NZ622408B2 - Method of forming a conductive image on a non-conductive surface - Google Patents
Method of forming a conductive image on a non-conductive surface Download PDFInfo
- Publication number
- NZ622408B2 NZ622408B2 NZ622408A NZ62240812A NZ622408B2 NZ 622408 B2 NZ622408 B2 NZ 622408B2 NZ 622408 A NZ622408 A NZ 622408A NZ 62240812 A NZ62240812 A NZ 62240812A NZ 622408 B2 NZ622408 B2 NZ 622408B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- metal
- coordination complex
- etching
- metal coordination
- onto
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 claims abstract description 120
- 239000002184 metal Substances 0.000 claims abstract description 120
- 239000000758 substrate Substances 0.000 claims abstract description 63
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 48
- 230000001603 reducing Effects 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000004020 conductor Substances 0.000 claims abstract description 11
- 230000005670 electromagnetic radiation Effects 0.000 claims abstract description 6
- 238000005530 etching Methods 0.000 claims description 28
- 230000005291 magnetic Effects 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 230000002829 reduced Effects 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000001020 plasma etching Methods 0.000 claims description 7
- 239000003638 reducing agent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229940035295 Ting Drugs 0.000 claims description 4
- 238000003486 chemical etching Methods 0.000 claims description 4
- 230000001590 oxidative Effects 0.000 claims description 4
- 230000003213 activating Effects 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000007747 plating Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 46
- 239000008367 deionised water Substances 0.000 description 25
- 150000002500 ions Chemical class 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 229920000106 Liquid crystal polymer Polymers 0.000 description 8
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
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- 239000004642 Polyimide Substances 0.000 description 6
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- 239000007921 spray Substances 0.000 description 6
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- 229910052782 aluminium Inorganic materials 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010329 laser etching Methods 0.000 description 4
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- 150000001768 cations Chemical class 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UEUDBBQFZIMOQJ-UHFFFAOYSA-K Ferric ammonium oxalate Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UEUDBBQFZIMOQJ-UHFFFAOYSA-K 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N HF Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M Lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- XMXNVYPJWBTAHN-UHFFFAOYSA-N Potassium chromate Chemical compound [K+].[K+].[O-][Cr]([O-])(=O)=O XMXNVYPJWBTAHN-UHFFFAOYSA-N 0.000 description 2
- VZJVWSHVAAUDKD-UHFFFAOYSA-N Potassium permanganate Chemical compound [K+].[O-][Mn](=O)(=O)=O VZJVWSHVAAUDKD-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N Silver nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atoms Chemical group 0.000 description 2
- 230000027455 binding Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
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- 239000003989 dielectric material Substances 0.000 description 2
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- 239000011810 insulating material Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000000670 limiting Effects 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 230000005298 paramagnetic Effects 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910052904 quartz Inorganic materials 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
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- 229910052682 stishovite Inorganic materials 0.000 description 2
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- AJVRSHNXSHMMCH-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;iron(3+);hydrate Chemical compound O.[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O AJVRSHNXSHMMCH-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L Ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N Aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 241000229754 Iva xanthiifolia Species 0.000 description 1
- 210000002381 Plasma Anatomy 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M Potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- IPAGMSBCYAQWPF-UHFFFAOYSA-N [Ag+2].[O-][Cr]([O-])(=O)=O Chemical compound [Ag+2].[O-][Cr]([O-])(=O)=O IPAGMSBCYAQWPF-UHFFFAOYSA-N 0.000 description 1
- 238000005296 abrasive Methods 0.000 description 1
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- 230000004075 alteration Effects 0.000 description 1
- 229920002892 amber Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QJIMNDWDOXTTBR-UHFFFAOYSA-L ammonium tetrachloroplatinate Chemical compound [NH4+].[NH4+].Cl[Pt-2](Cl)(Cl)Cl QJIMNDWDOXTTBR-UHFFFAOYSA-L 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cells Anatomy 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 239000002019 doping agent Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229960002413 ferric citrate Drugs 0.000 description 1
- 230000005294 ferromagnetic Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000003278 mimic Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- 231100000489 sensitizer Toxicity 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- -1 that is Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1673—Magnetic field
-
- 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
-
- 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
- C23C18/22—Roughening, e.g. by etching
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76879—Filling of holes, grooves or trenches, e.g. vias, with conductive material by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/104—Using magnetic force, e.g. to align particles or for a temporary connection during processing
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1157—Using means for chemical reduction
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/185—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method by making a catalytic pattern by photo-imaging
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
Abstract
The present invention relates to a method for forming a raised conductive image on a non-conductive or dielectric surface (15). The method comprising placing a metal coordination complex on a surface of the substrate, exposing the surface (15) to electromagnetic radiation (25), reducing the exposed complex, removing unexposed metal complex leaving an elemental metal image, drying the surface (15) and then plating the resulting elemental metal image with a highly conductive material. complex, removing unexposed metal complex leaving an elemental metal image, drying the surface (15) and then plating the resulting elemental metal image with a highly conductive material.
Description
METHOD OF FORMING A CONDUCTIVE IMAGE ON A NONCONDUCTIVE
SURFACE
William Wismann
CROSS REFERENCE TO D ATIONS
This application is related to and claims the benefit of (1) U.S.
ional Patent Application No. 61/525,662, filed in the name of William
Wismann on August 19, 2011, (2) U.S. Provisional Patent Application No.
,736, filed in the name of William Wismann on December 9, 2011, and
(3) is a continuation of U.S. Patent Application No. 13/403,797, filed in the name
of William Wismann on February 23, 2012, all of which are hereby incorporated
herein by reference in their ty.
FIELD
This invention relates to the field of electronic device
manufacture.
BACKGROUND
tive images on non-conductive or dielectric surfaces are
ubiquitous in today’s technology-driven world. Perhaps the most widely known
example of such are the integrated circuits found in virtually all electronic
devices. Integrated circuits result from a sequence of photographic and
chemical processing steps by which the circuits are gradually created on a
dielectric substrate such as a silicon wafer.
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A typical wafer is made out of ely pure silicon that is grown
into mono-crystalline cylindrical ingots, called boules, that are up to 300 mm in
diameter. The boules are then sliced into wafers about 0.75 mm thick and
polished to obtain a very smooth flat surface.
The formation of a circuit on a wafer requires numerous steps
that can be categorized into two major parts: front-end-of-line (FEOL)
processing and back- end-of-line (BEOL) processing.
FEOL processing refers to the formation of ts directly in the
silicon. The raw wafer is first subjected to y, the growth of crystals of
ultrapure silicon on the wafer wherein the crystals mimic the orientation of the
substrate.
After epitaxy, front-end surface engineering generally consists of
the steps of growth of the gate dielectric, traditionally n dioxide (SiO2),
patterning of the gate, patterning of the source and drain regions, and
subsequent implantation or ion of dopants to obtain the desired
complementary electrical properties. In c random access memory
(DRAM) devices, storage capacitors are also fabricated at this time, typically
d above the access transistor.
Once the s semiconductor devices have been created, they
must be interconnected to form the desired electrical circuits, which comprise
the BEOL n of the s. BEOL involves creating metal interconnecting
wires that are isolated by dielectric layers. The insulating material was
traditionally a form of silicate glass, SiO2, but other low dielectric constant
materials can be used.
The metal interconnecting wires often comprise aluminum. In an
approach to wiring called subtractive aluminum, blanket films of aluminum are
deposited, patterned and etched to form the wires. A dielectric material is then
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deposited over the exposed wires. The various metal layers are interconnected
by etching holes, called vias, in the insulating material and depositing tungsten
in the holes. This approach is still used in the fabrication of memory chips such
as DRAMs as the number of interconnect levels is small.
More recently, as the number of interconnect levels has
increased due to the large number of transistors that now need to be
interconnected in a modern rocessor, the timing delay in the wiring has
become icant, ing a change in wiring material from aluminum to
copper and from the silicon dioxides to newer low-K al. The result is not
only enhanced performance but reduced cost as well in that damascene
processing is substituted for subtractive aluminum technology, thereby
elimination several steps. In damascene processing, the dielectric material is
deposited as a blanket film, which is then patterned and etched leaving holes or
trenches. In single damascene processing, copper is then deposited in the
holes or es surrounded by a thin barrier film resulting in filled vias or wire
lines. In dual damascene technology, both the trench and via are fabricated
before the deposition of copper resulting in formation of both vias and wire lines
aneously, further reducing the number of processing steps. The thin
barrier film, called copper barrier seed (CBS), is necessary to prevent copper
diffusion into the dielectric. The ideal barrier film is as thin as possible. As the
presence of excessive barrier film competes with the available copper wire
cross section, formation of the thinnest continuous barrier represents one of the
greatest ongoing challenges in copper processing today.
As the number of interconnect levels increases, planarization of
the previous layers is required to ensure a flat surface prior to subsequent
lithography. Without it, the levels would become increasingly crooked and
extend e the depth of focus of available lithography, interfering with the
y to pattern. CMP (chemical mechanical planarization) is a processing
method to achieve such planarization although dry etch back is still sometimes
employed if the number of onnect levels is low.
The above s, gh described specifically with regard to
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silicon chip manufacture, is fairly generic for most types of printed circuits,
printed circuit boards, antennas, solar cells, solar thin films, semiconductors and
the like. As can be seen, the process is subtractive; that is a metal, usually
copper, is deposited uniformly over a substrate surface and then unwanted
metal, that is, metal that does not comprise some part of the final circuit, is
removed. A number of additive processes are known, which resolve some of
the problems associated with the subtractive process but which engender
problems of their own, a significant one of which involves adherence of a builtup
conducting layer to the substrate.
What is needed is an additive process for integrated circuit
fabrication that has all of the advantages of other additive processes but which
exhibits improved adhesion properties to ates.
[013a] Alternatively or additionally, what is needed is at least a useful
choice for the public.
SUMMARY
In one aspect this ion relates to a method of g a
conductive layer on a surface, comprising performing the ing steps in
order:
activating at least a portion of a non-conductive substrate e;
applying a magnetic field to the surface;
depositing a metal coordination complex on at least a part of the
activated portion of the surface;
ng the magnetic field;
exposing the metal coordination complex to electromagnetic ion;
reducing the metal coordination complex to elemental metal; removing
unreduced metal nation complex from the surface; drying the e; and
depositing a conductive material onto the surface.
[014a] The term ‘comprising’ as used in this specification and claims
means ‘consisting at least in part of’. When interpreting statements in this
specification and claims which include the term ‘comprising’, other es
besides the es prefaced by this term in each statement can also be
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present. Related terms such as ‘comprise’ and ‘comprised’ are to be
interpreted in similar manner.
In an aspect of this ion, activating the substrate surface
comprises g the surface.
In an aspect of this invention, etching the surface comprises
chemical etching.
In an aspect of this invention, chemical etching comprises acid
g, base etching or oxidative etching.
In an aspect of this invention, etching the surface comprises
ical g.
In an aspect of this invention, etching the surface comprises
plasma etching.
In an aspect of this invention, etching the surface comprises
laser- etching.
In an aspect of this invention, plasma or laser etching ses
etching in a pre-determined pattern.
In an aspect of this invention, the magnetic field has a magnetic
flux density of at least 1000 gauss.
In an aspect of this invention, the ic field is orthogonal to
the surface.
In an aspect of this invention, depositing a metal coordination
complex on at least a portion of the surface comprises using a mask.
In an aspect of this invention, the mask comprises an electronic
circuit.
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In an aspect of this invention, the onic t is selected
from the group consisting of an analog circuit, a digital circuit, a mixed-signal
circuit and an RF circuit.
An aspect of this invention is an analog t comprising a
conductive layer, the conductive layer being formed on a surface using the
method described herein.
An aspect of this invention is a digital circuit comprising a
conductive layer, the conductive layer being formed on a surface using the
method described herein.
An aspect of this invention is a mixed-signal t comprising a
conductive layer, the conductive layer being formed on a surface using the
method described herein.
An aspect of this invention is an RF circuit comprising a
conductive layer, the conductive layer being formed on a surface using the
method described herein.
In an aspect of this invention, exposing the metal coordination
complex to omagnetic radiation comprises microwave radiation, infrared
radiation, visible light radiation, iolet radiation, X-ray radiation or gamma
radiation.
In an aspect of this invention, reducing the metal coordination
complex to a zero oxidation state metal comprises using a combination of
metals and/or catalysts.
In an aspect of this invention, removing unreduced metal
nation complex from the surface comprises washing the e with a
solvent.
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In an aspect of this invention, drying the surface comprises drying
at ambient temperature or drying at elevated temperature.
In an aspect of this invention, drying the surface at ambient or
ed temperature comprises using a vacuum chamber.
In an aspect of this invention, depositing a conductive al
onto the e comprises electrolytic deposition of a metal onto the portion of
the surface comprising the d metal coordination complex.
In an aspect of this ion, olytic deposition of a metal
onto the portion of the surface comprising the reduced metal coordination
complex comprises:
contacting a negative terminal of a direct current power supply with at
least the portion of the surface comprising the d metal coordination
complex;
providing an aqueous solution comprising a salt of the metal to be
deposited, an electrode made of the metal immersed in the aqueous solution or
a combination thereof;
contacting a positive terminal of the direct current power supply with the
aqueous solution;
contacting at least the portion of the e comprising the reduced
metal coordination complex with the aqueous solution; and
turning on the power supply.
In an aspect of this invention, depositing a conductive al
onto the surface comprises electroless deposition of a metal onto the portion of
the surface comprising the reduced metal coordination x.
In an aspect of this invention, electrolessly depositing a metal
onto the portion of the surface comprising the reduced metal coordination
complex comprises ting at least the portion of the surface comprising the
metal coordination complex with a solution comprising a salt of the metal, a
complexing agent and a reducing agent.
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In an aspect of this invention, depositing a conductive material
onto the surface comprises deposition of a non-metallic conductive substance
onto the portion of the surface comprising the reduced metal coordination
In an aspect of this invention, the non-metallic conductive
material is deposited onto the portion of the surface comprising the reduced
metal coordination complex by electrostatic dispersion.
In an aspect of this invention, the entire non-conductive substrate
surface is activated and the metal coordination complex is deposited onto the
entire surface.
In an aspect of this invention, the entire non-conductive substrate
surface is activated and the metal coordination complex is deposited on a part
of the activated e.
DETAILED DESCRIPTION
Brief description of the figures
The figure herein is provided solely to assist in the understanding
of the present invention and is not intended nor is it to be construed as limiting
the scope of this invention in any manner whatsoever.
Figure 1 shows a substrate to be processed using the method of
this invention where the substrate is situated in an magnetic field such that the
field is orthogonal to the plane of the e of the ate.
Discussion
It is understood that, with regard to this ption and the
appended claims, reference to any aspect of this invention made in the singular
includes the plural and vice versa unless it is sly stated or guously
clear from the t that such is not intended.
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As used herein, any term of approximation such as, without
limitation, near, about, approximately, substantially, essentially and the like,
mean that the word or phrase modified by the term of approximation need not
be exactly that which is written but may vary from that written description to
some extent. The extent to which the description may vary will depend on how
great a change can be instituted and have one of ordinary skill in the art
ize the modified n as still having the properties, characteristics and
capabilities of the word or phrase unmodified by the term of approximation. In
general, but with the preceding discussion in mind, a numerical value herein
that is modified by a word of approximation may vary from the stated value by
±10%, unless expressly stated otherwise.
As used herein, the use of “preferred,” “preferably,” or “more
preferred,” and the like refers to preferences as they existed at the time of filing
of this patent application.
As used herein, a ctive layer” refers to an electrically
conductive surface, for example, without limitation, a d circuit.
As used herein, a “non-conductive ate” refers to a substrate
made of an electrically non-conductive material, sometimes referred to as an
insulator or a dielectric. Such als include, without limitation, minerals
such as , alumina, magnesia, zirconia and the like, glass and most plastics.
Specific non-limiting examples e FR4, which is the general grade
designation for fiberglass reinforced epoxy resin such as, without limitation,
DuPont Kapton® PV9103 polyimide and ULTRALAM® liquid crystal polymer
(Rogers Corporation, Chandler AZ).
As used herein, to “activate a non-conductive substrate surface,”
or a n thereof of, refers to rendering the surface more amenable to
interaction with and subsequent physical or chemical bonding to r
material that is disposed onto the surface of the ate. In an embodiment of
this invention, the other material can comprise a metal coordination complex. In
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addition, altering the surface properties also refers to rendering the e
more diffusive toward incident electromagnetic radiation. Altering the surface
properties can be accomplished by altering the aphy or the permeability
of the surface or a combination of the two. The topography of the surface can
be altered by mechanical or chemical means or a ation of the two.
Mechanical means of altering the surface properties of the
substrate include, without limitation, simple on of the surface such as with
sandpaper or another abrasive al, rasping the surface with a file, scoring
the e with a sharp object such as, without limitation, a tool bit, and laser
etching. Combinations of these and any other methods that result in an
abraded surface are within the scope of this invention.
In some embodiments, the surface may be prepared ab initio
using a mold that includes an abraded surface r and forming the
substrate with altered surface properties by disposing a molten polymer into the
mold. When removed, the molded object will have an altered surface as
ed to an object molded using a -surfaced mold. These methods
of altering a surface property are nown to those skilled in the art and
require no further description,
Chemical means of altering the surface properties of a substrate
include, without limitation, acid g, base etching, oxidative etching and
plasma etching.
Acid etching, as the name implies, refers to the use of a strong
acid such as sulfuric acid, hydrochloric acid and nitric acid. A mixture of
hydrochloric acid with nitric acid produces aqua regia, an extremely strong acid
which can be used to alter the surface properties of a substrate. Most
commonly, however, the surface to be acid etched is a glass and the acid use to
etch the glass is hydrofluoric acid. This, and other acid etching technologies are
well-known in the art and likewise require no detailed explanation.
Base etching is the converse of acid etching and involves the use
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of a basic nce to alter the topology of the surface of a substrate. Many
organic polymers are susceptible to chemical dissolution with basic substances.
For instance, without limitation, potassium hydroxide will react with polyesters,
polyimides and polyepoxides to alter their surface ties. Other materials
susceptible to base etching will be known those skilled in the art. All such
als are within the scope of this invention.
ive etching refers to the alteration of the surface properties
of a substrate by contacting the surface with a strong oxidant which as, without
limitation, potassium permanganate.
Plasma etching refers to the process of impacting the e of a
substrate with a peed stream of a glow rge of an appropriate gas.
The etching species may comprise charged ions or neutral atoms and radicals.
During the etch process, elements of the material being etched can chemically
react with the reactive species generated by the plasma. In addition, atoms of
the plasma- generating substance may imbed themselves at or just below the
surface of the substrate, further altering the properties of the surface. As with
the other methods of altering the properties of a surface, plasma etching is wellknown
in the art and needs no r description for the purposes of this
invention.
Laser etching is well-known in the art. Briefly, a laser beam is
ed at a e that is within the laser's focal plane. The laser's movement
is controlled by a computer. As the laser focal point is moved across the
surface, the material of the surface is, generally, vaporized thus leaving the
image being traced by the laser on the surface. With regard to this invention,
the laser may be used to impart an overall pattern on the surface of a substrate
or it may be used to trace the actual image to eventually be rendered
conductive onto the substrate.
Another means of altering the surface properties of a substrate
es exposing the surface of the substrate to a fluid that is know of found to
soften the surface, often with concomitant swelling of the e. When a
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coating material is applied to the swollen surface, the material can physically
ct at the boundary between it and the swollen surface, which can result
the material being more y bound to the e, in particular when the
coated ate is dried.
As used herein, "applying an magnetic field" to a substrate
surface es placing a surface of the substrate on or near a source of a
magnetic field. The magnetic field may be generated by either a permanent
magnet, an electromagnet or a combination thereof. A single magnet or
plurality of magnets may be used. The surface of the substrate that is in contact
with or near the magnet may be the surface opposite to that surface onto which
a metal coordination complex is to be deposited or it may be the surface onto
which a metal coordination complex is to be deposited. That is, the source of
the magnetic field may be above or below the substrate wherein "above" refers
to the activated surface of the substrate and "below" refers to the surface
opposite the activated surface. If the magnetic field is generated using a
permanent magnet, any type of magnet may be used so long as the field
strength is at least 1000 gauss, more preferably at least 2000 gauss. A
tly preferred permanent magnet is a neodymium magnet. It is also
preferred that a ent magnet have dimensions such that close to or all of
the activated surface of the substrate is contained within the dimensions of the
magnet. Such an arrangement is shown in Fig. 1. In Fig. 1, substrate 10 has
an ted e 15. Permanent magnet 20 is disposed below substrate 10
and positioned such that the magnetic field generated by the magnet is
orthogonal to activated surface 15, which is a presently preferred configuration.
As used herein, a "paramagnetic or ferromagnetic metal
coordination complex" is understood to have the meaning that would be
ascribed to these classes of metal xes by those skilled in the art. The
metal coordination complex must be ferro- or para- magnetic so that, when
disposed on the surface of the substrate, it is affected by the orthogonal
magnetic field. t being held to any particular theory, it is ed that the
complex, under the influence of the magnetic field, will either be drawn in toto
toward the source of the magnetic field and thereby be more deeply injected
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into the surface of the substrate or the field may cause the ligands of the
complex to align with the magnetic field thereby drawing the ligands further into
the substrate. A combination of the two processes may also occur. The result
in any case would be more tightly bound complex than that which would be
obtained without the influence of the magnetic field.
After the metal coordination complex is applied to the surface of
the substrate under the influence of the applied magnetic field, the source of the
magnetic field is removed.
The metal coordination complex coated substrate is then exposed
to omagnetic radiation to activate the metal nation complex toward a
ng agent. As used herein, electromagnetic radiation includes virtually the
entire spectrum of such, i.e., microwave, infrared, visible, ultraviolet, X-ray and
gamma ray radiation. The composition of the metal coordination complex can
be manipulated to render it sensitive to a particular range with the
omagnetic um or, if desired, sensitizer(s) may be added to the
complex when it is disposed on the substrate to render the complex
photosensitive or, if the complex is inherently photosensitive, to render it even
more so. As used here, "photosensitive" has its dictionary definition: sensitive
or responsive to light or other radiant energy, which would include each of the
types of radiation mentioned above.
re to ion renders a portion of the metal coordination
complex susceptible to reduction. The reducing agent will reduce the metal
coordination complex to tal metal. The reducing agent can be any
metal- inclusive salt wherein the metal has a reduction potential that is greater,
i.e., conventionally has a more negative reduction potential than the metal of the
nation complex. The following chart shows the reduction ial of a
number of common substances. Substances higher on the list are e of
reduction of those beneath it.
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Reducing agent Reduction potential (V)
Li −3.04
Na −2.71
Mg −2.38
Al −1.66
H2(g) + 2OH − −0.83
Cr −0.74
Fe −0.44
H2 0.00
Sn2+ +0.15
Cu+ +0.16
Ag +0.80
2Br− +1.07
2Cl− +1.36
Mn2+ + 4H2O +1.49
The elemental metal resulting from the reduction step is, of
course, insoluble in most solvents. Thus, washing the surface of the substrate
with an appropriate solvent, which is determined by the composition of the initial
metal nation complex, will remove unexposed complex leaving the metal.
The metal may be evenly dispersed over the e of the substrate if the
surface of the substrate was generally d or the metal may form a
discrete pattern if the substrate surface was exposed through a mask. A mask
is simply a al that is placed between the source of the electromagnetic
radiation and the surface of the substrate and which includes an image is to be
transferred to the surface of the substrate. The image may be a negative image
in which case the portions of the substrate surface that receive ion
corresponds to those portions of the mask that are transparent to the particular
radiation or the image may be a positive image in which case the portions of the
substrate surface that receive radiation correspond to those portions outside the
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image areas of the mask.
Once the unexposed metal coordination complex is removed, the
substrate with is dried to complete formation of the metal image.
The metal image can be used as is, plated with another metal or
coated with a non-metallic conductive material.
If the metal image is to be plated with another metal, such can be
accomplished electrolytically or electrolessly. In this manner a conductive metal
layer is formed only on the regions of the image comprising the metal image,
the result being a raised conductive surface.
Electroless plating of the metal image portions of the surface of
the substrate can be accomplished, without limitation, by contacting the surface
with a solution of a salt of a metal to be deposited in the presence of a
xing agent to keep the metal ions in solution and to stabilize the solution
generally. The surface with the complexed metal salt in contact with it or at
least near the surface is simultaneously or consecutively contacted with an
aqueous solution of a ng agent. The metal complex is reduced to afford
elemental metal which adheres to the metal image already on the surface of the
substrate; i.e., an electrolessly deposited layer of metal on metal results.
The metal complex solution and the reducing solution can be
rently sprayed onto the patterned substrate either from separate spray
units, the spray streams being directed so as to ect at or near the
substrate surface, or from a single spray unit having separate reservoirs and
spray tip orifices, the two s being mixed as they emerge from the spray
tip and impinge on the substrate e.
The electrodeposition process contemplated herein is well-known
in the art and need not be extensively bed. In brief, the elemental metal
image is connected to the negative terminal (cathode) of a direct t power
source, which may simply be a y but, more commonly, is a rectifier. The
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anode, which constitutes the second metal to be deposited onto the first metal
image, is connected to the positive terminal (anode) of the power source. The
anode and cathode are electrically connected by means of an electrolyte
on in which the imaged metal surface is submersed or bathed as by
t with a spray of the solution.
The electrolyte solution contains dissolved metal salts of the
metal to be plated as well as other ions that render the electrolyte conductive.
When power is applied to the system, the metallic anode is
oxidized to produce cations of the metal to be deposited and the positively
charged cations migrate to the cathode, i.e., the metal image on the substrate
surface, where they are reduced to the zero valence state metal and are
deposited on the surface.
In an embodiment of this ion, a solution of cations of the
metal to be deposited can be ed and the solution can be sprayed onto
the metalized construct.
The conductive material to be coated on the elemental metal
image may also comprise a non-metallic conductive substance such as, without
tion, carbon or a conductive polymer. Such materials may be deposited on
the metal image by techniques such as, without limitation, electrostatic powder
coating and electrostatic dispersion g, which may be conducted as a wet
(from solvent) or dry process. The process may be carried out by
electrostatically charging the metal image and then contacting the image with
nano- or micro- sized particles that have been electrostatically d with the
opposite charge to that applied to the metal image. In addition, to r
ensure that only the metal image is coated, the non- conductive ate may
be grounded to eliminate any possibility of an attractive charge developing on
the substrate or the substrate may be charged with the same polarity charge as
the substance to be deposited such that the substance is repelled by the
substrate.
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EXAMPLES
Example 1
1. DuPont Kapton PV9103 polyimide, in small sheets is chemically etched
using a mixture of 0.1 N KOH (5.6 grams ium hydroxide per 1 liter of
deionized water (DI)) with a 60% by weight on of isopropanol alcohol, for 2
to 4 minutes
2. The etched ide sheet is rinsed with DI water and dried for 30
minutes in an oven at 100 ºC.
3. 10 grams of ferric ammonium oxalate are suspended in 25ml of DI water
(in the darkroom) (Solution 1).
4. 10 grams of ferric ammonium oxalate are mixed with 1.0 gram of
potassium chlorate and 25 ml of DI water (also in the darkroom) (Solution 2).
. 2.3 grams of ammonium tetrachloroplatinate(II) are mixes with 1.7
grams of lithium chloride and 2ml of DI water (Solution 3).
6. ons 1, 2, and 3 are mixed together in equal amounts.
7. The etched polyimide sheet is placed on a 2000 gauss magnet that has
dimensions larger than those of the polyimide sheet and the mixture of Step 6 is
applied thinly over the surface of the sheet (in the darkroom) with a sponge
brush.
8. The coated polyimide sheet was air dried for 30 minutes (alternatively
the coated sheet may be placed an oven at 40 ºC for about 5 minutes or until
dry).
9. A mask comprising the desired pull tab image was placed on top of the
coating
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. The masked surface of the ide sheet was exposed to an ASC365
ultraviolet light source at full strength for no less than 3 minutes
11. The light source was d, the mask was separated from the
substrate surface and the surface was rinsed for 5 s with DI water and
then placed in a ethylenediamine tetraacetic acid (EDTA) bath sing 15
grams of EDTA per 1000ml of DI water 10 minutes.
12. The rinsed substrate was placed in an oven at 40 ºC for 5 minutes or
until dry.
13. The substrate was placed in a bath comprising Shipley Electroless
Cuposit 328 with 27.5% 328 (A-12.5%, L-12.5%, C-2.5%) and 72.5% DI 25 ºC
for 5 minute intervals to record plating.
14. The resulting copper-plated polymide was rinsed with DI water for 10
s and air dried for 30 minutes (or can be placed in an oven at 40 ºC for 5
minutes or until dry).
Example 2
1. A Rogers ULTRALAM 3000 liquid crystal polymer (LCP) sheet was
chemically etched with Electro-Brits E-prep 102, approximately 5% by volume
(40 grams per liter of sodium hydroxide)
2. The sheet was static rinsed followed by a double cascade rinse.
3. The rinsed etched sheet was then processed with E-Neutralizer and
then rinsed again.
4. The sheet was then dipped in a 10% solution of sulfuric acid for 10
seconds and rinsed.
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. 10 grams of silver nitrate were dissolved in 25 ml of DI water (in the
darkroom).
6. 5 grams of potassium chromate were mixed with 5 ml of DI water (in the
darkroom)
7. Drops of silver e were added to the potassium chromate solution
until a red precipitate formed. The mixture was allowed to stand for 24 hours
and then was filtered and diluted to 100 ml with DI water (in the darkroom)
8. The sheet was then placed on a 2000 gauss magnet and the silver
chromate mixture was thinly applied to it (in the darkroom) with a sponge brush.
9. The coated sheet was placed in an oven at 40 ºC for 10 minutes or until
dry.
. A pull test designed mask was placed on the coated surface of the LCP
sheet.
11. The masked LPC sheet was then exposed to ultraviolet light from an
ASC365 ultraviolet light source for 5 minutes.
12. The UV light source was removed, the LCP sheet was separated from
the mask and rinsed for 5 minutes with DI water and then placed in an EDTA
bath (15 grams of EDTA, per 1000ml of DI water) for 10 s.
13. The LCP sheet was then rinsed with DI for 10 s and put it into an
oven at 40 ºC for 5 minutes or until dry.
14. The LCP sheet was then placed in a bath comprising Shipley Electroless
Cuposit 328 with 27.5% 328 (1-12.5%, L-12.5%, C-2.5%) and 72.5% deionized
water at 25 ºC for 5 minute intervals to record plating.
. The copper-plated LCP sheet was d from the bath, rinsed for 10
6252342_4.docx
minutes and then placed in an oven at 40 ºC for 5 minutes until dry.
Example 3
1. A thin sheet (0.15" thickness) of FR4 was chemically etched with a 10%
solution of sulfuric acid for 3 minutes and then with a 6% solution of potassium
hydroxide.
2. The sheet was then rinsed with DI water.
3. 30 grams of ammonium ferric citrate (the green form, 7.5% ammonia,
% iron and 77.5% hydrated citric acid) was mixed with 35 ml of warm (50 ºC)
DI water (in the om) and then made up to a final volume of 50 ml with DI
water in an amber bottle (in the darkroom).
4. 1.8 grams of ammonium chloride in 20 ml of hot (70-80 ºC) DI water was
mixed with stirring with 3 grams of palladium(II) chloride until dissolved, and
then made up to 25 ml by on of DI water.
. The mixture was filtered and bottled when cool.
6. 6 drops of the um ferric citrate was added to 1 drop of palladium
chloride solution in a beaker until 20 ml of solution is obtained (in the darkroom).
7. The FR4 sheet was placed on a 2000 gauss magnet with dimensions
larger than those of the FR4 sheet and the coordinated complex solution was
sponge brushed thinly on the surface of the sheet (in the om).
8. The FR4 sheet was then place in an oven at 40 ºC for 10 minutes or
until dry.
9. A pull test designed mask was then placed on the treated surface of the
FR4 sheet.
6252342_4.docx
. The masked FR4 sheet was then exposed to UV light from an ASC365
ultraviolet emitter for 6 minutes.
11. The UV light source was removed, the mask separated from the FR4
sheet, the sheet was rinsed for 5 s with DI water and then was placed in
an EDTA bath (15 grams of EDTA, per 1000ml of DI water) 10 minutes.
12. The FR4 sheet was removed from the EDTA bath, rinsed with DI water
for 10 minutes and then placed in an oven at 40 ºC for 5 minutes or until dry.
13. The FR4 sheet was placed in a bath of Shipley Electroless Cuposit 328
with 27.5% 328 (A-12.5%, L-12.5%, C-2.5%) and 72.5% zed water at 25
ºC for 5 minute intervals to record plating.
14. The copper plated FR4 sheet was then rinsed for 10 minutes and put it
into an oven at 40 ºC for 5 minutes until dry.
6252342_4.docx
Claims (28)
1. A method of forming a conductive layer on a surface, comprising performing the following steps in order: ting at least a portion of a non-conductive substrate surface; applying a magnetic field to the surface; depositing a metal coordination complex on at least a part of the activated portion of the surface; removing the magnetic field; exposing the metal coordination complex to electromagnetic radiation; reducing the metal coordination complex to elemental metal; removing unreduced metal coordination complex from the surface; drying the surface; and depositing a conductive material onto the surface.
2. The method of claim 1, wherein activating the substrate surface comprises etching the e.
3. The method of claim 2, n etching the surface comprises chemical etching.
4. The method of claim 3, wherein chemical etching ses acid etching, base etching or oxidative etching.
5. The method of claim 2, wherein etching the surface comprises ical etching.
6. The method of claim 2, n etching the surface ses plasma etching.
7. The method of claim 2, wherein etching the surface comprises tching.
8. The method of claim 6, wherein plasma etching comprises etching in a 6252342_4.docx pre-determined pattern.
9. The method of claim 1, where the magnetic field has a ic flux density of at least 1000 gauss.
10. The method of claim 9, n the magnetic field is onal to the surface.
11. The method of claim 1, where depositing a metal coordination complex on at least a portion of the surface comprises using a mask.
12. The method of claim 11, wherein the mask comprises an electronic circuit.
13. The method of claim 12, wherein the electronic circuit is selected from the group consisting of an analog circuit, a digital circuit, a mixed-signal circuit and an RF circuit.
14. The method of claim 1, wherein exposing the metal coordination complex to electromagnetic radiation comprises microwave radiation, ed radiation, visible light radiation, ultraviolet radiation, X-ray radiation or gamma radiation.
15. The method of claim 1, where reducing the metal coordination complex to a zero oxidation state metal comprises using a combination of metals and/or catalysts.
16. The method of claim 1, wherein ng unreduced metal coordination complex from the surface comprises washing the surface with a solvent.
17. The method of claim 1, n drying the surface comprises drying at ambient temperature or drying at elevated temperature.
18. The method of claim 17, wherein drying the surface at ambient or 6252342_4.docx elevated temperature comprises using a vacuum chamber.
19. The method of claim 1, wherein ting a tive material onto the surface ses electrolytic deposition of a metal onto the n of the surface comprising the reduced metal nation complex.
20. The method of claim 19, wherein electrolytic deposition of a metal onto the portion of the surface comprising the reduced metal coordination complex comprises: contacting a negative al of a direct current power supply with at least the n of the surface comprising the reduced metal coordination complex; providing an aqueous solution comprising a salt of the metal to be deposited, an electrode made of the metal immersed in the aqueous solution or a combination thereof; contacting a positive terminal of the direct current power supply with the aqueous solution; contacting at least the portion of the surface comprising the reduced metal coordination x with the aqueous solution; and turning on the power supply.
21. The method of claim 1, wherein depositing a conductive material onto the surface comprises electroless deposition of a metal onto the portion of the surface sing the reduced metal coordination complex.
22. The method of claim 21, wherein electrolessly depositing a metal onto the portion of the surface comprising the reduced metal coordination complex comprises contacting at least the portion of the surface comprising the metal coordination complex with a solution comprising a salt of the metal, a complexing agent and a reducing agent.
23. The method of claim 1, wherein ting a conductive material onto the surface comprises deposition of a non-metallic conductive substance onto the portion of the surface comprising the reduced metal coordination complex. 6252342_4.docx
24. The method of claim 23, wherein the non-metallic tive material is deposited onto the portion of the surface comprising the reduced metal coordination complex by electrostatic dispersion.
25. The method of claim 1, wherein the entire non-conductive ate surface is activated and the metal coordination complex is deposited onto the entire surface.
26. The method of claim 1, wherein the entire non-conductive substrate surface is activated and the metal coordination complex is deposited on a part of the activated surface.
27. The method of claim 7, wherein laser g comprises etching in a pre-determined pattern.
28. A method of forming a conductive layer on a surface, the method being substantially as hereinbefore described with nce to the accompanying drawing and/or Examples. 6252342_4.docx W0 28473 SUBSTITUTE SHEET (RULE 26)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NZ716340A NZ716340B2 (en) | 2011-08-19 | 2012-08-16 | Circuits and substrates fabricated using a method of forming a conductive image on a non-conductive surface |
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161525662P | 2011-08-19 | 2011-08-19 | |
US61/525,662 | 2011-08-19 | ||
US201161568736P | 2011-12-09 | 2011-12-09 | |
US61/568,736 | 2011-12-09 | ||
US13/403,797 US8784952B2 (en) | 2011-08-19 | 2012-02-23 | Method of forming a conductive image on a non-conductive surface |
US13/403,797 | 2012-02-23 | ||
PCT/US2012/051193 WO2013028473A1 (en) | 2011-08-19 | 2012-08-16 | Method of forming a conductive image on a non-conductive surface |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ622408A NZ622408A (en) | 2016-03-31 |
NZ622408B2 true NZ622408B2 (en) | 2016-07-26 |
Family
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