CN116057204A - 用于将金属层无电流地施加到基板上的方法 - Google Patents
用于将金属层无电流地施加到基板上的方法 Download PDFInfo
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- CN116057204A CN116057204A CN202180054787.8A CN202180054787A CN116057204A CN 116057204 A CN116057204 A CN 116057204A CN 202180054787 A CN202180054787 A CN 202180054787A CN 116057204 A CN116057204 A CN 116057204A
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- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000000758 substrate Substances 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- -1 organosilane compound Chemical class 0.000 claims abstract description 11
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 8
- 239000002923 metal particle Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 150000004676 glycans Chemical class 0.000 claims description 9
- 229920001282 polysaccharide Polymers 0.000 claims description 9
- 239000005017 polysaccharide Substances 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 4
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 241000252506 Characiformes Species 0.000 claims description 3
- 150000001343 alkyl silanes Chemical class 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 claims description 2
- DTOOTUYZFDDTBD-UHFFFAOYSA-N 3-chloropropylsilane Chemical class [SiH3]CCCCl DTOOTUYZFDDTBD-UHFFFAOYSA-N 0.000 claims description 2
- WWBITQUCWSFVNB-UHFFFAOYSA-N 3-silylpropan-1-amine Chemical class NCCC[SiH3] WWBITQUCWSFVNB-UHFFFAOYSA-N 0.000 claims description 2
- MIPLZCIXHBJHRN-UHFFFAOYSA-N 3-silylpropanenitrile Chemical class [SiH3]CCC#N MIPLZCIXHBJHRN-UHFFFAOYSA-N 0.000 claims description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical class N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 108010039918 Polylysine Proteins 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920000656 polylysine Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920002113 octoxynol Polymers 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
-
- 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
- C23C18/1889—Multistep pretreatment with use of metal first
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/208—Multistep pretreatment with use of metal first
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—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
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Abstract
本发明涉及一种用于将金属层无电流地施加到基板上的方法，包括以下按照时间顺序的工作步骤：a)用蚀刻溶液处理要覆层的基板表面；b)用聚电解质或有机硅烷化合物处理要覆层的基板表面；c)用包含金属颗粒的溶液处理要覆层的表面；d)用包含要施加到基板上的金属的至少一种盐的溶液处理要覆层的表面。
Description
技术领域
本发明涉及一种用于将金属层无电流地施加到基板上的方法，以便提供经济的方法，借助于所述方法能够无真空地将非常薄的金属层施加在基板上。
背景技术
从现有技术中已知多种方法，以便给基板设置金属层。因此，无电流的方法以及借助电覆层来工作的方法提供经济的解决方案，而其他方法，例如借助真空或蒸汽工作的方法大多数情况下是明显成本更高的。
在已知的湿化学方法中，要覆层的表面通常首先经受清洁预处理。随后，要覆层的表面通常借助锡颗粒或钯颗粒来活化。基于钯的活化自1950年代起就在工业中执行。在活化之后，将表面在已知的方法中用金属盐溶液处理，所述金属盐溶液在表面上减少。当较厚的金属层是所期望的时，使用电镀覆层。与之相反，尤其在半导体技术的领域中使用无电流覆层，以便以相对低的耗费得到非常薄的金属覆层。
在所提及的方法中的挑战之一是实现所提及的金属种子层的足够强的附着并且这是有待实现的。为了实现该挑战，最常见的方法是使表面经受蚀刻工艺。这尤其在由玻璃构成的表面中执行，以便实现活性试剂在基板表面上的机械连接。然而，玻璃表面通过蚀刻工艺的粗糙化尤其对于高频应用是不理想的。聚合物在金属化之前也通常经受膨胀和蚀刻工艺，因为所述聚合物通常在再钝化法和再分配法中被使用。
发明内容
本发明基本如下目的，提供用于将金属层无电流地施加到基板上的方法，借助所述方法能够将超薄且平滑的金属层尽可能低成本地施加到基板上，其中金属层应当尽可能牢固地附着在基板上。
该目的根据本发明通过具有权利要求1的特征的方法实现。
在用蚀刻溶液处理要覆层的基板表面之后，首先用聚电解质或有机硅烷化合物处理要覆层的基板表面。接着，执行借助金属颗粒，尤其借助金颗粒、银颗粒、铜颗粒和/或铂颗粒的处理，以活化基板表面。这些金属颗粒通过之前施加的聚电解质或有机硅烷化合物固定在基板上。由此明显地提高起活化作用的金属颗粒在基板表面上的粘附。在接着用包含要施加到基板上的金属的盐的溶液对要覆层的表面进行处理时，能够将厚度为50nm至1000nm的超薄且平滑的金属层低成本地施加到基板上。通常，溶液在工作步骤d)中包含铜离子，例如硫酸铜。已证实的是，借助根据本发明的方法能够将特别薄且平滑的铜层施加到基板上。
将要覆层的基板表面在工作步骤b)中优选用聚电解质处理，所述聚电解质选自聚二烯丙基二甲铵(PDDA)、聚环氧乙烷(PEI)、聚丙烯酸(PAA)、聚苯乙烯磺酸盐(PSS)、聚环氧乙烷PEO和聚赖氨酸。这些聚电解质证实为对于金属颗粒，尤其金颗粒、银颗粒、铜颗粒和/或铂颗粒的固定是特别有效的。
在根据本发明的方法的一个特别优选的变型形式中，溶液在工作步骤d)中包含至少一种多聚糖，优选浓度为0.05％或更低。已证实的是，在覆层溶液中的多聚糖能够改变离子相互作用以及所施加的颗粒的大小，由此改进要施加的金属层的粘附。此外已观察到，借助多聚糖实现在无电流地施加金属层时的均匀的层生长。此外已证实的是，多聚糖用作为用于覆层溶液的稳定剂。假设，要施加的金属的颗粒大小，尤其铜颗粒的大小通过多聚糖减小。通过在覆层溶液中使用多聚糖还实现，可能减少玻璃基板的蚀刻。作为多聚糖源例如能够使用琼脂。
有利地，在方法步骤c)中存在金颗粒、银颗粒、铜颗粒和/或铂颗粒作为金纳米颗粒、银纳米颗粒、铜纳米颗粒和/或铂纳米颗粒，其中纳米颗粒优选具有大约5nm至100nm的直径并且优选具有带电的官能团。借助带电的官能团造成纳米颗粒和之前施加的聚电解质或之前施加的有机硅烷化合物之间的特别有利的静电的离子相互作用，由此纳米颗粒特别稳定地固定在要覆层的基板的表面上。有利地，工作步骤c)包含金纳米颗粒，尤其具有氯化金和柠檬酸的纳米颗粒，和优选至少一种表面活性剂，例如
是基于聚乙二醇的表面活性剂。尤其地，这种表面活性剂将颗粒的聚集趋势减小2倍。空间障碍将纳米颗粒稳定，其中聚乙二醇附加地改善润湿。可选地，也能够添加柠檬酸钠，以提高稳定性。
有利地，在工作步骤d)中金属盐以微型颗粒形式存在，尤其具有大约100nm至1000nm的直径。以这种方式方法能够由产生由聚电解质、纳米颗粒和微型颗粒构成的过渡层，借助于所述过渡层最终能够产生极其薄且极其平滑的金属覆层。
基板能够由聚合物或基于硅制成。然而，优选地，基板由玻璃制成，其中基板优选是具有留空部的中介层。玻璃中介层尤其应用在半导体领域中。因此，玻璃中介层允许热膨胀系数直接匹配于硅芯片。此外，由玻璃构成的中介层与硅相比提供更好的电特性。此外，这种中介层能够以面板大小获得并且提供高的互连密度。在玻璃中介层上的金属种子层还提供用于高传输和内存带宽应用的很有希望的解决方案。
通常，基板在工作步骤a)中用酸来处理。
优选地，将塑料基板在工作步骤b)之前用二甲基亚砜(DMSO)或N-甲基-2-吡咯烷酮(NMP)在大约25℃至60℃下并且接着用例如为DMSO的膨胀剂、例如为Triton-X的基于聚乙二醇的表面活性剂、氢氧化铵和/或氢氧化钠以及例如为甲醇、异丙醇或乙醇的醇来处理。玻璃基板通常用至少一种酸，例如硝酸、硫酸、食人鱼溶液、盐酸或王水或用钾盐、钠盐和/或双氟化铵盐来处理。
在根据本发明的方法的一个改进形式时，在工作步骤d)之后执行对经覆层的基板表面的电镀覆层。通过这种由无电流覆层和电镀覆层构成的组合能够填满中介层中的留空部。通过所述组合能够实现大于1μm的覆层厚度。
有利地，将基板在每个工作步骤之前和每个工作步骤之后用水，尤其蒸馏水冲洗，其中将基板在工作步骤d)之后优选用水和酸处理。
在根据本发明的方法的一个优选的变型形式中，在工作步骤d)中溶液还包含还原剂，尤其甲醛、联氨和/或乙醛酸。所述还原剂将工作步骤d)的金属盐的金属阳离子还原为元素金属。由此得到厚度为50nm至1000nm的超薄金属层。
如果作为工作步骤b)中的固定试剂应使用有机硅烷化合物，那么所述有机硅烷化合物优选选自亚烷基硅烷、氯丙基硅烷、氨丙基硅烷、硫代丙基硅烷和/或氰乙基硅烷和/或醚取代的、酯取代的和/或环氧树脂取代的烷基硅烷。
通常，在工作步骤d)中溶液具有大约10至12的pH值。
有利地，在工作步骤d)中溶液包含至少一种络合剂，例如EDTA，N,N,N’,N’-四基斯(2-羟丙基)乙二胺(四元)或酒石酸钾钠。
通常，在25℃至90℃的温度下执行工作步骤b)。
在设有贵金属颗粒的表面上能够形成金属层的根据本发明的方法也适合于表面等离子共振应用(OPR)以及适用于热敏的光子和光电的应用。所使用的纳米颗粒的大小，覆层率，pH值以及纳米颗粒密度影响要产生的金属层的形态学的和机械的特性。
具体实施方式
实例1：
将玻璃基板用丙酮和食人鱼溶液清洗一小时并且随后在10-20％的PDDA溶液中温育两小时。接着将样品用蒸馏水冲洗并且提供到具有金纳米颗粒的溶液中，所述溶液根据特克维奇法制造，其中颗粒大小＜100nm。溶液包含1％的氯化金、0.01％的Triton-X和0.3g/L的柠檬酸三钠。在纳米颗粒固定在基板上至少两小时之后，将样品重新冲洗并且提供到具有0.05％的琼脂、3.2g/L的五水硫酸铜、11.3g/L的酒石酸钾钠、5g的氢化钠(pH值为10至12)和32ML/L的甲醛的覆层浴中。在这种情况下，将琼脂用作为多聚糖源。通过在室温下改变2至20分钟的覆层时间，得到厚度为30μm至150μm的种子层。根据ASTM的胶带测试得到5B程度，这显示出强的粘附性。
实例2：
实例2根据实例1执行，除了PDDA由1g/L的支化聚乙烯(分子量25000至750000，PEI)替代。
实例3：
实例3根据实例1执行，除了PDDA由0.946g/L的(3-氨丙基)三乙氧基硅烷或APTES替代。
实例4：
实例4根据实例1执行，除了光反应性的、固化的聚酰亚胺或干层-环氧树脂-基板替代玻璃基板施加到硅基板或玻璃基板上。在PDDA/APTES中执行温育之前，将附加的膨胀处理和蚀刻处理作为预处理的一部分集成到所述方法中。在质子惰性的溶剂，例如二甲酰亚砜(DMSO)中的膨胀，在25℃至60℃下执行一分钟。随后，在溶液中进行20分钟至1小时的微蚀刻，所述溶液包含0.5至1％的例如为DMSO的水溶的膨胀剂、0.5至1％的例如为
的基于聚乙二醇的表面活性剂、1至3％的氢氧化铵和氢氧化钠化合物和10至30％的例如为甲醇、异丙醇或乙醇的醇化合物。随后，在基板被冲洗并且浸入聚电解质溶液中之前，用10％的硫酸处理所述基板。
Claims (18)
1.一种用于将金属层无电流地施加到基板上的方法，所述方法包括以下按照时间顺序的工作步骤：
a)用蚀刻溶液处理要覆层的基板表面；
b)用聚电解质或有机硅烷化合物处理要覆层的基板表面；
c)用包含金属颗粒的溶液处理要覆层的表面；
d)用包含要施加到所述基板上的金属的至少一种盐的溶液处理要覆层的表面。
2.根据权利要求1所述的方法，
其特征在于，
在工作步骤c)中所述溶液包含金颗粒、银颗粒、铜颗粒和/或铂颗粒，尤其胶体金。
3.根据权利要求1或2所述的方法，
其特征在于，
在工作步骤d)中所述溶液包含铜离子，例如硫酸铜。
4.根据上述权利要求中任一项所述的方法，
其特征在于，
在工作步骤b)中将所述要覆层的基板表面用聚电解质处理，所述聚电解质选自聚二烯丙基二甲铵(PDDA)、聚环氧乙烷(PEI)、聚丙烯酸(PAA)、聚苯乙烯磺酸盐(PSS)、聚环氧乙烷PEO和聚赖氨酸。
5.根据上述权利要求中任一项所述的方法，
其特征在于，
在工作步骤d)中所述溶液包含至少一种多聚糖，优选浓度为0.05％或更小。
6.根据权利要求2至5中任一项所述的方法，
其特征在于，
在工作步骤c)中所述金颗粒、银颗粒、铜颗粒和/或铂颗粒作为金纳米颗粒、银纳米颗粒、铜纳米颗粒和/或铂纳米颗粒存在，其中所述纳米颗粒优选具有大约5nm至100nm的直径并且优选具有带电的官能团。
7.根据上述权利要求中任一项所述的方法，
其特征在于，
在工作步骤c)中所述溶液包含金纳米颗粒，尤其是具有氯化金和柠檬酸的纳米颗粒，和优选至少一种表面活性剂，例如
8.根据上述权利要求中任一项所述的方法，
其特征在于，
在工作步骤d)中所述金属盐以微型颗粒的形式存在，尤其具有大约100nm至1000nm的直径。
9.根据上述权利要求中任一项所述的方法，
其特征在于，
所述基板由玻璃、聚合物或在硅的基础上制成，其中所述基板优选是具有留空部的中介层。
10.根据上述权利要求中任一项所述的方法，
其特征在于，
在工作步骤a)中，用酸处理所述基板。
11.根据上述权利要求中任一项所述的方法，
其特征在于，
将塑料基板在工作步骤b)之前用二甲酰亚砜(DMSO)或N-甲基-2-吡咯烷酮(NMP)在大约25℃至60℃下并且接着用例如为DMSO的膨胀剂、例如为
的基于聚乙二醇的表面活性剂、氢氧化铵和/或氢氧化钠以及例如为甲醇、异丙醇或乙醇的醇处理；或者其中用至少一种酸例如硝酸、硫酸、食人鱼溶液、盐酸或王水或用钾盐、钠盐和/或双氟化铵盐处理玻璃基板。
12.根据上述权利要求中任一项所述的方法，
其特征在于，
在工作步骤d)之后执行对经覆层的基板表面的电镀覆层。
13.根据上述权利要求中任一项所述的方法，
其特征在于，
将所述基板在每个工作步骤之前和之后用水处理，尤其用蒸馏水处理，其中所述基板在工作步骤d)之后优选用水和酸处理。
14.根据上述权利要求中任一项所述的方法，
其特征在于，
在工作步骤d)中，所述溶液还包含还原剂，尤其甲醛、联氨和/或乙醛酸。
15.根据上述权利要求中任一项所述的方法，
其特征在于，
作为有机硅烷化合物使用亚烷基硅烷、氯丙基硅烷、氨丙基硅烷、硫代丙基硅烷和/或氰乙基硅烷和/或醚取代的、酯取代的和/或环氧树脂取代的烷基硅烷。
16.根据上述权利要求中任一项所述的方法，
其特征在于，
在工作步骤d)中所述溶液具有大约10至12的pH值。
17.根据上述权利要求中任一项所述的方法，
其特征在于，
在工作步骤d)中，所述溶液包含至少一种络合剂，例如EDTA，N,N,N’,N’-四基斯(2-羟丙基)乙二胺(四元)或酒石酸钾钠。
18.根据上述权利要求中任一项所述的方法，
其特征在于，
在25℃至90℃的温度执行工作步骤b)。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102020123633.6A DE102020123633A1 (de) | 2020-09-10 | 2020-09-10 | Verfahren zum stromlosen Aufbringen einer Metallschicht auf ein Substrat |
| DE102020123633.6 | 2020-09-10 | ||
| PCT/EP2021/073250 WO2022053298A1 (de) | 2020-09-10 | 2021-08-23 | Verfahren zum stromlosen aufbringen einer metallschicht auf ein substrat |
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| CN116057204A true CN116057204A (zh) | 2023-05-02 |
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| Country | Link |
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| US (1) | US20230313383A1 (zh) |
| JP (1) | JP2023548732A (zh) |
| KR (1) | KR20230079357A (zh) |
| CN (1) | CN116057204A (zh) |
| DE (1) | DE102020123633A1 (zh) |
| WO (1) | WO2022053298A1 (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB905047A (en) * | 1959-06-30 | 1962-09-05 | Clevite Corp | Chemical plating of copper and copper-lead alloys |
| US4634619A (en) * | 1981-10-13 | 1987-01-06 | Surface Technology, Inc. | Process for electroless metal deposition |
| CN101853782A (zh) * | 2009-03-31 | 2010-10-06 | 海力士半导体有限公司 | Ulsi半导体器件的具有自组装单分子层的铜线及形成方法 |
| CN103189149A (zh) * | 2010-09-13 | 2013-07-03 | 凯密特尔有限责任公司 | 表面涂覆方法和使用该方法涂覆的物体的用途 |
| WO2013143961A1 (en) * | 2012-03-29 | 2013-10-03 | Atotech Deutschland Gmbh | Method for promoting adhesion between dielectric substrates and metal layers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1551867A (en) * | 1923-12-17 | 1925-09-01 | San Jose Spray Mfg Co | Pulverulent copper sulphate and process of producing same |
| DE1255435B (de) * | 1959-06-30 | 1967-11-30 | Clevite Corp | Alkalisches waessriges Bad zum stromlosen Plattieren mit Kupfer oder mit Kupfer-Blei-Legierungen |
| GB1209018A (en) * | 1968-06-20 | 1970-10-14 | Rheinisch Westfalisches Elek Z | A porous powder electrode framework for alkaline storage batteries |
| US6290088B1 (en) * | 1999-05-28 | 2001-09-18 | American Air Liquide Inc. | Corrosion resistant gas cylinder and gas delivery system |
| JP2001288249A (ja) * | 2000-04-05 | 2001-10-16 | Hitachi Ltd | 光硬化性樹脂組成物とその製造方法及びそれを用いた製品 |
| US7169215B2 (en) * | 2004-01-02 | 2007-01-30 | Ramot At Tel Aviv University Ltd. | Copper molybdenum electroless deposition process and materials |
| US20090023011A1 (en) * | 2007-07-20 | 2009-01-22 | Hewlett-Packard Development Company, L.P. | Systems and Methods for Forming Conductive Traces on Plastic Substrates |
| US8795542B2 (en) * | 2011-07-26 | 2014-08-05 | Intermolecular, Inc. | Removal of silicon nitrides during manufacturing of semiconductor devices |
-
2020
- 2020-09-10 DE DE102020123633.6A patent/DE102020123633A1/de active Pending
-
2021
- 2021-08-23 US US18/024,550 patent/US20230313383A1/en active Pending
- 2021-08-23 CN CN202180054787.8A patent/CN116057204A/zh active Pending
- 2021-08-23 KR KR1020237008948A patent/KR20230079357A/ko unknown
- 2021-08-23 WO PCT/EP2021/073250 patent/WO2022053298A1/de active Application Filing
- 2021-08-23 JP JP2023515317A patent/JP2023548732A/ja active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB905047A (en) * | 1959-06-30 | 1962-09-05 | Clevite Corp | Chemical plating of copper and copper-lead alloys |
| US4634619A (en) * | 1981-10-13 | 1987-01-06 | Surface Technology, Inc. | Process for electroless metal deposition |
| CN101853782A (zh) * | 2009-03-31 | 2010-10-06 | 海力士半导体有限公司 | Ulsi半导体器件的具有自组装单分子层的铜线及形成方法 |
| CN103189149A (zh) * | 2010-09-13 | 2013-07-03 | 凯密特尔有限责任公司 | 表面涂覆方法和使用该方法涂覆的物体的用途 |
| WO2013143961A1 (en) * | 2012-03-29 | 2013-10-03 | Atotech Deutschland Gmbh | Method for promoting adhesion between dielectric substrates and metal layers |
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| WO2022053298A1 (de) | 2022-03-17 |
| KR20230079357A (ko) | 2023-06-07 |
| JP2023548732A (ja) | 2023-11-21 |
| DE102020123633A1 (de) | 2022-03-10 |
| US20230313383A1 (en) | 2023-10-05 |
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