
29 | 琥珀酸 | 50 | 2.27 | 4 | 一般 | 差 | |
30 | 山梨酸钾 | 50 | 8.25 | 1 | 一般 | 一般 | |
31 | 葡糖酸钠 | 50 | 6.82 | 1 | 一般 | 差 | |
32 | 乙酸 | 50 | 2.36 | 4 | 差 | 一般 | |
33 | 氨 | 50 | ≥12 | 1 | 一般 | 差 | |
34 | 吡啶甲酸 | 50 | 3.17 | 1 | 差 | 差 |
35 | 硼酸 | 50 | 3.65 | 1 | 差 | 差 | |
36 | 硫氰酸铵 | 50 | 4.98 | 1 | 差 | 差 | |
37 | L-抗坏血酸 | 50 | 2.34 | 1 | 差 | 差 | |
38 | 亚硫酸铵 | 50 | 8.19 | 1 | 差 | 差 |
证明了相对于比较例中的水溶液,操作实施例中所用的化合物制备的用于表面处理的水溶液减少了进行过软熔处理后的锡镀膜的变色和翘曲。
在表2所示的处理条件下,依照操作实施例1对操作实施例1-4的化合物或使用马来酸盐制备的用于表面处理的水溶液进行了评价。将操作实施例1-4中的化合物或马来酸以50克/升的量加入水中;对于磷酸二氢铵水溶液,使用磷酸或氨调节pH值,对于多磷酸钠水溶液,使用磷酸或氢氧化钠调节pH值,对于马来酸或L-精氨酸水溶液,使用乙酸或氢氧化钠调节pH值,对于甘氨酸水溶液,使用乙酸或氨调节pH值;对于用于表面处理的水溶液各自进行最佳pH值测试。与此同时,浴温在25-60℃变化,该温度范围被认为是常用的浴温范围,还研究了温度的影响。
评价结果列于表2。
表2
比较例 | 化合物 | pH值 | 浴温℃ | 外观 | 变色 | 翘曲 |
5 | 磷酸二氢铵 | 4.3 | 25 | 1 | 良好 | 良好 |
6 | 磷酸二氢铵 | 4.3 | 40 | 1 | 优秀 | 良好 |
7 | 磷酸二氢铵 | 4.3 | 60 | 1 | 优秀 | 优秀 |
比较例39 | 磷酸二氢铵 | 2 | 25 | 4 | 一般 | 一般 |
比较例40 | 磷酸二氢铵 | 6 | 25 | 1 | 一般 | 差 |
8 | 多磷酸钠 | 2 | 25 | 1 | 一般 | 良好 |
9 | 多磷酸钠 | 6 | 25 | 1 | 优秀 | 优秀 |
10 | 多磷酸钠 | 8 | 40 | 1 | 优秀 | 良好 |
11 | 多磷酸钠 | 8 | 60 | 1 | 优秀 | 良好 |
12 | 多磷酸钠 | 10 | 25 | 1 | 优秀 | 良好 |
13 | 多磷酸钠 | 10 | 40 | 1 | 优秀 | 优秀 |
14 | 甘氨酸 | 6.2 | 40 | 1 | 优秀 | 优秀 |
15 | 甘氨酸 | 6.2 | 60 | 1 | 优秀 | 优秀 |
16 | 甘氨酸 | 4 | 25 | 1 | 优秀 | 良好 |
17 | 甘氨酸 | 9 | 25 | 1 | 一般 | 良好 |
18 | L-精氨酸 | 12 | 40 | 1 | 优秀 | 优秀 |
19 | L-精氨酸 | 12 | 60 | 1 | 优秀 | 良好 |
比较例41 | 马来酸 | 4 | 25 | 1 | 优秀 | 一般 |
20 | 马来酸 | 6 | 25 | 1 | 优秀 | 良好 |
比较例42 | 马来酸 | 9 | 25 | 1 | 优秀 | 一般 |
当pH为2-6(比较例39和40)的时候,磷酸的铵盐获得了良好的“翘曲”结果,但是如操作实施例1和5-7所示,当pH值为4.21-4.3时,也获得了良好的外观、变色和翘曲结果。另外,在25-60℃的温度范围内也观察到了良好的结果。
另外,如操作实施例2和8-13所示,当pH为2-10的时候,多磷酸钠得到了良好的外观、变色和翘曲结果。在25-60℃的温度范围内进行观察到这些良好的结果。
如操作实施例4和14-17所示,当pH值为4-9时,甘氨酸获得了良好的外观、变色和翘曲结果。在25-60℃的温度范围内观察到这些良好的结果。
如操作实施例3[sic],18和19所示,当pH值为4-9时,L-精氨酸得到了良好的外观、变色和翘曲结果。
如比较例41和42所示,尽管当pH值为4或9时,马来酸未得到良好的“翘曲”结果,但是在pH值等于6时,马来酸获得了各种性质的良好结果。
如表3所示使用两种化合物制备本发明的用来对锡薄膜进行表面处理的溶液,并依照操作实施例1所示进行评价。用于表面处理的水溶液的浴温为40℃。
表3
比较例 | pH | 外观 | 变色 | 翘曲 | ||
24 | 磷酸二氢铵25克/升 | 甘氨酸25克/升 | 4.65 | 1 | 优秀 | 优秀 |
25 | 磷酸二氢铵25克/升 | 多磷酸钠25克/升 | 5.86 | 1 | 优秀 | 优秀 |
26 | 甘氨酸25克/升 | 多磷酸钠25克/升 | 7.81 | 1 | 优秀 | 良好 |
操作实施例27和28(焊料润湿性测试)
在与操作实施例1和5相同的条件下制备进行过锡薄膜表面处理的引线框,不同之处在于,操作实施例1和5中用于表面处理的水溶液的处理温度为60℃。在105℃、100%相对湿度的条件下对制得的引线框进行4小时和8小时的防潮性测试(PCT(105℃,100%相对湿度,4或8小时)),使用SAT-5000 Solder Checker(RHESCA Co.,Ltd.),通过月牙图法(meniscograph method)测量进行防潮性测试之后的镀膜的零交叉时间,从而评价其焊料润湿性。测量条件如下。
零交叉时间测量条件
焊料浴: Sn/Pb=63/37
浴温: 235℃
浸入深度:1毫米
浸没速度:10毫米/秒
浸没时间:5秒
焊剂: 钝化松香
表4显示了上述测试测得的结果。
表4
镀锡电流密度安/平方分米 | 处理溶液 | 防潮性测试之后的焊料润湿性 | ||
处理后 | PCT 4小时 | PCT 8小时 | ||
5 | 操作实施例1 | 0.2秒 | 0.3秒 | 1秒 |
5 | 操作实施例5 | 0.2秒 | 0.3秒 | 1.1秒 |
15 | 操作实施例1 | 0.2秒 | 0.3秒 | 0.3秒 |
15 | 操作实施例5 | 0.2秒 | 0.3秒 | 0.3秒 |
20 | 操作实施例1 | 0.2秒 | 0.3秒 | 0.4秒 |
20 | 操作实施例5 | 0.2秒 | 0.3秒 | 0.3秒 |
对各种电流密度调节镀锡时间,使得镀膜厚度一致。操作实施例1和5中用于表面处理的水溶液得到良好的焊料润湿性。
根据本发明的锡镀膜表面处理溶液,可以形成具有极佳的耐腐蚀性和抗翘曲性的薄膜。也即是说,可以通过在对锡镀膜软熔处理之前使用本发明的表面处理溶液,减少锡薄膜加热之后的变色,形成具有良好可焊性的锡薄膜。
Claims (1)
1.一种用来在金属上形成锡镀膜的方法,该方法包括以下步骤:
a)制备表面上具有金属的基片;
b)用酸活化该基片;
c)在活化后的基片上镀锡;
d)使用选自以下的水溶液处理所述锡镀膜:
(1)pH值为3-5的包含磷酸的铵盐的水溶液;
(2)pH值为2-10的包含多磷酸盐的水溶液;
(3)pH值为4.5-8.5的包含马来酸盐的水溶液;
(4)pH值为7-12的包含L-精氨酸的水溶液;
(5)pH值为4-7的包含甘氨酸的水溶液;
(6)包含磷酸的铵盐和多磷酸盐的混合物的水溶液,该水溶液的pH为4-7;
(7)包含甘氨酸和磷酸的铵盐的混合物的水溶液,该水溶液的pH值为4-6;或
(8)包含甘氨酸和多磷酸盐的混合物的水溶液,该水溶液的pH值为7-9;和
e)对锡薄膜进行软熔处理。
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JP2010070838A (ja) * | 2008-09-22 | 2010-04-02 | Rohm & Haas Electronic Materials Llc | 金属表面処理水溶液および金属表面のウィスカ抑制方法 |
US8491713B2 (en) | 2009-01-14 | 2013-07-23 | Atotech Deutschland Gmbh | Solution and process for increasing the solderability and corrosion resistance of a metal or metal alloy surface |
JP5464869B2 (ja) * | 2009-03-02 | 2014-04-09 | Dowaメタルテック株式会社 | Sn被覆銅又は銅合金及びその製造方法 |
JP5464876B2 (ja) * | 2009-03-17 | 2014-04-09 | Dowaメタルテック株式会社 | Sn被覆銅又は銅合金及びその製造方法 |
CN102002700B (zh) * | 2010-12-09 | 2012-05-09 | 湖南华菱湘潭钢铁有限公司 | 钢板表面短期防锈蚀覆膜工艺方法 |
CN102242383B (zh) * | 2011-06-30 | 2014-04-16 | 上海华友金裕微电子有限公司 | 一种太阳能焊带电镀的后处理方法 |
CN102776496B (zh) * | 2012-04-20 | 2014-03-05 | 昆山艾森半导体材料有限公司 | 高温回流用锡层防变色剂及其制备方法和使用方法 |
CN102677037B (zh) * | 2012-05-25 | 2013-09-11 | 广州市天承化工有限公司 | 一种化学锡后处理溶液组合物 |
CN103212921B (zh) * | 2012-06-26 | 2015-03-18 | 深圳市堃琦鑫华股份有限公司 | 一种还原剂组合物及其制备方法、一种焊接方法 |
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CN110753457A (zh) * | 2019-11-05 | 2020-02-04 | 江苏上达电子有限公司 | 一种提高cof化锡后保存寿命的方法 |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4306917A (en) * | 1979-12-29 | 1981-12-22 | Nihon Parkerizing Co., Ltd. | Conversion coating solutions for treating metallic surfaces |
US4331518A (en) * | 1981-01-09 | 1982-05-25 | Vulcan Materials Company | Bismuth composition, method of electroplating a tin-bismuth alloy and electroplating bath therefor |
US5470636A (en) * | 1991-03-15 | 1995-11-28 | Yamaha Corporation | Magnetic recording medium and method of producing it |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3338725A (en) * | 1964-05-14 | 1967-08-29 | M & T Chemicals Inc | Novel plating process and composition |
US3949058A (en) * | 1973-12-20 | 1976-04-06 | Union Oil Company Of California | Production of ammonium polyphosphates |
JPS581085B2 (ja) | 1975-03-14 | 1983-01-10 | 三菱瓦斯化学株式会社 | メタノ−ルノ セイセイホウホウ |
JPS5253739A (en) * | 1975-10-30 | 1977-04-30 | Nippon Steel Corp | Surface treatment of galvanized steel |
JPS5782491A (en) | 1980-11-11 | 1982-05-22 | Seiko Instr & Electronics Ltd | Copper-tin alloy plating bath |
JPS6014116B2 (ja) * | 1981-06-25 | 1985-04-11 | 日本鋼管株式会社 | 電気錫メツキ鋼ストリツプの木目模様発生防止方法 |
JPS5947396A (ja) * | 1982-09-08 | 1984-03-17 | Toyo Kohan Co Ltd | シ−ムレス缶用電気めつきぶりき |
US4992259A (en) | 1990-01-03 | 1991-02-12 | Johnson & Johnson Consumer Products, Inc. | Stable oral composition of zinc |
JPH059785A (ja) * | 1991-07-09 | 1993-01-19 | Furukawa Electric Co Ltd:The | リフロー錫および錫合金めつき法の前処理方法 |
US5661219A (en) * | 1993-09-06 | 1997-08-26 | Nof Corporation | Curable composition, thermal latent acid catalyst, method of coating, coated article, method of molding and molded article |
JP3366724B2 (ja) | 1994-04-20 | 2003-01-14 | 日本ペイント株式会社 | 金属表面用化成処理水溶液 |
US6319543B1 (en) * | 1999-03-31 | 2001-11-20 | Alpha Metals, Inc. | Process for silver plating in printed circuit board manufacture |
US6361823B1 (en) * | 1999-12-03 | 2002-03-26 | Atotech Deutschland Gmbh | Process for whisker-free aqueous electroless tin plating |
US7628903B1 (en) * | 2000-05-02 | 2009-12-08 | Ishihara Chemical Co., Ltd. | Silver and silver alloy plating bath |
JP4759891B2 (ja) * | 2001-09-13 | 2011-08-31 | 株式会社村田製作所 | セラミックス電子部品の製造方法 |
AU2002338038B2 (en) | 2001-09-27 | 2005-08-18 | Tanabe Seiyaku Co., Ltd. | Aqueous ecabet sodium solution preparation |
JP3621370B2 (ja) * | 2001-11-07 | 2005-02-16 | 株式会社大和化成研究所 | めっき方法による二次電池用電極材料 |
CN1363552A (zh) | 2002-01-18 | 2002-08-14 | 马东文 | 甘氨酸锌(C4H8O4NnZn)的制备方法及其应用 |
CN1515295A (zh) | 2003-01-08 | 2004-07-28 | 上海盛平医药科技有限公司 | 黄芪注射液及其制备方法 |
JP4461295B2 (ja) * | 2003-06-03 | 2010-05-12 | 石原薬品株式会社 | 中性光沢スズ−亜鉛合金メッキ浴 |
JP2005097669A (ja) * | 2003-09-24 | 2005-04-14 | Ishihara Chem Co Ltd | メッキ表面の後処理液、及び後処理方法 |
-
2005
- 2005-08-22 JP JP2005240431A patent/JP4733468B2/ja active Active
-
2006
- 2006-08-18 TW TW095130387A patent/TWI348501B/zh active
- 2006-08-21 US US11/507,221 patent/US8043662B2/en active Active
- 2006-08-21 CN CN200610126251XA patent/CN1924091B/zh active Active
- 2006-08-21 EP EP06254373.1A patent/EP1757715B1/en active Active
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-
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- 2013-03-29 KR KR1020130034258A patent/KR101299114B1/ko active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4306917A (en) * | 1979-12-29 | 1981-12-22 | Nihon Parkerizing Co., Ltd. | Conversion coating solutions for treating metallic surfaces |
US4331518A (en) * | 1981-01-09 | 1982-05-25 | Vulcan Materials Company | Bismuth composition, method of electroplating a tin-bismuth alloy and electroplating bath therefor |
US5470636A (en) * | 1991-03-15 | 1995-11-28 | Yamaha Corporation | Magnetic recording medium and method of producing it |
Non-Patent Citations (1)
Title |
---|
JP昭57-82491A 1982.05.22 |
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