# US 2019/0168485 A1 · Method for Making Porous Graphene Membranes and Membranes Produced Using the Method > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0168485 A1 - Document ID: US20190168485A1 - Status: Published application - Kind: A1 - Application number: 16/308,127 - Filed: 2017-06-09 - Published: 2019-06-06 - Earliest claimed: 2016-06-10 - Assignees: ETH Zurich; Heiq Materials AG - Applicants: ETH Zurich; HeiQ Materials AG - Inventors: Murray Height; Hyung Gyu Park; Kyoungjun Choi - Web page: https://patentgrep.com/patent/US20190168485A1 ## CPC - B32B 9/007: {comprising carbon, e.g. graphite, composite carbon} - A41D 31/102: Waterproof and breathable - B01D 67/0062: {by micromachining techniques, e.g. using masking and etching steps, photolithography} - B01D 67/0072: {by deposition from the gaseous phase, e.g. sputtering, CVD, PVD} - B01D 69/1071: {Woven, non-woven or net mesh} - B01D 69/108: {Inorganic support material} - B01D 71/021: {Carbon} - B01D 71/0211: {Graphene or derivates thereof} - B32B 9/041: {of metal} - C01B 32/186: by chemical vapour deposition [CVD] - C23C 16/26: Deposition of carbon only - B01D 2323/64: Use of a temporary support - B01D 2325/04: Characteristic thickness - B32B 2305/026: Porous - B32B 2307/724: Permeability to gases, adsorption - B32B 2307/7265: Non-permeable - B32B 2437/00: Clothing - B32B 2457/00: Electrical equipment - B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites - C01B 2204/04: Specific amount of layers or specific thickness - C01P 2006/16: Pore diameter - H10D 62/882: {Graphene} - H10P 14/24: using chemical vapour deposition [CVD] - H10P 14/272: {using mask materials other than SiO2 or SiN} - H10P 14/2923: {being conductive materials, e.g. metallic silicides} - H10P 14/3406: {Carbon, e.g. diamond-like carbon} - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - A41D: OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - 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) - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS - H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract Method for making a porous graphene layer of a thickness of less than 100 nm with pores having an average size in the range of 5-900 nm, includes the following steps: providing a catalytically active substrate catalyzing graphene formation under chemical vapor deposition conditions, the catalytically active substrate in or on its surface being provided with a plurality of catalytically inactive domains having a size essentially corresponding to the size of the pores in the resultant porous graphene layer; chemical vapor deposition using a carbon source in the gas phase and formation of the porous graphene layer on the surface of the catalytically active substrate. The pores in the graphene layer are in situ formed due to the presence of the catalytically inactive domains. ## Claims ### Claim 1 A method for making a porous graphene layer having a thickness of less than 100 nm with pores having an average size in the range of 5-900 nm, said method comprising: providing a catalytically active substrate to catalyze the graphene formation under chemical vapor deposition conditions, said catalytically active substrate in or on its surface being provided with a plurality of catalytically inactive domains having a size essentially corresponding to the size of the pores in the resultant porous graphene layer; chemical vapor deposition using a carbon source in the gas phase and formation of the porous graphene layer on the surface of the catalytically active substrate, the pores in the graphene layer in situ being formed due to the presence of the catalytically inactive domains. ### Claim 2 (depends on 1) The method according to claim 1, wherein the catalytically active substrate with the plurality of catalytically inactive domains prior to the step of chemical vapor deposition is subjected to a step of annealing in a chemically reducing environment. ### Claim 3 (depends on 1) The method according to claim 1, wherein said catalytically active substrate with a plurality of catalytically inactive domains is produced by spraying or physical vapor deposition of a catalytically inactive material or of a material catalytically inactivating the substrate and subsequent thermal annealing to form the plurality of catalytically inactive domains. ### Claim 4 (depends on 1) The method according to claim 1, wherein the catalytically active substrate is a substrate comprising e an elemental metal selected from the first group consisting of Cu, Ni, Pt, Ru, Ir, Rh or a mixture thereof, and wherein the catalytically inactive domains are due to the presence of a metal different from said first group in said domains. ### Claim 5 (depends on 1) The method according to claim 1, wherein the catalytically inactive domains have an average size between 5-900 nm. ### Claim 6 (depends on 1) The method according to claim 1, wherein the porous graphene layer has a thickness of less than 50 nm. ### Claim 7 (depends on 1) The method according to claim 1, wherein subsequent to the chemical vapor deposition of the porous graphene layer, the porous graphene layer is removed from the substrate, and subsequent transfer to another substrate. ### Claim 8 (depends on 7) The method according to claim 7, wherein a delaminated porous graphene layer is subsequently attached to a porous substrate on one or both sides of the porous graphene membrane. ### Claim 9 (depends on 7) The method according to claim 7, wherein the substrate is reused for a next manufacturing process of the porous graphene layer. ### Claim 10 (depends on 1) The method according to claim 1, wherein the method is a continuous or a batch process. ### Claim 11 (depends on 1) The method according to claim 1, wherein the pores have an average size of 10-500 nm. ### Claim 12 (depends on 1) The method according to claim 1, wherein, in the step of chemical vapor deposition, the carbon source is provided as a flow mixture of hydrocarbon and hydrogen at a volumetric ratio of 1-1000 parts hydrocarbon per part of hydrogen. ### Claim 13 (depends on 1) The method according to claim 1, wherein, for the making of the substrate on a catalytically active substrate, a metal layer is produced using a metal which is not catalytically active, then, after the pressure is lowered to baseline values at or below 0.0002 Pa, the substrate is first heated to a temperature in the range of 900-1200° C. to anneal in a chemically reducing environment for a time span in the range of 30-120 minutes. ### Claim 14 (depends on 1) Use of a porous graphene layer as produced using the method according to claim 1 as a waterproof and highly breathable membrane for textile applications; water barrier membranes; pressure equalizer membranes for electronics including cell phones and handheld devices; filters; gas separation membranes; and electronic components for conductive, semi-conductive or electricity generating applications. ### Claim 15 (depends on 1) A porous graphene layer as produced using the method according to claim 1, with a thickness of less than 100 nm and with the pores having an average size of 5-900 nm. ### Claim 16 (depends on 1) The method according to claim 1, wherein the catalytically active substrate with the plurality of catalytically inactive domains prior to the step of chemical vapor deposition is subjected to a step of annealing in a chemically reducing hydrogen environment. ### Claim 17 (depends on 1) The method according to claim 1, wherein the catalytically active substrate is furnished with a plurality of catalytically inactive domains subjected to a step of annealing in a chemically reducing environment, in hydrogen, prior to the step of chemical vapor deposition. ### Claim 18 (depends on 1) The method according to claim 1, wherein the catalytically active substrate with the plurality of catalytically inactive domains prior to the step of chemical vapor deposition is subjected to a step of annealing in a chemically reducing hydrogen environment, and wherein conditions for this annealing are chosen as follows: 50-90 vol-% H2, in an inactive carrier gas, including inert gases including Ar, He and Ne or N2, at a temperature of 900-1200° C., for a time span of 30-120 minutes. ### Claim 19 (depends on 1) The method according to claim 1, wherein the catalytically active substrate with the plurality of catalytically inactive domains prior to the step of chemical vapor deposition is subjected to a step of annealing in a chemically reducing hydrogen environment, and wherein conditions for this annealing are chosen as follows: 70-85 vol-% H2, in an inactive carrier gas selected from the group consisting of Ar, He, Ne, N2, and mixtures thereof, at a temperature of 950-1100° C., at a pressure of 1 to 100000 Pa for a time span of 30-120 minutes. ### Claim 20 (depends on 1) The method according to claim 1, wherein the catalytically active substrate with the plurality of catalytically inactive domains prior to the step of chemical vapor deposition is subjected to a step of annealing in a chemically reducing hydrogen environment, and wherein conditions for this annealing are chosen as follows: 70-85 vol-% H2, in an inactive carrier gas, at a temperature of 950-1100° C., at a pressure of 10-100 Pa for a time span of 60-90 minutes. ### Claim 21 (depends on 1) The method according to claim 1, wherein said catalytically active substrate with a plurality of catalytically inactive domains is produced by spraying or physical vapor deposition, in the form of sputtering, e-beam evaporation or particle spraying, of a catalytically inactive material or of a material catalytically inactivating the substrate and subsequent thermal annealing to form the plurality of catalytically inactive domains. ### Claim 22 (depends on 1) The method according to claim 1, wherein the catalytically active substrate is a substrate comprising an elemental metal selected from the first group consisting of Cu, Ni, Pt, Ru, Ir, Rh or a mixture thereof, and wherein the catalytically inactive domains are due to the presence of a metal different from said first group in said domains, wherein the metal different from said first group is selected from the second group consisting of: molybdenum, tungsten, niobium, gold, silver, zirconium, chromium or a mixture/alloy thereof or from metal oxides including aluminium oxide. ### Claim 23 (depends on 1) The method according to claim 1, wherein the catalytically inactive domains have an average size of 10-100 nm. ### Claim 24 (depends on 1) The method according to claim 1, wherein the catalytically inactive domains have an average size of 10-50 nm. ### Claim 25 (depends on 1) The method according to claim 1, wherein the porous graphene layer has a thickness of less than 50 nm and wherein the catalytically inactive domains have an average size of 10-50 nm. ### Claim 26 (depends on 1) The method according to claim 1, wherein the porous graphene layer has a thickness of less than 20 nm. ### Claim 27 (depends on 1) The method according to claim 1, wherein the porous graphene layer has a thickness of less than 10 nm. ### Claim 28 (depends on 1) The method according to claim 1, wherein the porous graphene layer has a thickness of less than 5 nm. ### Claim 29 (depends on 1) The method according to claim 1, wherein subsequent to the chemical vapor deposition of the porous graphene layer, the porous graphene layer is removed from the substrate, using at least one of a mechanical and an electrochemical method, electrochemical delamination, or disengagement by mechanical actuation, including ultrasonic actuation or thermal actuation, and subsequent transfer to another substrate. ### Claim 30 (depends on 1) The method according to claim 1, wherein subsequent to the chemical vapor deposition of the porous graphene layer, the porous graphene layer is removed from the substrate via van der Waals peeling, and subsequent transfer to another substrate. ### Claim 31 (depends on 7) The method according to claim 7, wherein delaminated porous graphene layer is subsequently attached to a porous substrate on one or both sides of the porous graphene membrane, wherein the porous substrate is selected from the group of: fabric of woven, non-woven or knit construction, and metal or ceramic mesh, or foam. ### Claim 32 (depends on 1) The method according to claim 1, wherein the pores have an average size of 20-100 nm. ### Claim 33 (depends on 1) The method according to claim 1, wherein a density of the pores is 0.1-100×1010 cm2. ### Claim 34 (depends on 1) The method according to claim 1, wherein a density of the pores is 0.1-500×1010 cm2. ### Claim 35 (depends on 1) The method according to claim 1, wherein a density of the pores is 0.5-150×1010 cm2. ### Claim 36 (depends on 1) The method according to claim 1, wherein a density of the pores is 1-10×1010 cm2. ### Claim 37 (depends on 1) The method according to claim 1, wherein, in the step of chemical vapor deposition, the carbon source chosen to be saturated or unsaturated hydrocarbons is provided as a flow mixture of hydrocarbon and hydrogen at a volumetric ratio of 1-1000 parts hydrocarbon per part of hydrogen. ### Claim 38 (depends on 1) The method according to claim 1, wherein, in the step of chemical vapor deposition, the carbon source, chosen to be methane, ethane, ethylene, acetylene and mixtures thereof, is provided as a flow mixture of hydrocarbon and hydrogen at a volumetric ratio of 1-10 parts hydrocarbon per part of hydrogen. ### Claim 39 (depends on 1) The method according to claim 1, wherein, in the step of chemical vapor deposition, the carbon source, chosen to be methane, ethane, ethylene, acetylene and mixtures thereof, is provided as a flow mixture of hydrocarbon and hydrogen at a volumetric ratio of 1-10 parts hydrocarbon per part of hydrogen, and wherein the hydrocarbon and hydrogen gases are mixed with a carrier gas including argon or nitrogen or are used at 1-20 vol-% in concentration mixed with hydrogen at an overall pressure in the range of 10-10000 Pa. ### Claim 40 (depends on 1) The method according to claim 1, wherein, in the step of chemical vapor deposition, the carbon source, chosen to be methane, ethane, ethylene, acetylene and mixtures thereof, is provided as a flow mixture of hydrocarbon and hydrogen at a volumetric ratio of 600-800 parts hydrocarbon per part of hydrogen, wherein the hydrocarbon and hydrogen gases are mixed with a carrier gas including argon or nitrogen or are used at 1-20 vol-% in concentration mixed with hydrogen at an overall pressure in the range of 10-200 or 80-120 Pa, and wherein a CVD process is carried out at a temperature of 300-1200° C., for a time span of 1-12 hours. ### Claim 41 (depends on 1) The method according to claim 1, wherein, in the step of chemical vapor deposition, the carbon source, chosen to be methane, ethane, ethylene, acetylene and mixtures thereof, is provided as a flow mixture of hydrocarbon and hydrogen at a volumetric ratio of 1-20, wherein a CVD process is carried out a temperate of 300-800° C. for a time span of 2-4 hours. ### Claim 42 (depends on 1) The method according to claim 1, wherein, for making of the substrate on a catalytically active substrate in the form of a copper foil, a metal layer is produced using tungsten metal which is not catalytically active, and wherein such a contiguous layer which is 1-10 nm thick is in a first step produced via physical vapor deposition at a chamber pressure from 2.0×10−5 to 3.0×10−4 Pa. ### Claim 43 (depends on 1) The method according to claim 1, wherein, for making of the substrate on a catalytically active substrate in the form of a copper foil, a metal layer is produced using tungsten metal which is not catalytically active, wherein such a contiguous layer which is 1-10 nm thick is in a first step produced via physical vapor deposition at a chamber pressure from 2.0×10−5 to 3.0×10−4 Pa, and wherein a deposition rate of 0.01-1.0 Å/s is used. ### Claim 44 (depends on 1) A porous graphene layer as produced using the method according to claim 1, with a thickness of less than 100 nm and with the pores having an average size of 5-900 nm for use as a waterproof and highly breathable membrane for textile applications; barrier membranes or pressure equalizer membranes for electronics including cell phones and handheld devices; filters; gas separation membranes; electronic components for conductive, semi-conductive and/or electricity generating applications.