# US 10,370,759 B2 · Substrate that is electrically conductive on at least one of the faces of same provided with a stack of thin layers for growing carbon nanotubes (CNTs) > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,370,759 B2 - Document ID: US10370759B2 - Status: Granted - Kind: B2 - Application number: 14/894,489 - Filed: 2014-05-27 - Published: 2016-04-28 - Granted: 2019-08-06 - Earliest claimed: 2013-05-28 - Assignees: Commissariat A L'energie Atomique Et Aux Energies Alternatives - Applicants: Commissariat A L'energie Atomique Et Aux Energies Alternatives - Inventors: Hanako Okuno; Raphael Ramos; Jean Dijon - Web page: https://patentgrep.com/patent/US10370759B2 ## CPC - C23C 16/26: Deposition of carbon only - B01J 23/745: Iron - B01J 27/24: Nitrogen compounds - B32B 15/012: {one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy} - B32B 15/013: {one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium} - B32B 15/017: {one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium} - C01B 32/16: Preparation - C01B 32/162: characterised by catalysts - C23C 16/0272: {Deposition of sub-layers, e.g. to promote the adhesion of the main coating} - C23C 28/023: {only coatings of metal elements only} - H01G 11/36: Nanostructures, e.g. nanofibres, nanotubes or fullerenes - B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites - B82Y 40/00: Manufacture or treatment of nanostructures - H01M 4/625: {Carbon or graphite} - H10K 30/821: {comprising carbon nanotubes} - Y02E 60/10: Energy storage using batteries - 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 (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10) - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract The invention concerns a substrate that is electrical conductive on at least one of the faces of same, provided with a stack of thin layers comprising at least one layer of catalyst material suitable for accelerating the growth of carbon nanotubes, characterized in that the stack comprises the sequence of thin layers deposited in the following order on top of said at least one electrically conductive face of the substrate: a) optionally, a metal made from metal M or a layer of a metal alloy made from metal M or a graphene layer; b) a titanium layer (Ti); c) an aluminum layer (Al); d) a layer of catalyst material(s) for the growth of carbon nanotubes. The invention also concerns a functional substrate (6) comprising a substrate coated with a carbon nanotube (NTC) mat, a production method and the uses of such a functional substrate. ## Claims ### Claim 1 A substrate which is electrically conducting on at least one of its faces, provided with a stack of thin layers comprising at least one layer of catalyst material appropriate for accelerating the growth of carbon nanotubes, wherein the stack comprises the sequence of thin layers deposited in the following order above said at least one electrically conducting face of the substrate: a/ metal layer made of metal M or layer made of metal alloy based on the metal M or layer made of graphene; b/ titanium (Ti) layer; c/ aluminum (Al) layer; d/ layer of material(s) which are catalysts of the growth of carbon nanotubes. ### Claim 2 (depends on 1) The substrate as claimed in claim 1, being a bulk metal substrate. ### Claim 3 (depends on 2) The bulk metal substrate as claimed in claim 2, the metal of the substrate being chosen from copper (Cu), aluminum (Al), stainless steel, nickel (Ni) or platinum (Pt). ### Claim 4 (depends on 1) The substrate as claimed in claim 1, being a substrate coated with one or more thin electrically conducting layers forming said electrically conducting face. ### Claim 5 (depends on 4) The substrate as claimed in claim 4, the thin electrically conducting layers) being chosen from titanium nitride (TiN), tantalum nitride (TaN) or graphene. ### Claim 6 (depends on 4) The substrate as claimed in claim 4, being an electrically insulating substrate, such as a substrate made of silicon (Si) or made of silicon dioxide (SiO2). ### Claim 7 (depends on 1) The substrate as claimed in claim 1, the metal M of the metal layer deposited directly on the electrically conducting face of the substrate being chosen from iron (Fe), chromium (Cr), nickel (Ni), cobalt (Co) or palladium (Pd), and also from all the binary, ternary or quaternary alloys between these metals. ### Claim 8 (depends on 1) The substrate as claimed in claim 1, the material(s) which is(are) catalyst(s) of the growth of the carbon nanotubes (CNTs) of the layer of the top of the stack being chosen from iron (Fe), chromium (Cr), nickel (Ni), cobalt (Co) or palladium (Pd), and also from all the binary, ternary or quaternary alloys between these metals. ### Claim 9 (depends on 1) The substrate as claimed in claim 1, the layer deposited directly on the electrically conducting face of the substrate and the layer of material which is a catalyst of the growth of carbon nanotubes being composed of the same material. ### Claim 10 (depends on 1) The substrate as claimed in claim 1, the thickness of the layer deposited directly on the electrically conducting face of the substrate being between 1 and 20 nm. ### Claim 11 (depends on 1) The substrate as claimed in claim 1, the thickness of the Ti layer being between 2 and 10 nm. ### Claim 12 (depends on 1) The substrate as claimed in claim 1, the thickness of the Al layer being between 2 and 10 nm. ### Claim 13 (depends on 1) The substrate as claimed in claim 1, the thickness of the layer of materials which are catalysts of the growth of carbon nanotubes being between 0.2 and 5 nm. ### Claim 14 (depends on 1) The substrate as claimed in claim 1, the stack being as follows: bulk substrate made of copper or of aluminum/Fe/Ti/Al/Fe, the iron (Fe) layer directly in contact with the bulk substrate having a thickness of between 1 and 10 am. ### Claim 15 (depends on 1) The substrate as claimed in claim 1, the stack being as follows: bulk substrate made of stainless steel/Ti/Al/Fe. ### Claim 16 (depends on 1) The substrate as claimed in claim 1, the stack being as follows: substrate made of titanium nitride (TiN) or tantalum nitride (TaN) in the form of thin layers/Fe/Ti/Al/Fe, the iron (Fe) layer directly in contact with the substrate having a thickness of between 10 and 20 nm. ### Claim 17 (depends on 1) The substrate as claimed in claim 1, the stack being as follows: bulk substrate covered with one or more layers made of graphene/Fe/Ti/Al/Fe, the iron (Fe) layer directly in contact with the graphene having a thickness of between 1 and 10 nm. ### Claim 18 (depends on 1) A functional substrate comprising a substrate as claimed in claim 1 coated with a mat of carbon nanotubes (CNTs). ### Claim 19 (depends on 18) The functional substrate as claimed in claim 18, the CNTs density being greater than 1012/cm2, indeed even 1013/cm2. ### Claim 20 (depends on 1, 18) A process for the preparation of a functional substrate as claimed in claim 18, according to which the following stages are carried out: preparation, by vacuum evaporation, of the stack of thin layers with the metal layer made of metal M or layer made of metal alloy based on the metal M or layer made of graphene (2), on the electrically conducting face of the substrate as claimed in claim 1; growth of mat of carbon nanotubes (CNTs) on the stack according to a chemical vapor deposition (CVD) technique, enhanced or not enhanced by plasma and activated or nonactivated by hot wires (Hot Wire CVD or HWCVD). ### Claim 21 (depends on 20) The process as claimed in claim 20, according to which, before carrying out the growth stage, the layer of catalyst materials is oxidized by means of an air plasma. ### Claim 22 A substrate which is electrically conducting on at least one of its faces, provided with a stack of thin layers comprising at least one layer of catalyst material appropriate for accelerating the growth of carbon nanotubes, wherein the stack comprises the sequence of thin layers deposited in the following order above said at least one electrically conducting face of the substrate: b/ titanium (Ti) layer; c/ aluminum (Al) layer; d/ layer of materials which are catalysts of the growth of carbon nanotubes.