TWI638821B - 金屬觸媒及其製備與應用 - Google Patents
金屬觸媒及其製備與應用 Download PDFInfo
- Publication number
- TWI638821B TWI638821B TW106128243A TW106128243A TWI638821B TW I638821 B TWI638821 B TW I638821B TW 106128243 A TW106128243 A TW 106128243A TW 106128243 A TW106128243 A TW 106128243A TW I638821 B TWI638821 B TW I638821B
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- Taiwan
- Prior art keywords
- metal catalyst
- patent application
- scope
- item
- palladium
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 149
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 88
- 239000002184 metal Substances 0.000 title claims abstract description 88
- 238000004519 manufacturing process Methods 0.000 title 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 29
- 125000003118 aryl group Chemical group 0.000 claims abstract description 20
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000000460 chlorine Chemical group 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 239000011630 iodine Chemical group 0.000 claims abstract description 9
- 229910052740 iodine Chemical group 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical group [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 62
- 238000007747 plating Methods 0.000 claims description 33
- 238000007772 electroless plating Methods 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 23
- MVQVNTPHUGQQHK-UHFFFAOYSA-N 3-pyridinemethanol Chemical compound OCC1=CC=CN=C1 MVQVNTPHUGQQHK-UHFFFAOYSA-N 0.000 claims description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- -1 hydroxy, methoxy Chemical group 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 12
- 150000008045 alkali metal halides Chemical class 0.000 claims description 12
- 239000002738 chelating agent Substances 0.000 claims description 11
- 239000012685 metal catalyst precursor Substances 0.000 claims description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- PTMBWNZJOQBTBK-UHFFFAOYSA-N pyridin-4-ylmethanol Chemical compound OCC1=CC=NC=C1 PTMBWNZJOQBTBK-UHFFFAOYSA-N 0.000 claims description 7
- QUXLCYFNVNNRBE-UHFFFAOYSA-N 6-methylpyridin-2-amine Chemical compound CC1=CC=CC(N)=N1 QUXLCYFNVNNRBE-UHFFFAOYSA-N 0.000 claims description 6
- SHNUBALDGXWUJI-UHFFFAOYSA-N pyridin-2-ylmethanol Chemical compound OCC1=CC=CC=N1 SHNUBALDGXWUJI-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- GNCLPNMQEGMNTG-UHFFFAOYSA-N 2-methylpyridin-4-amine Chemical compound CC1=CC(N)=CC=N1 GNCLPNMQEGMNTG-UHFFFAOYSA-N 0.000 claims description 3
- BXGYBSJAZFGIPX-UHFFFAOYSA-N 2-pyridin-2-ylethanol Chemical compound OCCC1=CC=CC=N1 BXGYBSJAZFGIPX-UHFFFAOYSA-N 0.000 claims description 3
- CMBSSVKZOPZBKW-UHFFFAOYSA-N 5-methylpyridin-2-amine Chemical compound CC1=CC=C(N)N=C1 CMBSSVKZOPZBKW-UHFFFAOYSA-N 0.000 claims description 3
- UENBBJXGCWILBM-UHFFFAOYSA-N 6-methylpyridin-3-amine Chemical compound CC1=CC=C(N)C=N1 UENBBJXGCWILBM-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- YPWSASPSYAWQRK-UHFFFAOYSA-N 2-pyridin-3-ylethanol Chemical compound OCCC1=CC=CN=C1 YPWSASPSYAWQRK-UHFFFAOYSA-N 0.000 claims description 2
- DWPYQDGDWBKJQL-UHFFFAOYSA-N 2-pyridin-4-ylethanol Chemical compound OCCC1=CC=NC=C1 DWPYQDGDWBKJQL-UHFFFAOYSA-N 0.000 claims description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000002563 ionic surfactant Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims 1
- 235000007715 potassium iodide Nutrition 0.000 claims 1
- 239000000243 solution Substances 0.000 description 54
- 238000012360 testing method Methods 0.000 description 26
- 238000000576 coating method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910001431 copper ion Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000002500 ions Chemical group 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000009863 impact test Methods 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 3
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- QMDUEBURHKSKDG-UHFFFAOYSA-N 1-pyridin-3-ylethanol Chemical compound CC(O)C1=CC=CN=C1 QMDUEBURHKSKDG-UHFFFAOYSA-N 0.000 description 1
- HVOAMIOKNARIMR-UHFFFAOYSA-N 1-pyridin-4-ylethanol Chemical compound CC(O)C1=CC=NC=C1 HVOAMIOKNARIMR-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- ORLGLBZRQYOWNA-UHFFFAOYSA-N 4-methylpyridin-2-amine Chemical compound CC1=CC=NC(N)=C1 ORLGLBZRQYOWNA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 235000000981 Brassica parachinensis Nutrition 0.000 description 1
- 241001604868 Brassica rapa var. parachinensis Species 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229950011175 aminopicoline Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BHZSLLSDZFAPFH-UHFFFAOYSA-L palladium(2+);difluoride Chemical compound F[Pd]F BHZSLLSDZFAPFH-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
本揭露提供一種金屬觸媒,係具有如式(1)或式(2)所示之結構,其中,M係鈀、銅、鉑、鎳或銀離子基;X為氟、氯、溴或碘;以及L為含氮芳香環之螯合基。本揭露亦提供上述金屬觸媒之製備方法以及應用。
Description
本揭露係有關於一種金屬觸媒,特別是有關於一種適用於化學鍍之金屬觸媒、其製備方法、及此金屬觸媒於化學鍍之應用。
化學鍍膜又被稱為無電鍍膜,係指鍍覆液中之金屬離子在被控制的條件下,從鍍覆液中持續析鍍到經過活化的基材表面的還原反應,以不須電力之方式在基材上鍍膜,達到基材的金屬化。化學鍍膜的鍍層均勻,均一性佳,因此可應用於精密零件或是深孔內部等一般電鍍不易操作之基材上。此外,經過適當的前處理後,即使是非導體基材也可利用化學鍍膜鍍上金屬層。因此,化學鍍膜被廣泛應用於非導體的金屬化等。
在化學鍍膜的過程中,需使用觸媒(又稱催化劑)對基材表面進行活性化處理。活化步驟是控制化學鍍膜沉積速率的關鍵因素。雖然現有的催化劑已大致符合需求,但並非各方面皆令人滿意,特別是催化劑的操作範圍仍需進一步改善。
本揭露提供一種金屬觸媒,係具有如式(1)或式(2)所示之結構:
其中,M為鈀、銅、鉑、鎳或銀;X為氟、氯、溴或碘;以及L為含氮芳香環之螯合基。
本揭露更提供一種金屬觸媒之製備方法,包括:將金屬鹽類與鹼金屬鹵化物於水中混合,反應以形成金屬觸媒前驅物,其中上述金屬鹽類為含有鈀、銅、鉑、鎳或銀之鹽類;以及將上述金屬觸媒前驅物與含氮芳香環之螯合劑反應,以形成金屬觸媒。
本揭露又提供一種金屬觸媒,是以上述金屬觸媒之製備方法所製得的金屬觸媒。
本揭露另提供一種化學鍍膜之方法,包括:將基材浸置於含有上述金屬觸媒之溶液中,其中上述溶液之pH值為2~12;以及將浸置過上述金屬觸媒溶液之基材浸置於化學鍍膜溶液中。
為讓本發明之上述目的、特徵及優點能更明顯易懂,下文特舉數個較佳實驗例,並配合所附的圖式,作詳細說明如下。
第1圖為關於本揭露之一實施例之鍍膜層的掃描式電子顯微
影像。
第2圖為關於本揭露之另一實施例之鍍膜層的掃描式電子顯微影像。
第3圖為關於本揭露之背光測試時之判定標準。
以下說明內容所述及之任一實施例即使同時揭露了複數個技術特徵,也不意味著利用本發明者必需同時實施該任一實施例中的所有技術特徵。換句話說,只要不影響實施可能性,本技術領域具有通常知識者可依據本發明之揭露內容並視需求或設計理念來選擇性地實施一部分而非全部的技術特徵,藉此增加本發明實施時的彈性。
在進行化學鍍時,需以催化劑對基材表面進行前處理,以活化基材表面。然而現有的催化劑均需在強鹼的條件下(例如,pH值為9-11)進行。若將催化劑調整為非強鹼環境,則催化劑催化效率變差,且會產生沉澱。然而,在強鹼環境下,容易對基材造成不必要的腐蝕,特別是樹脂或玻璃。因此對鹼敏感之基材,則不能使用此種催化劑。再者,使用強鹼之催化劑於進行活化之後,需對基板進行沖洗或中和,使基板順利進行下一個步驟。沖洗或中和的步驟,亦造成成本的上升。因此需要一種能夠於廣泛的pH值範圍內皆可使用的催化劑。
基於上述,本揭露提供一種金屬觸媒,係能夠應用在廣泛pH值範圍內,解決上述問題。
本揭露的實施例提供一種金屬觸媒,係具有如式(1)
或式(2)所示之結構:
其中,M為鈀、銅、鉑、鎳或銀離子基;X為氯、氟、溴、或碘;以及L為含氮芳香環之螯合基。
在本揭露的實施例中,金屬離子基:氯、氟、溴、或碘:螯合基之莫耳數比(M:X:L)為1:2:2。在其他實施例中,金屬離子基:氯、氟、溴、或碘:螯合基之莫耳數比(M:X:L)為1:1:3。金屬離子基所使用之金屬為可形成配位錯合物之金屬,特別是過渡金屬。較佳為選自由鈀,銅,鉑,鎳,及銀所組成之群組。在本揭露的一些實施例中,金屬為鈀。在本揭露的另一些實施例中,金屬為鎳。在本揭露的又一些實施例中,金屬為銀。
在上述中,X為氯、氟、溴、或碘。鹵素原子,具有較大之負電性(或拉電子能力強),因此與金屬的連結能更加穩固,有助於提升金屬觸媒對不同pH值之水溶液溶解性。
在上述中,L為含氮芳香環之螯合基,其以氮原子上的孤電子對與金屬的空軌域配位形成錯合物。具體而言,含氮芳香環之螯合基可包括(但不限於)下列結構:
其中,螯合基上至少一碳上的氫係被R、或Q所取代:
R係碳數為1~6之烴基;
,其中Z為羥基、甲氧基或乙氧基,a為1至6之整數;
Q係COOH,COOR1,COR1,NHR1,或NR1R2,其中R1及R2各自獨立地為氫;或是碳數為1~6之烴基。
在本揭露中,碳數為1~6之烴基係表示飽和或不飽和,直鏈、支鏈或環狀之碳數為1~6之烴基。例如,甲烷基、乙烷基、丙烷基、丁烷基、戊烷基、己烷基等直鏈烷基;還丙烷基、環丁烷基、環戊烷基、環己烷基等環烷基;2-甲基丙烷基、2-甲基丁烷基、2-甲基戊烷基、3-甲基戊烷基等具有支鏈的烷基;乙
烯基、丙烯基、丁烯基、戊烯基、己烯基等烯基;乙炔基、丙炔基、丁炔基、戊炔基、己炔基等炔基。
在一實施例中,L之含氮芳香環之螯合基具有吡啶結構。以下以吡啶結構為例,說明L的具體結構,但可理解的是,以下的說明係為了清楚說明本揭露,並非用於限定本揭露,下述之說明亦可用於其他含氮芳香環。
且至少一碳上的氫係被R、或Q所取代:
R係碳數為1~6之烴基;
,其中Z為羥基、甲氧基或乙氧基,a為1至6之整數;
Q係COOH,COOR1,COR1,NHR1,或NR1R2,其中R1及R2各自獨立地為氫;或是碳數為1~6之烴基。
在上述具有取代基之吡啶中,可具有羥基。推論羥基上的氧具有孤電子對,及具有拉電子的能力,因此與金屬的連結能更加穩固,有助於提升金屬觸媒對不同pH值之水溶液溶解性。具有羥基取代基之吡啶,舉例而言可包括(但不限於)2-吡啶甲醇、3-吡啶甲醇、4-吡啶甲醇、2-吡啶乙醇、3-吡啶乙醇、4-吡啶乙醇等。
在上述具有取代基之吡啶中,亦可具有兩個以上之取代基。舉例而言,其中一個取代基為甲基,另一個取代基為胺基。胺基中的氮具有孤電子對(或具有拉電子的能力),因而能使
金屬觸媒能夠在廣泛pH值之水溶液具有溶解性。具有兩個取代基的吡啶,舉例而言可包括(但不限於)4-胺基-6-甲基吡啶、3-胺基-6-甲基吡啶、2-胺基-6-甲基吡啶、2-胺基-5-甲基吡啶、或2-胺基-4-甲基吡啶等。
本揭露的至少一實施例提供一種金屬觸媒之製備方法,包括將一金屬鹽類與一鹼金屬鹵化物混合於去離子水中,反應形成金屬觸媒前驅物,其中金屬鹽類為含有鈀、銅、鉑、鎳或銀之鹽類,之後再加入一含氮芳香環之螯合劑,以形成金屬觸媒。
在至少一實施例中,含有鈀之鹽類,可包含,但不限於,鈀之鹵化物,例如:氯化鈀、氟化鈀、溴化鈀、碘化鈀;乙酸鈀;硫酸鈀;硝酸鈀;氯化鈀鉀;氯化鈀鈉。金屬鹽類也可為含有鎳之鹽類,其包含,但不限於,鎳之鹵化物,例如:氯化鎳、氟化鎳、溴化鎳、碘化鎳;醋酸鎳;硫酸鎳;硝酸鎳。
在至少一實施例中,金屬觸媒之製備方法中,含有金屬鹽類之濃度,為10~1000mg/L之間,亦可為100~500mg/L之間,150~250mg/L之間。
在至少一實施例中,金屬觸媒之製備方法中,其中鹼金屬鹵化物可為氯的鹼金屬鹽類、或碘的鹼金屬鹽類或其組合。例如,為氟化鉀、氯化鉀、溴化鉀或碘化鉀。
在至少一實施例中,金屬鹽類之金屬離子基與鹼金屬鹵化物之鹵基之莫耳比例為1:1至1:3之間。
金屬鹽類與鹼金屬鹵化物之反應條件,可在室溫下進行,但也可依照實際需求而進行調整,例如約20~60℃。時間
可為5分鐘至24小時,例如可為約6~15小時。
在上述反應過程中,金屬鹽類與鹼金屬鹵化物於溶液中產生金屬觸媒之前驅物,其為金屬離子與鹵素的錯合物。在一實施例中,當使用氯化鈀為金屬鹽類、氯化鉀為鹼金屬鹵化物時,所形成的前驅物為K2PdCl4。
形成金屬觸媒前驅物之後,接著添加含氮芳香環之螯合劑,以形成金屬觸媒。其中螯合劑可使用如前述之含有氮之芳香環。以吡啶為例,可包括(但不限於)具有羥基之2-吡啶甲醇、3-吡啶甲醇、4-吡啶甲醇、2-吡啶乙醇、3-吡啶乙醇、4-吡啶乙醇等;或是具有胺基之4-胺基-6-甲基吡啶、3-胺基-6-甲基吡啶、2-胺基-6-甲基吡啶、2-胺基-5-甲基吡啶、或2-胺基-4-甲基吡啶等。
在至少一實施例中,金屬鹽類之金屬離子基與含氮芳香環之螯合基之莫耳比例為1:1至1:3之間。
在至少一實施例中,含氮芳香環之螯合劑與金屬觸媒前驅物的反應條件,可依照實際需求進行。例如溫度可為20~100℃、20~95℃或約60~100℃。時間可為5分鐘至48小時,例如可為約5~24小時。
在至少一實施例中,本揭露的金屬觸媒為結晶型(crystalline),其可進一步以過濾步驟將金屬觸媒產物從溶液中分離,並再結晶得到純化的金屬觸媒,以用於後續步驟。在另一些實施例中,也可將含有金屬觸媒的反應溶液直接應用在後續步驟。
以上述方法合成的金屬觸媒可配置成催化劑溶液,催化劑溶液可應用於化學鍍膜以鍍覆各式基板。
以上述方法配置的催化劑溶液,可以使用酸或鹼將催化劑之pH值調整為所需範圍。其pH值範圍可為酸性至鹼性。本揭露的實施例提供之催化劑溶液其pH值為2~12。在一實施例中,可應用於pH值為3~12,在其他實施例中,pH值可為2~8或3~8。由於本揭露所揭示的金屬觸媒,可配製成於任意所需的pH值範圍的催化劑溶液,進而可廣泛地應用於各種基材上,除了無機基材之外,亦可應用於對鹼性溶液敏感之熱固性樹脂、熱塑性樹脂或玻璃基板。
在至少一實施例中,用於調整pH值之酸包含有機酸、無機酸或其鹽類。有機酸包含,但不限於單羧酸和多羧酸,例如苯甲酸、馬來酸、乙酸。無機酸包含,但不限於鹽酸、硫酸、硼酸、磷酸及硝酸。用於調整pH值之鹼包含有機鹼、無機鹼或其鹽類。有機鹼包括胺類及含氮的雜環化合物。無機鹼包含氨、金屬氫氧化物、金屬氧化物、金屬氫化物。
本揭露的實施例提供之催化劑溶液因具有在廣範圍的pH值(pH2~12),在至少一實施例可為pH3~12,皆能有效率地進行催化的特性,因此能夠適用於各種基板。特別是對強鹼耐受性差聚醯亞胺與玻璃的基板。其他適用的基板尚包括陶瓷基板、半導體基板、印刷基板、熱固性樹脂基板、熱塑性樹脂基板、紙或布等。玻璃基板包括鈉玻璃、鉛玻璃、硼玻璃、鈉鈣玻璃、硼矽酸玻璃、鋁硼矽酸玻璃、無水矽玻璃、石英玻璃等。
經過本揭露之金屬觸媒活化處理後的基板,可進行各種化學鍍,例如銅、銅合金、鎳或鎳合金。在一實施例中,可
於印刷電路板(PCB)中,沉積銅或銅合金以形成通孔或盲孔,亦可應用於製備銅箔。
用於化學鍍之銅離子的來源通常為含銅鹽類,包含,但不限於含銅的鹵化物、硝酸鹽、硫酸鹽、乙酸鹽、以及含銅的其他有機鹽類或無機鹽類。其中以硫酸銅、氯化銅、硝酸銅、氫氧化銅為佳。
在上述中,銅鹽的含量依設計調整,例如0.5g/L至30g/L。在本實驗例中,以硫酸銅10g/L進行(銅離子含量為2.5g/L)。
用於化學鍍之鎳離子的來源通常為含鎳鹽類,包含,但不限於含鎳的鹵化物、或硫酸鹽。其中以硫酸鎳、鹵化鎳為佳。
以化學鍍將基板金屬化的步驟,依順序包括清潔基板、調質、微蝕刻、活化、還原、鍍覆之步驟。以下將進一步詳細說明化學鍍之各步驟。在各步驟之間,可視需要對經過處理之基板進行水洗或烘乾之步驟。
首先,將欲進行化學鍍之基板表面以清水或溶劑溶脹劑進行清潔及去汙。藉由此步驟將基板表面清潔及清除油漬,並將孔壁去汙。可使用任何習知之溶劑溶脹劑,例如甘醇醚以及其相關之醚乙酸鹽。在本實驗例中,以含有二乙二醇單丁醚之溶脹劑進行。
溶劑溶脹劑處理之後可施加促進劑。促進劑包括硫酸、鉻酸、高錳酸鹼族鹽。本實驗例以高錳酸鉀進行。
接著,可使用中和劑中和促進劑所留下之殘留物。常用之中和劑為過氧化氫和硫酸之酸性水溶液。在本實驗例中,
是以70v%硫酸和30v%過氧化氫水溶液作為中和劑。
對於已經經過中和之基板,施加酸或鹼性調質劑。可使用習知的調質劑,以具有聚胺之鹼性界面活性劑為佳。
對於經過調質劑處理之基板,進行微蝕刻。微蝕刻可使用習知之蝕刻組成物,例如硫酸。藉由微蝕刻,可在基板表面提供微粗糙化之表面,以增強後續進行化學鍍時,觸媒及鍍覆金屬離子的附著。
接著,對經過微蝕刻之基板,進行預浸。可使用市售產品,在本實驗例中,使用硫酸與非離子型界面活性劑混合液,其中,硫酸與非離子型界面活性劑重量份比為3000:1。
接著,使用本揭露之實施例的含有金屬觸媒之催化劑,活化經過預浸之基板。施加催化劑的方法可使用例如浸置、噴灑或霧化等。由於活化步驟是控制化學鍍膜沉積速率的關鍵因素,因此施加催化劑的時間以及溫度可依照實際需求進行調整。一般而言,施加催化劑的時間約為0.1~10分鐘,例如,可為0.1~5分鐘,0.1~3分鐘。施加催化劑的溫度約為室溫至80℃,例如可為室溫至65℃,室溫至55℃。
接著將經過活化之基板,以還原劑進行還原。還原劑可將催化劑中之金屬離子還原成金屬狀態。常用之還原劑為二甲基胺硼烷(DMAB)或硼氫化鈉。施加還原劑的方法可使用浸置、噴灑或霧化等方法。施加還原劑的時間約為0.1~10分鐘,例如可為0.1~5分鐘,0.1~3分鐘。施加催化劑的溫度約為室溫至80℃,例如可為室溫至65℃,室溫至55℃。
接著,以含有金屬之鍍覆液對經過還原劑處理之基
板進行化學鍍膜。鍍覆液中之金屬離子可為銅、銅合金、鎳、或鎳合金或其組合。鍍覆的操作條件可將基板浸置於鍍覆液中,亦可將鍍覆液噴灑於基板上。施加鍍覆劑的時間,可依照對鍍膜的厚度的需求而設定,一般而言約為0.1~30分鐘,例如可為0.1~20分鐘,0.1~10分鐘。鍍覆進行的溫度可依照所希望的反應速度而設定,溫度過高會降低鍍覆的安定性,溫度過低則反應進行速度過慢,一般而言約為20℃至80℃,例如可為20℃至65℃,25℃至45℃。
對基板進行鍍覆之後,可視需求進一步對有金屬沉積之基板進行防鏽處理。
以下藉由實施例,更具體且詳細地說明關於本揭露之金屬觸媒。以下之實施例是為了進一步說明本揭露,並非用以限定本揭露之範疇。
將0.1g氯化鈀(PdCl2)及0.2g氯化鉀(KCl)混合於50ml去離子水中,於室溫下,混合10小時。接著,加入1.1ml 3-吡啶甲醇(3-pyridinemethanol),於80~100℃之溫度下,混合24小時。之後,以抽氣減壓裝置過濾,得到結晶狀之鈀觸媒。
所得到之鈀觸媒,具有以下結構。其H-NMR核磁譜圖(DMSO-d6,400MHz):δ H:4.57-4.58(d,4H),5.57-5.60(t,2H),7.49-7.52(dd,2H),7.89-7.91(d,2H),8.62-8.63(d,2H),8.71(s,2H。
將0.1g氯化鈀(PdCl2)及0.2g氯化鉀(KCl)混合於600ml去離子水中,於室溫下,攪拌10小時。接著,加入1.1ml 3-吡啶甲醇(3-pyridinemethanol),於80~100℃之溫度下,混合24小時。所得到之溶液中,鈀離子的濃度大約為100ppm。
除了以2-吡啶甲醇(2-(hydroxymethyl)pyridine)取代實驗例1中之3-吡啶甲醇以外,係與實驗例1進行同樣的操作方法,得到鈀觸媒。
除了以2-胺基-6-甲基吡啶(2-amino-6-methylpyridine)取代實驗例1中之3-吡啶甲醇以外,係與實驗例1進行同樣的操作方法,得到鈀觸媒。
除了以碘化鉀(KI)取代實驗例1中之氯化鉀以外,係與實驗例1進行同樣的操作方法,得到鈀觸媒。且鈀觸媒為粉末狀。
所得到之鈀觸媒,具有如下結構,其H-NMR核磁譜圖(DMSO-d6,400MHz):δ H:4.57-4.58(d,4H),5.57-5.60(t,2H),
7.49-7.52(dd,2H),7.89-7.91(d,2H),8.62-8.63(d,2H),8.71(s,2H)。
除了以硫酸鎳取代實驗例1中之氯化鈀以外,係與實驗例1進行同樣的操作方法,得到鎳觸媒。
將0.1g氯化鈀(PdCl2)及0.1g氯化鉀(KCl)混合於600ml去離子水中,於室溫下,混合10小時。接著,加入145.6μL3-吡啶甲醇(3-pyridinemethanol),於80~100℃之溫度下,混合24小時。所得到之溶液中,鈀離子的濃度大約為100ppm。
使用市售之鈀觸媒(Atotech Deutschaland Gmbh),其含有鈀離子濃度200ppm,溶液pH值10~11。
除了以鹽酸(HCl)取代實驗例1中之氯化鉀之外,係與實驗例1進行同樣的操作方法,合成鈀觸媒。然而,溶液中無法得到鈀觸媒結晶。
由實驗例1、5及比較實驗例2之結果可得知,於合成
步驟中添加鹼金屬鹵化物為可幫助鈀觸媒形成結晶。推測其原因為添加了鹼金屬鹵化物,因此溶液中產生一金屬離子與鹵素的錯合物之中間產物,此過程有助於形成本揭露的實施例之觸媒結構。
將實驗例1及比較實驗例1之鈀觸媒,配製成鈀濃度為200ppm之溶液,緩慢逐次滴入HCl以調整溶液之pH值。以pH值檢測儀(型號:HM-25R,購自科協儀器股份有限公司)測定溶液之pH值,並觀察溶液是否產生沉澱。實驗結果,含有實驗例1之鈀觸媒的溶液在pH值為3~9.7之間時,溶液均維持澄清。相較之下,含有比較實驗例1之鈀觸媒的溶液在pH值為6時,溶液中產生沉澱。
由上述實驗結果可得知,本揭露的實施例之鈀觸媒對於pH之耐受性較佳,在pH值為3~12之間,皆不產生沉澱。
將經過清潔步驟之基材通孔板(采鑫科技股份有限公司製),以作為調質劑之12~20v%二乙二醇單丁醚水溶液由李長榮化學股份有限公司製得)於約75℃處理約75秒之後,以水洗洗去調質劑。接著以微蝕劑之20w%硫酸水溶液(LCY公司製得)於約30℃處理約30秒之後,以清水沖洗。使用80g/L硫酸混合液,(李長榮化學工業股份有限公司製得)作為預浸液,以約28℃處理約20秒,並且以水洗淨基板。接著,添加含有各實驗例所合成之觸媒之催化劑,於約45℃反應約40秒之後,以水沖洗。接著再以0.05M含有二甲基胺硼烷(李長榮化學工業股份有限公司製得)作為還原劑之溶液,於約35℃處理約30秒之後,以水洗淨還原劑。以化
學銅鍍覆液(李長榮化學工業股份有限公司製得,銅離子含量2.5-4g/L)進行金屬沉積,反應溫度約為35℃,反應時間約為7分鐘。最後以水沖洗基板,得到具有金屬沉積之基板。
將具有金屬沉積之基板烘乾,切割測試孔。以砂紙將測試孔磨至半孔,同時也將測試孔背面磨至可背光觀察之厚度。將具有測試孔橫截面之基板,置於光學顯微鏡下。觀察倍數為50X,顯微鏡之光源位於樣本後方。以顯微鏡觀察透射通過測試孔之可見光並評估鍍膜品質。若鍍膜完整,則毫無光線透射通過測試孔,在顯微鏡的觀察時呈現黑色。若鍍膜有缺損,則光線透射通過測試孔,在顯微鏡的觀察時呈現亮點。依照第3圖之參考樣本對鍍膜給予背光試驗D1至D10的評價,其中D1為最差,D10為最優良。將評價為D8以上之鍍膜評為「○」。
溫度衝擊試驗評估係參照IPC-TM-650之2.6.8b。將經化學鍍膜的基材樣品,以電鍍增厚至25μm。將錫爐升溫至288℃之後,將基材樣品置於熔融錫表面,10秒鐘後,取出置於室溫至冷卻,重複此步驟3次。將經過溫度衝擊試驗後之基材樣品切片,孔壁沒有浮雕的現象,即通過溫度衝擊試驗,評價為優良「○」。
在鍍膜步驟中,使用實驗例製備而得的金屬觸媒,配置成以鈀離子濃度計為200ppm之催化劑溶液,接著再添加500ppm之銅離子。
使用實驗例1所獲得之鈀觸媒,再陸續配置成觸媒濃度以鈀離子濃度計為70、90、100、150、200、250ppm之催化劑溶液(以下稱鈀觸媒濃度),使用此催化劑溶液進行化學鍍膜。接著,將所得到之鍍膜進行背光試驗及溫度衝擊試驗,並進行評估。將評估結果顯示於表2。
由上述實驗結果可得知,本揭露的實施例的鈀觸媒在70~250ppm之濃度範圍內,皆能良好地進行化學鍍膜。其背光測試及溫度衝擊試驗之結果優良,所得到的鍍膜具有優異之均一性,且上述實驗例,均不漏光。
使用實驗例6所獲得之鎳觸媒,配置成鎳觸媒濃度為1000ppm之催化劑溶液,使用催化劑溶液進行化學鍍膜。接著,將所得到之鍍膜進行背光試驗。背光級數評價為D9,顯示為優良。
由實驗例1及6可知,本揭露的實施例之觸媒(鈀觸媒、鎳觸媒),皆能良好地進行化學鍍膜,得到鍍膜具有優異的均一性。
使用實驗例7所獲得之鈀觸媒,配置成鈀觸媒濃度為200ppm之催化劑溶液,使用催化劑溶液進行化學鍍膜。接著,將所得到之鍍膜進行背光試驗。背光級數評價為D9,顯示為優良。
由實驗例1及7可知,本揭露的實施例之鈀觸媒,在
金屬離子基:氟、氯、溴或碘:螯合基之莫耳數比(M:X:L)為1:2:2及1:1:3時,皆能良好地進行化學鍍膜,得到的鍍膜具有優異的均一性。
使用實驗例1所獲得之鈀觸媒,配置成鈀觸媒濃度為200ppm之催化劑溶液,並調整pH值。使用此不同pH值之催化劑溶液,進行化學鍍膜。接著,將所得到之鍍膜進行背光試驗及溫度衝擊試驗,並進行評估。將評估結果顯示於表3。
使用比較實驗例1所獲得之鈀觸媒,配置成鈀觸媒濃度為200ppm之催化劑溶液,並調整pH值為pH3。使用此催化劑溶液,進行化學鍍膜。接著,將所得到之鍍膜進行背光試驗。背光試驗的結果如第5圖所示,背光級數評價為D2,顯示為不良。
由上述實驗結果可得知,本揭露的實施例的鈀觸媒在pH值為3~12之範圍內,皆能良好地進行化學鍍膜,具有優異的耐pH性質,能在廣泛的pH值範圍內進行化學鍍膜。且鍍膜之背光試驗的評估結果優良,所得到的鍍膜具有優異之均一性。並且溫度衝擊試驗之結果優良。
使用實驗例1、3、4所獲得之鈀觸媒,配置成鈀觸媒濃度為200ppm之催化劑溶液,並調整pH值。使用此不同pH值之
催化劑溶液,進行化學鍍膜。接著,將所得到之鍍膜進行背光試驗,並進行評估。將評估結果顯示於表4。
由上述實驗結果可得知,實驗例1、3、4在pH值為3~12之範圍內,皆能良好地進行化學鍍膜。此外,實驗例5在pH值為3~12之範圍內,亦能良好地進行化學鍍膜。本揭露的實施例的鈀觸媒,在pH值為3~12之範圍內具有優異的耐pH性質,能在廣泛的pH值範圍內進行化學鍍膜,且鍍膜之背光試驗的評估結果優良,所得到的鍍膜具有優異之均一性。
使用實驗例1及比較實驗例1所獲得之鈀觸媒,配置成鈀觸媒濃度為200ppm之催化劑溶液,並添加500ppm之銅離子,進行化學鍍膜。接著,將所得到之鍍膜以掃描式電子顯微鏡(JEOL JSM-5600)進行掃描,並進行背光測試。其結果如第1圖及第2圖所示。第1圖為使用實驗例1之鈀觸媒所配置之催化劑溶液,於添加500ppm銅離子之情形下進行鍍膜。由電子影像可得知,鍍膜平整無漏光。其背光測試的結果,評價為D10,顯示為優良。第2圖為使用比較實驗例1之鈀觸媒所配置之催化劑溶液,於添加500ppm銅離子之情形下進行鍍膜。由電子影像可得知,鍍膜不平整,且有缺損。其背光測試的結果,評價為D2,顯示為不良。
由上述實驗例1及比較實驗例1之結果可得知,本揭露的實施例的鈀觸媒具有良好的銅離子耐受性,即使在銅離子濃度為500ppm時,仍然能夠良好地進行化學鍍膜,且鍍膜之背光試驗的評估結果優良,所得到的鍍膜具有優異之均一性。
此外如同實驗例1~4的觸媒溶液在pH3~12均無沉澱,且使用此觸媒溶液所獲得之鍍膜其背光試驗的評估結果為D8以上。
藉由本揭露的實施例所提供之金屬觸媒,可達到在廣泛的溶液pH值範圍皆能夠進行鍍膜均一性優異之化學鍍膜。
Claims (21)
- 一種金屬觸媒,係具有如式(1)或式(2)所示之結構:其中,M係鈀、銅、鉑、鎳或銀離子基;X為氟、氯、溴或碘;以及L為含氮芳香環之螯合基,其中該螯合基係為:且該螯合基上至少一碳上的氫係被R、或Q所取代,其中R係飽和或不飽和,直鏈、支鏈或環狀之碳數為1~6之烴基;,其中Z為羥基、甲氧基或乙氧基,a為1至6之整數;Q係COOR1,COR1,NHR1,或NR1R2,其中R1及R2各自獨立地為氫;或是碳數為1~6之烴基;當Q=COOR1時,R1不為氫;其中當該金屬觸媒具有如式(I)之結構時,該螯合基不為4-吡啶甲醇。
- 如申請專利範圍第1項所述之金屬觸媒,其中該螯合基為吡啶、2-吡啶甲醇、3-吡啶甲醇、4-吡啶甲醇、2-吡啶乙醇、3-吡啶乙醇、4-吡啶乙醇、4-胺基-6-甲基吡啶、3-胺基-6-甲基吡啶、2-胺基-6-甲基吡啶、2-胺基-5-甲基吡啶、或2-胺基-4-甲基吡啶。
- 如申請專利範圍第1項所述之金屬觸媒,其中M為鈀或鎳離子基。
- 如申請專利範圍第2項所述之金屬觸媒,其中M為鈀或鎳離子基;X為氟、氯、溴或碘。
- 如申請專利範圍第4項所述之金屬觸媒,其中該螯合基為3-吡啶甲醇、2-吡啶甲醇或2-胺基-6-甲基吡啶。
- 如申請專利範圍第1項所述之金屬觸媒,其中該觸媒為結晶型(crystalline)。
- 種金屬觸媒之製備方法,包括:將一金屬鹽類與一鹼金屬鹵化物於水中混合,反應以形成一金屬觸媒前驅物,其中該金屬鹽類為含有鈀、銅、鉑、鎳或銀之鹽類;以及將該金屬觸媒前驅物與一含氮芳香環之螯合劑反應,以形成一如申請專利範圍第1~6項中任一項所述之金屬觸媒。
- 如申請專利範圍第7項所述之金屬觸媒之製備方法,更包括一過濾步驟,以將該金屬觸媒從該混合液中分離。
- 如申請專利範圍第7項所述之金屬觸媒之製備方法,其中該鹼金屬鹵化物為氯化鉀、碘化鉀、氟化鉀、或溴化鉀或其組合。
- 如申請專利範圍第7項所述之金屬觸媒之製備方法,其中該含有鈀離子的鹽類包括鈀之鹵化物、乙酸鈀、硫酸鈀或硝酸鈀。
- 如申請專利範圍第7項所述之金屬觸媒之製備方法,其中該含氮芳香環之螯合劑為,且至少一碳上的氫係獨立被R、或Q所取代:R係飽和或不飽和,直鏈、支鏈或環狀之碳數為1~6之烴基;,其中Z為羥基、甲氧基或乙氧基,a為1至6;Q係COOH,COOR1,COR1,NHR1,或NR1R2,其中R1及R2各自獨立地為氫;或是碳數為1~6之烴基。
- 如申請專利範圍第7項所述之金屬觸媒之製備方法,其中,該含氮芳香環之螯合劑為3-吡啶甲醇、2-吡啶甲醇或2-胺基-6-甲基吡啶。
- 如申請專利範圍第7項所述之金屬觸媒之製備方法,其中形成該金屬觸媒前驅物之步驟,係於20~60℃下、反應5分鐘至24小時。
- 如申請專利範圍第7項所述之金屬觸媒之製備方法,其中該金屬觸媒前驅物與該含氮芳香環之螯合劑係於20~100℃下且反應5分鐘至48小時。
- 如申請專利範圍第7項所述之金屬觸媒之製備方法,其中,該金屬觸媒前驅物與該含氮芳香環之螯合劑反應的步驟係於20-95℃下且反應5-24小時。
- 如申請專利範圍第7項所述之金屬觸媒之製備方法,其中,該金屬鹽類之該鈀、銅、鉑、鎳或銀、該鹼金屬鹵化物之鹵基及該含氮芳香環之螯合劑反應摩爾比為1:3-1:1-3。
- 一種金屬觸媒,其是以如申請專利範圍第7至17項中任一項所述之製備方法所製得。
- 一種化學鍍膜之方法,包括:將一基材浸置於一含有如申請專利範圍第1~6項中任一項所述之金屬觸媒之溶液中,其中該溶液之pH值為2~12;以及將浸置過該金屬觸媒溶液之該基材浸置於一化學鍍膜溶液中。
- 如申請專利範圍第18項所述之化學鍍膜之方法,其中在將該基材浸置於金屬觸媒溶液之前,更包括:將該基材浸置於包含一種或多種離子性界面活性劑之一調節劑中;將浸置過該調節劑之該基材,浸置於一微蝕刻溶液中;及將浸置過該微蝕溶液之該基材,浸置於一預浸溶液中。
- 如申請專利範圍第18項所述之化學鍍膜之方法,其中,該含有金屬觸媒之溶液的pH值小於8。
- 如申請專利範圍第18項所述之化學鍍膜之方法,於該浸置過該金屬觸媒溶液之該基材浸置於該化學鍍膜溶液之前,更包括將浸置過該金屬觸媒溶液之該基材浸置於一還原劑中。
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KR102033824B1 (ko) | 2019-10-17 |
TW201806964A (zh) | 2018-03-01 |
EP3287465A1 (en) | 2018-02-28 |
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