CN1993499A - 无电解镀金液 - Google Patents
无电解镀金液 Download PDFInfo
- Publication number
- CN1993499A CN1993499A CNA2005800260775A CN200580026077A CN1993499A CN 1993499 A CN1993499 A CN 1993499A CN A2005800260775 A CNA2005800260775 A CN A2005800260775A CN 200580026077 A CN200580026077 A CN 200580026077A CN 1993499 A CN1993499 A CN 1993499A
- Authority
- CN
- China
- Prior art keywords
- plating solution
- compound
- gold plating
- electroless gold
- gold
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 77
- 239000010931 gold Substances 0.000 title claims abstract description 54
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 54
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 53
- -1 hydrogensulfite compound Chemical class 0.000 claims abstract description 30
- 150000002344 gold compounds Chemical class 0.000 claims abstract description 11
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 29
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 abstract description 4
- 229910000679 solder Inorganic materials 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 abstract description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 abstract description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 abstract description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 abstract description 2
- 229940079826 hydrogen sulfite Drugs 0.000 abstract 2
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 abstract 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- WVEIDOWVCXKNJU-UHFFFAOYSA-J S([O-])(O)=O.[Au+3].[Na+].S([O-])(O)=O.S([O-])(O)=O.S([O-])(O)=O Chemical compound S([O-])(O)=O.[Au+3].[Na+].S([O-])(O)=O.S([O-])(O)=O.S([O-])(O)=O WVEIDOWVCXKNJU-UHFFFAOYSA-J 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 229960001484 edetic acid Drugs 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- JEOOVNWNJKBHRG-UHFFFAOYSA-N [Na+].[S--].[S--].[Au+3] Chemical compound [Na+].[S--].[S--].[Au+3] JEOOVNWNJKBHRG-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000006174 pH buffer Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- JCDVTZPJEWWGHU-UHFFFAOYSA-N gold sulfurous acid Chemical compound [Au].S(O)(O)=O JCDVTZPJEWWGHU-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 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
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- XKUKSGPZAADMRA-UHFFFAOYSA-N glycyl-glycyl-glycine Chemical compound NCC(=O)NCC(=O)NCC(O)=O XKUKSGPZAADMRA-UHFFFAOYSA-N 0.000 description 2
- YMAWOPBAYDPSLA-UHFFFAOYSA-N glycylglycine Chemical compound [NH3+]CC(=O)NCC([O-])=O YMAWOPBAYDPSLA-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- UCGZDNYYMDPSRK-UHFFFAOYSA-L trisodium;gold;hydroxy-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[Na+].[Au].OS([S-])(=O)=O.OS([S-])(=O)=O UCGZDNYYMDPSRK-UHFFFAOYSA-L 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 108010008488 Glycylglycine Proteins 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JYGLJXMZMDYLQX-UHFFFAOYSA-N [Au].S(=O)(=O)(O)OC#N Chemical compound [Au].S(=O)(=O)(O)OC#N JYGLJXMZMDYLQX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 239000007998 bicine buffer Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000002950 deficient Effects 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
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 108010067216 glycyl-glycyl-glycine Proteins 0.000 description 1
- 229940043257 glycylglycine Drugs 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229940076131 gold trichloride Drugs 0.000 description 1
- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical compound [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- UJLXKYSGBFPPAD-UHFFFAOYSA-N gold;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Au].OC(=O)CC(O)(C(O)=O)CC(O)=O UJLXKYSGBFPPAD-UHFFFAOYSA-N 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1642—Substrates other than metallic, e.g. inorganic or organic or non-conductive semiconductor
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
本发明提供一种毒性低、能在中性附近使用的、焊锡粘附性和被膜粘附性良好的非氰系置换型无电解镀金液。所述无电解镀金液，其特征在于，含有非氰系水溶性金化合物、和亚硫酸氢化合物。该镀液优选进一步含有硫代硫酸化合物、氨基羧酸化合物。作为亚硫酸氢化合物，可以使用亚硫酸氢钠、亚硫酸氢钾、亚硫酸氢铵等。
Description
技术领域
本发明涉及一种镀覆技术，特别是涉及一种非氰系的置换型无电解镀金液。
背景技术
置换型无电解镀金液正被用作为以提高印刷电路板的电路、端子等的软钎料(焊锡)粘附性、提高还原型金镀层等的粘附性为目的的中间层。出于这种目的而使用的很多镀金液，作为金化合物使用了毒性物质的氰化合物，而从对环境、作业性的关心出发，正需求不使用毒性物质的非氰系镀金液。
作为非氰系置换型无电解镀金液，曾提出了下述的专利申请：使用亚硫酸金化合物的无电解镀金液(例如参照专利文献1、专利文献2)；使用亚硫酸金盐、或氯金酸盐的无电解镀金液(例如参照专利文献3)；使用亚硫酸金、氯化金、硫代硫酸金、或巯基羧酸金的无电解镀金液(例如参照专利文献4)；等等。这些专利文献所记载的无电解镀金液由于是非氰系，因此毒性低，虽然可在中性附近使用，但是存在焊锡的粘附性和被膜粘附性差的问题。再者，所谓被膜粘附性是表示置换型无电解镀金被膜与基底的粘附性，置换型无电解镀金被膜作为中间层使用的场合，是表示与被膜的基底及被膜的上层的粘附性。
专利文献1：日本专利第3030113号公报
专利文献2：特开2003-13249号公报
专利文献3：特开平8-291389号公报
专利文献4：特开平10-317157号公报
发明内容
鉴于上述实际状况，本发明的目的在于，提供一种毒性低、能在中性附近使用、焊锡粘附性和被膜粘附性良好的非氰系置换型无电解镀金液。
本发明者们调查了对置换型无电解镀金被膜的焊锡粘附性和被膜粘附性造成不良影响的原因，结果发现与基底金属被膜、例如基底镍被膜的不均匀的置换是个问题。具体地讲，镀金被膜剥离后的基底镍被膜上可看到孔蚀等的不均匀的腐蚀痕的场合，由于置换型无电解镀金被膜上也存在某些缺陷，因此焊锡粘附性和被膜粘附性差，反之，没有不均匀的腐蚀痕的场合，焊锡粘附性和被膜粘附性良好。
于是，研究了剥离金后的基底镍被膜没有不均匀的腐蚀痕那样的浴组成，结果发现添加亚硫酸氢化合物(酸式亚硫酸化合物)有效，据此可以得到焊锡粘附性和被膜粘附性良好的镀金被膜。
即，本发明是如下的发明。
(1)一种置换型无电解镀金液，其特征在于，含有非氰系水溶性金化合物、和亚硫酸氢化合物。
(2)如上述(1)所述的置换型无电解镀金液，其特征在于，进一步含有硫代硫酸化合物。
(3)如上述(1)或(2)所述的置换型无电解镀金液，其特征在于，进一步含有氨基羧酸化合物。
(4)一种镀金物，其特征在于，使用上述(1)～(3)的任一项所述的置换型无电解镀金液制作而成。
作为在本发明的镀液中使用的非氰系水溶性金化合物，如果是非氰系、水溶性，则没有特别限定，但其特征在于作为添加剂含有亚硫酸氢化合物。
发明效果
根据本发明，可提供毒性低、能在中性附近使用、焊锡粘附性和被膜粘附性良好的非氰系置换型无电解镀金液。特别是可提供能改善与粘合强度低的无铅焊锡的粘合强度的非氰系置换型无电解镀金液。
具体实施方式
以下对本发明的置换型无电解镀金液详细地说明。
本发明的无电解镀金液是非氰系水溶性金化合物和亚硫酸氢化合物的水溶液。
作为非氰系水溶性金化合物，如果是非氰系的金化合物就没有特别限定，可优选使用亚硫酸金、硫代硫酸金、硫代氰酸金、氯金酸、或它们的盐。本发明的无电解镀金液，在镀液中优选含有按金浓度计为0.1～100g/L的这些金化合物，按金浓度计更优选含有0.5～20g/L。当金浓度小于0.1g/L时，金的置换速度明显变慢，而大于100g/L时效果饱和，没有优点。
作为亚硫酸氢化合物，可以使用亚硫酸氢盐，例如碱金属盐、碱土类金属盐、铵盐等，优选亚硫酸氢钠、亚硫酸氢钾、亚硫酸氢铵等。亚硫酸氢化合物在镀液中优选含有0.1～400g/L，更优选含有5～200g/L。亚硫酸氢化合物的浓度小于0.1g/L时，防止基底镍不均匀腐蚀的效果低，大于400g/L则效果饱和、没有优点。
本发明的无电解镀金液优选进一步含有硫代硫酸化合物。通过含有硫代硫酸化合物，所得到的镀覆膜的焊锡粘附性提高。作为硫代硫酸化合物，可以使用硫代硫酸的碱金属盐、碱土类金属盐、铵盐等，优选硫代硫酸钠、硫代硫酸钾、硫代硫酸铵等。硫代硫酸化合物在镀液中优选含有1mg/L～10g/L，更优选含有10～1000mg/L。硫代硫酸化合物的浓度小于1mg/L时，提高焊锡粘合强度的效果低，大于10g/L则效果饱和、没有优点。
另外，本发明的镀金液优选进一步含有作为配位剂的氨基羧酸化合物，作为氨基羧酸化合物，可举出乙二胺四乙酸、羟乙基乙二胺三乙酸、二羟乙基乙二胺二乙酸、丙二胺四乙酸、二亚乙基三胺五乙酸、三亚乙基四胺六乙酸、甘氨酸、甘氨酰甘氨酸、甘氨酰甘氨酰甘氨酸、二羟乙基甘氨酸、亚氨基二乙酸、羟乙基亚氨基二乙酸、次氮基三乙酸、次氮基三丙酸、或它们的碱金属盐、碱土类金属盐、铵盐等。镀液中的氨基羧酸化合物的浓度优选为0.1～200g/L，更优选是1～100g/L。氨基羧酸化合物的浓度小于0.1g/L时，作为配位剂的效果缺乏，大于200g/L则效果饱和、没有优点。
另外，本发明的无电解镀金液，优选作为稳定剂含有亚硫酸化合物。作为亚硫酸化合物，可举出亚硫酸、或亚硫酸的碱金属盐、碱土类金属盐、铵盐等。作为镀液中的亚硫酸化合物的浓度，优选为0.1～200g/L，更优选为1～100g/L。小于0.1g/L时不呈现作为稳定剂的效果，超过200g/L则效果饱和、没有优点。
另外，本发明的无电解镀金液，也可以根据需要添加作为pH缓冲剂的磷酸系化合物。
作为磷酸系化合物，可举出磷酸、焦磷酸、或这些酸的碱金属盐、碱土类金属盐、铵盐、磷酸二氢碱金属盐、磷酸二氢碱土类金属盐、磷酸二氢铵、磷酸氢二碱金属盐、磷酸氢二碱土类金属盐、磷酸氢二铵等。镀液中的磷酸系化合物的浓度优选为0.1～200g/L，更优选是1～100g/L。
本发明的镀金液的pH，优选使用作为pH缓冲剂的上述化合物调节成pH4～10，更优选调节成pH5～9。
另外，本发明的镀金液，优选在浴温10～95℃下使用，更优选在浴温50～85℃下使用。
镀液的pH、及浴温在上述范围外的场合，存在镀覆速度慢、容易引起浴分解等的问题。
在进行了印刷电路板的基底镀镍等之后，使用本发明的镀金液镀覆的镀覆膜，没有与基底镍镀膜的不均匀置换，成为焊锡的粘附性和被膜粘附性良好的镀金被膜。镀金被膜剥离后的基底镍被膜上看不到不均匀的腐蚀痕。
实施例
通过以下所示的实施例和比较例对本发明的优选实施方式进行说明。
实施例1～5、和比较例1～2
作为置换型无电解镀金液，制备了表1所示的各组成的镀液，作为被镀材料，使用抗蚀剂开口部为Ф0.6mm的贴铜印刷电路板，采用以下的工艺进行镀覆。
酸性脱脂(45℃，5分钟)
→软蚀刻(25℃，2分钟)
→酸洗(25℃，1分钟)
→活化(活化剂：Nikko Metal Plating制，KG-522)
(25℃，pH＜1.0，5分钟)
→酸洗(25℃，1分钟)
→无电镀镍-磷
(镀液：Nikko Metal Plating制，KG-530，被膜中磷品位约7％)
(88℃，pH4.5，30分钟)
→置换型无电解镀金(表1所记载的镀液、镀覆条件)
→还原型无电解镀金
(镀液：Nikko Metal Plating制，KG-560)
(70℃，pH5.0，30分钟)
(除酸洗→活化之间以外，全部加入1分钟的水洗工序)
象以下那样对所得到的镀覆物进行评价。
基底镍镀膜的腐蚀状态，使用Nikko Metal Plating制的金剥离剂オ一ラムストリッパ一710(25℃，0.5分钟)剥离置换型无电解镀金被膜后，使用SEM按2000倍进行观察，目视观察有无腐蚀痕(点蚀)。
焊锡粘附强度，进行置换型无电解镀金处理之后，使用Ф0.6mm的Sn-3.0Ag-0.5Cu无铅焊锡球，在软熔炉(即回流炉)中在峰温度250℃下进行加热粘接后，使用ディヅ公司制的粘合力试验机4000、采用加热式突出部拉伸(bump pull)方式进行测定。
被膜粘附性，在置换型无电解镀金后进行还原型无电解镀金，使用带进行剥离试验，目视观察有无被膜剥离。剥离试验，是将玻璃纸带(ニチバン公司制的セロテ一プ(注册商标))粘合在镀覆膜上，然后剥离带，目视确认在带一侧是否附着有镀覆膜的试验。
镀膜厚度使用精工电子工业(株)制的荧光X射线膜厚计SFT-3200进行测定。
评价结果示于表1。
表1-1
| 实施例 | |||||
| 1 | 2 | 3 | 4 | ||
| 浴组成 | 金化合物添加剂添加剂稳定剂配位剂pH缓冲剂 | 亚硫酸金钠：1g/L(金)亚硫酸氢钠：5g/L硫代硫酸钠：50mg/L亚硫酸钠：10g/L次氮基三乙酸：10g/L磷酸氢二钠：20g/L | 氯金酸钠：1g/L(金)亚硫酸氢钠：20g/L-亚硫酸钠：20g/L次氮基三乙酸：10g/L磷酸三钠：20g/L | 亚硫酸金钠：1g/L(金)亚硫酸氢钠：50g/L硫代硫酸钠：100mg/L亚硫酸钠：10g/L乙二胺四乙酸：10g/L磷酸二氢钠：30g/L | 亚硫酸金钠：1g/L(金)亚硫酸氢钠：100g/L硫代硫酸钠：75mg/L亚硫酸钠：5g/L乙二胺四乙酸：5g/L磷酸二氢钠：20g/L |
| 镀覆条件 | pH | 7.5 | 7.5 | 7.5 | 7.5 |
| 处理温度(℃) | 80 | 80 | 80 | 80 | |
| 处理时间(分) | 20 | 20 | 20 | 20 | |
| 评价结果 | 膜厚(μm) | 0.05 | 0.05 | 0.05 | 0.05 |
| 点蚀 | 无 | 无 | 无 | 无 | |
| 焊锡粘附强度 | 2211 | 1955 | 2221 | 2248 | |
| 被膜粘附性 | 无剥离 | 无剥离 | 无剥离 | 无剥离 | |
焊锡粘附强度的单位为gf(n＝20)
表1-2
| 实施例 | 比较例 | |||
| 5 | 1 | 2 | ||
| 浴组成 | 金化合物添加剂添加剂稳定剂配位剂pH缓冲剂 | 氯金酸钠：1g/L(金)亚硫酸氢钠：200g/L-亚硫酸钠：10g/L次氮基三乙酸：20g/L磷酸氢二钠：30g/L | 亚硫酸金钠：1g/L(金)--亚硫酸钠：10g/L乙二胺四乙酸：10g/L磷酸二氢钠：30g/L | 氰化金钾：2g/L(金)--柠檬酸：30g/L乙二胺四乙酸：10g/L- |
| 镀覆条件 | pH | 7.5 | 7.5 | 5.0 |
| 处理温度(℃) | 80 | 80 | 90 | |
| 处理时间(分) | 20 | 20 | 5 | |
| 评价结果 | 膜厚(μm) | 0.05 | 0.05 | 0.05 |
| 点蚀 | 无 | 有 | 有 | |
| 焊锡粘附强度 | 1972 | 1609 | 1506 | |
| 被膜粘附性 | 无剥离 | 有剥离 | 有剥离 | |
焊锡粘附强度的单位为gf(n＝20)
由表1的结果知道，使用本发明的无电解镀金液得到的被膜，在基底镍镀膜上没有腐蚀痕(点蚀)，焊锡粘附性、被膜粘附性优异。
Claims (4)
1.一种置换型无电解镀金液，其特征在于，含有非氰系水溶性金化合物和亚硫酸氢化合物。
2.如权利要求1所述的置换型无电解镀金液，其特征在于，进一步含有硫代硫酸化合物。
3.如权利要求1或2所述的置换型无电解镀金液，其特征在于，进一步含有氨基羧酸化合物。
4.一种镀金物，其特征在于，使用权利要求1～3的任一项所述的置换型无电解镀金液制作而成。
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| CN108220934A (zh) * | 2018-01-22 | 2018-06-29 | 昆山成功环保科技有限公司 | 一种无氰化学浸金溶液 |
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| KR101444687B1 (ko) * | 2014-08-06 | 2014-09-26 | (주)엠케이켐앤텍 | 무전해 금도금액 |
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| CN102286736A (zh) * | 2011-08-29 | 2011-12-21 | 深圳市化讯应用材料有限公司 | 一种置换型化学镀金液 |
| CN108220934A (zh) * | 2018-01-22 | 2018-06-29 | 昆山成功环保科技有限公司 | 一种无氰化学浸金溶液 |
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| US20070209548A1 (en) | 2007-09-13 |
| EP1813696B1 (en) | 2018-12-26 |
| US7396394B2 (en) | 2008-07-08 |
| CN1993499B (zh) | 2010-09-29 |
| JPWO2006051637A1 (ja) | 2008-05-29 |
| EP1813696A1 (en) | 2007-08-01 |
| EP1813696A4 (en) | 2011-08-24 |
| HK1104934A1 (en) | 2008-01-25 |
| WO2006051637A1 (ja) | 2006-05-18 |
| TWI306906B (en) | 2009-03-01 |
| KR20070046195A (ko) | 2007-05-02 |
| TW200615398A (en) | 2006-05-16 |
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