# US 10,865,477 B2 · Method and system for the localized deposit of metal on a surface > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,865,477 B2 - Document ID: US10865477B2 - Status: Granted - Kind: B2 - Application number: 15/018,148 - Filed: 2016-02-08 - Published: 2017-08-10 - Granted: 2020-12-15 - Earliest claimed: 2016-02-08 - Assignees: Illinois Tool Works Inc. - Applicants: Illinois Tool Works Inc - Inventors: Zhigang Xiao - Web page: https://patentgrep.com/patent/US10865477B2 ## CPC - C23C 16/455: characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber - C23C 16/047: {using irradiation by energy or particles} - C23C 16/14: Deposition of only one other metal element - C23C 16/45514: {Mixing in close vicinity to the substrate} - H10P 14/432: {using selective deposition} - Y02P 10/25: Process efficiency - 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) - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract The present disclosure is directed to a method and system for the localized deposition of a metal layer on a surface. The method involves introducing at least two gaseous reactants to a substrate surface that is locally heated by a laser. The surface is heated to a temperature at which the gaseous reactants undergo a reaction that results in metal crystal growth on the substrate surface. The reaction is maintained for a desired period of time and under desired conditions to produce a localized deposit of a metal layer on the heated zone of the substrate. In some embodiments, the gas outlets and the laser may be moved in a controlled manner so that a metal layer may be deposited in a desired pattern on the substrate surface. ## Claims ### Claim 1 A method for the localized deposition of a metal layer comprising: (a) introducing a first gaseous reactant, the first gaseous reactant comprising a metal-containing precursor, and a second gaseous reactant to a surface of a substrate, wherein the first and second gaseous reactants are introduced to the surface of the substrate through one or more gas outlets; and (b) directing a laser against a location on the substrate surface that is adjacent to the one or more gas outlets, thereby heating a zone of the surface to a temperature at which the first and second gaseous reactants react to produce a metal and an acidic byproduct, such that a metal layer is deposited on the heated zone of the substrate surface; (c) moving the one or more gas outlets and the laser in a controlled manner so as to deposit the metal layer in a desired pattern on the substrate surface; and repeating (a), (b) and (c) to perform three-dimensional printing of a plurality of layers of the metal onto the substrate, in which the surface onto which at least one subsequent metal layer is deposited on a prior metal layer deposited by (a) and (b), each of the plurality of the layers comprising a corresponding pattern and the one or more gas outlets and the laser follow the pattern to deposit the corresponding layer, wherein the metal deposited on the surface of the substrate such that the metal layer can be separated from the substrate. ### Claim 2 (depends on 1) The method of claim 1, wherein the one or more gas outlets are configured to introduce a mixture of the first and second gaseous reactants substantially evenly across the heated zone of the surface. ### Claim 3 (depends on 1) The method of claim 1, wherein the first and second gaseous reactants are introduced through a single outlet, the diameter of the outlet being less than the diameter of the heated zone. ### Claim 4 (depends on 3) The method of claim 3, wherein the outlet has a diameter that is between about 50% and about 95% of the diameter of the heated zone. ### Claim 5 (depends on 1) The method of claim 1, in which the first gaseous reactant and the second gaseous reactant are introduced through separate gas outlets. ### Claim 6 (depends on 1) The method of claim 1, wherein the heated zone has a diameter that is less than 10 mm. ### Claim 7 (depends on 1) The method of claim 1, wherein the heated zone has a diameter that is less than 5 mm. ### Claim 8 (depends on 1) The method of claim 1, wherein the one or more gas outlets are positioned between about 3 mm and about 20 mm above the substrate surface. ### Claim 9 (depends on 8) The method of claim 8, wherein the one or more gas outlets are positioned between about 5 mm and about 10 mm above the substrate surface. ### Claim 10 (depends on 1) The method of claim 1, wherein the metal of the metal-containing precursor is a transition metal. ### Claim 11 (depends on 1) The method of claim 1, wherein the metal-containing precursor has the formula MXn, in which: M is a transition metal, X is a halogen, and n is an integer selected from the group consisting of 5 and 6; and the second gaseous reactant is H2. ### Claim 12 (depends on 11) The method of claim 11, in which the transition metal is selected from the group consisting of tungsten (W), molybdenum (Mo), tantalum (Ta), titanium (Ti), rhenium (Re), niobium (Nb), nickel (Ni), and hafnium (Ht); and the halogen is selected from the group consisting of fluorine, chlorine, and bromine. ### Claim 13 (depends on 11) The method of claim 11, in which the metal-containing precursor is selected from the group consisting of tungsten hexafluoride and tungsten hexachloride. ### Claim 14 (depends on 1) The method of claim 1, wherein the deposited metal layers are monocrystalline. ### Claim 15 (depends on 14) The method of claim 14, wherein the deposited metal layers are monocrystalline tungsten. ### Claim 16 (depends on 1) The method of claim 1, in which the substrate is a silicon wafer. ### Claim 17 (depends on 1) The method of claim 1, further comprising cooling, with a cooling system, at least one of: a gas outlet through which at least one of the first gaseous reactant or the second gaseous reactant are introduced; or a gas line through which at least one of the first gaseous reactant or the second gaseous reactant are delivered to the gas outlet. ### Claim 18 (depends on 1) The method of claim 1, wherein the surface of the substrate is heated to a temperature of at least 300 degrees Celsius. ### Claim 19 A method for the localized deposition of a metal layer comprising: (a) introducing a first gaseous reactant, the first gaseous reactant comprising a metal-containing precursor, and a second gaseous reactant to a surface of a substrate, wherein the first and second gaseous reactants are introduced to the surface of the substrate through one or more gas outlets; and (b) directing a laser against a location on the substrate surface that is adjacent to the one or more gas outlets, thereby heating a zone of the surface to a temperature at which the first and second gaseous reactants react, such that a metal layer is deposited on the heated zone of the substrate surface, wherein the metal deposited on the surface of the substrate such that the metal layer can be separated from the substrate. ### Claim 20 (depends on 19) The method of claim 19, further comprising cooling, with a cooling system, at least one of: a gas outlet through which at least one of the first gaseous reactant or the second gaseous reactant are introduced; or a gas line through which at least one of the first gaseous reactant or the second gaseous reactant are delivered to the gas outlet.