EP3510179A1 - Metal active component formation in hybrid materials - Google Patents
Metal active component formation in hybrid materialsInfo
- Publication number
- EP3510179A1 EP3510179A1 EP17849717.8A EP17849717A EP3510179A1 EP 3510179 A1 EP3510179 A1 EP 3510179A1 EP 17849717 A EP17849717 A EP 17849717A EP 3510179 A1 EP3510179 A1 EP 3510179A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- substrate
- precursor formulation
- metal precursor
- active component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 80
- 239000002184 metal Substances 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title description 11
- 239000000758 substrate Substances 0.000 claims abstract description 53
- 239000002243 precursor Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000009472 formulation Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910013720 M(NO3)n Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 2
- 150000001767 cationic compounds Chemical class 0.000 claims 2
- 229910001411 inorganic cation Inorganic materials 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000002159 nanocrystal Substances 0.000 description 13
- 239000002105 nanoparticle Substances 0.000 description 11
- 238000010952 in-situ formation Methods 0.000 description 10
- -1 polypropylene Polymers 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000000470 constituent Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000001066 destructive effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 150000003947 ethylamines Chemical class 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000012462 polypropylene substrate Substances 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film 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
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
-
- 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
- C23C18/02—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 thermal decomposition
- C23C18/08—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 thermal decomposition characterised by the deposition of metallic material
-
- 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
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
- C23C18/145—Radiation by charged particles, e.g. electron beams or ion irradiation
-
- 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
- C23C18/1667—Radiant energy, e.g. laser
-
- 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
- C23C18/1675—Process conditions
- C23C18/1682—Control of atmosphere
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
Definitions
- the disclosure generally relates to techniques and a solution composition for in-situ formation of metal nanocrystal coating in compounds of various shapes.
- Hybrid compounds are defined as composite materials that consist of two or more chemically different constituents (e.g., a first part and a second part) that possess at least one property that does not exist in either constituent separately.
- a hybrid compound can be described as any of organic-inorganic, block copolymer networks, hydrogels inorganic-inorganic, sol-gels.
- the first part provides the hybrid compound's shape (such as, for example, shape-defining organic ligands in a MOF)
- the second part provides the hybrid's function (such as heterogeneous catalysis in zeolites).
- a suitable framework for the hybrid compounds is a porous network. Such a framework can be utilized in many applications, as it provides high surface areas and easy access to the active sites of the compound.
- An additional advantage of hybrid compounds is the ability to control the optical, electronic, magnetic, chemical or mechanical properties of the compound by changing only one of the constituents through relatively mild synthetic conditions (e.g., temperature, etc.).
- the most primitive example of a hybrid compound is a flat substrate with an active material coating.
- the flat substrate may include a polymer or ceramic surface and the active material may include catalytically active metal nanocrystals.
- porous hybrid materials there are many possible applications for utilizing porous hybrid materials discussed in the related art. Such applications are typically used as various membranes and filters. For example, a water filtration/purification process can be performed with porous hybrid material due to their high porosity and a possibility of filtration based on chemical affinity as well as size and antibacterial filtration.
- the porosity and functionalization characteristics of the hybrid materials allow for use of such materials as effective fuel (i.e., hydrogen) and gas (i.e., CO2) storage devices and possible candidates for controlled drug delivery, as well as ion exchange materials.
- effective fuel i.e., hydrogen
- gas i.e., CO2
- Additional applications based on the same principles include gas/electrochemical sensors; composite electrolyte materials (for example, solid-state lithium batteries or supercapacitors) and various composite devices for electronic and optoelectronic applications including light-emitting diodes, photodiodes, solar cells, and field effect transistors.
- porous hybrid compounds include heterogeneous catalysis, which often requires an active metallic or organometallic moiety inside a large-surface area porous framework.
- One of the most prominent examples of such systems is an automobile catalytic converter. All those applications require a presence of an inorganic, typically metal, active species embedded into the porous scaffold.
- Common metals employed in these kinds of applications are silver, gold, platinum, and palladium.
- One existing technique for producing porous hybrid compounds includes separately preparing the structural units of hybrid constituents and then combining them together, typically using either organic or inorganic synthesis. This technique is often referred to as "building blocks strategy.” The major disadvantages of this technique are relatively low process control capabilities and relatively low variety of the possible structural units.
- Another existing technique for producing porous hybrid compounds includes preparation of one constituent separately and then forming the second one in situ.
- in situ formation of the scaffold usually includes preparation of the active component (for example, metal nanoparticles) as a precursor, and then using it as a template for the formation of an organic network.
- This approach has similar disadvantages: structures that are built on or around nanoparticles usually have a low structural variability. Additionally, using the nanoparticles as a precursor limits their choice to those with templating capabilities.
- In situ formation of the active component includes first preparing the scaffold (organic or inorganic) and then impregnating the scaffold with the active particles or moieties.
- the disadvantages of this techniques typically include shallow particle permeation with unequal distribution, and harsh conditions often required for the particle formation.
- the latter limits the choice of the scaffolding constituent predominantly to inorganic ones (zeolites or sol-gels) and limits the choices of the active constituents to those resistive to high temperatures or invasive chemical reagents.
- a common technique for in situ synthesis of metal nanoparticles in polymer scaffolds includes thermal annealing of a metal-ion embedded in a polymer thin film.
- the polymer acts as a reducing agent, whereby an electron is extracted from the polymer and donated to the metal-ion.
- This irreversible oxidation of the polymer scaffold leads to degradation, which has detrimental effects on the whole system's stability and durability.
- the various aspects of the disclosed embodiments provide non-destructive method for in situ formation of active component coating either inside or on top of heterogeneous compound with high nanoparticle loading and high control of nanoparticles size distribution and metal layer thickness.
- the in-situ formation may be of metal nanocrystal coating in compounds of various shape, ranging from flat to porous.
- the coating can be of various densities, ranging from a uniform polycrystalline layer to a coating of separate nanocrystals (nanoparticles) on a surface of a substrate.
- Some example embodiments include a method for forming a metal active component.
- the method includes applying a metal precursor formulation on a substrate; and exposing the metal precursor formulation applied on the substrate to a low-energy plasma, wherein the low-energy plasma is operated according to a set of exposure parameters.
- Some example embodiments include metal active component comprising: a metal precursor formulation; and a substrate at least partially covered by the metal precursor formulation, wherein the metal precursor formulation is applied on the substrate, wherein the metal precursor formulation applied on the substrate is exposed to a low- energy plasma, wherein the low-energy plasma is operated according to a set of exposure parameters.
- Figure 1 is a cross-section scanning electron microscope (SEM) image of gold
- Figure 2 is a SEM image of silver nanoparticles formed on a polypropylene filter.
- Figure 3 is another SEM image of silver nanoparticles formed on a polypropylene filter. (Example II)
- Figure 4 is a SEM image of silver nanoparticles formed on a polytetrafluoroethylene (PTFE) filter. (Example III)
- a non-destructive method for in situ formation of metallic coatings is provided.
- the disclosed method allows the in situ formation with precise control over metal layer thickness or density of separate nanocrystals.
- the substrate for the coating may be, for example, a flat substrate, a porous material, and the like.
- the porous substrates may be membranes and filters utilized in applications, such as fuel and gas storage devices, ion exchange materials, gas/electrochemical sensors, composite electrolyte materials (e.g., solid-state lithium batteries or supercapacitors), various composite devices for electronic and optoelectronic applications (e.g., LEDs, photodiodes, solar cells, FETs, etc.), and heterogeneous catalysis (e.g., an automobile catalytic converter).
- applications such as fuel and gas storage devices, ion exchange materials, gas/electrochemical sensors, composite electrolyte materials (e.g., solid-state lithium batteries or supercapacitors), various composite devices for electronic and optoelectronic applications (e.g., LEDs, photodiodes, solar cells, FETs, etc.), and heterogeneous catalysis (e.g., an automobile catalytic converter).
- applications such as fuel and gas storage devices, ion exchange materials, gas/electrochemical sensors,
- the substrate can be formed of materials including, but not limited to, macroporous polymers, foams, MOFs, COFs, zeolites, metal oxide networks, sol-gels, activated 3D carbon, commercial filters, and membranes.
- the substrate may be pre-treated for better adhesion.
- the metal active component formation method utilizes growth of metallic nanocrystals.
- the nanocrystals can be grown to be interconnected, thereby forming a network or a uniform layer; or they can remain as separate nanostructures on a surface.
- the density of the nanostructures, as well as the thickness of the metal layer, can be precisely controlled.
- the active component formation method is performed using a low temperature technique that allows a wide choice of substrates (both organic and inorganic) and a wide choice of metals as active component material. Further, the method operates with any type of substrate material, including commercial plastics, glass, and ceramics.
- the precursor for the metal component is a solution of organic solvents and metal salts.
- a substrate (either organic or inorganic) is covered with a solution (formulation) of a metal precursor.
- applying the solution may be performed using printing, drop-casting, spin-coating, smearing, dip-coating or any other conventional deposition method.
- the substrate is then placed in the plasma apparatus under a low vacuum and exposed to plasma radiation at a preconfigured power and exposure duration.
- the metal precursor undergoes a reduction process, and metal nanocrystals are formed on soaked surfaces of either flat substrate or surface areas of the porous material.
- the behavior of the nanocrystals is governed by the precursor formulation and concentration. As such, in low concentrations, the nanocrystals remain relatively small and remain scattered on a surface. In higher precursor concentrations, the nanocrystals grow large and interconnect, forming a network of crystals or a uniform polycrystalline layer. The particles are attached to the substrate via physical adsorption and/or intramolecular chemical bonds.
- the plasma utilized by the formation method is a low energy plasma, such as a radio frequency (RF) plasma or another non-thermal plasma.
- RF radio frequency
- the use of low energy plasma enables the conduction of a chemical reaction without creating high temperatures on the surface of the porous substrate/compound/scaffold.
- the disclosed process would not thermally damage or otherwise harm the surface or deeper layers of the substrate.
- the metal nanoparticles include any metal feature that can be adhered or bounded to the porous materials.
- metal of the metal nanoparticles as referred to herein includes any metal alloys, bi-metal alloys, mixtures of various types of metals, or combinations thereof.
- the formation is performed by exposing the substrate to a low-energy and nonthermal plasma, a gas such as Argon, Nitrogen, Oxygen, Hydrogen, Air, and the like.
- a gas such as Argon, Nitrogen, Oxygen, Hydrogen, Air, and the like.
- the substrate is placed in a chamber and exposed to a gas plasma (such as, for example, Argon and Nitrogen plasma) as determined by a set of exposure parameters including, for example, power, RF frequency, gas flow rate, and time duration for the exposure.
- the values of the set of exposure parameters are determined based, in part, on the type of the substrate, precursor solution, gas type, the means of application, or a combination thereof.
- the values of the set of exposure parameters may be as follows: the power is between 5W (watt) and 600W, the plasma RF frequency is between 50 Hz and 5 GHz, the gas flow rate is between 2 SCCM (standard cubic centimeter per minute) and 50 SCCM, and the exposure time is between 1 second and 30 minutes.
- the precursor solution is applied by a means including, but not limited to, drop-casting, spray-coating, immersion, and the like.
- the precursor solution may be composed of different metal cations, and different contractions thereof.
- the resulting metal active component may include of various types of metals, bi-metals, alloys, or a combination thereof.
- the precursor solution in its basic form, includes metal cations with at least one type of solvent.
- the metal cations include any of M(NO3)n, M(SO4)n, MCln, and HmMCIn+m, and MN, where "M” is a metal atom (or any appropriate metal alloy) with a valence of "n", H is hydrogen, NO3 is nitrate, SO4 is sulfate, CI is chloride, "N” is alkyl-, alyl-, aceto-, and other organic moieties, and "m” is a valence of the counter ion.
- the metal cation may be in the form of organic and inorganic salts of gold, silver, platinum, palladium, copper, nickel, or a combination thereof, to get metallic and bimetallic nanoparticles. Further, the metal cations may be provided in gels, colloids, suspensions, dispersions, organic-inorganic compounds, and so on. The metal cations may be stabilized by a counter ion, e.g., forming an organometallic complex, such that they are connected by coordinate bonds rather than by ionic bonds.
- the precursor solution may be in a form of solution, dispersion, suspension, gel, or colloid.
- the solvents that may be used in the precursor solution include, but are not limited to, alcohols, water, toluene, dioxane, cyclohexanol, dimethyl sulfoxide (DMSO), formamides, ethylamines, glycols, glycol ethers, glycerol, propylene carbonate, and acetonitrile.
- the precursor solution can contain other additives such as, but not limited to, organic molecules, polymers, conductive polymers, carbon nanotubes (CNT), densifiers, surfactants, and the like. Such additives can be used to change the viscosity and surface tension.
- the resulting metal active component may be in the form of metal particles in the range of 1 -100 nm (nanometer) and up to 10 ⁇ (micrometer).
- the particle size can be controlled by the choice of substrate material, choice of solvent/solvent mixture, precursor concentration, gas flow, and processing time.
- the particle shape can be controlled by changing the choice of substrate material and the choice of precursor type.
- the arrangement of the particles into separate nanocrystals or interconnected metallic polycrystalline layers can be controlled by the solution formulation and metal precursor concentration.
- the nanocrystal distribution, density layer thickness, or a combination thereof, can be controlled by the choice of solvent/solvent mixture, precursor concentration, gas type, gas flow, and processing time.
- Example I The solution includes the metal precursor HAuCU in the concentration of 10 percentage by weight (wt. %) in a mixture including water in the concentration of 10 wt. %, propylene glycol in the concentration of 20 wt. %, and ethylene glycol in the concentration of 60 wt. %.
- Activated carbon 3D substrate is immersed in the precursor solution for 1 min to soak the solution inside the scaffold. Then, the activated carbon substrate with solution is placed in a vacuum chamber and exposed to argon plasma.
- the chamber is set with the following exposure parameters: RF frequency, power, gas flow rate, and time; having the values: 13.56 MHz, 50 W, 20 SCCM gas flow rate, and 15 minutes, respectively.
- the pressure at the chamber is 0.6 mbar.
- an activated carbon substrate is filled inside and covered outside by gold nanoparticles of 20 nm size.
- a cross-section SEM image of the gold nanoparticles formed on an activated carbon 3D matrix is shown in Fig. 1 .
- Example II The solution includes metal precursor AgNO3 in the concentration of 20 wt. % in a mixture including water in the concentration of 52 wt. %, propylene glycole in the concentration of 22 wt. % and n-propanol in the concentration of 6 wt.%.
- a polypropylene network substrate is immersed in the precursor solution for 1 min to soak the solution inside the scaffold. Then, the polypropylene network substrate with solution is placed in a vacuum chamber and exposed to argon plasma.
- the chamber is set with the following exposure parameters: RF frequency, power, gas flow rate, and time; having the values: 13.56 MHz, 100 W, 40 SCCM gas flow rate, and 10 minutes, respectively.
- the pressure at the chamber is 0.8 mbar.
- a polypropylene substrate is filled inside and covered outside by silver nanoparticles of 60 nm size.
- a SEM image of silver nanoparticles formed on a polypropylene filter are shown in Figs. 2 and 3.
- Example III The solution includes metal precursor PtCl2 in the concentration of 20 wt. % in a mixture including water 10 wt. %, n-propanol in the concentration of 20 wt. %, and dipropylene glycol methyl ether in the concentration of 50 wt.%.
- a polytetrafluoroethylene (PTFE) substrate immersed in the precursor solution for 1 min to soak the solution inside the scaffold. Then, the PTFE substrate with solution is placed in a vacuum chamber and exposed to argon plasma.
- the chamber is set with the following exposure parameters: RF frequency, power, gas flow rate, and time; having the values: 13.56 MHz, 150 W, 25 SCCM gas flow rate, and 15 minutes, respectively.
- a PTFE substrate is filled inside and covered outside by platinum nanoparticles of 5 nm size.
- a SEM image of silver nanoparticles formed on a polytetrafluoroethylene (PTFE) filter is shown in Fig. 4.
- Example IV The solution includes a metal precursor chloroplatinic acid [H3O]PtCl6 in the concentration of 0.01 wt. % in a mixture including water in the concentration of 10 wt. %, propylene glycol in the concentration of 20 wt. %, and ethylene glycol in the concentration of 60 wt. %.
- a droplet of the solution is deposited on a polyethylene tertphtalate (PET) slide and smeared. Then, the composition of the substrate with the solution is placed in a vacuum chamber and exposed to nitrogen plasma.
- PET polyethylene tertphtalate
- the chamber is set with the following exposure parameters: RF frequency, power, gas flow rate, and time; having the values 13.56 MHz, 50 W, 20 SCCM gas flow rate, and 15 minutes, respectively.
- the pressure at the chamber is 0.3 mbar.
- the substrate is coated by a non-continuous coating of separate platinum nanoparticles of 20-40 nm size, and is later used for catalytic reaction in an organic photovoltaic cell.
- the phrase "at least one of” followed by a listing of items means that any of the listed items can be utilized individually, or any combination of two or more of the listed items can be utilized. For example, if a system is described as including "at least one of A, B, and C," the system can include A alone; B alone; C alone; A and B in combination; B and C in combination; A and C in combination; or A, B, and C in combination.
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US6951666B2 (en) * | 2001-10-05 | 2005-10-04 | Cabot Corporation | Precursor compositions for the deposition of electrically conductive features |
US7258899B1 (en) * | 2001-12-13 | 2007-08-21 | Amt Holdings, Inc. | Process for preparing metal coatings from liquid solutions utilizing cold plasma |
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