CN101675186B - 向非导电基底施用金属涂层的方法 - Google Patents
向非导电基底施用金属涂层的方法 Download PDFInfo
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- CN101675186B CN101675186B CN2008800145982A CN200880014598A CN101675186B CN 101675186 B CN101675186 B CN 101675186B CN 2008800145982 A CN2008800145982 A CN 2008800145982A CN 200880014598 A CN200880014598 A CN 200880014598A CN 101675186 B CN101675186 B CN 101675186B
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- complexing agent
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- salt
- metal
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 239000000758 substrate Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title claims abstract description 19
- 238000000576 coating method Methods 0.000 title claims abstract description 19
- 239000008139 complexing agent Substances 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 10
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- NMUOATVLLQEYHI-UHFFFAOYSA-N iminoaspartic acid Chemical compound OC(=O)CC(=N)C(O)=O NMUOATVLLQEYHI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 24
- 239000010970 precious metal Substances 0.000 claims description 15
- -1 metals ion Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 10
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- 229940095064 tartrate Drugs 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- 229950006191 gluconic acid Drugs 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- WTLNOANVTIKPEE-UHFFFAOYSA-N 2-acetyloxypropanoic acid Chemical compound OC(=O)C(C)OC(C)=O WTLNOANVTIKPEE-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- YZQUECUNLLXRTM-UHFFFAOYSA-N 1-(pyridin-2-yldiazenyl)naphthalene-2-carbaldehyde Chemical compound O=CC1=CC=C2C=CC=CC2=C1N=NC1=CC=CC=N1 YZQUECUNLLXRTM-UHFFFAOYSA-N 0.000 claims description 2
- RJNYNDHYSJRRDW-UHFFFAOYSA-N 4-(pyridin-2-yldiazenyl)benzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1N=NC1=CC=CC=N1 RJNYNDHYSJRRDW-UHFFFAOYSA-N 0.000 claims description 2
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 2
- LGDFHDKSYGVKDC-UHFFFAOYSA-N 8-hydroxyquinoline-5-sulfonic acid Chemical compound C1=CN=C2C(O)=CC=C(S(O)(=O)=O)C2=C1 LGDFHDKSYGVKDC-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 2
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012190 activator Substances 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 32
- 239000010949 copper Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000011135 tin Substances 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 229910052763 palladium Inorganic materials 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 9
- 238000001465 metallisation Methods 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical compound C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 description 1
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical compound C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical group NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N Sec-butyl alcohol Natural products CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 229940022663 acetate Drugs 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical class [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical group [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 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
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- 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
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- 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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明描述了向非导电基底施用金属涂层的新型方法,包括下述步骤:(a)使该基底与包含贵金属/第IVA族金属溶胶的活化剂接触,以获得经过处理的基底,(b)使所述经过处理的基底与包含下述物质的溶液的组合物接触:(i)Cu(II)、Ag、Au或Ni可溶金属盐或其混合物,(ii)0.05至5摩尔/升的第IA族金属氢氧化物,和(iii)所述金属盐的金属离子的络合剂,其中使用亚氨基琥珀酸或其衍生物作为所述络合剂。
Description
技术领域
本发明涉及向非导电基底施用金属涂层的方法,并涉及该方法中所用的组合物。
背景技术
涂覆非导电表面的多种方法是已知的。在湿化学法中,首先将要被金属化的表面在适当的预处理后催化,然后以无电方式金属化,此后如果必要,以电解方式金属化,或直接以电解方式金属化。
但是,根据使用无电金属化的第一变体的方法具有经证实的缺点,因为该无电金属化浴的工艺管理困难,来自该浴的废水的处理复杂且成本高,并且由于该金属化浴的低沉积速度,该方法冗长并因此同样成本高。
尤其对塑料部件(例如用于卫生配件和用于汽车工业)和用作电器外壳的部件(屏蔽电磁辐射)的金属涂层而言,无电金属化法是成问题的。在这类模制部件的处理中,通常相对大量的处理溶液从一个处理浴被带入下一处理浴,因为这些部件具有一定的形状,凭借该形状,在将部件提起时从浴中带出处理溶液。由于无电金属化浴通常含有显著量的有毒甲醛和络合物形成体,它们的去除很困难,因此在它们的处理中,这些浴大量损失且必须以复杂方式处置。
为此,开发出了一系列金属化法,借此可以在没有无电金属化的情况下用金属直接涂覆非导电表面(参见,例如EP 0298298A2、US 4,919,768、EP 0320601A2、US 3,984,290、EP 0456982A1和WO 89/08375A1)。
在EP 0616053A1中,公开了非导电表面的直接金属化方法,其中该表面首先用清洁剂/调节剂溶液处理,此后用活化剂溶液(例如钯胶体溶液) 处理,用锡化合物稳定,然后用含有比锡更贵的金属的化合物以及碱金属氢氧化物和络合物形成体的溶液处理。此后该表面可以在含有还原剂的溶液中处理,最后电解金属化。
WO 96/29452涉及由非导电材料制成的基底的表面的选择性或部分电解金属化方法,为进行该涂覆法,该基底被固定到塑料涂覆的固定元件上。所提出的方法包括下述步骤:a)用含氧化铬(VI)的蚀刻溶液预处理该表面;然后立即b)用钯/锡化合物的胶态酸性溶液处理该表面,小心防止预先接触促吸附溶液;c)用含有能被锡(II)化合物还原的可溶金属化合物、碱金属或碱土金属氢氧化物和至少足以防止金属氢氧化物沉淀的量的该金属的络合物形成剂的溶液处理该表面;d)用电解金属化溶液处理该表面。
EP 0616053A1和WO 96/29452中所述的方法的缺点在于,它们要求使用贵金属,例如钯,这是非常昂贵的金属。
因此,本发明的目的是提供需要较少量的贵金属(例如钯)将要被金属涂覆的非导电基底的表面活化的方法。
发明概要
通过向非导电基底施用金属涂层的方法实现了该目的,该方法包括下述步骤:
(a)使所述基底与包含贵金属/第IVA族金属溶胶的活化剂接触,以获得经过处理的基底,
(b)使所述经过处理的基底与包含下述物质的溶液的组合物接触:
(i)Cu(II)、Ag、Au或Ni可溶金属盐或其混合物,
(ii)0.05至5摩尔/升的第IA族金属氢氧化物和
(iii)所述金属盐的金属离子的络合剂,
其中使用亚氨基琥珀酸或其衍生物作为所述络合剂。
发明详述
已经出乎意料地发现,使用亚氨基琥珀酸或其衍生物可以显著减少活 化剂中贵金属(例如钯)的量。
适用于本发明的亚氨基琥珀酸衍生物包括具有下示式(I)的那些:
其中R1选自由H、Na、K、NH4、Ca、Mg、Li和Fe组成的组,R2选自R2选自由
-CH2-COOR1、-CH2-CH2-COOR1、-CH2-CH2-OH、-CH2-CHOH-CH3和-CH2-CHOH-CH2OH组成的组,且
R3选自由H、-CH2-COOR1、-CH2-CH2-COOR1、-CH2-CH2-OH、-CH2-CHOH-CH3和-CH2-CHOH-CH2OH组成的组。
在DE 19850359A1中描述了上述化合物。WO 00/26398描述了通过在微生物存在下的发酵而基于碳水化合物制造式(I)的化合物及其混合物的方法。
优选地,该亚氨基琥珀酸衍生物是具有下述结构式的亚氨基琥珀酸钠盐:
要根据本发明的方法涂覆的非导电基底不受特别限制。这些基底包括结构致密的塑料部件,例如梳子或被设计成在第三维度中具有显著扩展的制品,如咖啡壶、电话听筒、水管配件等。但是,也可以根据本发明涂覆 其它非导电基底,例如陶瓷基底或其它金属氧化物非导电基底。此外,可以涂覆小表面,例如印刷电路板的通孔壁。
在基底包含其上具有金属层的非导电材料的情况下,例如电路板制造中所用的覆铜基底,则可任选用化学蚀刻剂将基底微蚀刻。这种化学蚀刻剂的实例包括含有铬酸和硫酸的混合物的标准蚀刻剂。使用该微蚀刻步骤,以使该金属层(例如该基底的铜层部分)准备好进行后继电镀。在蚀刻后可以包括酸浸和水洗。
在用活化剂处理该基底之前,可以将其浸在含有NaCl、SnCl2和HCl的商业预浸液中,预浸液的pH值低于大约0.5。
然后用包含贵金属/第IVA族金属溶胶的活化剂处理所述基底。贵金属包含Ag或Au或第VIII族贵金属,包括Ru、Rh、Pd、Os、Ir、Pt或这类贵金属的各种混合物。优选的贵金属是第VIII族贵金属,尤其是包含钯的金属。
本发明的活化剂以下述方式制备:存在过量的第IVA族金属化合物还原剂,即,与制造该活化剂所用的贵金属化合物(例如二价Pd)相比,存在化学计量过量的还原剂(例如二价锡)。这样,该活化剂(例如Pd/Sn溶胶)具有可充当还原剂的残留二价Sn。
可用的第IVA族金属包括例如Ge、Sn和Pb或其混合物,Sn是优选的。
该活化剂优选含有与贵金属相比化学计量过量的第IVA族金属。该第IVA族金属基本处于其最低氧化态,以使其可用于将形成该活化剂所用的更贵的金属盐还原。由于第IVA族金属与用于形成该活化剂的贵金属盐相比也以化学计量过量使用,与该活化剂结合的所述过量的第IVA族金属也基本处于其最低氧化态。这样制备的、具有过量的处于其最低氧化态的第IVA族金属的活化剂也可用于将后面与该活化剂接触的第IB族或其它更贵的金属盐(例如本文所述的铜盐)还原。该第IVA族金属优选以盐的形式使用,例如以卤化物、尤其是氯化物的形式使用,但在任何情况下,其存在量使得该第IVA族金属与活化剂的贵金属的摩尔比为4∶1至95∶1, 尤其是10∶1至55∶1,优选15∶1至50∶1。在这方面可用的一些具体的第IVA族金属盐包括溶解在稀盐酸中的PbCl2、SnCl2、或GeCl2与GeCl4的混合物。优选的第IVA族金属包括锡,尤其是氯化亚锡形式的锡。
活化剂的制备是常规的,并描述在美国专利3,011,920和美国专利3,682,671中。
在已施用活化剂溶液后,将该经过处理的基底清洗,然后用包含Cu(II)、Ag、Au或Ni可溶金属盐、第IA族金属氢氧化物和作为前述金属盐(包括Ag+、Ag2+、Au+、Au2+和Ni2+盐)的金属离子的络合剂的亚氨基琥珀酸(衍生物)的上述组合物处理。该金属盐优选是Cu(II)盐。
在该浴中可以使用0.0002至0.2摩尔/升、尤其是0.004至0.01摩尔/升的所述金属盐,在该浴中,溶剂优选包含水。
所述浴以0.05至5摩尔/升、优选1至3摩尔/升、最优选1.5至2摩尔/升的量包含第IA族金属氢氧化物。在这方面,该第IA族金属包含Li、Na、K、Rb、Cs或其混合物,尤其是Li、Na、K及其混合物,优选为包含Li的金属。
在向非导电基底施用金属涂层的方法中所用的组合物进一步包含根据上式(I)的亚氨基琥珀酸或其盐或其衍生物作为络合剂。
该亚氨基琥珀酸钠盐可以形成五配位的络合物。该络合物经由氮原子和所有四个羧基形成。各种金属离子的一些络合物形成常数显示在下表中:
金属离子 | Mg2+ | Ca2+ | Mn2+ | Fe2+ | Fe3+ | Cu2+ | Ag+ | Zn2+ | Ni2+ | Co2+ |
Log K | 6.1 | 5.2 | 7.7 | 8.2 | 15.2 | 13.1 | 3.9 | 10.8 | 12.2 | 10.5 |
该络合剂以下述量使用:其足以使该浴在基底上形成薄的致密的富含金属的催化膜(该催化膜具有对于后面电镀而言的充足电导率),并同时产生相对清洁的金属表面。一般而言,该络合剂以0.005至1摩尔/升、优选0.01至0.3摩尔/升、最优选0.03至0.15摩尔/升的量使用。
除了该亚氨基琥珀酸或亚氨基琥珀酸衍生物络合剂之外,可以使用第 二络合剂。这些第二络合剂通常以0.05至1.0摩尔/升、优选0.2至0.5摩尔/升的量使用。合适的第二络合剂包括选自由下述物质组成的组的络合剂:乙酸盐、乙酰丙酮、柠檬酸、1,2-二氨基环己烷-N,N,N’,N’-四乙酸、二甲基乙二肟(50%二氧杂环己烷)、2,2’-联吡啶、乙醇胺、乙二胺、乙二胺N,N,N’,N’-四乙酸、甘氨酸、N’-(2-羟乙基)乙二胺-N,N,N’-三乙酸、8-羟基-2-甲基喹啉(50%二氧杂环己烷)、8-羟基喹啉-5-磺酸、乳酸、次氮基三乙酸、1-亚硝基-2-萘酚(75%二氧杂环己烷)、草酸盐、1,10-菲咯啉、邻苯二甲酸、哌啶、1,2-丙二胺、吡啶、吡啶-2,6-二甲酸、1-(2-吡啶基偶氮)-2-萘酚(PAN)、4-(2-吡啶基偶氮)间苯二酚(PAR)、邻苯二酚-3,5-二磺酸盐、8-羟基喹啉、水杨酸、琥珀酸、5-磺基水杨酸、酒石酸、巯基乙酸、硫脲、三乙醇胺、三亚乙基四胺(trien)、1,1,1-三氟-3-2’-噻吩甲酰丙酮(TTA)。
对铜离子而言,优选的第二络合剂是链烷醇胺,包含例如单乙醇胺。除单乙醇胺外,在这方面可用的链烷醇胺包括下述低碳链烷醇胺:二乙醇胺、三乙醇胺、单异丙醇胺、二异丙醇胺、三异丙醇胺、单仲丁醇胺、二仲丁醇胺、2-氨基-2-甲基-1-丙二醇、2-氨基-2-乙基-1,3-丙二醇、2-二甲基氨基-2-甲基-1-丙醇、三(羟甲基)氨基甲烷、和链烷醇胺的各种混合物。
可以使用其它弱络合剂,例如其它胺,包括脂族和环状胺,例如具有最多10个碳原子的芳族胺,所有这些都描述在Kirk-Othmer,Encyclopedia of Chemical Technology“Amines”中。另外,可以使用具有最多8个碳原子的单羧酸和多羧酸和它们的盐,包括氨基酸。这些酸也描述在Kirk-Othmer,ld.“Carboxylic Acids”和“Amino Acids”中。在这方面,优选的酸包括葡糖酸、乳酸、乙酸和酒石酸。
用在本发明方法中的组合物可优选由组分套件(kit-of-parts)获得,所述组分套件包含组合物(A)和(B),其中组合物(A)包含:
(A1)所述亚氨基琥珀酸或其衍生物,
(A2)所述可溶金属盐
且其中组合物(B)包含:
(B1)所述第IA族金属氢氧化物。
使用这两种组分(A)和(B)是有利的,因为组分(A)包含本发明方法中所用的基本化合物,而组分(B)是调节最终组合物的pH值的碱性溶液。使用这种独立的碱性溶液能够更简单地控制该浴在运行条件下的碱度。
上述水溶性金属盐的各种阴离子包括无机酸阴离子或其混合物,例如卤素阴离子(即F-、Cl-、Br-或I-,Cl-尤其优选)、硫酸根或碳酸根阴离子,低分子量有机酸阴离子(例如甲酸根或乙酸根阴离子)或水杨酸根阴离子等。另外,可以使用前述阴离子的混合物以及类似盐的阴离子,例如CuCl22KCl.2H2O、CuCl22NaCl.2H2O和它们的各种本领域已知的对等物。
如上所述,使用亚氨基琥珀酸或其衍生物可以显著降低该活化剂中贵金属(例如钯)的量。
根据本发明,该活化剂包含至少10毫克/升的钯作为贵金属,优选30-50毫克/升。
根据例如EP-A-0538006或EP-A-0913502中所述的现有技术方法,活化剂需要至少200毫克/升、例如250毫克/升钯的高得多的浓度。
在与活化剂接触后,用包含Cu(II)、Ag、Au或Ni可溶金属盐或其混合物、第IA族金属氢氧化物和亚氨基琥珀酸络合剂的溶液的组合物处理该基底,例如在高于60℃的温度处理例如大约10分钟。浴温度可为49℃至82℃。处理时间为4至12分钟或更久(这对制造用途而言是典型的),但是可以根据该浴的温度和条件在该范围以外变动。所用时间实际是提供形成导电膜所用的最佳金属覆盖或提供所需的最低覆盖所必需的时间。然后通过本领域公知的方法以电解方式涂覆该导电膜。
如果在酸性氧化介质中将该涂层微蚀刻,则可最佳地实现后继电镀,从而使所述以电解方式施用的金属涂层(例如铜)的粘合性和形态最优化。微蚀刻是通过本领域中常规的酸性氧化剂实现的,但是,已经发现,即使在微蚀刻溶液中短期暴露(例如大约1.5分钟)也会造成电导率损失,如果微蚀刻进行大约2分钟,则该涂层损失其基本所有的电导率,这意味着 其很可能从基底上被完全除去。
因此,在已经用铜浴处理基底后,例如,然后优选将其用水清洗并施以中和和还原浴以消除这一问题。该中和和还原浴将该经过处理的表面上的残留碱中和,并且也改进了导电膜对氧化性的化学微蚀刻剂的耐受性。
该中和和还原步骤可以分开进行,即,在使用第一酸中和浴和第二还原浴的分开的步骤中进行。
在这方面可用的还原剂概括地公开在美国专利4,005,051和EP-A-0616053中。
然后可以用附加的金属涂层或最终金属涂层以电解方式涂覆所述经过处理的基底。换言之,向本文所述的基底施用如上所述的组合物包括向非金属基底施用金属涂层的第一步骤(在两步法中)。在该第一步骤中,在基底表面上获得涂层,其与施用本发明组合物之前的基底的电导率相比,显著降低了该基底的电阻率。因此,本发明涉及两步法,其中先通过施用电阻率为大约0.04至12kΩ/cm、尤其是0.8至6kΩ/cm的非常薄的金属涂层来提高电导率。
通过下述实施例进一步例证本发明。
实施例1
制备如下所示的两种组合物(A)和(B):
组合物(A):
(A1)根据下表1,
(A2)大约4.0重量%CuSO4·5H2O,
(A3)根据下表1,
(A4)任选地,大约0.01重量%的表面活性剂,
其余是水。
组合物(B):
(B1)6.0重量%氢氧化钠,
(B2)9.0重量%氢氧化锂,
其余是水。
组合物(A)的pH值为4.1,其密度为1.2053克/立方厘米。组合物(B)的pH值为13,其密度为1.12克/立方厘米。
将90毫升/升的组合物(A)和300毫升/升的组合物(B)混合,以获得包含上述组分和成分的浴。
总之,制备包含下表1中所示的量的络合剂的四个浴。
用含有氧化铬(V)的蚀刻溶液在70℃处理由ABS制成的板(NovodurP2MC)10分钟。在清洗处理后,通过在室温用还原剂处理基底1分钟,将粘附到基底表面上的铬(VI)化合物还原成铬(III)化合物。
在进一步清洗处理后,在溶液中在40℃处理该基底3分钟(或4分钟),该溶液如下构成:活化剂:含有40毫克/升氯化钯形式的钯(远少于传统用量:200克/升Pd)、35克/升氯化亚锡(18.5克/升Sn)和350毫升/升的盐酸的胶体溶液,pH为1或更低。
在活化剂处理后,再清洗该基底。
在清洗处理后,将该基底浸入包含下表1中所述量的络合剂的、由上述组合物(A)和(B)获得的浴中。表1还列出了与吸附到基底表面上的钯、锡和铜的量有关的测量结果(根据所用络合剂的量)。
实验进一步表明,使用亚氨基琥珀酸络合剂能够在上述钯浓度下获得完全金属涂覆的HBS板。
此外,通过从ABS表面上除去金属涂层而获得的溶液之间的比较表明,已用亚氨基琥珀酸络合剂处理的表面在活化剂中钯浓度降低的情况下具有明显较高的铜浓度,并具有较低的锡浓度。
最后,添加和未添加亚氨基琥珀酸络合剂的组合物之间的比较表明,未用络合剂处理的那些基底表面具有较少的铜,因此没有获得完全的涂覆。
实施例1中获得的结果概括在下表1中。
表1:在用活化剂AKI(40毫克/升钯)获得的表面上的吸附测量结果
从上述实验结果中看出,使用亚氨基琥珀酸络合剂在联系Cu的步骤中在基底表面上产生明显较高的铜金属沉积。在此实验中,络合剂的总摩尔含量保持恒定以更好地比较结果。金属铜是通过氧化还原反应与Sn交换而沉积的:
Cu2++Sn(0)吸收在基底表面上→Cu(0)吸收在基底表面上+Sn2+
氧化的Sn2+离子溶解在溶液中。因此,Cu(0)的提高的沉积造成吸收的Sn(0)量降低,这从表1中也可看出。
涉及使用这种络合剂的方法可以在活化剂中低至40至50毫克/升Pd的浓度下进行。根据现有技术方法,需要活化剂中至少150毫克/升Pd的浓度。
可以比现有技术的络合溶液更容易地制备包含该亚氨基琥珀酸络合剂的溶液,最后,它们在碳酸盐形成方面的长期稳定性提高。
吸收在基底表面上的金属Cu(0)的较高量导致在其上沉积优异的最终金属涂层。相反,使用表1中所示的浴1和3的处理没有产生非导电表面 的完全金属化表面。
实施例2
进行下述实验以显示优异的金属化结果:
用水洗涤经过表1中所列的浴处理的基底,然后施以后继铜电镀步骤。使用市售铜电镀浴 HT(Atotech Deutschland GmbH),其含有250克/升硫酸铜、50克/升硫酸、50ppm氯离子和增亮剂。
在25℃的电镀液温度和3A/dm2的电流密度进行电镀操作15分钟。
金属化结果:
浴1:差:表面被铜不完全覆盖。
浴2:好:表面被铜完全覆盖。
浴3:差:表面被铜不完全覆盖。
浴4:好:表面被铜完全覆盖。
Claims (12)
1.向非导电基底施用金属涂层的方法,包括下述步骤:
(a)使基底与包含贵金属/第IVA族金属溶胶的活化剂接触,以获得经过处理的基底,
(b)使所述经过处理的基底与包含下述物质的溶液的组合物接触:
(i)Cu(II)、Ag、Au或Ni可溶金属盐或其混合物,
(ii)0.05至5摩尔/升的第IA族金属氢氧化物,和
(iii)所述金属盐的金属离子的络合剂,
其特征在于使用亚氨基琥珀酸或其衍生物作为所述络合剂。
2.根据权利要求1的方法,其中除所述亚氨基琥珀酸或其衍生物之外,所述组合物进一步包含第二络合剂。
3.根据权利要求1的方法,其中所述络合剂以0.005至1摩尔/升的量使用。
4.根据权利要求2的方法,其中所述第二络合剂以0.05至1.0摩尔/升的量使用。
5.根据权利要求4的方法,其中所述第二络合剂以0.2至0.5摩尔/升的量使用。
6.根据权利要求5的方法,其中所述第二络合剂选自由葡糖酸、乳酸、乙酸和酒石酸和它们的盐组成的组。
7.权利要求1的方法,其中所述组合物由组分套件获得,所述组分套件包含组合物(A)和(B),其中组合物(A)包含:
(A1)所述亚氨基琥珀酸或其衍生物,
(A2)所述可溶金属盐
且其中组合物(B)包含:
(B1)所述第IA族金属氢氧化物。
9.根据权利要求8的组合物,进一步包含0.05至5摩尔/升的第IA族金属氢氧化物。
10.根据权利要求8的组合物,进一步以0.05至1.0摩尔/升的量包含第二络合剂,所述第二络合剂选自由葡糖酸及其盐、乙酸及其盐、乙酰丙酮、柠檬酸、1,2-二氨基环己烷-N,N,N’,N’-四乙酸、2,2’-联吡啶、乙醇胺、乙二胺、乙二胺N,N,N’,N’-四乙酸、甘氨酸、N’-(2-羟乙基)乙二胺-N,N,N’-三乙酸、8-羟基喹啉-5-磺酸、乳酸及其盐、次氮基三乙酸、草酸盐、1,10-菲咯啉、邻苯二甲酸、哌啶、1,2-丙二胺、吡啶、吡啶-2,6-二甲酸、1-(2-吡啶基偶氮)-2-萘酚、4-(2-吡啶基偶氮)间苯二酚、邻苯二酚-3,5-二磺酸盐、8-羟基喹啉、水杨酸、琥珀酸、5-磺基水杨酸、酒石酸及其盐、巯基乙酸、硫脲、三乙醇胺、三亚乙基四胺、1,1,1-三氟-3-2’-噻吩甲酰丙酮组成的组。
11.根据权利要求10的组合物,其以0.2至0.5摩尔/升的量包含第二络合剂。
12.根据权利要求11的组合物,其中所述第二络合剂选自由葡糖酸、乳酸、乙酸和酒石酸和它们的盐组成的组。
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EP2581469B1 (en) * | 2011-10-10 | 2015-04-15 | Enthone, Inc. | Aqueous activator solution and process for electroless copper deposition on laser-direct structured substrates |
ES2688876T3 (es) * | 2012-02-01 | 2018-11-07 | Atotech Deutschland Gmbh | Baño de chapado no electrolítico de níquel |
EP2784181B1 (en) * | 2013-03-27 | 2015-12-09 | ATOTECH Deutschland GmbH | Electroless copper plating solution |
CN104916820B (zh) * | 2015-05-12 | 2017-05-10 | 北京理工大学 | 一种新型锂离子电池用导电材料掺杂硅基负极材料及制备方法 |
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