TWI626332B - 供無電電鍍之銅表面活化之方法 - Google Patents
供無電電鍍之銅表面活化之方法 Download PDFInfo
- Publication number
- TWI626332B TWI626332B TW103110919A TW103110919A TWI626332B TW I626332 B TWI626332 B TW I626332B TW 103110919 A TW103110919 A TW 103110919A TW 103110919 A TW103110919 A TW 103110919A TW I626332 B TWI626332 B TW I626332B
- Authority
- TW
- Taiwan
- Prior art keywords
- copper
- metal
- palladium
- aqueous solution
- deposit
- Prior art date
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 56
- 239000010949 copper Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000003213 activating effect Effects 0.000 title claims abstract description 14
- 238000007772 electroless plating Methods 0.000 title claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 83
- -1 palladium ions Chemical class 0.000 claims abstract description 76
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 53
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 33
- 238000009713 electroplating Methods 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims description 62
- 239000000758 substrate Substances 0.000 claims description 46
- 150000001879 copper Chemical class 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 11
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000531 Co alloy Inorganic materials 0.000 claims description 5
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 4
- 150000002940 palladium Chemical class 0.000 claims description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 2
- YAWYUSRBDMEKHZ-UHFFFAOYSA-N [2-hydroxyethyl(phosphonomethyl)amino]methylphosphonic acid Chemical compound OCCN(CP(O)(O)=O)CP(O)(O)=O YAWYUSRBDMEKHZ-UHFFFAOYSA-N 0.000 claims 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 229910018104 Ni-P Inorganic materials 0.000 abstract description 4
- 229910018536 Ni—P Inorganic materials 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 description 17
- 238000007747 plating Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 230000004913 activation Effects 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000012190 activator Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000085 borane Inorganic materials 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
- 238000004140 cleaning Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000521 B alloy Inorganic materials 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910001096 P alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000005844 autocatalytic reaction Methods 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 description 2
- 229940005631 hypophosphite ion Drugs 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SJBOEHIKNDEHHO-UHFFFAOYSA-N 2-[2-aminoethyl(carboxymethyl)amino]acetic acid Chemical compound NCCN(CC(O)=O)CC(O)=O SJBOEHIKNDEHHO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- RGHXWDVNBYKJQH-UHFFFAOYSA-N nitroacetic acid Chemical compound OC(=O)C[N+]([O-])=O RGHXWDVNBYKJQH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- HTIMQENIYIHRMC-UHFFFAOYSA-N propane-1,1,2-triamine Chemical compound CC(N)C(N)N HTIMQENIYIHRMC-UHFFFAOYSA-N 0.000 description 1
- XNYADZUHUHIGRZ-UHFFFAOYSA-N propane-1,1,3-triamine Chemical compound NCCC(N)N XNYADZUHUHIGRZ-UHFFFAOYSA-N 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
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- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1841—Multistep pretreatment with use of metal first
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
-
- 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
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- 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
- C23C18/44—Coating with noble metals using reducing agents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
- H01L21/76849—Barrier, adhesion or liner layers formed in openings in a dielectric the layer being positioned on top of the main fill metal
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- 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
- H05K3/24—Reinforcing the conductive pattern
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
本發明係關於一種用於使銅或銅合金表面活化，以藉由無電(自身催化)電鍍在其上沉積金屬或金屬合金層之方法，其中不想要的孔隙之形成受到抑制。使該銅或銅合金表面與鈀離子、至少一種膦酸酯化合物及鹵離子接觸，隨後無電(自身催化)沉積金屬(諸如鈀)或金屬合金(諸如Ni-P合金)。
Description
本發明係關於一種用於使銅或銅合金表面活化，以在其上連續無電(自身催化)電鍍金屬或金屬合金之方法。該方法尤其可用於製造印刷電路板及IC基板，以及用於半導體金屬化方法中。
藉由無電(自身催化)電鍍將各種金屬及金屬合金選擇性沉積於由銅或銅合金製成之特徵上係用於製造印刷電路板及IC基板，以及在(例如)微晶片製造中使半導體裝置金屬化之常見方法。鈀係待沉積於此等銅或銅合金特徵上之金屬之一實例。用於此目的之金屬合金之實例為鎳合金(諸如Ni-P合金)及鈷合金(諸如Co-Mo-P及Co-W-P合金)。
銅或銅合金表面在於其上無電(自身催化)電鍍金屬或金屬合金之前需要進行活化。使銅或銅合金表面活化之最重要手段係藉由用浸鍍法電鍍鈀來沉積鈀晶種層，此係氧化還原反應，其中銅被氧化，而存在於活化溶液中之鈀離子被還原成金屬態。然後，此鈀晶種層係作為電鍍基底以用於藉由無電(自身催化)電鍍將金屬或金屬合金層沉積於銅或銅合金特徵上。所用活化溶液通常係酸性。
US 7,285,492 B2中揭示一種使銅或銅合金表面活化，以於其上連續無電沉積金屬或金屬合金之方法。首先使基板與包含含羧基的有機酸或其鹽之水溶液及界面活性劑之清洗溶液接觸。然後，使該清潔
基板與包含鈀離子及含羧基的有機酸或其鹽之加工溶液接觸。然後，可藉由無電(自身催化)電鍍將金屬或金屬合金層沉積於該活化基板上。
自酸性溶液以浸鍍法電鍍鈀導致在經活化銅或銅合金特徵之表面區域上形成不想要的孔隙。若該銅或銅合金特徵係用於焊接或引線接合之接觸墊，則此等孔隙會(例如)降低焊接點及焊線之可靠性。
本發明之目標係在用包含鈀離子之酸性活化劑溶液使銅或銅合金表面活化，以進行連續無電(自身催化)電鍍時抑制形成不想要的孔隙。
該目標係藉由一種使銅或銅合金表面活化以藉由無電(自身催化)電鍍在其上沉積金屬或金屬合金層之方法解決，其包括以下順序之步驟：i.提供包括銅或銅合金表面之基板，ii.使該基板與以下組分接觸：a.含鈀離子來源之水溶液，b.含膦酸酯化合物之水溶液，c.含鹵離子來源之水溶液，及iii.藉由無電電鍍將金屬或金屬合金層沉積於步驟ii中所得之經活化銅或銅合金表面上，其中在步驟ii中未使用包含羧基而不含膦酸酯基之有機酸或其鹽。
藉由本發明方法可成功抑制在銅或銅合金表面區域中形成不想要的孔隙。
欲藉由本發明方法活化之銅及銅合金表面係(例如)印刷電路板、IC基板或半導體基板(諸如矽晶圓)上之接觸區域。
在本發明之第一實施例中，使包含銅或銅合金表面與包含鈀離子來源、至少一種膦酸酯化合物及鹵離子之水溶液接觸，其中除含羧基的膦酸酯化合物(諸如2-膦醯丁烷-1,2,4-三羧酸)以外，該溶液不含任何含羧基的有機酸或其鹽。
該第一實施例之方法包括以下順序之步驟：i.提供包括銅或銅合金表面之基板，ii.使該基板與包含鈀離子來源、至少一種膦酸酯化合物及鹵離子之水溶液接觸，及iii.藉由無電電鍍將金屬或金屬合金層沉積於步驟ii中所得之經活化銅或銅合金表面上，其中在步驟ii中未使用包含羧基而不含膦酸酯基之有機酸或其鹽。
本發明第一實施例之水溶液中之鹵離子較佳係選自由氯離子、溴離子及碘離子組成之群。最佳地，該第一實施例之水溶液中之鹵離子係氯離子。鹵離子來源較佳係選自相應酸或者鹼金屬鹽或銨鹽，諸如HCl、NaCl、KCl及NH4Cl。該第一實施例之水溶液中之鹵離子之濃度較佳係在0.1至100mg/l，更佳0.5至50mg/l，最佳5至30mg/l之範圍內。
已發現，若鹵離子濃度過高，則活化作用較弱，且活化步驟可能無法起始無電(自身催化)電鍍之後續的自身催化反應。
在本發明之第二實施例中，使該包括銅或銅合金表面之基板與包含鈀離子來源及至少一種膦酸酯化合物之第一水溶液接觸，其中該
第一水溶液不含任何含羧基而不含膦酸酯基，且不含鹵離子的有機酸或其鹽。
該第二實施例之第一水溶液係第一實施例之步驟ii中所應用的相同溶液，只是不含鹵離子。
隨後，使該基板與包含鹵離子之第二水溶液接觸。
鈀離子可在使用期間自第一水溶液轉移至第二水溶液，特別係若在第一與第二水溶液間不進行漂洗。
本發明第二實施例之第二水溶液可另外包含膦酸酯化合物。
該第二實施例之方法包括以下順序之步驟：i.提供包括銅或銅合金表面之基板，ii.使該基板與包含鈀離子來源及至少一種膦酸酯化合物之第一水溶液接觸，iii.使該基板與包含至少一種鹵離子來源之第二水溶液接觸，及iv.藉由無電(自身催化)電鍍將金屬或金屬合金層沉積於步驟ii中所得之經活化銅或銅合金表面上，其中不將包含羧基而不含膦酸酯基之有機酸或其鹽用於步驟ii中所應用的第一水溶液中。
較佳地，步驟iii中所應用的第二水溶液不含額外鈀離子。「額外」意指提供鈀離子來源，且不將可藉由將基板自第一水溶液轉移至第二水溶液而自該第一水溶液帶入該第二水溶液之鈀離子計算在內。
本發明第二實施例之第二水溶液中之鹵離子較佳係選自由氯離子、溴離子及碘離子組成之群。最佳地，該第一實施例之水溶液中之鹵離子係氯離子。鹵離子來源較佳係選自相應的酸或鹼金屬鹽或銨鹽，諸如HCl、NaCl、KCl及NH4Cl。
該第二實施例之第二水溶液中之鹵離子之濃度在很大程度上取
決於該第二水溶液之操作溫度。在20℃下，鹵離子之濃度較佳係在1至50g/l，更佳2至20g/l，最佳5至15g/l之範圍內。若在使用期間將該第二水溶液加熱至30℃，則鹵離子之濃度必須降至較佳1至1000mg/l，更佳2至300mg/l，最佳10至150mg/l。溫度範圍介於20與30℃之間之第二水溶液中所需的鹵離子工作濃度範圍可藉由常規實驗獲得。
已發現，若本發明之第二實施例之第二水溶液中之鹵離子濃度對該浴之各別操作溫度而言係過高，則活化作用較弱，且活化步驟可能無法啟動後續的自身催化反應。
若根據所選pH值適當調節溫度及處理時間，則本發明第二實施例中之第二水溶液之pH值可在寬廣範圍內選擇。較佳地，pH係在1.0至7.0，更佳1.5至5.0之範圍內。
本發明之兩個實施例之鈀離子來源係選自水溶性鈀鹽，諸如硫酸鈀。兩個實施例之各別水溶液之鈀離子濃度較佳係在0.01至1g/l，更佳0.05至0.3g/l之範圍內。
本發明膦酸酯化合物係含有-C-PO(OH)2及/或-C-PO(OR2)基團之有機化合物。
本發明之兩個實施例之該至少一種膦酸酯化合物較佳係選自由下列組成之群：1-羥乙烷-1,1-二膦酸、羥乙基-胺基-二(亞甲基膦酸)、羧甲基-胺基-二(亞甲基膦酸)、胺基-參(亞甲基膦酸)、乙二胺-四(亞甲基膦酸)、己二胺基-四(亞甲基膦酸)、二伸乙基三胺-五(亞甲基膦酸)及2-膦醯丁烷-1,2,4-三羧酸。
本發明之兩個實施例之該至少一種膦酸酯化合物之濃度較佳係在0.3至20mmol/l，更佳1.5至8mmol/l之範圍內。
本發明之兩個實施例之包含鈀離子之水溶液之pH值較佳係在0.5至4.0，更佳1.0至2.0之範圍內。
本發明之兩個實施例中所使用的水溶液中之其他可選組分係(例如)界面活性劑、用於將水溶液調節至所需pH值之酸或鹼、緩衝劑及鈀離子錯合劑。鈀離子之適宜錯合劑為氮化有機化合物，諸如羥乙胺。
當本發明之第一及第二實施例之包含鈀離子之水溶液與包括銅或銅合金表面之基板接觸時，該等水溶液較佳維持在20至60℃，更佳30至45℃之溫度下。
該包括銅或銅合金表面之基板較佳與本發明之第一及第二實施例之包含鈀離子之水溶液接觸20至180s，更佳45至90s。
當本發明之第二實施例之步驟iii中所應用的水溶液與包括銅或銅合金表面之基板接觸時，該水溶液較佳維持在15至50℃，更佳18至38℃之溫度下。本發明之第二實施例中之相應接觸時間較佳係在20至180s，更佳45至90s之範圍內。
包括銅或銅合金表面之基板可藉由(例如)以下方式與本發明之第一及第二實施例中所應用的該(等)水溶液接觸：將該基板浸入該(等)水溶液中或將該(等)水溶液噴灑於該基板上。
然後用作為電鍍基底之鈀晶種層使該銅或銅合金表面活化，以在其上連續無電(自身催化)電鍍金屬或金屬合金層。
較佳地，在藉由無電(自身催化)電鍍沉積金屬或金屬合金層之前，用水漂洗該包含經活化銅或銅合金表面之基板。
藉由無電(自身催化)電鍍沉積於該經活化銅或銅合金表面上之金屬或金屬合金層係選自由鈀、鈀合金、鎳合金及鈷合金組成之群。
適宜的無電(自身催化)電鍍浴組合物包含至少一種金屬離子來源、還原劑、一或多種錯合劑及較佳一或多種穩定劑。
用於將純鈀層沉積於該經活化銅或銅合金表面上之無電(自身催化)電鍍浴組合物較佳包含鈀離子來源(諸如氯化鈀、硝酸鈀、乙酸
鈀、硫酸鈀)；選自甲酸、其衍生物或鹽之還原劑及氮化錯合劑(諸如乙二胺、1,3-二胺基-丙烷、1,2-雙(3-胺基-丙基-胺基)-乙烷、2-二乙基-胺基-乙基-胺、二伸乙基三胺、二伸乙基三胺-五乙酸、硝基乙酸、N-(2-羥基-乙基)-乙二胺、乙二胺-N,N-二乙酸、2-(二甲基胺基)-乙基-胺、1,2-二胺基-丙基-胺、1,3-二胺基-丙基-胺、3-(甲基胺基)-丙基-胺、3-(二甲基胺基)-丙基-胺、3-(二乙基-胺基)-丙基-胺、雙-(3-胺基-丙基)-胺、1,2-雙-(3-胺基-丙基)-烷基-胺、二伸乙基三胺、三伸乙基-四胺、四伸乙基-五胺、五伸乙基-六胺及其混合物)。此等用於沉積鈀層之無電電鍍浴組合物及適宜電鍍條件係揭示於EP 0 698 130 B1及EP 11184919.6中。
用於將Pd-P合金層沉積於該經活化銅或銅合金表面上之適宜無電(自身催化)電鍍浴組合物包含次磷酸根離子作為還原劑。
用於將Pd-B合金層沉積於該經活化銅或銅合金表面上之適宜無電(自身催化)電鍍浴組合物包含硼烷化合物作為還原劑。
用於沉積Ni-P合金層之適宜電鍍浴組合物包含鎳離子來源、作為還原劑之次磷酸根離子、錯合劑(諸如羥基羧酸或其鹽)及至少一種穩定劑(諸如含鉛離子、銻離子及硫的有機穩定劑)。用於沉積Ni-P合金之適宜無電(自身催化)電鍍條件係此項技術中已知。
用於沉積Ni-B合金層之適宜無電(自身催化)電鍍浴組合物包含硼烷化合物作為還原劑。
用於沉積三元鎳合金Ni-M-P或Ni-M-B(其中M為金屬，諸如鉬或鎢)之適宜無電(自身催化)電鍍浴組合物另外包含M離子源。
用於沉積三元鈷合金Co-M-P或Co-M-B(其中M為金屬，諸如鉬或鎢)之適宜無電(自身催化)電鍍浴組合物較佳包含鈷離子來源、M離子來源、還原劑(諸如次磷酸根離子(含磷合金)或硼烷化合物(含硼合金))、至少一種錯合劑(諸如羥基羧酸或其鹽)及至少一種穩定劑。用
於沉積三元鈷合金層之適宜電解(自身催化)電鍍浴組合物係(例如)揭示於EP 12159365.1中。
銅或銅合金層中不想要的孔隙之形成在本發明之兩個實施例中受到抑制。此外，在將金屬或金屬合金層無電(自身催化)電鍍於經活化銅或銅合金表面上期間未觀察到不想要的的漏鍍或滲鍍。沉積於包含經活化銅或銅合金表面之基板上之金屬或金屬合金層在其上亦具有足夠附著力。
現將藉由參考以下非限制性實例來說明本發明。
實例
所有實例中均使用包含銅表面之印刷電路板基板。首先用包含硫酸及過氧化氫之水溶液清洗該等基板。然後，藉由不同方法使銅表面活化，用水漂洗，並藉由無電(自身催化)電鍍自包含鈀離子來源、作為還原劑之甲酸鈉及氮化錯合劑之水性電鍍浴組合物將鈀層沉積於經活化銅表面上。
用光學顯微鏡及該電鍍基板之橫截面樣品研究沉積鈀層後之不想要的孔隙之存在。
實例1(比較例)
在清洗後，用含有100ppm鈀離子及硫酸之水溶液使基板之銅表面活化。然後，用水漂洗該基板，並藉由無電(自身催化)電鍍將厚度為約100nm之鈀層沉積於該經活化銅表面上。
在該銅表面與該藉由無電(自身催化)電鍍所沉積的鈀層之界面中存在不想要的孔隙。亦使樣品接受膠帶測試，在此期間，該沉積鈀層自底層銅剝離。因此，該銅表面與該藉由無電(自身催化)電鍍沉積於其上的鈀層間之黏著力係不足。
實例2(比較例)
在清洗後，用100ppm鈀離子及1g/l檸檬酸之水溶液(pH值為1.5)
使基板之銅表面活化。此活化劑溶液係揭示於US 7,285,492 B2中。使該活化劑溶液在活化期間保持在35℃下，並使該基板在該活化劑溶液中浸沒1分鐘。然後，用水漂洗該活化基板，並藉由無電(自身催化)電鍍將厚度為約100nm之鈀層沉積於經活化銅表面上。
使樣品接受膠帶測試，在此期間，該沉積鈀層自底層銅剝離。因此，該銅表面與該藉由無電(自身催化)電鍍沉積於其上的鈀層間之黏著力係不足。
實例3
在清洗後，根據本發明之第一實施例，用100ppm鈀離子、1g/l胺基三甲基膦酸酯及15ppm氯離子之水溶液(pH值為1.5)使基板之銅表面活化。使該活化劑溶液在活化期間保持在35℃下，並使該基板在該活化劑溶液中浸沒1分鐘。然後，用水漂洗該活化基板，並藉由無電(自身催化)電鍍將厚度為約100nm之鈀層沉積於經活化銅表面上。
使樣品接受膠帶測試，在此期間，發現鈀層在底層銅上具有良好附著力。在該銅表面與該藉由無電(自身催化)電鍍所沉積的鈀層之界面中未檢測到孔隙。
實例4
在清洗後，根據本發明之第二實施例，藉由使基板在100ppm鈀離子及1g/l胺基三甲基膦酸酯之第一水溶液中浸沒1分鐘使該基板之銅表面活化。該水溶液不含鹵素離子。該第一水溶液之pH值為1.5，且溫度為35℃。然後，使該基板在1g/l胺基三甲基膦酸酯及10g/l氯離子之第二水溶液中浸沒1分鐘。該第二水溶液之pH為4.5，且溫度為20℃。然後用水漂洗該活化基板，並藉由無電(自身催化)電鍍將厚度為約100nm之鈀層沉積於經活化銅表面上。
使樣品接受膠帶測試，在此期間，發現鈀層在底層銅上具有良好附著力。在該銅表面與該藉由無電(自身催化)電鍍所沉積的鈀層之
界面中未檢測到孔隙。
Claims (13)
- 一種使銅或銅合金表面活化以藉由無電(自身催化)電鍍於其上沉積金屬或金屬合金層之方法，其包括以下順序之步驟：i.提供包括銅或銅合金表面之基板，ii.使該基板與以下組分接觸：a.含有鈀離子來源之水溶液，b.含有膦酸酯化合物之水溶液，c.含有鹵離子來源之水溶液，及iii.藉由無電電鍍將金屬或金屬合金層沉積於該步驟ii中所得之經活化銅或銅合金表面上，其中在步驟ii中未使用包含羧基而不含膦酸酯基之有機酸或其鹽。
- 如請求項1之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中在步驟ii中使該基板與一種包含鈀離子來源、至少一種膦酸酯化合物及鹵離子之水溶液接觸。
- 如請求項2之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中鈀離子之濃度係在0.01至1g/l之範圍內。
- 如請求項2或3之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中該至少一種膦酸酯化合物之濃度係在0.3至20mmol/l之範圍內。
- 如請求項2之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中鹵離子之濃度係在0.1至100mg/l之範圍內。
- 如請求項2之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中該等鹵離子為氯離子。
- 如請求項1之使銅或銅合金表面活化以沉積金屬或金屬合金層之 方法，其中在步驟ii中使該基板與包含鈀離子來源及至少一種膦酸酯化合物且不含鹵離子之第一水溶液接觸，然後與包含鹵離子之第二水溶液接觸。
- 如請求項7之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中該第一水溶液中之鈀離子濃度係在0.01至1g/l之範圍內。
- 如請求項7或8之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中該第一水溶液中之至少一種膦酸酯之濃度係在0.3至20mmol/l之範圍內。
- 如請求項7或8之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中該第二水溶液中之鹵離子為氯離子。
- 如請求項1、2、7及8中任一項之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中該鈀離子來源為水溶性鈀鹽。
- 如請求項1、2、7及8中任一項之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中該至少一種膦酸酯化合物係選自由下列組成之群：1-羥乙烷-1,1-二膦酸、羥乙基-胺基-二(亞甲基膦酸)、羧甲基-胺基-二(亞甲基膦酸)、胺基-參(亞甲基膦酸)、乙二胺-四(亞甲基膦酸)、己二胺基-四(亞甲基膦酸)、二伸乙基三胺-五(亞甲基膦酸)及2-膦醯丁烷-1,2,4-三羧酸。
- 如請求項1、2、7及8中任一項之使銅或銅合金表面活化以沉積金屬或金屬合金層之方法，其中該步驟iii中所沉積的金屬或金屬合金係選自由鈀、鈀合金、鎳合金及鈷合金組成之群。
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| EP13160785.5A EP2784180B1 (en) | 2013-03-25 | 2013-03-25 | Method for activating a copper surface for electroless plating |
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| TW201922969A (zh) | 2017-08-03 | 2019-06-16 | 美商電子墨水股份有限公司 | 包含鈀之導電墨水組成物及用於製造其之方法 |
| KR102041850B1 (ko) | 2019-04-08 | 2019-11-06 | (주)엠케이켐앤텍 | 인쇄회로기판의 구리표면에 무전해 팔라듐 도금을 실시하기 위한 전처리 공정으로 금스트라이크 도금방법, 도금액 조성물 및 전처리 후의 무전해 팔라듐 도금과 무전해 금도금 방법 |
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| US4066517A (en) * | 1976-03-11 | 1978-01-03 | Oxy Metal Industries Corporation | Electrodeposition of palladium |
| JP2649750B2 (ja) * | 1991-06-13 | 1997-09-03 | 石原薬品 株式会社 | 銅系素材上への選択的無電解めっき方法 |
| JPH0711448A (ja) * | 1993-06-29 | 1995-01-13 | Ishihara Chem Co Ltd | 銅系素材選択型無電解めっき用触媒液 |
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| JP2011042836A (ja) * | 2009-08-21 | 2011-03-03 | Okuno Chemical Industries Co Ltd | プリント配線板用触媒残渣除去剤 |
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| KR101418194B1 (ko) * | 2010-12-01 | 2014-07-31 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Ｐｄ 또는 Ｐｄ를 주성분으로 하는 합금의 표면처리제, 및 구리표면의 표면 피막층 구조 |
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| CN105051254B (zh) | 2018-04-20 |
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