TW201621083A - 金屬化基板表面的方法及具有金屬化表面的基板 - Google Patents
金屬化基板表面的方法及具有金屬化表面的基板 Download PDFInfo
- Publication number
- TW201621083A TW201621083A TW103142351A TW103142351A TW201621083A TW 201621083 A TW201621083 A TW 201621083A TW 103142351 A TW103142351 A TW 103142351A TW 103142351 A TW103142351 A TW 103142351A TW 201621083 A TW201621083 A TW 201621083A
- Authority
- TW
- Taiwan
- Prior art keywords
- substrate
- metallizing
- decane
- high molecular
- surface according
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000001465 metallisation Methods 0.000 title abstract description 11
- 239000010415 colloidal nanoparticle Substances 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- -1 silane compound Chemical class 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 238000007772 electroless plating Methods 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 56
- 229910052707 ruthenium Inorganic materials 0.000 claims description 56
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 48
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 37
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 37
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 229910052763 palladium Inorganic materials 0.000 claims description 28
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 27
- 125000003277 amino group Chemical group 0.000 claims description 15
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 238000000454 electroless metal deposition Methods 0.000 claims description 14
- 229910052732 germanium Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002923 metal particle Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 5
- 239000004584 polyacrylic acid Substances 0.000 claims 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 38
- 239000003054 catalyst Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 19
- 230000004048 modification Effects 0.000 description 12
- 238000012986 modification Methods 0.000 description 12
- 239000003638 chemical reducing agent Substances 0.000 description 11
- 239000003446 ligand Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical class CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- FEBJSGQWYJIENF-UHFFFAOYSA-N nickel niobium Chemical compound [Ni].[Nb] FEBJSGQWYJIENF-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 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 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PEXBBTCNDBSFHT-UHFFFAOYSA-N NCCNCCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound NCCNCCCC(C(OC)(OC)OC)CCCCCCCC PEXBBTCNDBSFHT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000006664 bond formation reaction Methods 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- SXPGQGNWEWPWQZ-UHFFFAOYSA-N 4-(triethoxymethyl)dodecan-1-amine Chemical compound NCCCC(C(OCC)(OCC)OCC)CCCCCCCC SXPGQGNWEWPWQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- LGRDPUAPARTXMG-UHFFFAOYSA-N bismuth nickel Chemical compound [Ni].[Bi] LGRDPUAPARTXMG-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28568—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table the conductive layers comprising transition metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
- H01L21/486—Via connections through the substrate with or without pins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/14625—Optical elements or arrangements associated with the device
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14643—Photodiode arrays; MOS imagers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/131—Interconnections, e.g. wiring lines or terminals
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
一種金屬化矽基板表面的方法,其包括以下步驟。首先,提供一矽基板。接著,利用矽烷化合物對所述矽基板的表面進行改質。然後,將多個膠體奈米粒子團附著於矽基板的所述表面,其中每一個膠體奈米粒子團包括鈀奈米粒子及包覆所述鈀奈米粒子的高分子聚合物。最後,進行無電鍍金屬沉積,以形成無電鍍金屬層於矽基板的所述表面上。
Description
本發明是有關於一種金屬化基板表面的方法及一種具有金屬化表面的基板,且特別是有關於一種金屬化矽基板表面的方法及一種具有金屬化表面的矽基板。
一般金屬化矽基板表面的方法有網印銀漿製程、混成銀漿製程、噴墨製程等及蒸鍍製程等。隨著銀漿之價格日漸增加,該些製程的成本逐漸升高。另一種金屬化矽基板表面的方法為蒸鍍製程,然而蒸鍍製程的步驟繁多,此外,蒸鍍金屬需要昂貴的金屬靶材。
一般認為,利用電化學技術來金屬化基板較為理想的方法之一,而無電鍍金屬沉積的反應通常需要觸媒。舉例而言,印刷電路板領域中,一般無電鍍鎳製程使用之觸媒為錫鈀膠體。然而,使用錫鈀膠體觸媒必須先將基板表面進行微蝕形成孔洞結構,以利於觸媒粒子附著於基板表面。若要在光滑的矽基板表面進行觸媒沉積,就需要解決觸媒粒子與矽基板面附著力不佳的問題。
本發明實施例提供一種金屬化矽基板表面的方法,其以無電鍍法進行金屬沉積,並利用改質表面與膠體奈米粒子團之間的化學鍵結,增加無電鍍金屬層與矽基板表面的附著力。
本發明實施例提供一種金屬化矽基板表面的方法,其包括以下步驟。首先,提供一矽基板。接著,利用矽烷化合物對所述矽
基板的表面進行改質。然後,將多個膠體奈米粒子團附著於矽基板的所述表面,其中每一個膠體奈米粒子團包括至少一鈀奈米粒子及包覆至少一所述鈀奈米粒子的至少一高分子聚合物。最後,進行無電鍍金屬沉積,以形成無電鍍金屬層於矽基板的所述表面上。
另一方面,本發明實施例還提供一種具有金屬化表面的基板。所述具有金屬化表面的基板包括一矽基板、一附著層及一無電鍍金屬層。所述矽基板具有矽烷改質表面。附著層是附著於所述矽烷改質表面,並且,所述附著層是由多個膠體粒子團所形成,每一個膠體粒子團包括至少一金屬粒子及包覆至少一所述金屬粒子的至少一高分子聚合物。其中,所述附著層與所述改質表面之間具有化學鍵結。
為使能更進一步瞭解本發明之特徵及技術內容,請參閱以下有關本發明之詳細說明與附圖,但是此等說明與所附圖式僅係用來說明本發明,而非對本發明的權利範圍作任何的限制。
1‧‧‧矽基板
10、10’‧‧‧表面
2、2’‧‧‧附著層
3‧‧‧無電鍍金屬層
圖1A至圖1D為本發明一實施例之具有金屬化表面的基板在製作過程中的側視示意圖;圖2為本發明一實施例之利用矽烷化合物對矽基板進行表面改質的步驟流程圖(圖5-4);圖3為本發明一實施例之矽基板表面經改質至超音波震盪的結構變化示意圖(圖5-13);圖4為本發明一實施例之合成聚乙烯吡咯烷酮包覆奈米鈀的步驟流程圖(圖5-7);圖5為本發明一實施例之膠體奈米粒子團的結構示意圖(圖3-24);圖6為本發明一實施例之矽鎳接面物理機械性測試結果圖;圖7A及圖7B是聚乙烯吡咯烷酮包覆奈米鈀溶液濃度為50ppm的拉拔測試結果示意圖(圖5-23)。
請參圖1A至圖1D,圖1A至圖1D為本發明一實施例之具有金屬化表面的基板在製作過程中的側視示意圖,並顯示本發明一實施例之金屬化基板表面的方法。
參圖1A及圖1B,首先,提供一矽基板1,然後,利用矽烷化合物對所述矽基板1的表面10進行改質。以胺基矽烷化合物對矽基板1的表面10進行改質,主要是利用胺基矽烷化合物具有水解敏感中心,可做為有機材料及無機材料之間結合的橋樑,所以利用胺基矽烷化合物的官能基來改變矽基板1表面10的性質。具體而言,本發明實施例是藉由表面單層自組裝(Self Assembly Monolayer,SAM)的製程對矽基板1進行表面改質,該製程可以在一般室溫下進行。
所述表面改質之機制可以分為四個步驟:水解(hydrolysis)、縮和(condensation)、氫鍵結(hydrogen bonding)及形成鍵結(bond formation)。這四個步驟中的起始步驟-水解-為速率決定步驟,經過此水解步驟之後接下來的兩個步驟-縮和、氫鍵結-為自發反應。在最後形成鍵結的步驟中須將水除去,以形成共價鍵。可透過以下兩種方式對矽基板1進行除水。一是加熱(例如置於烘箱以120℃烘烤約30至90分鐘,二是抽真空(例如抽真空2至6小時)。
本實施例之表面改質的步驟中,所使用的胺基矽烷化合物的分子式例如為(X)3SiY,其中X為接枝的觸手,X例如為-OCH3、-OCH2CH3或-Cl,Y是胺官能基,是矽烷表面改質的關鍵,Y可以是烯烃(olefin)、巰(thiol)、胺(amin)、鹵代烃(halocarbon)、烃(hydrocarbon)或其他的有機官能基。
使用具有胺官能基的矽烷對矽基板1的表面10進行改質之後,(例如在矽基板1表面10塗佈上具胺官能基的矽烷層,)矽基板1的表面10’帶正電性,可與帶有負電表面的分子做結合。具
有胺官能基的矽烷可以使矽基板1表面10’帶有正電性,是由於胺官能基在酸性環境下易於趨向質子化(protonate)。藉此,此具有胺官能基的矽烷化合物可作為觸媒吸附層來增加觸媒與矽基材表面10’的附著力,進而增加無電鍍金屬層與矽基材表面10’的附著力。
本發明實施例中,可使用官能基上帶有不同數量胺基群之矽烷化合物作為塗佈材料,以對矽基板1表面10進行改質。這些胺基矽烷化合物例如為3-氨基丙基三乙氧基矽烷(3-aminopropyltriethoxysilane,APS)、N-(2-氨乙基)-3-氨丙基三甲氧基矽烷(N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,EDA)或二乙烯三胺基丙基三甲氧基矽烷((3-trimethoxysilyl-propyl)diethylenetriamine,DETA)。
3-氨基丙基三乙氧基矽烷(APS)具有下列結構式:
N-(2-氨乙基)-3-氨丙基三甲氧基矽烷(EDA)具有下列結構式:
二乙烯三胺基丙基三甲氧基矽烷(DETA)具有下列結構式:
於本發明一實施例中,使用具有胺官能基的矽烷對矽基板1的表面10進行改質之後,矽基板1表面10’的正電性可由以下這些四級胺基團所提供:=NH+-、=NH2 +-、-NH3 +及-NH2。
接著,請參圖1C,將多個膠體奈米粒子團附著於矽基板1之所述改質表面10’,以形成一附著層2。其中,每一個所述膠體奈米粒子團包括至少一個鈀奈米粒子及至少一個高分子聚合物,其中,所述高分子聚合物是包覆所述鈀奈米粒子。舉例來說,所述高分子聚合物是選自聚乙烯吡咯烷酮(Polyvinylpyrrolidone,PVP)、聚乙烯醇(Polyvinyl alcohol,PVA)、聚丙烯酸(Polyacrylic acid,PAA)及前述高分子聚合物之任意組合所組成之群組其中之一。
相較於習知的錫鈀膠體觸媒單純以鈀原子吸附於矽基板1表面10’,所述膠體奈米粒子團具有高分子聚合物包覆在鈀奈米粒子的外層,並以所述高分子聚合物與改質表面10’產生化學鍵結,以附著於改質表面10’。此外,相對於習知的錫鈀膠體觸媒,所述膠體奈米粒子團附著在改質表面10’的量也較多。
本發明一實施例是使用濕式製程製備膠體奈米粒子,具體而言,所述濕式製程是用還原劑將受穩定劑保護的金屬前驅物
(precursor)還原。所述穩定劑可為配體(ligand)或者高分子聚合物(polymer),且所述穩定劑在膠體奈米粒子的合成中可影響膠體奈米粒子的大小及穩定性。因此,在備膠體奈米粒子的濕式製程中,可依據實際需求選擇適合的穩定劑。舉例來說,富含氮的配體或者可水溶的配體等,都是適合用來保護鈀膠體粒子的配體。富含氮的配體例如為鄰二氮菲(phenanthroline)或對氨基苯磺酸鈉(sodium sulfanilat),可水溶的配體例如為異腈(isocyanides)。所述還原劑可為醇類,例如甲醇、乙醇、丙醇、異丙醇、丁醇及乙二醇等。
值得一提的是,利用控制配體的濃度可達到控制膠體奈米粒子之粒徑大小的效果,整體來說,選擇長鏈的配體、增加穩定劑的濃度及拉長反應時間都可以促成具有較小粒徑的膠體奈米粒子。
於本發明一實施例中,這些附著於矽基板1之改質表面10’的膠體奈米粒子團可為聚乙烯吡咯烷酮包覆奈米鈀(Polyvinylpyrrolidone Capped Palladium,PVP-Pd)。也就是說,聚乙烯吡咯烷酮(Polyvinylpyrrolidone,PVP)可用來作為鈀奈米粒子的穩定劑。聚乙烯吡咯烷酮的聚合物尾端或環段分散在溶劑中所產生的分子立體屏障,可有效阻止奈米粒子的聚集。
比起分子量較小的聚乙烯吡咯烷酮,大分子量的聚乙烯吡咯烷酮被吸附於粒子表面的比例較高,此外,聚乙烯吡咯烷酮的分子量越大,鈀奈米粒子外的吸附層也越厚。因此,分子量越大的聚乙烯吡咯烷酮,所形成的膠體奈米粒子的粒徑也越大。然而,影響膠體奈米粒子之粒徑大小的因素不僅僅只有聚乙烯吡咯烷酮的分子量,溶液的pH值、反應溫度及不同的還原劑皆會對成核和結晶成長速率有影響,其中,粒徑大小與還原劑的還原能力成反比。於本發明一實施例中,聚乙烯吡咯烷酮的分子量例如為5000至10000,每一個所述膠體奈米粒子團的粒徑例如為5奈米至10
奈米。
接著,請參圖1D,進行無電鍍金屬沉積製程,以形成一層無電鍍金屬層3於矽基板1的表面10’上。無電鍍金屬沉積,或可稱為自催化鍍金屬沉積(Autocatalytic Plating),是先在工作物表面形成具有催化力的金屬面,或是利用工作物表面本身的催化作用,以化學還原方法,使金屬離子變成金屬狀態析出。
雖然無電鍍金屬沉積與一般電鍍金屬沉積不同,但還是可以把兩者類比,可以將無電鍍金屬沉積的氧化還原反應分作陰陽極,如下列(a)式至(f)式,各式中R代表還原劑,Mn+代表金屬離子,M代表金屬。無電鍍金屬沉積之反應中的電子是由還原劑氧化(式b)或是氫氣氧化(式d)所提供。
陽極:
脫氫(Dehydrogenation):RH→R+H (a)
氧化(Oxidation):R+OH-→ROH+e- (b )
再結合(Recombination):H+H→H2 (c)
氧化(Oxidation):H+OH-→H2O+e- (d)
陰極:
金屬沉積(Metal deposition):Mn++ne-→M (e)
析氫(Hydrogen evolution):2H2O+2e-→H2+2OH- (f)
無電鍍金屬沉積之反應中,作為陽極者為還原劑,所述還原劑可為次磷酸鈉、甲醛、聯胺、硼氫化物或胺基硼烷,而各還原劑對於不同金屬沉積的催化活性也不同。
值得一提的是,所述無電鍍金屬沉積之反應中,能以附著於該矽基板1改質表面10’的膠體奈米粒子團作為起始觸媒,而金屬還原至待鍍表面(亦即該矽基板1的表面10’)之後,會做自身還原的觸媒。
本發明一實施例中,所述無電鍍金屬沉積為無電鍍鎳金屬沉積,而形成於該矽基板1表面10’上的無電鍍金屬層3為鎳金屬
層,其中,可以次磷酸鈉作為無電鍍鎳金屬沉積之還原劑。在較高溫度時,不穩定的次磷酸根離子放出氫原子,然後被觸媒吸收,引發後續的無電鍍鎳反應,以形成無電鍍鎳金屬層於該矽基板1的表面10’上。
綜上所述,本發明實施例之金屬化基板表面的方法以無電鍍法進行金屬沉積,可使金屬鍍層的均一性良好,孔隙度較小,不論矽基板1之幾何形狀如何複雜,各部份析鍍的厚度可近乎一致,並可控制所希望的厚度。此外,以無電鍍法進行金屬沉積可不需電鍍設備。
本發明實施例之金屬化基板表面的方法針對無電鍍金屬層3的形成做進一步的改進,利用胺基矽烷化合物對矽基板1的表面10進行改質,在矽基板1表面10與胺基矽烷化合物之間形成鍵結,以胺基矽烷化合物作為有機材料與無機材料之間結合的橋梁。更重要的是,本發明實施例之金屬化基板表面的方法更利用膠體奈米粒子團形成附著層2’,以改質表面10’的胺官能基與膠體奈米粒子團之間的化學鍵結取代凡得瓦爾力(Van der Waals force)結合,以增加無電鍍金屬層3與矽基板1表面10’的附著力。
另一方面,本發明實施例還提供一種具有金屬化表面的基板。參圖1D,所述具有金屬化表面的基板包括一矽基板1、一附著層2’及一無電鍍金屬層3。矽基板1具有矽烷改質表面10’。附著層2’是附著於該矽烷改質表面10’,且附著層2’是由複數個膠體粒子團所形成。每一個所述膠體粒子團包括至少一個金屬粒子及包覆所述金屬粒子的至少一個高分子聚合物。無電鍍金屬層3是經由附著層2’結合於該改質表面10’上,其中該附著層2’與該改質表面10’之間具有化學鍵結。
首先,提供一矽基板,例如N型摻雜的P型矽晶片,並以離
子水潤洗矽基板表面。接著,利用胺基矽烷化合物對該矽基板的待鍍表面進行改質。所述表面改質的步驟可大致包括以下幾個階段:表面氫氧基團(OH group)的生成、液相沉積及烘烤。以下具體說明所述表面改質的步驟。
請參圖2,圖2為本發明一實施例之利用矽烷化合物對矽基板進行表面改質的步驟流程圖。首先,將矽基板浸泡於2%氫氟酸溶液裡2分鐘,以去除矽基板表面的氧化層,再以離子水潤洗矽基板表面。然後,以無水乙醇浸泡矽基板大致5分鐘進行表面氧化,以於矽基板的待鍍表面成長氫氧基團,再將所述矽基板浸泡入二乙烯三胺基丙基三甲氧基矽烷(3-[2-(2-Aminoethylamine)ethyl-amino]propyltrimethoxysilane,ETAS)溶液,該溶液中,無水乙醇比二乙烯三胺基丙基三甲氧基矽烷體積比為99比1,所述二乙烯三胺基丙基三甲氧基硅烷的結構式如下:
矽基板浸泡於二乙烯三胺基丙基三甲氧基矽烷溶液的時間例如為10、20、30或60分鐘,其中,浸泡大致30分鐘是較佳的改質時間。值得一提的是,本實施例是以無水乙醇進行矽基板的表面氧化,以獲得較均勻的表面改質結果。
將矽基板從改質溶液中取出後,以室溫靜置乾燥約2分鐘,待矽基板表面的溶劑自然蒸散,以避免無電鍍金屬沉積層的表面產生水痕紋路。接著,將矽基板放置在預先加熱至250℃的加熱板上烘烤大致10分鐘。
最後,再將矽基板浸入無水乙醇並以超音波震盪大致10分鐘,震盪完後以去離子水潤洗。此步驟是為了將以物理吸附方式沉積在單層自組裝結構外的胺基矽烷分子震掉。請參圖3,圖3為本發明一實施例之矽基板表面經改質至超音波震盪的結構變化示意圖。在進行超音波震盪前,胺基矽烷分子會以多層的方式堆疊,在進行超音波震盪之後,自組裝結構的厚度可下降並且成為單層。至此確立本實施例矽烷表面改質的步驟。
接著,將該經表面改質的矽基板浸入聚乙烯吡咯烷酮包覆奈米鈀溶液中。聚乙烯吡咯烷酮包覆奈米鈀溶液的合成方法詳述如下。請參圖4,圖4為本發明一實施例之合成聚乙烯吡咯烷酮包覆奈米鈀的步驟流程圖。首先將約0.285克的聚乙烯吡咯烷酮(Poly(N-vinyl-2-pyrrolidone))溶於約44毫升的去離子水中,所述聚乙烯吡咯烷酮的分子量為8000,且具有下列的結構式:
接著,再將含有鈀離子的前驅物硝酸鈀(Pd(NO3)2‧2H2O,重量約為0.329克)溶於此溶液中,此時溶液呈現褐色。接著,加入約1毫升的甲醛當作還原劑,再緩緩加入5毫升、1N的氫氧化鈉(NaOH),溶液由褐色轉為黑色,所述聚乙烯吡咯烷酮包覆奈米鈀溶液即製備完成。
使用時可將所述聚乙烯吡咯烷酮包覆奈米鈀溶液稀釋至所需要的濃度,並將其加熱至40℃,再將矽基板浸入浸泡約5分鐘。本實施例中,所使用的聚乙烯吡咯烷酮包覆奈米鈀溶液的濃度例如為50ppm、100ppm、1250ppm及2500ppm。此外,請參圖5,圖5為本發明一實施例之膠體奈米粒子團的結構示意圖。本實施例中膠體奈米粒子團的粒徑大致為5奈米,聚乙烯吡咯烷酮分子
包覆奈米鈀的情形與硫化鋅(ZnS)被聚乙烯吡咯烷酮分子保護劑包覆的方式相似,如圖5,聚乙烯吡咯烷酮分子是以其氧原子端包覆鈀奈米粒子。值得一提的是,膠體奈米粒子團溶液的濃度越高,附著在矽基板表面的顆粒數越多,並且,隨著膠體奈米粒子團溶液濃度的上升,附著在矽基板表面的膠體奈米粒子團也越大。
所述膠體奈米粒子團除了可與具胺官能基的矽烷改質表面形成化學鍵結,還可作為無電鍍金屬沉積的起始觸媒,藉以增加無電鍍金屬層與矽基板表面的附著力。
接著,進行無電鍍鎳金屬沉積,以形成無電鍍鎳金屬層於該矽基板的待鍍表面上。詳細而言,將浸泡過膠體奈米粒子團溶液的矽基板取出後以去離子水潤洗,接著浸泡入由台灣桃園縣的歐恩吉公司所提供的無電鍍鎳液(型號:9026M Electrodes Nickel),浸泡條件為80℃、pH 4.9,浸泡時間例如為5秒至180秒。至此確利本實施例之金屬化基板表面的方法。
藉由掃描式電子顯微鏡(Scanning Electron Microscope,SEM),可觀察無電鍍鎳沉積的膜厚成長情形。隨著膠體奈米粒子團溶液(聚乙烯吡咯烷酮包覆奈米鈀溶液)的濃度越高,矽基板接面的無電鍍鎳磷合金顆粒越多也越大,而不管使用何種濃度的膠體奈米粒子團溶液,皆不影響無電鍍金屬沉積的鍍率表現。本發明一實施例中,形成厚度約200奈米的無電鍍鎳金屬層,沉積時間可控制在大致1分鐘。
以下將對經由上述實施例之金屬化基板表面的方法所製作而成的試片及經其他不同實驗條件所製作而成的試片進行物理機械性測試。請參圖6,圖6為本發明一實施例之矽鎳接面物理機械性測試結果圖。
測試矽鎳接面附著力使用的方法為ASTM D4541測試方法。測試方式是先將經不同實驗條件的試片使用大量的環氧樹酯黏附在一玻璃基板上,再以環氧樹酯塗抹於直徑10公釐的錠子上
再黏附於待測面上,靜置3小時後置入烘箱以70℃烘烤2個小時,爾後從烘箱取出待冷卻以拉拔機垂直拉拔測得一壓力讀值。試片1的實驗條件為僅用商用錫鈀膠體觸媒吸附於矽基板表面;試片2的實驗條件為使用二乙烯三胺基丙基三甲氧基矽烷(ETAS)表面改質於矽基板表面,並使用商用錫鈀膠體觸媒催化;試片3的實驗條件為使用二乙烯三胺基丙基三甲氧基矽烷(ETAS)表面改質於矽基板表面之後,將該矽基板浸入濃度50ppm的聚乙烯吡咯烷酮包覆奈米鈀(PVP-Pd)溶液;試片4的實驗條件為使用二乙烯三胺基丙基三甲氧基矽烷(ETAS)表面改質於矽基板表面之後,將該矽基板浸入濃度100ppm的聚乙烯吡咯烷酮包覆奈米鈀(PVP-Pd)溶液。實驗結果如圖6及下表。
從上表的結果來看可以得知經二乙烯三胺基丙基三甲氧基矽烷(ETAS)表面改質並搭配聚乙烯吡咯烷酮包覆奈米鈀(PVP-Pd)的附著力皆優於商用錫鈀膠體觸媒,並且由兩組商用錫鈀膠體觸媒實驗條件可以發現使用二乙烯三胺基丙基三甲氧基矽烷(ETAS)成功提高觸媒附著於矽晶表面的能力;另一方面,從圖6可以發現使用聚乙烯吡咯烷酮包覆奈米鈀(PVP-Pd)的測試結果標準差較大。
而事實上二乙烯三胺基丙基三甲氧基矽烷(ETAS)表面改質搭配聚乙烯吡咯烷酮包覆奈米鈀(PVP-Pd)的系統在進行拉拔測試時會有兩種裂面,無論是聚乙烯吡咯烷酮包覆奈米鈀(PVP-Pd)溶液的濃度50ppm還是100ppm,皆是如此。請參圖7A及圖7B,
圖7A及圖7B顯示聚乙烯吡咯烷酮包覆奈米鈀(PVP-Pd)溶液濃度為50ppm的拉拔測試結果示意圖。7A顯示拉拔測試的其中一種裂面,如圖所示,鎳層完全與矽晶表面分離的屬於完全異相分離。圖7B顯示拉拔測試有破片之情形,局部的矽鎳接面的緊密附著可導致拉拔測試時的破裂面是在矽晶片,此種分離屬於矽與矽之間的同相分離。
矽鎳接面完全分離的情形下,聚乙烯吡咯烷酮包覆奈米鈀(PVP-Pd)溶液的濃度為50ppm的實驗組的附著力測試結果為6.44MPa,而濃度為100ppm的實驗組的附著力測試結果為8.47MPa;在發生局部矽與矽之間的同相分離的情形下,聚乙烯吡咯烷酮包覆奈米鈀(PVP-Pd)溶液的濃度為50ppm的實驗組的附著力測試結果為13.73MPa,而濃度為100ppm的實驗組的附著力測試結果為13.54MPa。
本發明實施例以電化學沉積技術可取代網印銀漿製程、電鍍銅、化學鍍鎳等技術,藉以將低製程成本。此外,以矽烷化合物改質矽基板表面,並且以聚乙烯吡咯烷酮包覆奈米鈀附著於改質表面,不僅可增強接面附著力,且具有全製程皆為濕製程的優點,比起化學氣相蒸鍍製程,成本可相對減低許多。
以上所述僅為本發明的實施例,其並非用以限定本發明的專利保護範圍。任何熟習相像技藝者,在不脫離本發明的精神與範圍內,所作的更動及潤飾的等效替換,仍為本發明的專利保護範圍內。
1‧‧‧矽基板
10’‧‧‧表面
2’‧‧‧附著層
3‧‧‧無電鍍金屬層
Claims (21)
- 一種金屬化基板表面的方法,包括:提供一矽基板;利用至少一矽烷化合物對所述矽基板的一表面進行改質;將多個膠體奈米粒子團附著於所述矽基板的所述表面,其中每一個所述膠體奈米粒子團包括至少一鈀奈米粒子及包覆至少一所述鈀奈米粒子的至少一高分子聚合物;以及進行一無電鍍金屬沉積,以形成一無電鍍金屬層於所述矽基板的所述表面上。
- 如請求項1所述之金屬化基板表面的方法,其中將多個所述膠體奈米粒子團附著於所述矽基板的所述表面的步驟中,更進一步包括:配製一膠體奈米粒子團溶液,所述膠體奈米粒子團溶液包括多個所述膠體奈米粒子團;以及將所述矽基板浸入所述膠體奈米粒子團溶液。
- 如請求項1所述之金屬化基板表面的方法,其中至少一所述矽烷化合物具有至少一胺官能基。
- 如請求項1所述之金屬化基板表面的方法,其中利用至少一所述矽烷化合物對所述矽基板的所述表面進行改質的步驟中,更進一步包括:以至少一所述矽烷化合物配製一矽烷化合物溶液;將所述矽基板浸入於所述矽烷化合物溶液;靜置所述矽基板;以及對所述矽基板進行除水。
- 如請求項4所述之金屬化基板表面的方法,其中對所述矽基板進行除水的步驟之後,更進一步包括:將所述矽基板浸入一無水溶液並以超音波震盪。
- 如請求項4所述之金屬化基板表面的方法,其中將所述矽基板浸入於至少一所述矽烷化合物的步驟之前,更進一步包括:將所述矽基板浸入於一無水乙醇。
- 如請求項1所述之金屬化基板表面的方法,其中至少一所述矽烷化合物具有下列結構式:
- 如請求項1所述之金屬化基板表面的方法,其中至少一所述高分子聚合物是選自聚乙烯吡咯烷酮、聚乙烯醇、聚丙烯酸及前述高分子聚合物之任意組合所組成之群組其中之一。
- 如請求項1所述之金屬化基板表面的方法,其中至少一所述高分子聚合物具有下列結構式:
- 如請求項9所述之金屬化基板表面的方法,其中至少一所述高分子聚合物是以其氧原子端包覆至少一所述鈀奈米粒子。
- 如請求項9所述之金屬化基板表面的方法,其中至少一所述高分子聚合物的分子量為5000至10000。
- 如請求項9所述之金屬化基板表面的方法,其中每一個所述膠體奈米粒子團的粒徑為5奈米至10奈米。
- 一種具有金屬化表面的基板,包括:一矽基板,具有一矽烷改質表面;一附著層,附著於所述矽烷改質表面,所述附著層由多個膠體粒子團所形成,每一個所述膠體粒子團包括至少一金屬粒子及包覆至少一所述金屬粒子的至少一高分子聚合物;以及一無電鍍金屬層,經由所述附著層結合於所述改質表面上;其中所述附著層與所述改質表面之間具有化學鍵結。
- 如請求項13所述之具有金屬化表面的基板,其中所述無電鍍金屬層為鎳金屬層或鎳合金層。
- 如請求項13所述之具有金屬化表面的基板,其中所述矽烷改質表面包括一矽烷層,所述矽烷層具有至少一胺官能基。
- 如請求項15所述之具有金屬化表面的基板,其中至少一所述胺官能基具有1至3個胺基群。
- 如請求項13所述之具有金屬化表面的基板,其中至少一所述 高分子聚合物是選自聚乙烯吡咯烷酮、聚乙烯醇、聚丙烯酸及前述高分子聚合物之任意組合所組成之群組其中之一。
- 如請求項13所述之具有金屬化表面的基板,其中至少一所述高分子聚合物具有下列結構式:
- 如請求項18所述之具有金屬化表面的基板,其中至少一所述高分子聚合物是以其氧原子端包覆至少一所述金屬粒子。
- 如請求項18所述之具有金屬化表面的基板,其中至少一所述高分子聚合物的分子量為5000至10000。
- 如請求項18所述之具有金屬化表面的基板,其中每一個所述膠體奈米粒子團的粒徑為5奈米至10奈米。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW103142351A TWI540222B (zh) | 2014-12-05 | 2014-12-05 | 金屬化基板表面的方法及具有金屬化表面的基板 |
US14/957,787 US9514965B2 (en) | 2014-12-05 | 2015-12-03 | Substrate surface metallization method and substrate having metallized surface manufactured by the same |
US15/343,029 US9875984B2 (en) | 2014-12-05 | 2016-11-03 | Substrate surface metallization method and substrate having metallized surface manufactured by the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW103142351A TWI540222B (zh) | 2014-12-05 | 2014-12-05 | 金屬化基板表面的方法及具有金屬化表面的基板 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201621083A true TW201621083A (zh) | 2016-06-16 |
TWI540222B TWI540222B (zh) | 2016-07-01 |
Family
ID=56094961
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103142351A TWI540222B (zh) | 2014-12-05 | 2014-12-05 | 金屬化基板表面的方法及具有金屬化表面的基板 |
Country Status (2)
Country | Link |
---|---|
US (1) | US9514965B2 (zh) |
TW (1) | TWI540222B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11331883B2 (en) | 2018-09-28 | 2022-05-17 | National Tsing Hua University | Diffusion barrier structure, and conductive laminate and manufacturing method thereof |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10660217B2 (en) * | 2017-05-30 | 2020-05-19 | Jun Yang | Methods of fast fabrication of single and multilayer circuit with highly conductive interconnections without drilling |
TWI672175B (zh) | 2017-10-20 | 2019-09-21 | 國立清華大學 | 自吸附觸媒組成物、自吸附觸媒組成物的製造方法以及無電鍍基板的製造方法 |
CN109692707A (zh) * | 2017-10-23 | 2019-04-30 | 卫子健 | 自吸附催化剂组成物及其制造方法、及无电镀基板的制造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5990984A (en) * | 1995-11-16 | 1999-11-23 | Viratec Thin Films, Inc. | Coated polymer substrate with matching refractive index and method of making the same |
WO2003035389A1 (fr) * | 2001-10-25 | 2003-05-01 | Matsushita Electric Works, Ltd. | Substrat de support a film mince composite, substrat de support a film conducteur transparent et corps emetteur pour eclairage de panneau |
TWI274662B (en) * | 2002-03-29 | 2007-03-01 | Toray Industries | Laminated film, filter for display and display |
US7854995B1 (en) * | 2004-07-14 | 2010-12-21 | Keystone Investment Corporation | High density dual helical gear |
JP4475186B2 (ja) * | 2005-06-30 | 2010-06-09 | 富士ゼロックス株式会社 | 情報記録媒体の製造方法 |
JP2009135044A (ja) * | 2007-11-30 | 2009-06-18 | Tdk Corp | 透明導電材料及び透明導電体 |
GB201212407D0 (en) | 2012-07-12 | 2012-08-22 | Intrinsiq Materials Ltd | Composition for forming a seed layer |
FR2993666B1 (fr) * | 2012-07-19 | 2015-03-27 | Commissariat Energie Atomique | Procede de fabrication d'une colonne d'enrichissement de chromatographie |
-
2014
- 2014-12-05 TW TW103142351A patent/TWI540222B/zh active
-
2015
- 2015-12-03 US US14/957,787 patent/US9514965B2/en active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11331883B2 (en) | 2018-09-28 | 2022-05-17 | National Tsing Hua University | Diffusion barrier structure, and conductive laminate and manufacturing method thereof |
Also Published As
Publication number | Publication date |
---|---|
US20160163567A1 (en) | 2016-06-09 |
US9514965B2 (en) | 2016-12-06 |
TWI540222B (zh) | 2016-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10056505B2 (en) | Multi shell metal particles and uses thereof | |
US9105696B1 (en) | Method of coating surface of substrate hole with layer of reduced graphene oxide | |
TWI540222B (zh) | 金屬化基板表面的方法及具有金屬化表面的基板 | |
JP2019517625A (ja) | 化学的還元法を用いたコアシェル構造の銀コーティング銅ナノワイヤの製造方法 | |
US20020197404A1 (en) | Method of activating non-conductive substrate for use in electroless deposition | |
EP3844325B1 (en) | Metal-cnt composite, production method and materials therefor | |
TW201416490A (zh) | 用於形成種晶層之組成物 | |
KR20150145892A (ko) | 은 코팅 구리 나노 와이어 및 이의 제조 방법 | |
JP6047707B2 (ja) | 前処理液を用いた無電解銅メッキ方法 | |
JP6165063B2 (ja) | 導電性粒子およびその製造方法 | |
US10543510B2 (en) | Method for modifying surface of non-conductive substrate and sidewall of micro/nano hole with rGO | |
US9932676B2 (en) | Pretreatment solution for electroless plating and electroless plating method | |
TW200835809A (en) | Metal layer-coated substrate and process for the production thereof | |
KR101599103B1 (ko) | 코어-쉘 금속 입자의 제조방법 | |
WO2017057301A1 (ja) | 導電層形成用塗布液及び導電層の製造方法 | |
US9875984B2 (en) | Substrate surface metallization method and substrate having metallized surface manufactured by the same | |
TW201720956A (zh) | 用於印刷電路板和通孔的無電極金屬化的環保穩定催化劑 | |
EP2971231A2 (en) | Multi shell metal particles and uses thereof | |
TWI617700B (zh) | 無電極電鍍的方法 | |
TW201422855A (zh) | 載持鍍覆處理用觸媒粒子之基板之處理方法 | |
JP2011153372A (ja) | 金属多層積層電気絶縁体とその製造方法 | |
TW201720957A (zh) | 用於印刷電路板和通孔的無電極金屬化的環保穩定催化劑 | |
JP5648229B2 (ja) | 無電解めっき金属皮膜の製造方法及びめっき被覆基板 | |
JP2006052101A (ja) | セラミックス基材表面への金属皮膜形成方法及び金属化処理セラミックス基材 | |
CN112063998B (zh) | 一种超薄铜/石墨烯复合箔的制备方法 |