WO2020046429A1 - Procédé de production de substrats métalliques nanostructurés utilisables en spectroscopie raman exaltée de surface ou dans des applications similaires - Google Patents

Procédé de production de substrats métalliques nanostructurés utilisables en spectroscopie raman exaltée de surface ou dans des applications similaires Download PDF

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WO2020046429A1
WO2020046429A1 PCT/US2019/028826 US2019028826W WO2020046429A1 WO 2020046429 A1 WO2020046429 A1 WO 2020046429A1 US 2019028826 W US2019028826 W US 2019028826W WO 2020046429 A1 WO2020046429 A1 WO 2020046429A1
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copper
dendrites
layer
metal
bath
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Lloyd PLOOF
Jody Ray MC REDMOND
Thomas Joseph BASILE
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Priority to EP19731362.0A priority patent/EP3844324A1/fr
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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
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    • 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
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • 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
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    • 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
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • 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
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • Especially useful structures for Surface Enhanced Raman Spectroscopy include precious metal nanostructures in the range of 0.01 to 100 um, specifically in the range of 0.05- 0.2 um, i.e., 50 to 200 nanometers.
  • Gao, Wang, Wang, Zhang, et al. discuss how to grow silver nanosheet assembled films on copper by growing dendrites made of silver. The method employed there was not easily reproducible and the adhesion of the silver film was very poor.
  • Maxwell, Emory, and Nie discuss use of colloidal silver particles to form a nano structured silver film. This method is expensive, slow, susceptible to many variables, and not easy to scale.
  • Jin, Xu, Xiong, Jing, Zhang, Sun, and Han discuss a process for galvanically depositing silver on Cu2O crystals, but those crystals were electrostatically deposited and of a different morphology from copper oxide dendrites.
  • the novel method included herein is cost effective, readily reproducible, and easily scaled for production.
  • This method creates a framework of copper oxide dendrites to produce the desired geometry and then coats those dendrites with a metal by immersion (galvanic replacement) chemistry, electroless disposition, or electrolytic deposition to coat the dendrites to create metal coated-dendrites in the range of 0.01-100 um.
  • the metal used to coat the dendrites would typically a monetary metal, e.g., noble metal such as gold or silver, or equivalent such as palladium or platinum, but could be any suitable metal from the group formed of silver, gold, platinum, palladium, nickel, tin, or combinations of them, or from any such metal that may be deposited on such copper oxide dendrites by immersion, electroless deposition, or electrolytic deposition.
  • the process for forming a nano-scale substrate suitable for use in Surface Enhanced Raman Spectroscopy (SERS) and/or other similar applications starts with a substrate having thereon a layer of copper, which may be solid, copper, sheet, bar, or other form.
  • the copper may have any purity, but should preferably 80% copper or better.
  • This is subjected to oxidation in a process bath to form a layer copper oxide dendrites thereon having a length on the order of up to 100 pm, and a width of 0.5 to 10 pm.
  • the substrate and dendrites are cleaned and rinsed, and then a noble metal or equivalent is deposited onto the copper oxide dendrites.
  • the metal coated dendrites are subjected to cleaning and rinsing such that the noble-metal coated dendrites are suitable for SERS and/or other suitable applications.
  • the copper layer maybe subjected to oxidation in an aqueous reagent bath with sulfur compounds and oxidizers, carried out at an elevated temperature on the order of 90 ° C. This should result in dendrites in lengths from less than one micron up to a hundred microns, preferably from 50 to 200 nanometers.
  • the preferred noble metal maybe gold or silver, but can be selected from the group consisting of Ag, Au, Pa and Pt, or selected from a broader group consisting of Ag, Au, Sn, Ni, Cu, Pt, Pa, Rh and Zn.
  • Fig. 1 is an electron micrograph of a layer of cupric oxide dendrites taken a magnification of 5000 using a scanning electron microscope.
  • Fig. 2 is an electron micrograph of a layer of silver-coated cupric oxide dendrites taken a magnification of 5000 using a scanning electron microscope.
  • Chemistries and methods to produce copper oxide dendrites are well known, and these have been used to increase adhesion between subsequent layers of circuit boards in electronics, to increase subsequent paint adhesion on copper, and to blacken copper for optic applications. These chemistries are reactive, and can be acidic or alkaline and may have chlorites, chlorides, sulfur compounds, and oxidizers in them. The appearance of the copper oxide surface may range from a light gray, through brown, to black, but might be other colors depending on the formula of the chemistry.
  • the dendrites may range in length from 0.01 to 100 um and may be needle shaped, fern like, nodular, or fan shaped. (See Figure 1).
  • cupric oxide dendrites While the technology for producing cupric oxide dendrites has been available for some time, no one has attempted to coat these dendrites with another metal, and specifically, no one has employed plated or coated copper oxide dendrites for Surface Enhanced Raman Spectroscopy. This material may also have applications in electronics, magnetics, batteries, solar cells, and others.
  • cupric oxide dendrites Coating these cupric oxide dendrites with various metals may be carried out with certain galvanic replacement (immersion) chemistries, certain autocatalytic reduction (electroless) chemistries, and certain electrolytic deposition chemistries. Cupric oxide dendrites could also be coated via chemical vapor deposition, physical vapor deposition, sputtering or any other method that might be used to deposit metals on a surface.
  • the method of this invention is as follows:
  • a suitable base of copper is formed.
  • This may be copper sheet, pellet, rod, bar, etc., but most preferably a copper sheet of appropriate size and thickness, in any purity up to 100% copper, but most preferably greater than 80% copper.
  • This may favorably be a copper coated substrate on any base material substrate including, but not limited to, steel, stainless steel, aluminum, glass, plastic, or any other material suitably coated with copper.
  • the afore-mentioned base is then cleaned in a suitable solvent or aqueous cleaner until no surface contamination remains.
  • the cleaned substrate is rinsed in clean water, immersed in an acid solution to remove any unwanted oxides, and then rinsed in clean water again.
  • the cleaned substrate may preferably be chemically polished to produce an optically smooth surface.
  • the chemical polish is followed by another rinse in water.
  • the base is then immersed in a bath of a reactive oxidizing solution for sufficient time to produce the cupric oxide dendrites.
  • This bath may be alkaline or acidic and may have a suitable oxidizer and a sulfur containing compound, among other chemistries, depending on the process selected.
  • the temperature of this bath may be anywhere from room temperature to 200 deg. F. (I.e., 90 deg. C), and the time in the bath can range from a few seconds to several minutes.
  • the base and dendrites are then rinsed extremely well in good quality water and immersed in an appropriate solution of galvanic displacement chemistry, electroless deposition chemistry, or electrolytic deposition chemistry among others, to deposit the desired metal on the framework of the cupric oxide.
  • This chemistry may be acid, alkaline or neutral and may deposit one or more of the following metals: Silver, Gold, Tin, Nickel, Copper, Platinum, Palladium, Rhodium, Zinc, or any other equivalent metal capable of being deposited.
  • the time in this solution may vary from a few seconds to several hours depending on the solution and the desired amount of metal to be deposited.
  • the resulting cupric oxide framework coated with metal may now be suitable for Surface Enhanced Raman Spectroscopy, Solar Cells, Electronics, Magnetics, Batteries, and other applications.
  • This process and the resulting metal/cupric oxide framework can be optimized to produce consistent morphologies and extremely consistent micro- or nano-topographies, as needed for the desired application.
  • This process can be optimized to produce larger or smaller framework sizes with other metal or material combinations.

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  • Chemical & Material Sciences (AREA)
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  • General Physics & Mathematics (AREA)
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Abstract

Selon l'invention, un cadre de dendrites d'oxyde de cuivre est formé sur un substrat de cuivre, et ces dendrites sont ensuite revêtus ou plaqués d'argent, d'or ou d'un métal équivalent pour créer des dendrites revêtus de métal présentant des nanostructures, favorablement dans une plage de 50 à 200 nanomètres. Le cadre de dendrites revêtus de métal s'utlise de manière appropriée en spectroscopie Raman exaltée de surface et dans d'autres applications pratiques.
PCT/US2019/028826 2018-08-28 2019-04-24 Procédé de production de substrats métalliques nanostructurés utilisables en spectroscopie raman exaltée de surface ou dans des applications similaires Ceased WO2020046429A1 (fr)

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CA3114745A CA3114745A1 (fr) 2018-08-28 2019-04-24 Procede de production de substrats metalliques nanostructures utilisables en spectroscopie raman exaltee de surface ou dans des applications similaires
EP19731362.0A EP3844324A1 (fr) 2018-08-28 2019-04-24 Procédé de production de substrats métalliques nanostructurés utilisables en spectroscopie raman exaltée de surface ou dans des applications similaires

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US62/723,635 2018-08-28
US16/156,612 US10829846B2 (en) 2018-08-28 2018-10-10 Process for producing nanostructured metal substrates for use in Surface Enhanced Raman Spectroscopy or similar applications
US16/156,612 2018-10-10

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CN113433110A (zh) * 2021-06-22 2021-09-24 西安邮电大学 原位置换法生成金银枝晶花状纳米结构衬底的制备方法

Citations (6)

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