CN109576684A - A kind of method of polymeric film surface chemical plating - Google Patents
A kind of method of polymeric film surface chemical plating Download PDFInfo
- Publication number
- CN109576684A CN109576684A CN201910088158.1A CN201910088158A CN109576684A CN 109576684 A CN109576684 A CN 109576684A CN 201910088158 A CN201910088158 A CN 201910088158A CN 109576684 A CN109576684 A CN 109576684A
- Authority
- CN
- China
- Prior art keywords
- chemical plating
- film surface
- polymeric film
- solution
- functionalization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000126 substance Substances 0.000 title claims abstract description 78
- 238000007747 plating Methods 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229920006254 polymer film Polymers 0.000 claims abstract description 31
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 27
- 230000004913 activation Effects 0.000 claims abstract description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012530 fluid Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 9
- ZIQCCIAIROIHHR-UHFFFAOYSA-N benzene;boric acid Chemical compound OB(O)O.C1=CC=CC=C1 ZIQCCIAIROIHHR-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000006557 surface reaction Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 51
- 229960002050 hydrofluoric acid Drugs 0.000 description 21
- 239000004926 polymethyl methacrylate Substances 0.000 description 15
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- -1 poly terephthalic acid Glycol ester Chemical class 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910001096 P alloy Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 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
- 230000006378 damage Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—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
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- 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
-
- 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
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
-
- 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
- C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
Landscapes
- Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a kind of methods of polymeric film surface chemical plating, comprising: A1: thin polymer film being placed in functionalization solution, 10~120min of grafting is stood at a temperature of 20~25 DEG C, so that the polymeric film surface is grafted pyridine groups；A2: sample obtained by the step A1 is placed in activated solution, persistently stirs 5~30min under the conditions of 20~25 DEG C of temperature；A3: sample obtained by the step A2 being placed in chemical plating fluid, preset temperature is adjusted to, and persistently stirs 15~45min.Polymer surfaces have been grafted pyridine groups by the present invention, pyridine groups can provide chemisorption site for active ion, pyridine groups have stronger suction-operated to activating ion or atom, there is the surface of catalytic activity to make thin polymer film after activation, and then polymeric film surface is made smoothly to plate metal layer.
Description
Technical field
The invention belongs to electroless plating technology field more particularly to a kind of methods of polymeric film surface chemical plating.
Background technique
Since thin polymer film has good thermal stability, insulating properties and photoelectric characteristic, in recent years by more and more
Applied to microelectronics Packaging, auto industry and photoelectric device etc..Thus the metallization of thin polymer film causes widely
Concern.But due to polymeric film surface can low and intrinsic adhesion strength it is weak, cause its metallization to become a problem.It is common
The method of polymer thin film metallization have magnetron sputtering, physical vapour deposition (PVD) and chemical vapor deposition etc..But these methods
It to environmental requirement height, often needs to carry out under vacuum conditions, and equipment is expensive, it is complicated for operation, it limits its application.Chemical plating energy
Efficiently solve this problem.Chemical plating is a kind of self-catalyzed reaction, and metal ion is gone back in active surface in plating process
Original, to obtain the coat of metal.Chemical plating is applicable to most polymers, and coating is uniform, and thickness is controllable.Also, chemical plating
It can be carried out in atmospheric environment, it is easy to operate and at low cost, it is a kind of polymer surfaces method for metallising well.
However, the thin polymer film that polymer especially surface roughness is very low, surface can be usually very low, therefore surface
Without catalytic activity, it is difficult to carry out electroless deposition, therefore, before chemical plating need to carry out its surface certain pretreatment.Often
Preprocess method has roughing in surface, surface plasma processing.However, roughing in surface will usually use hexavalent chromium,
Environmental pollution is serious, and surface plasma processing can generate certain destruction to surface.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of methods of polymeric film surface chemical plating, particularly, should
Method provides a kind of pair of pretreated method of polymeric film surface, and polymeric film surface is made to be grafted pyridine groups, so that
Polymeric film surface has catalytic activity after activation, goes on smoothly subsequent chemical plating.
To solve the above problems, the technical solution of the present invention is as follows:
A kind of method of polymeric film surface chemical plating, comprising:
A1: polymeric film surface functionalization: thin polymer film is placed in functionalization solution, in 20~25 DEG C of temperature
Lower standing is grafted 10~120min, so that the polymeric film surface is grafted pyridine groups；
A2: polymer surface activation: sample obtained by the step A1 is placed in activated solution, in 20~25 DEG C of temperature
Under the conditions of persistently stir 5~30min, obtain being adsorbed with activating ion or bond object film；
A3: chemical plating: sample obtained by the step A2 is placed in chemical plating fluid, preset temperature is adjusted to, persistently stirs
15~45min is mixed, plating operation is carried out.
Specifically, the step A1 is specifically included:
Thin polymer film is cleaned and dried；
Thin polymer film is placed in configured functionalization solution, grafting 10min is stood at a temperature of 20~25 DEG C,
Deionized water cleaning, drying.
Preferably, the chemical composition of the functionalization solution is selected from one of following:
2vt% fluoboric acid, 1vt% hydrofluoric acid, 0.005~0.02moL/L 4- nitro tetrafluoro boric acid benzene father-in-law, 0.005~
0.04moL/L surfactant, 1~4vt%4- vinylpyridine；Or
2vt% concentrated hydrochloric acid, 1vt% hydrofluoric acid, 0.005~0.02moL/L 4- nitro tetrafluoro boric acid benzene father-in-law, 0.005~
0.04moL/L surfactant, 1~4vt%4- vinylpyridine；Or
2vt% dilute sulfuric acid, 1vt% hydrofluoric acid, 0.005~0.02moL/L 4- nitro tetrafluoro boric acid benzene father-in-law, 0.005~
0.04moL/L surfactant, 1~4vt%4- vinylpyridine.
Specifically, the step A2 is specifically included:
Configure activated solution；
Sample obtained by the step A1 is placed in configured activated solution, is persistently stirred at a temperature of 20~25 DEG C
5~30min, deionized water cleaning are dry.
Preferably, the group of the activated solution becomes 0~0.1moL/L Nickel dichloride hexahydrate, 0.0001~0.001moL/L
Palladium chloride, 20~50vt% concentrated hydrochloric acid, 0.15~0.3vt% hydrofluoric acid or 0~0.1moL/L Nickel dichloride hexahydrate, 0.0001
~0.001moL/L silver nitrate, 20~50vt% concentrated hydrochloric acid, 0.15~0.3vt% hydrofluoric acid.
Preferably, the chemical plating fluid includes metal salt, reducing agent and additive.
The present invention also provides a kind of methods of polymeric film surface chemical plating, make thin polymer film in the solution first
Surface grafting can provide the functionalization group in chemisorption site for active ion, then be activated in activated solution, it
Carry out chemical plating in chemical plating fluid again afterwards.
In preferred embodiment, the functionalization group is pyridine groups.
Specifically, being grafted the functionalization group in polymeric film surface is that thin polymer film is placed in ethylene containing 4-
Grafting is stood in the functionalization solution of yl pyridines, so that the polymeric film surface is grafted pyridine groups.
Specifically, the activation is that the sample after the grafting is placed in activated solution to be persistently stirred to react, wherein
Contain hydrofluoric acid in the activated solution.
The present invention due to using the technology described above, makes it have the following advantages that and actively imitate compared with prior art
Fruit:
(1) chemical plating method provided by the invention is to make polymeric film surface functionalization first, is then activated, and finally will
The thin polymer film handled well is infiltrated into chemical plating fluid.Surface-functionalized is by making its table in polymeric film surface grafting
The group of mask functionalization, the group can effective adsorption activation ion, so that chemical plating be made to go on smoothly；In preferred mode
In, polymer surfaces are grafted pyridine groups, pyridine groups have stronger suction-operated to activating ion or atom, can be
Active ion provides chemisorption site, so that making thin polymer film after activation has the surface of catalytic activity, to make to gather
It closes object film surface and smoothly plates metal layer；The present invention by design surface functionalization step solve surface energy polymer it is low,
The problem of can't be catalytic surface, and avoid roughing in surface, surface plasma processing bring negative effect；
(2) for the present invention, activation processing is the committed step before chemical plating, in work in preferred embodiment of the invention
Hydrofluoric acid is added when changing liquid configuration, is reacted using hydrofluoric acid with metal or semiconductor base and generates active hydrogen atom, reactive hydrogen is former
Activating ion is directly reduced into activated atom by son, to enhance suction-operated；
(3) concentration of palladium chloride or silver nitrate is only 0.0001~0.001moL/L in the preferred embodiment of the invention, expensive
The dosage of metal ion is few compared in conventional activation liquid, can reach preferable activation effect using seldom precious metal ion, have
Reduce costs to effect；And operating procedure of the invention can be carried out directly under room temperature and atmospheric environment, no equipment requirement, behaviour
Make simple and at low cost.
Detailed description of the invention
Fig. 1 is the method flow diagram of Inventive polymers film surface chemical plating；
Fig. 2 is the schematic diagram of Inventive polymers film surface chemical plating；
Fig. 3 is the XPS N1s core spectrogram on 2 sample after activation surface of embodiment；
Fig. 4 is the electron scanning micrograph of 2 chemical nickel phosphorus plating layer surface of embodiment；
Fig. 5 is the X-ray energy spectrogram of 2 chemical nickel phosphorus plating layer surface of embodiment.
Specific embodiment
Below in conjunction with the drawings and specific embodiments to a kind of method of polymeric film surface chemical plating proposed by the present invention
It is described in further detail.According to following explanation and claims, advantages and features of the invention will be become apparent from.
Embodiment 1
With reference to Fig. 1, a kind of method for present embodiments providing polymeric film surface chemical plating, thin polymer film be can be
Polymethyl methacrylate (PMMA), polymethylacrylic acid (PMAA), Polymethacrylimide (PMI), poly terephthalic acid
Glycol ester (PET), polyamide (PA), polypropylene (PP), polyvinyl chloride (PVC), polyvinyl alcohol (PVA) etc. are most of organic thin
Film, and polymer film thickness can be deposited on metal or semiconductor base, thin polymer film can down to several hundred nanometers
To be prepared using the conventional method of this field.The method of the present embodiment includes:
A1: thin polymer film is placed in functionalization solution by polymeric film surface functionalization, in 20~25 DEG C of temperature
Lower standing is grafted 10~120min, and polymeric film surface is made to be grafted pyridine groups；
A2: sample obtained by step A1 is placed in activated solution, in 20~25 DEG C of temperature conditions by polymer surface activation
5~30min is persistently stirred down, obtains being adsorbed with activating ion or bond object film；
A3: sample obtained by step A2 is placed in chemical plating fluid, is adjusted to preset temperature, persistently stirs 15 by chemical plating
~45min carries out plating operation.Chemical plating fluid includes metal salt, reducing agent and additive, and mixing time can be according to required plating
Thickness degree determines that chemical plating temperature is adjusted according to plating metal and chemical plating fluid pH.
Chemical plating method provided in this embodiment is to make polymeric film surface functionalization first, is then activated, and finally will
The thin polymer film handled well is infiltrated into chemical plating fluid.Surface-functionalized is by making its table in polymeric film surface grafting
The group of mask functionalization, the group can effective adsorption activation ion, so that chemical plating be made to go on smoothly.With reference to Fig. 3, excellent
In the mode of choosing, polymer surfaces pyridine groups are grafted, pyridine groups have stronger absorption to activating ion or atom
Effect, can provide chemisorption site for active ion, so that making thin polymer film after activation has the surface of catalytic activity,
To make polymeric film surface smoothly plate metal layer.The present invention solves polymer table by design surface functionalization step
Face energy is low, can't be the problem of catalytic surface, and avoids roughing in surface, the surface plasma processing negative shadow of bring
It rings.
Specifically, it is specifically included referring to Fig. 2, step A1:
A101: thin polymer film deionized water is cleaned by ultrasonic 30~60s, drying；
A102: configuration feature solution；
A103: thin polymer film is placed in the configured functionalization solution of step A102, at a temperature of 20~25 DEG C
Stand 10~120min of grafting, deionized water cleaning, drying；
Wherein, step A101 and step A102 can be carried out with exchange sequence or simultaneously.
Further, the chemical composition of functionalization solution selects one of following:
2vt% fluoboric acid, 1vt% hydrofluoric acid, 0.005~0.02moL/L 4- nitro tetrafluoro boric acid benzene father-in-law, 0.005~
0.04moL/L surfactant, 1~4vt%4- vinylpyridine；Or
2vt% concentrated hydrochloric acid, 1vt% hydrofluoric acid, 0.005~0.02moL/L 4- nitro tetrafluoro boric acid benzene father-in-law, 0.005~
0.04moL/L surfactant, 1~4vt%4- vinylpyridine；Or
2vt% dilute sulfuric acid, 1vt% hydrofluoric acid, 0.005~0.02moL/L 4- nitro tetrafluoro boric acid benzene father-in-law, 0.005~
0.04moL/L surfactant, 1~4vt%4- vinylpyridine.4-vinylpridine in functionalization solution provides pyridyl group
Any one of thin polymer film placement in the above solution can be made polymeric film surface be grafted pyridine groups by group.
Specifically, step A2 is specifically included:
A201: configuration activated solution；
A202: sample obtained by step A1 is placed in the activated solution of step A201 configuration, is held at a temperature of 20~25 DEG C
5~30min of continuous stirring, deionized water cleaning are dry.
Further, the group of activated solution becomes 0~0.1moL/L Nickel dichloride hexahydrate, 0.0001~0.001moL/L chlorine
Change palladium, 20~50vt% concentrated hydrochloric acid, 0.15~0.3vt% hydrofluoric acid or 0~0.1moL/L Nickel dichloride hexahydrate, 0.0001~
0.001moL/L silver nitrate, 20~50vt% concentrated hydrochloric acid, 0.15~0.3vt% hydrofluoric acid.
Activation processing is the committed step before chemical plating, and common activation method is divided into two-step method, that is, uses stannous chloride
Acid solution reuses palladium chloride solution after being sensitized and is activated, but such method is poor to the adsorption effect of activating ion.
Hydrofluoric acid is added in the present embodiment in activated solution, is reacted using hydrofluoric acid with substrate and generates active hydrogen atom, will activate from
Son is directly reduced into activated atom, to enhance activation point, then increases suction-operated, therefore the present embodiment can have
Effect improves activation effect.The concentration of palladium chloride or silver nitrate is only 0.0001~0.001moL/L in the present embodiment, noble metal from
The dosage of son is few compared in conventional activation liquid, can reach preferable activation effect using seldom precious metal ion, effectively drop
Low cost.In addition the operating procedure of the present embodiment can be carried out directly under room temperature and atmospheric environment, no equipment requirement, operation letter
List and cost bottom.Moreover, to polymeric film surface carry out functionalization after, be not necessarily to sensitising step, can directly to its into
Row is activated, and subsequent reduction step can also omit, and simplifies conventional pretreatment technique.
Illustrate that temperature is 25 DEG C of room temperature to not doing in the following description.
Embodiment 2
Polymethylacrylic acid (PMAA) film surface chemical plating Mi-P alloy, the steps include:
1, PMAA film is prepared；Respectively using acetone, alcohol and deionized water to having a size of 1 × 2cm2Silicon wafer surpassed
After sound cleaning, immerses and carry out Si-Hization processing 3 minutes in the HF solution that volume by volume concentration is 5%, silicon wafer is placed in and is configured
Grafting solution in, at room temperature carry out graft reaction 30 minutes after, be cleaned by ultrasonic with deionized water and dried.In silicon chip surface
Obtain the PMAA polymer film that thickness is about 150nm.Above-mentioned grafting solution preparation method is as follows: first by the deionized water of 50mL
Be added beaker in, then sequentially add under magnetic stirring the lauryl sodium sulfate of 0.1g, the fluoboric acid of 1mL, 0.5mL hydrogen
The p-nitrophenyl diazonium tetrafluoroborate of fluoric acid, the methacrylic acid of 2mL and 0.1g, stirs to clarify.
2, PMAA thin polymer film deionized water is cleaned by ultrasonic 1min, be dried for standby.
3, configuration feature solution:
4, the sample after cleaning is placed in functionalization solution, at room temperature, stands grafting 10min, deionization
Water rinsing, drying.
5, activated solution is configured:
6, step 4 gained sample is placed in activated solution, is continuously stirred at room temperature 20min.
7, step 6 gained sample is placed in acid chemical plating liquid, adjusts the temperature to 80 DEG C, continued under stirring condition,
Chemical plating 15min, deionized water are rinsed, are dried.Wherein, chemical constituent is nickel sulfate: 25g/l, ortho phosphorous acid in chemical plating fluid
Sodium: 25g/L, sodium citrate: 10g/L, sodium acetate: 10g/L, thiocarbamide: 0.1mg/L, pH value: 4.3~4.8.
Using the surface of X-ray photoelectron spectroscopic analysis sample after activation, Fig. 3 is N1s core spectrogram, from the figure 3, it may be seen that sample
Product surface is able to detect that pyridine groups (- C5H5N), show the grafting pyridine groups success of PMAA film surface.
To the sample after drying using scanning electron microscope observe sample surfaces, i.e. Fig. 4, as seen from the figure, sample surfaces
There is one layer of film uniformly, fine and close, and Fig. 5 shows that sample surfaces contain nickel phosphorus atoms, therefore the plating on PMAA film surface
Upper one layer nickel phosphorous layer uniformly, fine and close.
Embodiment 3
Polyacrylic acid (PAA) film surface electroless copper, the steps include:
1, PAA film is prepared: by 1 × 2cm2Nickel sheet be placed in the chemical graft solution of PAA, connect at room temperature
After branch reaction 30 minutes, it is cleaned by ultrasonic with deionized water and is dried.The PAA polymerization that thickness is about 150nm is obtained on nickel sheet surface
Object film.Above-mentioned chemical graft solution preparation method is as follows: the deionized water of 50mL being added in beaker first, then stirs in magnetic force
Mix down the acrylic acid and 0.1g of the fluoboric acid of lauryl sodium sulfate, 1mL for sequentially adding 0.1g, the hydrofluoric acid of 0.5mL, 2mL
P-nitrophenyl diazonium tetrafluoroborate, stir to clarify.
2, substrate surface will be grafted on having a size of 1 × 2cm2PAA film with deionized water be cleaned by ultrasonic 1min, dry it is standby
With.
3, configuration feature solution:
4, step 2 gained sample is placed in functionalization solution, at room temperature, stands grafting 10min, deionization
Water rinsing, drying.
5, activated solution is configured:
6, step 4 gained sample is placed in activated solution, is continuously stirred at room temperature 30min.
7, step 6 gained sample is placed in chemical bronze plating liquid, adjusts the temperature to 35 DEG C, continued under stirring condition, changed
Plating 30min is learned, deionized water is rinsed, dried.Wherein, the chemical composition of chemical plating fluid be 7.5g/L copper sulphate, 15g/L formaldehyde,
22g/L disodium ethylene diamine tetraacetate, 15g/L sodium potassium tartrate tetrahydrate, 10g/L sodium hydroxide.
By above-mentioned steps, PAA film surface obtains uniform metal copper coating.
Embodiment 4
Polymethyl methacrylate (PMMA) film surface Electroless Deposited Ni-B Alloy, the steps include:
1, PMMA film is prepared: will be having a size of 1 × 2cm2Copper sheet be placed in the chemical graft solution of PMMA, in room temperature
After lower progress graft reaction 30 minutes, it is cleaned by ultrasonic with deionized water and is dried.Obtaining thickness on copper sheet surface is about 150nm's
PMMA polymer film.Above-mentioned chemical graft solution preparation method is as follows: the deionized water of 50mL being added in beaker first, then
Sequentially add under magnetic stirring the lauryl sodium sulfate of 0.1g, the fluoboric acid of 1mL, the hydrofluoric acid of 0.5mL, 2mL methyl
The p-nitrophenyl diazonium tetrafluoroborate of methyl acrylate and 0.1g, stirs to clarify.
2, substrate surface will be grafted on having a size of 1 × 2cm2PMMA film with deionized water be cleaned by ultrasonic 1min, drying
It is spare.
3, configuration feature solution:
4, step 2 gained sample is placed in step 3 solution, at room temperature, stands grafting 10min, deionization
Water rinsing, drying.
5, activated solution is configured:
6, step 4 gained sample is placed in the solution that step 5 is configured, is continuously stirred at room temperature 30min.
7, step 6 gained sample is placed in acid chemical plating liquid, adjusts the temperature to 80 DEG C, continued under stirring condition,
Chemical plating 30min, deionized water are rinsed, are dried.Wherein, the chemical composition of chemical plating fluid is nickel sulfate: 50g/L, dimethyl amine
Borine: 2.5g/L, sodium citrate: 25g/L, lactic acid: 25g/L, stabilizer 1mg/L, pH value: 6.
By above-mentioned steps, PMMA film surface obtains uniform Ni-B alloy layer.
Embodiment 5
Polymethyl methacrylate (PMMA) film surface electroless cobalt plating-Fe-P alloy, the steps include:
1, PMMA film is prepared: respectively using acetone, alcohol and deionized water to having a size of 1 × 2cm2Silicon wafer surpassed
After sound cleaning, immerses and carry out Si-Hization processing 3 minutes in the HF solution that volume by volume concentration is 5%, silicon wafer is placed in and is configured
Grafting solution in, at room temperature carry out graft reaction 30 minutes after, be cleaned by ultrasonic with deionized water and dried.In silicon chip surface
Obtain the PMMA polymer film that thickness is about 150nm.Above-mentioned grafting solution preparation method is as follows: first by the deionized water of 50mL
Be added beaker in, then sequentially add under magnetic stirring the lauryl sodium sulfate of 0.1g, the fluoboric acid of 1mL, 0.5mL hydrogen
The p-nitrophenyl diazonium tetrafluoroborate of fluoric acid, the methyl methacrylate of 2mL and 0.1g, stirs to clarify.
It 2, is 1 × 2cm by the size for grafting on substrate surface2PMMA film with deionized water be cleaned by ultrasonic 1min, dry
It does spare.
3, configuration feature solution:
4, step 2 gained sample is placed in step 3 solution, at room temperature, stands grafting 10min, deionization
Water rinsing, drying.
5, activated solution is configured:
6, step 4 gained sample is placed in step 4 acquired solution, is continuously stirred at room temperature 30min.
7, step 6 gained sample is placed in chemical plating fluid, adjusts the temperature to 80 DEG C, continued under stirring condition, chemistry
35min is plated, deionized water is rinsed, dried.Wherein, the chemical composition of chemical plating fluid be cobaltous sulfate: 20g/L, ferric sulfate: 10g/L,
Sodium hypophosphite: 30g/L, sodium citrate: 85g/L, ammonium chloride: 15g/L, manganese sulfate: 5g/L.
By above-mentioned steps, PMMA film surface obtains uniform Co-Fe-P alloy layer.
In embodiment described above, used chemical reagent is bought from market, wherein fluoboric acid selection purchase is dense
Degree is 40%, and it is 40% that hydrofluoric acid, which selects purchase concentration, and it is 95% that 4-vinylpridine, which selects purchase concentration,.
In summary embodiment it is found that a kind of polymeric film surface chemical plating provided by the invention method, exist first
Make polymeric film surface grafting that can provide the functionalization group in chemisorption site for active ion in solution, is then activating
It is activated in solution, carries out chemical plating in chemical plating again later.
In preferred embodiment, functionalization group is pyridine groups.
It specifically, is that thin polymer film is placed in vinylpyridine containing 4- in the graft-functionalized group of polymeric film surface
Grafting is stood in the functionalization solution of pyridine, so that polymeric film surface is grafted pyridine groups.
Specifically, activation is that the sample after the grafting is placed in activated solution to be persistently stirred to react, wherein activation
Contain hydrofluoric acid in solution.
Embodiments of the present invention are explained in detail above in conjunction with attached drawing, but the present invention is not limited to above-mentioned implementations
Mode.Even if to the present invention, various changes can be made, if these variations belong to the model of the claims in the present invention and its equivalent technologies
Within enclosing, then still fall within the protection scope of the present invention.
Claims (10)
1. a kind of method of polymeric film surface chemical plating characterized by comprising
A1: polymeric film surface functionalization: thin polymer film is placed in functionalization solution, quiet at a temperature of 20~25 DEG C
10~120min of grafting is set, so that the polymeric film surface is grafted pyridine groups；
A2: polymer surface activation: sample obtained by the step A1 is placed in activated solution, in 20~25 DEG C of temperature conditions
5~30min is persistently stirred down, obtains being adsorbed with activating ion or bond object film；
A3: chemical plating: sample obtained by the step A2 is placed in chemical plating fluid, preset temperature is adjusted to, persistently stirs 15
~45min carries out plating operation.
2. the method for polymeric film surface chemical plating according to claim 1, which is characterized in that the step A1 is specific
Include:
Thin polymer film is cleaned and dried；
Thin polymer film is placed in configured functionalization solution, at a temperature of 20~25 DEG C stand grafting 10min, go from
Sub- water cleaning, drying.
3. the method for polymeric film surface chemical plating according to claim 2, which is characterized in that the functionalization solution
Chemical composition be selected from it is one of following:
2vt% fluoboric acid, 1vt% hydrofluoric acid, 0.005~0.02moL/L 4- nitro tetrafluoro boric acid benzene father-in-law, 0.005~
0.04moL/L surfactant, 1~4vt%4- vinylpyridine；Or
2vt% concentrated hydrochloric acid, 1vt% hydrofluoric acid, 0.005~0.02moL/L 4- nitro tetrafluoro boric acid benzene father-in-law, 0.005~
0.04moL/L surfactant, 1~4vt%4- vinylpyridine；Or
2vt% dilute sulfuric acid, 1vt% hydrofluoric acid, 0.005~0.02moL/L 4- nitro tetrafluoro boric acid benzene father-in-law, 0.005~
0.04moL/L surfactant, 1~4vt%4- vinylpyridine.
4. the method for polymeric film surface chemical plating according to claim 1, which is characterized in that the step A2 is specific
Include:
Configure activated solution；
Sample obtained by the step A1 is placed in configured activated solution, persistently stir 5 at a temperature of 20~25 DEG C~
30min, deionized water cleaning are dry.
5. the method for polymeric film surface chemical plating according to claim 4, which is characterized in that the activated solution
Group becomes 0~0.1moL/L Nickel dichloride hexahydrate, 0.0001~0.001moL/L palladium chloride, 20~50vt% concentrated hydrochloric acid, 0.15
~0.3vt% hydrofluoric acid or 0~0.1moL/L Nickel dichloride hexahydrate, 0.0001~0.001moL/L silver nitrate, 20~50vt%
Concentrated hydrochloric acid, 0.15~0.3vt% hydrofluoric acid.
6. the method for polymeric film surface chemical plating according to claim 1, which is characterized in that the chemical plating fluid packet
Include metal salt, reducing agent and additive.
7. a kind of method of polymeric film surface chemical plating, which is characterized in that make polymeric film surface in the solution first
Grafting can provide the functionalization group in chemisorption site for active ion, then be activated in activated solution, Zhi Houzai
Chemical plating is carried out in chemical plating fluid.
8. the method for polymeric film surface chemical plating according to claim 7, which is characterized in that the functionalization group
For pyridine groups.
9. the method for polymeric film surface chemical plating according to claim 8, which is characterized in that in thin polymer film table
It is to be placed in thin polymer film in the functionalization solution containing 4-vinylpridine to stand grafting that face, which is grafted the functionalization group,
So that the polymeric film surface is grafted pyridine groups.
10. the method for polymeric film surface chemical plating according to claim 7 or 8, which is characterized in that the activation is
Sample after the grafting is placed in activated solution and is persistently stirred to react, wherein contains hydrofluoric acid in the activated solution.
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| CN111501030A (en) * | 2020-05-26 | 2020-08-07 | 电子科技大学 | Surface modification system before chemical plating and method for double modifying polymer substrate surface |
| JPWO2021167009A1 (en) * | 2020-02-19 | 2021-08-26 | ||
| CN113981421A (en) * | 2021-07-09 | 2022-01-28 | 西安电子科技大学 | A method for preparing rewritable metal electrode on plastic surface |
| CN115110071A (en) * | 2022-07-29 | 2022-09-27 | 电子科技大学 | Pretreatment method for chemical plating of insulating substrate and chemical plating method |
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| CN110117783A (en) * | 2019-04-19 | 2019-08-13 | 广东工业大学 | A kind of method of Electroless Nickel Plating of Aluminum Alloy mixed metal activation |
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| JP7569053B2 (en) | 2020-02-19 | 2024-10-17 | 学校法人 芝浦工業大学 | Plated Substrate |
| CN111501030A (en) * | 2020-05-26 | 2020-08-07 | 电子科技大学 | Surface modification system before chemical plating and method for double modifying polymer substrate surface |
| CN111501030B (en) * | 2020-05-26 | 2021-03-02 | 电子科技大学 | Surface modification system before chemical plating and method for double modifying polymer substrate surface |
| CN113981421A (en) * | 2021-07-09 | 2022-01-28 | 西安电子科技大学 | A method for preparing rewritable metal electrode on plastic surface |
| CN115110071A (en) * | 2022-07-29 | 2022-09-27 | 电子科技大学 | Pretreatment method for chemical plating of insulating substrate and chemical plating method |
| CN115110071B (en) * | 2022-07-29 | 2023-09-01 | 电子科技大学 | Electroless plating pretreatment method and electroless plating method for insulating substrate |
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