# US 11,993,850 B2 · Three-dimensional laser-assisted printing of structures from nanoparticles > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,993,850 B2 - Document ID: US11993850B2 - Status: Granted - Kind: B2 - Application number: 17/170,405 - Filed: 2021-02-08 - Published: 2021-06-03 - Granted: 2024-05-28 - Earliest claimed: 2018-08-08 - Assignees: The Curators of the University of Missouri - Applicants: The Curators of the University of Missouri - Inventors: Heng Pan; Chinmoy Podder; Wan Shou; Xiaowei Yu - Web page: https://patentgrep.com/patent/US11993850B2 ## CPC - C23C 18/127: {Preformed particles} - B22F 1/0545: Dispersions or suspensions of nanosized particles - B22F 10/25: Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS] - B28B 1/001: {Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material (selective deposition modelling of metallic powder B22F10/00; rapid manufacturing of 3D objects in general and in particular of plastics B29C64/00)} - B33Y 10/00: Processes of additive manufacturing - B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials - C23C 18/1295: {with after-treatment of the deposited inorganic material} - C23C 18/143: {Radiation by light, e.g. photolysis or pyrolysis} - B22F 2304/054: Particle size between 1 and 100 nm - C23C 18/08: characterised by the deposition of metallic material - 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) - B22F: WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER (making alloys by powder metallurgy C22C); APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER - B28B: SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER (foundry moulding B22C; working stone or stone-like material B28D; shaping of substances in a plastic state, in general B29C; making layered products not composed wholly of these substances B32B) - B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract A method for manufacturing a component comprising bombarding nanoparticles in a dispersion with a laser to transform the ligand and cause the nanoparticles to drop out of the dispersion and deposit onto a substrate; and bombarding additional nanoparticles in the dispersion with the laser to transform the ligand and cause the nanoparticles to drop out of the dispersion and deposit onto the nanoparticles previously deposited out of the dispersion. ## Claims ### Claim 1 A method for manufacturing a metal-containing component comprising: bombarding nanoparticles comprising metal nanoparticles and a ligand complexed therewith in a dispersion with a laser to transform the ligand and cause the metal nanoparticles to drop out of the dispersion and deposit onto a substrate; and bombarding additional nanoparticles in the dispersion with the laser to transform the ligand and cause the metal nanoparticles to drop out of the dispersion and deposit onto the metal nanoparticles previously deposited out of the dispersion. ### Claim 2 (depends on 1) The method of claim 1 wherein the laser is a femtosecond laser. ### Claim 3 (depends on 1) The method of claim 1 wherein the laser has a pulse repetition rate from about 120 kHz to about 27 MHz. ### Claim 4 (depends on 1) The method of claim 1 wherein the metal nanoparticles comprise: (a) at least one metal selected the metals of groups 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, and combinations thereof; (b) a transition metal or a combination of transition metals; (c) a noble metal or a combination of noble metals; (d) Fe, Co, Ni, Cu, Pd, Ag, Sn, Pt, Au, or a combination thereof; or (f) bimetallic CoPt, FePt, or Co50Ni50. ### Claim 5 (depends on 1) The method of claim 1 wherein the nanoparticles comprise M(0)-ligand complexes, where M(0) is one or more metals at neutral charge or approximately neutral charge. ### Claim 6 (depends on 5) The method of claim 5 wherein M(0) comprises: (a) at least one metal selected the metals of groups 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, and combinations thereof; (b) a transition metal or a combination of transition metals; (c) a noble metal or a combination of noble metals; (d) Fe, Co, Ni, Cu, Pd, Ag, Sn, Pt, Au, or a combination thereof; or (f) bimetallic CoPt, FePt, or Co50Ni50. ### Claim 7 (depends on 1) The method of claim 1 wherein the dispersion is essentially free of metal salts. ### Claim 8 (depends on 1) The method of claim 1 wherein the dispersion is essentially free of a dye or reducing agent for metal ions. ### Claim 9 (depends on 1) The method of claim 1 wherein deposition of the metal nanoparticle occurs in the absence of a dye, reducing agent for metal ions, or a dye terminated ligand. ### Claim 10 (depends on 1) The method of claim 1 wherein metal ions are not reduced in the dispersion. ### Claim 11 (depends on 1) The method of claim 1, further comprising feeding the dispersion to a reaction vessel, wherein the metal nanoparticles are the only type of metal-containing component present in the dispersion fed to the reaction vessel. ### Claim 12 (depends on 1) The method of claim 1 wherein the dispersion comprises a liquid carrier comprising an organic solvent. ### Claim 13 (depends on 1) The method of claim 1 wherein the dispersion has a concentration of the nanoparticles that is from about 0.01 wt % to 20 wt %, and/or the dispersion comprises a liquid carrier and has a liquid carrier concentration of from about 80 wt % to 99.99 wt %. ### Claim 14 (depends on 1) The method of claim 1 wherein the dispersion consists essentially of the nanoparticles and the liquid carrier. ### Claim 15 (depends on 1) The method of claim 1 wherein the ligand transformation is caused by laser-driven hot-carrier effect. ### Claim 16 (depends on 1) The method of claim 1 wherein the nanoparticles have a particle size of less than 10 nm. ### Claim 17 (depends on 1) The method of claim 1 wherein the ligand comprises at least one from the group selected from among thiols, amines, carboxylic acids, phosphines, and phosphine oxides. ### Claim 18 (depends on 1) The method of claim 1 wherein the ligand comprises a fatty acid amine. ### Claim 19 (depends on 1) The method of claim 1 wherein the ligand comprises oleylamine, octadecylamine, and hexadecylamine. ### Claim 20 (depends on 1) The method of claim 1 wherein the substrate comprises at least one selected from the group consisting of glass, ceramics, silicon, conductive, metal, and polymer substrates. ### Claim 21 (depends on 1) The method of claim 1, further comprising: spincoating nanoparticles onto the substrate prior to said bombarding nanoparticles with the laser, and/or continuing to bombard additional nanoparticles in the dispersion with the laser to transform the ligand and cause the metal nanoparticles to drop out of the dispersion and deposit onto the metal nanoparticles previously deposited out of the dispersion to grow a three-dimensional structure. ### Claim 22 A method for manufacturing a component comprising: bombarding nanoparticles and a ligand complexed therewith in a dispersion with a laser to transform the ligand and cause the nanoparticles to drop out of the dispersion and deposit onto a substrate; and bombarding additional nanoparticles in the dispersion with the laser to transform the ligand and cause the nanoparticles to drop out of the dispersion and deposit onto the nanoparticles previously deposited out of the dispersion. ### Claim 23 (depends on 22) The method of claim 22 wherein the nanoparticles comprise at least one of: (a) semiconductor nanoparticles, (b) dielectric nanoparticles; and/or (c) metal oxide nanoparticles.