CN109252148A - 在感光性树脂的表面形成金属层的方法 - Google Patents
在感光性树脂的表面形成金属层的方法 Download PDFInfo
- Publication number
- CN109252148A CN109252148A CN201810373443.3A CN201810373443A CN109252148A CN 109252148 A CN109252148 A CN 109252148A CN 201810373443 A CN201810373443 A CN 201810373443A CN 109252148 A CN109252148 A CN 109252148A
- Authority
- CN
- China
- Prior art keywords
- photoresist
- metal layer
- ion
- nickel
- layer
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 title abstract description 11
- 229920005989 resin Polymers 0.000 title abstract description 11
- 238000007747 plating Methods 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 238000002203 pretreatment Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229920002120 photoresistant polymer Polymers 0.000 claims description 50
- 229920001721 polyimide Polymers 0.000 claims description 23
- 239000004642 Polyimide Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000007772 electroless plating Methods 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- -1 amine compound Chemical class 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 150000002118 epoxides Chemical class 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 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 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 claims description 3
- 239000006174 pH buffer Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 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 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000010944 silver (metal) Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 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 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- PSDYQSWHANEKRV-UHFFFAOYSA-N [S]N Chemical compound [S]N PSDYQSWHANEKRV-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 208000007578 phototoxic dermatitis Diseases 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 9
- 230000003213 activating effect Effects 0.000 abstract description 6
- 238000009713 electroplating Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 42
- 239000000758 substrate Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HPAXFNMMMBLYJU-UHFFFAOYSA-N copper sulfamic acid Chemical compound [Cu].S(N)(O)(=O)=O HPAXFNMMMBLYJU-UHFFFAOYSA-N 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
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- 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
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- C23C18/48—Coating with alloys
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
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- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1862—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by radiant energy
- C23C18/1868—Radiation, e.g. UV, laser
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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Abstract
本发明提供一种在特定的感光性树脂表面形成金属层的方法，包含以下步骤：(i)前处理，使用碱性水溶液对感光性树脂的表面进行清洁及预活化；(ii)表面改质，将感光性树脂浸泡于表面改质剂中，形成有机改质层；(iii)表面活化，加入触媒金属离子，使有机改质层与触媒金属离子形成金属离子错合物；(iv)还原反应，用还原剂将金属离子错合物还原成纳米金属触媒；(v)化学镀，将感光性树脂浸泡于化学镀液中，形成导电金属层；(vi)热处理，将感光性树脂于100‑250℃的条件下烘烤；及(vii)电镀增厚，将烘烤后的感光性树脂进行电镀，增厚导电金属层。
Description
技术领域
本发明涉及一种在感光性树脂的表面形成金属层的方法，特别是指对特定的感光性聚酰亚胺树脂表面金属化，以形成金属层的方法。
背景技术
聚酰亚胺为软性印刷电路板及IC封装业界常用的基材材料，其为具有可扰性、耐化学溶剂性(耐化性)、耐高温且不导电的有机材料。随着电子产品的薄型化及多功能化的趋势，高布线密度及导孔微小化已成为软性印刷电路板的基本需求。然而，一般非感光性的聚酰亚胺耐化性佳，因此不容易通过化学蚀刻制作平面及垂直导体沟槽，往往需要透过雷射锁孔或干式蚀孔搭配光阻进行微导孔的加工，再施以化学处理活化，才能形成金属层，制程较为复杂。然而，即使在非感光性的聚酰亚胺上能够形成金属层，此金属层与聚酰亚胺的结合强度并不高，且在制作多层板时，容易被高温烘压制程破坏。
而感光性聚酰亚胺有别于传统聚酰亚胺，其具有感光成孔的加工特色，无需额外使用雷射锁孔或干式蚀孔搭配光阻进行垂直导电单元的制作。然而，目前仍未存在一种实用的方法，能够在感光性聚酰亚胺树脂上形成高结合强度的金属层。
发明内容
本发明提供一种在特定的感光性树脂的表面形成金属层的方法，其包括前处理步骤、湿式化学表面改质步骤，以及金属化步骤。此方法可以应用在特定的感光性聚酰亚胺树脂，结合其感光成孔的特性，能使多层积体垂直导电单元的金属导线制作制程更为精简。
根据本发明，提供一种在感光性树脂的表面形成金属层的方法。所述感光性树脂包含(a)环氧化合物、(b)感光性聚酰亚胺及(c)光起始剂。环氧化合物占感光性树脂的固体重量的5-40％。感光性聚酰亚胺具有式(1)的结构：
其中m、n各自独立为1至600；X为四价有机基团，其主链部份含脂环族基团；Y为二价有机基团，其主链部份含硅氧烷基团；Z为二价有机基团，其支链部份至少含酚基或羧基，此感光性聚酰亚胺占感光性树脂的固体重量的30-90％。光起始剂占感光性树脂的固体重量的0.1-15％。
所述在感光性树脂的表面形成金属层的方法包含下列步骤：
(i)前处理，使用碱性水溶液对感光性树脂的表面进行清洁及预活化；
(ii)表面改质，将感光性树脂浸泡于表面改质剂中，在感光性树脂上形成有机改质层。表面改质剂选自式(2)至式(6)中的至少一种胺基化合物的水溶液：
其中n＝1-3，R1为NH2、NHCH3或NH(CH3)2，R2为H或CmH2mNH2，m＝1-3，R3为NH2、SH或OH，R4为SH、
(iii)表面活化，加入触媒金属离子，使有机改质层与触媒金属离子在该感光性树脂表面形成金属离子错合物；
(iv)还原反应，用还原剂将附着于感光性树脂表面的金属离子错合物还原成纳米金属触媒；
(v)化学镀，将已形成纳米金属触媒的感光性树脂浸泡于化学镀液中，形成导电金属层；
(vi)热处理，将已形成导电金属层的感光性树脂于100-250℃的条件下烘烤；以及
(vii)电镀增厚，将烘烤后的感光性树脂进行电镀，增厚导电金属层。
在一个实施例中，表面改质步骤(ii)中的浸泡时间为1-20分钟，且表面改质剂的胺基化合物的浓度为0.1-10g/L，温度为30-75℃。
在一个实施例中，表面活化步骤(iii)加入的触媒金属离子为包括Cu、Ni、Ag、Au或Pd离子的酸性水溶液。
在一个实施例中，还原反应步骤(iv)加入的还原剂为次磷酸钠、硼氢化钠、二甲基胺硼烷或联胺水溶液。
在一个实施例中，化学镀步骤(v)加入的化学镀液包含铜离子、镍离子、螯合剂、还原剂、pH缓冲剂、界面活性剂及pH调整剂。
在一个实施例中，化学镀液中铜离子的来源为硝酸铜、硫酸铜、氯化铜或氨基磺酸铜。
在一个实施例中，化学镀液中镍离子的来源为硫酸镍、硝酸镍、氯化镍、硫酸镍或氨基磺酸镍。
在一个实施例中，化学镀液中的螯合剂为柠檬酸钠、酒石酸钾钠或乙二胺四乙酸。
在一个实施例中，化学镀步骤(v)形成的导电金属层厚度为50-200nm。
在一个实施例中，热处理步骤(vi)的烘烤时间为10-60分钟。
在一个实施例中，前处理步骤(i)还包括以平行紫外光或电浆对感光性树脂的表面进行清洁及预活化。
在一个实施例中，当以平行紫外光进行前处理步骤(i)时，平行紫外光的照射波长为100-280nm，表面累积辐照强度为1-20J/cm2，且照射时间为1-30分钟。
在一个实施例中，当以电浆进行前处理步骤(i)时，输出功率为100-5000W，且处理时间为0.5-30分钟。
在一个实施例中，电镀增厚步骤(vii)是将导电金属层的厚度增加至12-18μm。
为使本发明的上述及其他方面更为清楚，下文特举实施例，配合文字进行详细说明。
具体实施方式
本发明所述的在感光性树脂的表面形成金属层的方法包括下列步骤：
(i)表面处理(前处理)
(ii)表面开环(改质)
(iii)触媒粒子吸附(表面活化)
(iv)触媒粒子还原
(v)化学镀(无电电镀)
(vi)热处理
(vii)电镀
(viii)除水风干。
本发明中，作为基材(基板)在其上形成金属层的感光性树脂，主要成分是感光性聚酰亚胺。感光性树脂的成分包括(a)环氧化合物、(b)感光性聚酰亚胺以及(c)光起始剂。感光性聚酰亚胺具有式(1)的结构：
其中m、n各自独立为1至600；X为四价有机基团，其主链部份含脂环族基团，较佳为不含苯环的脂环族基团，包含(但不限于)
Y为二价有机基团，其主链部份含硅氧烷基团，例如下列所示：
其中Y的链长以短为佳(p＝0)，最长可到p＝20，过长将破坏感光性聚酰亚胺的性质。Z为二价有机基团，其支链部份至少含酚基或羧基。酚基或羧基的含量约占感光性聚酰亚胺摩尔数的5-30％，并可通过调整支链覆盖基的摩尔比来控制显影的时间，当支链酚基或羧基的含量较高，则碱性显影液对其溶解性较佳，则可提升其显影性。Z可包括但不限于下列基团：
感光性聚酰亚胺占感光性树脂的固体重量的30-90％；环氧化合物占感光性树脂的固体重量的5-40％；而光起始剂占感光性树脂的固体重量的0.1-15％。这类感光性聚酰亚胺由于表面有硅氧烷基团、酰亚胺环基团与羧基等基团，较容易与本发明使用的表面改质剂的胺基进行耦合反应。
(i)表面处理(前处理)
首先，对感光性树脂基材进行表面清洁及预活化。使用的方法包括照射平行紫外光、电浆以及以碱性水溶液浸泡，可以选择其中一种，或多种一起配合使用。当以平行紫外光进行前处理时，平行紫外光的照射波长为100-280nm，表面累积辐照强度为1-20J/cm2，且照射时间为1-30分钟；当以电浆进行前处理时，输出功率为100-5000W，且处理时间为0.5-30分钟。本实施例中是以平行紫外光照射10分，接着以40℃、5M浓度的KOH水溶液，浸泡感光性树脂基材数分钟后取出。浸泡碱性水溶液的目的是为了使式(1)的感光性树脂表面的羰基(C＝O)开环，形成一层含有大量羰酸基(COOH)的有机改质层。接着以去离子水冲洗，将表面残留的碱性水溶液或其他有机物冲洗干净。
(ii)表面改质
其次，浸泡感光性树脂于表面改质剂内，对感光性树脂表面的羰酸基(COOH)及羟基(OH)官能基表面进一步改质。表面改质剂可选自下式(2)至式(6)中的至少一种胺基化合物的水溶液，且胺基化合物的浓度为0.1-10g/L：
其中n＝1-3，R1为NH2,NHCH3或NH(CH3)2，R2为H或CmH2mNH2，m为1-3，R3为NH2、SH或OH，R4为SH、 且改质反应温度为30-75℃(较佳为50℃)，浸泡时间为1-20分钟。表面改质剂可与感光性树脂表面的硅氧烷基团、酰亚胺环基团及羧基等有机基团进行耦合反应。
(iii)表面活化
接着，将感光性树脂基材浸泡于活化液，活化液例如为含有钯金属离子水溶液，其包含0.4g/L的氯化钯及0.4g/L的氯化铵，温度为30℃且浸泡时间为2分钟，活化液中的金属离子将与有机改质层形成错合物。在其他实施例中，也可以使用其他金属离子的酸性水溶液作为活化液，例如Cu、Ni、Ag或Au。
(iv)还原反应
继续将上述步骤(iii)中活化后的感光型树脂基材浸泡于含有还原剂的水溶液中，进行钯金属离子的还原反应。还原液组成含有28.6g/L次磷酸钠及去离子水，操作温度为30℃且浸泡时间为2分钟。也可使用如硼氢化钠、二甲基胺硼烷或联胺水溶液等的其它种类还原剂。
(v)化学镀
目前的感光性树脂基材的表面已有触媒离子还原后产生的金属钯。接着进行无电电镀，使纳米金属颗粒沉积在感光型聚酰亚胺基板表面并形成金属导电层(膜)，其沉积厚度为50-200nm。无电电镀液较佳选用无甲醛配方的无电电镀液，配成pH＝9且操作温度为50℃的水溶液。
在一个实施例中，化学镀液较佳包含铜离子、镍离子、螯合剂、还原剂、pH缓冲剂、界面活性剂及pH调整剂。其中铜离子的来源为硝酸铜、硫酸铜、氯化铜或氨基磺酸铜；镍离子的来源为硫酸镍、硝酸镍、氯化镍、硫酸镍或氨基磺酸镍；螯合剂为柠檬酸钠、酒石酸钾钠或乙二胺四乙酸。
(vi)热处理
然后，透过热处理促使感光性树脂基材表面与金属导电层间的交联反应，进而提升感光性树脂基材表面与金属导电层间的附着力。本实施例中，热处理的操作温度范围为150℃且反应时间为60分钟，然而时间跟温度可依需求进行调整。
(vii)电镀
最后，选用含有化学添加剂的电镀铜液进行电镀增厚，加厚金属导电层，其电镀厚度为18μm。所使用的电镀铜溶液组成如下：CuSO4.5H2O：100g/L
H2SO4：127.4g/L
PEG8000(聚乙二醇)：0.2g/L
SPS(聚二硫二丙烷磺酸钠)：0.004g/L。
经上述实施例步骤处理后，形成在感光性树脂上的金属层，其抗撕强度可达0.7kgf/cm；在150℃的温度下放置168小时后，其抗撕强度依然可维持于0.6kgf/cm。反之，不进行表面改质(省略步骤ii)直接形成的金属层，其抗撕强度仅有0.2kgf/cm左右，可知本发明的方法能够提高金属层的抗撕强度达3倍以上。
另外，在一般多层电路板的制程中，每层金属层完成后需要经过循环烘压制程，以多次高温高压的制程方式压合增层的高分子层与金属层，以增加异质材料层间的密合度。然而，传统在聚酰亚胺/感光性聚酰亚胺上形成金属层的方法，其形成的金属层经由循环烘压处理后，反而会大幅降低金属层的抗撕强度(低于1/10)。然而，本发明在感光性树脂上形成的金属层，在经由多次高温185℃及高压24.5kgf/cm的循环烘压制程后，其抗撕强度依然可维持0.5kgf/cm左右，因此能够用于多层板的制作。
综上所述，按照本发明的步骤，在感光性树脂上形成的金属层，不但具有较高的抗撕强度，且可应用于多层软性印刷电路板、多层HDI印刷电路板的增层制程及IC载板的半加成制程。此外，本发明的方法相较传统非感光性树脂及其他非感光性高分子的湿式金属化及增层制程相对简易，传统非感光性树脂都须依赖干式蚀刻、雷射锁孔及机械锁孔的加工方法，接着再搭配除胶渣/除光阻、中和处理、粗化及金属化制程等制作程序；而本发明使用的感光性树脂可透过照紫外光成型，不会产生胶渣，省略除胶渣与中和处理的程序，可有效节省制程成本、降低多道药水处理的失效率并提升生产速率。
虽然本发明以实施例说明如上，但这些实施例并非用以限制本发明。本领域的通常知识者在不脱离本发明技艺精神的范畴内，可以对这些实施例进行等效实施或变更，因此本发明的保护范围应以其后所附的权利要求为准。
Claims (13)
1.一种在感光性树脂的表面形成金属层的方法，所述感光性树脂包含(a)环氧化合物、(b)感光性聚酰亚胺及(c)光起始剂；该环氧化合物占该感光性树脂的固体重量的5-40％；该感光性聚酰亚胺具有式(1)的结构：
其中m、n各自独立为1至600；X为四价有机基团，其主链部份含脂环族基团；Y为二价有机基团，其主链部份含硅氧烷基团；Z为二价有机基团，其支链部份至少含酚基或羧基，该感光性聚酰亚胺占该感光性树脂的固体重量的30-90％；该光起始剂占该感光性树脂的固体重量的0.1-15％，
所述方法包含下列步骤：
(i)前处理，使用碱性水溶液及平行紫外光或电浆对该感光性树脂的表面进行清洁及预活化；
(ii)表面改质，将该感光性树脂浸泡于表面改质剂中，在该感光性树脂上形成有机改质层，该表面改质剂选自式(2)至式(6)中的至少一种胺基化合物的水溶液：
其中n＝1-3，R1为NH2、NHCH3或NH(CH3)2，R2为H或CmH2mNH2，m＝1-3，R3为NH2、SH或OH，R4为SH、
(iii)表面活化，加入触媒金属离子，使该有机改质层与该触媒金属离子在该感光性树脂表面形成金属离子错合物；
(iv)还原反应，用还原剂将附着于该感光性树脂表面的该金属离子错合物还原成纳米金属触媒；
(v)化学镀，将已形成纳米金属触媒的该感光性树脂浸泡于化学镀液中，形成导电金属层；
(vi)热处理，将已形成导电金属层的该感光性树脂于100-250℃的条件下烘烤；以及
(vii)电镀增厚，将烘烤后的感光性树脂进行电镀，增厚该导电金属层。
2.如权利要求1所述的方法，其中表面改质步骤(ii)中的浸泡时间为1-20分钟，且该表面改质剂的胺基化合物的浓度为0.1-10g/L，温度为30-75℃。
3.如权利要求1所述的方法，其中表面活化步骤(iii)加入的该触媒金属离子为包括Cu、Ni、Ag、Au或Pd离子的酸性水溶液。
4.如权利要求1所述的方法，其中还原反应步骤(iv)加入的该还原剂为次磷酸钠、硼氢化钠、二甲基胺硼烷或联胺水溶液。
5.如权利要求1所述的方法，其中化学镀步骤(v)加入的该化学镀液包含铜离子、镍离子、螯合剂、还原剂、pH缓冲剂、界面活性剂及pH调整剂。
6.如权利要求5所述的方法，其中该铜离子的来源为硝酸铜、硫酸铜、氯化铜或氨基磺酸铜。
7.如权利要求5所述的方法，其中该镍离子的来源为硫酸镍、硝酸镍、氯化镍、硫酸镍或氨基磺酸镍。
8.如权利要求5所述的方法，其中该螯合剂为柠檬酸钠、酒石酸钾钠或乙二胺四乙酸。
9.如权利要求1所述的方法，其中化学镀步骤(v)形成的该导电金属层厚度为50-200nm。
10.如权利要求1所述的方法，其中热处理步骤(vi)的烘烤时间为10-60分钟。
11.如权利要求10所述的方法，其中当以平行紫外光进行前处理时，该平行紫外光的照射波长为100-280nm，表面累积辐照强度为1-20J/cm2，且照射时间为1-30分钟。
12.如权利要求1所述的方法，其中当以电浆进行前处理时，输出功率为100-5000W，且处理时间为0.5-30分钟。
13.如权利要求1所述的方法，其中该电镀增厚步骤(vii)中，是将该导电金属层的厚度增加至12-18μm。
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| JP2019019406A (ja) | 2019-02-07 |
| KR20190099112A (ko) | 2019-08-26 |
| TW201908521A (zh) | 2019-03-01 |
| TWI624563B (zh) | 2018-05-21 |
| US20190017175A1 (en) | 2019-01-17 |
| JP6585777B2 (ja) | 2019-10-02 |
| KR102105988B1 (ko) | 2020-05-04 |
| CN109252148B (zh) | 2021-02-26 |
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