# US 9,005,694 B2 · Method for producing thin layers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,005,694 B2 - Document ID: US9005694B2 - Status: Granted - Kind: B2 - Application number: 13/699,050 - Filed: 2011-05-20 - Published: 2013-05-23 - Granted: 2015-04-14 - Earliest claimed: 2010-05-21 - Assignees: Centre National de la Recherche Scientifique (CNRS); Universite De Strasbourg - Applicants: Gabriela Popa; Gero Decher; Fouzia Boulmedais; Olivier Felix; Pierre Schaaf; Jean-Claude Voegel; Joseph Hemmerle; Peng Zhao - Inventors: Gabriela Popa; Gero Decher; Fouzia Boulmedais; Olivier Felix; Pierre Schaaf; Jean-Claude Voegel; Joseph Hemmerle; Peng Zhao - Web page: https://patentgrep.com/patent/US9005694B2 ## CPC - B05D 1/02: performed by spraying - B05D 1/34: Applying different liquids or other fluent materials simultaneously - B05D 1/36: Successively applying liquids or other fluent materials, e.g. without intermediate treatment - C23C 18/1204: {inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds} - B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02) - 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) ## Abstract The invention relates to a method for providing organic, semi-organic, mineral, inorganic and hybrid thin layers and thin layers containing nanoparticles, by simultaneous or alternate spraying of solutions of reactive partners (that is polymer/polymer interacting by hydrogen bonding, polyelectrolyte/small oligo-ion, inorganic compounds, etc.) on the surface of a solid substrate. ## Claims ### Claim 1 Method for the continuous deposition on a substrate of a thin homogeneous layer of a product obtained from at least two reactive partners, characterised in that it involves the: simultaneous continuous spraying, or alternate continuous spraying of two reactive partners of inorganic nature, on said substrate, using separate sprayers, of at least two liquids each containing one of the reactive partners or a mixture thereof, such that clouds of droplets are produced containing droplets of micro and nanometric size which interact together mainly at the level of a liquid film of controlled thickness comprised between 0.1 μm and 100 μm that forms on contact with a free surface of the substrate, and wherein the thickness of said thin homogeneous layer of product, formed from said liquid film, is mainly controlled by the duration of said continuous spraying, except where two reactive partners are of polymer nature, interact by electrostatic interactions, and are deposited by simultaneous spraying; wherein the sprayers comprise nozzles arranged so that spraying jets of the liquids from the nozzles arrive at the surface of the substrate along a direction essentially orthogonal with respect to the latter. ### Claim 2 (depends on 1) Method according to claim 1, characterised in that one at least of the reactive partners is of complementary inorganic nature. ### Claim 3 (depends on 1) Method according to claim 1, characterised in that said reactive partners lead to the product to be deposited by chemical reaction. ### Claim 4 (depends on 1) Method according to claim 1, characterised in that said reactive partners lead to the product to be deposited by physical or physical-chemical interaction. ### Claim 5 (depends on 1) Method according to claim 1, characterised in that the reactive partners include a mineral, inorganic, organic or nanoparticle type product, a solvent of said product and a non-solvent of said product. ### Claim 6 (depends on 1) Method according to claim 1, characterised in that the spraying of the different liquids against said substrate is carried out in an alternate manner. ### Claim 7 (depends on 1) Method according to claim 1, characterised in that the spraying of the different liquids against said substrate is carried out in a simultaneous manner. ### Claim 8 (depends on 1) Method according to claim 1, characterised in that the reactive partners are aqueous solutions of complementary inorganic cations and anions. ### Claim 9 (depends on 1) Method according claim 1, characterised in that one of the reactive partners is a small organic molecule, a polymer or a nanoparticle. ### Claim 10 (depends on 1) Method according to claim 1, characterised in that the surface of the substrate and the spraying nozzles are moveable in relation with each other, so as to ensure the deposition of the thin layer on all of the substrate and to improve the homogeneity of the thin layer. ### Claim 11 Method for the continuous deposition on a substrate of a thin homogeneous layer of a product obtained from at least two reactive partners, characterised in that it involves the: simultaneous continuous spraying, or alternate continuous spraying of two reactive partners of inorganic nature, on said substrate, using separate sprayers, of at least two liquids each containing one of the reactive partners or a mixture thereof, such that clouds of droplets are produced containing droplets of micro and nanometric size which interact together mainly at the level of a liquid film of controlled thickness comprised between 0.1 μm and 100 μm that forms on contact with a free surface of the substrate, and wherein the thickness of said thin homogeneous layer of product, formed from said liquid film, is mainly controlled by the duration of said continuous spraying, except where two reactive partners are of polymer nature, interact by electrostatic interactions, and are deposited by simultaneous spraying; wherein the sprayers comprise nozzles; wherein a screen is provided with an opening calibrated to select central parts of spraying jets from the nozzles and avoid the contamination of the surface by the edges of the jets. ### Claim 12 (depends on 1) Method according to claim 1, characterised in that a screen is interposed between the nozzle(s) and an overlapping point of the spraying jets provided with at least one opening passing alternatively in front of the spraying jets to control the collisions and interactions of sprayed droplets. ### Claim 13 (depends on 1) Method according to claim 1, characterised in that the solubility of the material of the thin layer deposited is lower than the solubility of the reactive partners in the liquid spraying solutions. ### Claim 14 (depends on 1) Method according to claim 1, characterised in that the interaction between the reactive partners is controlled by determination of one at least of the following adjustment parameters: concentration of the reactive partners in each liquid and viscosity of each of the spraying liquids containing the reactive partners; composition and nature of the solvent present in each of the liquids sprayed; temperature of the liquids sprayed; dimension, density, speed and polydispersity of the droplets as a function of the geometry and the nature of the spraying nozzles; variation of the angles at the tip of the dispersion cones of the spraying jets; distance between the nozzles and the surface of the substrate to coat; slope of said surface with respect to the main axis of the spraying jets; flow rate of the spraying jets of the different liquids; flow rate of the carrier gas used for the sprayings; nature, temperature, flow rate and/or pressure of the carrier gas used for the sprayings; nature of the solid support. ### Claim 15 (depends on 1) Method according to claim 1, characterised in that, prior to the deposition of said thin layer, the surface of the substrate to coat is rendered adhesive, by adsorption of PEI, by surface nucleation or by mineralisation of said substrate. ### Claim 16 (depends on 1) Method according to claim 1, characterised in that it is used for depositing a thin layer of different crystals selected from calcium phosphate, calcium fluoride, calcium oxalate, Prussian blue, silver chloride, iron phosphate, copper sulphide (CuS), zinc sulphide (ZnS), cadmium sulphide, indium sulphide, tin sulphide, lead sulphide, arsenic sulphide, antimony sulphide, molybdenum disulphide, manganese sulphide, iron sulphide (FeS2), cobalt sulphide, nickel sulphide and lanthanum sulphide, copper selenide (Cu2Se), silver selenide, zinc selenide, antimony selenide, indium selenide, cadmium selenide, bismuth selenide, lanthanum selenide, copper tellurate, cadmium tellurate, indium tellurate, lanthanum tellurate, copper oxide, zinc oxide, manganese oxide, cerium oxide, copper and indium sulphide, cadmium and zinc sulphide, cadmium and indium sulphide, the composites zinc sulphide/bismuth sulphide, bismuth selenide/antimony, and selenide. ### Claim 17 (depends on 1) Method according to claim 1, characterised in that the substrate is a bio-material. ### Claim 18 (depends on 1) Method according to claim 1, characterised in that the thin layer deposited moreover comprises a substance of interest selected from antibiotics, anti-inflammatory agents, antibacterial agents, anticancer agents, DNA, RNA, and plasmids. ### Claim 19 (depends on 1) Method according to claim 1, characterised in that the thin layer deposited further comprises a substance used in catalysis, in optics, or in optoelectronics, or has magnetic properties. ### Claim 20 Method for the continuous deposition on a substrate of a thin homogeneous layer of a product obtained from at least two reactive partners, characterised in that it involves the: simultaneous continuous spraying, or alternate continuous spraying of two reactive partners of inorganic nature, on said substrate, using separate sprayers comprising nozzles, of at least two liquids each containing one of the reactive partners or a mixture thereof, such that clouds of droplets are produced containing droplets of micro and nanometric size which interact together mainly at the level of a liquid film of controlled thickness comprised between 0.1 μm and 100 μm that forms on contact with a free surface of the substrate, and wherein the thickness of said thin homogeneous layer of product, formed from said liquid film, is mainly controlled by the duration of said continuous spraying, except where two reactive partners are of polymer nature, interact by electrostatic interactions, and are deposited by simultaneous spraying; wherein the sprayers comprise nozzles; wherein a screen is interposed between the nozzle(s) and an overlapping point of spraying jets from the nozzles provided with at least one opening passing alternatively in front of the spraying jets to control the collisions and interactions of sprayed droplets.