Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/34—Applying different liquids or other fluent materials simultaneously
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • 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
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds

Definitions

• the present invention relates to a novel process for obtaining organic, inorganic, mineral, hybrid or nanoparticle thin films by alternating or simultaneous sputtering of different solutions.
• spraying is used for various industrial applications: automobile industry, food industry, chemical industry, paper industry, electronics industry, etc.
• Spraying is a complex technique found in industry and in nature (rain, waterfalls, in the oceans). It is the subject of numerous scientific publications and patents. This important area of engineering has pushed theorists to develop models to describe the phenomenon of spraying and engineers to conduct different studies (change of key parameters for spraying: shape / diameter of the nozzle, liquid-gas mixture, adaptation of the spray for a precise application, characterization of the jets according to several methods, find other fields of application for the spraying).
• spray-aerosols that can vaporize a liquid by the pressurized gas that is in the aerosol
• sprays delivered by a carrier gas it is necessary to to distinguish the environmental gas playing a passive role for example for single-component nozzles and the carrier gas playing an active role for nozzles with 2 or more compounds
• the liquid-gas mixture can be done in different ways depending on the geometry of the nozzle, by generating a rotating device sprayer, electrostatic spraying, ultrasonic spraying, etc.
• the techniques for implementing all these nozzles are well known to those skilled in the art. For example, the presence of gas is not mandatory in certain specific cases. However, more commonly the invention is at atmospheric pressure or reduced pressure.
• the spraying method has already been used to obtain polyelectrolyte multilayers. It is much faster than the dip method in the case of nano-thin layers of polyelectrolytes.
• the alternating spray multilayer construction is already known (see WO 99/35520 and US Pat.
• the present invention proposes to use simultaneous or alternating spraying to obtain thin organic, inorganic, mineral, hybrid or nanoparticle-containing layers.
• the methods used to obtain thin layers of materials are essentially chemical vapor deposition ("CVD” or “chemical vapor deposition” in English), physical vapor deposition (“PVD” or “physical vapor deposition” in English). English), molecular beam epitaxy, plasma deposition, pulsed laser deposition, sol-gel deposition, electrochemical deposition or electrostatic deposition.
• the thin layers are obtained using external factors: either by heating the substrate ("Versality of chemical pyrolisis deposition", Patil PS, Materials Chemistry and Physics, Volume 59, Issue 3, June 15, 1999, Pages 185-198, either by evaporating the solutions (CVD), or by using lasers ("pulsed laser deposition”), etc.
• a particularly interesting technique for the production of a wide variety of inorganic thin films is the well-described Successiv Ionic Layer Adsorption and Reaction (SILAR) method (Nicolau, YF Appl., Sci., 1985, 22-3, 1061- 1074, US 4675207, Nicolau, YF et al., J. Cryst., Growth, 1988, 92, 128-142, Pathan, HM, et al., Bull, Mater Sci., 2004, 27 (2), 85-111. ).
• SILAR Successiv Ionic Layer Adsorption and Reaction
• the CVD spraying method for example, has already been used for the deposition of conductive thin films for microelectronics (Highly-conducting indium-tin-oxide transparent films manufactured by spray CVD using ethanol solution of indium (III) chloride and tin (II) chloride, "Sawada Y. et al., Thin Solid Films, Volume 409, Issue 1, 22 April 2002, Pages 46-50 A solution of indium chloride with different percentages of tin chloride was sprayed with an atomizer on a substrate heated to 350 ° C used in the cosmetics industry.
• No. 5,215,789 also describes a method for depositing inorganic materials on a substrate. This process consists in producing positively charged ions and migrating them in a negatively charged zone. A substrate is placed between the two areas, and this results in a uniform deposit of a thin layer of a coating material on the surface of the substrate that interferes with the passage of the ionized flux. The deposit is made in a vacuum chamber.
• a colloidal suspension is forced through an ultrasonic nebulizer, which sprays a fine "mist of particles" onto a heated substrate.
• the coating can be dense or porous, with a thickness of 1 to several hundred microns.
• the invention described in WO 00/39358 allows the preparation of systems requiring durable and chemically resistant coatings or coatings having other specific chemical or physical properties.
• this method is particularly useful for depositing ceramic coatings.
• dense ceramic coatings on porous substrates provide improved performance electrodes in devices such as fuel cells.
• a supercritical fluid can be used. This is described in PCT Patent Application WO 85/00993. It is reported in this application that the resulting solution is high in pressure and projected through an orifice in a region of relatively low pressure. The spray thus formed allows the coating of a substrate and the low pressure makes it possible, by evaporation of the solvent, to avoid any agglomeration bonded to said solvent. This device can also be used to recover a fine powder.
• the object of the present application makes it possible to obtain thin layers by alternating or simultaneous sputtering of the reaction partner solutions while minimizing or even eliminating some of the disadvantages described above.
• the so-called “layer by layer” method (also known as “LbL” technique), which is applied predominantly with polyanions and polycations, has thus been extended in the present invention by means of spraying solutions, preferably aqueous.
• the method according to the present invention is based on the simultaneous sputtering of several solutions containing said partners. reactions on the surface of a substrate.
• the thin layers obtained by the process according to the present invention can be amorphous, crystalline or polycrystalline with variable density and porosity.
• the thin layer obtained is rather amorphous.
• the thin layer obtained is rather polycrystalline.
• the process according to the present invention applies not only to polyanions and polycations, but also to many other types of reaction partners: oppositely charged polyelectrolytes and oligo-ions, polymers interacting via hydrogen bonds, polyelectrolytes with nanoparticles , and even complementary inorganic compounds.
• the general condition to be observed for the formation of thin layers according to the present invention is the rapid interaction between the reaction partners, allowing them to deposit / crystallize / precipitate rapidly on the surface of the substrate.
• the rapid formation of certain inorganic or polymer-based complexes for example is therefore particularly suitable for the process of the present invention. This is explained by fast physicochemical interactions, such as, for example, the formation of electrostatic bonds.
• the diversity of the nature of the thin layers that can be formed by the process according to the present invention is a major advantage.
• the method according to the present invention is extremely convenient to use and allows to deposit thin layers on large substrate surfaces.
• the extreme homogeneity of the thin films produced by the process of the present invention has been demonstrated by the observation of optical interference in visible light. This property allows their application in the manufacture of various devices, for example optical, or simply in scientific studies.
• the uniform color of the thin layers exposed to white light indicates a constant refractive index and therefore a uniform thickness, said thickness of the thin layer typically reaching from a few hundred nanometers to several tens of microns, depending on the spraying time (of a few seconds to several tens of minutes).
• the method of the present invention has the advantage of forming thin layers very rapidly. In a few minutes it is possible to reach micrometric thicknesses.
• the technique described in the present application is based on the use of aqueous solutions, "ecological" method with no other solvent than water.
• the spraying method according to the present invention is easily used for covering large areas with homogeneous layers.
• a great originality of the process according to the present invention stems from the use of at least two soluble aqueous inorganic solutions at room temperature which will react after spraying to give a layer of inorganic crystals. Solutions are sprayed on a surface and their mixture leads to the formation of inorganic thin layers.
• the spraying can be carried out according to two modes: the alternating spraying of the solutions or the simultaneous spraying of the solutions. These two approaches open up great prospects for many applications.
• the present invention is a reproducible method, easy to put into practice with aqueous solutions and an atomizer which leads to a thin layer whose thickness can vary according to different parameters (spraying time, concentration, type of atomizer, gas bearer or not ..).
• the transition from the laboratory scale to the industrial scale can be done in an easy way.
• the invention consists of a method of deposition on a substrate of a thin layer of a product obtained from at least two reaction partners.
• the method according to the invention involves the simultaneous or alternating spraying, on said substrate, using separate sprays, of at least two liquids each containing one of the reaction partners (organic, inorganic, mineral or nanoparticles) or a mixture thereof, so that they interact with each other mainly at the level of a liquid film with a controlled thickness of between 0.1 ⁇ m and 100 ⁇ m which is formed in contact with the free surface of the substrate, except for the case where two reaction partners of polymer nature, each of identical chemical nature, interact by electrostatic interactions (1 polyanion and 1 polycation) and are deposited by simultaneous sputtering, and also excluding the case where all the reaction partners are deposited by alternating sputtering, except for the case where at least the two partners are of inorganic nature.
• spray relates to the production of a cloud of droplets, that is to say containing droplets of micro or nanometric size suspended in the gas which contains them and which may optionally transport them, or the space which contains them (in the case of an ultrasonic nozzle).
• a “nozzle” is a device that allows such a spray.
• the droplets can touch within the cloud they form. These collisions can cause inter-droplet coalescence. Thus several (two or more) droplets can gather and mix to form a single droplet.
• film refers to a liquid layer formed on a substrate by spraying according to the present invention.
• the thickness of the liquid layer may be between about ten nanometers and several hundred microns.
• the film comprises one (or more) solvent (s), preferably water, and "solutes", that is to say the reaction partners.
• solvent preferably water
• solutes that is to say the reaction partners.
• the reaction between the reaction partners within the liquid film leads to the formation of a product at a supersaturated concentration which will cling to and settle on the surface of the solid support in the form of a thin layer.
• the method according to the invention makes it possible to obtain a film having a thickness of 0.1 to 50 ⁇ m.
• solvent any product or substance allowing the dissolution of another product.
• solvent molecules participate in the structure of the thin layer. It is possible to vary the viscosity of the solvent in order to modulate the characteristics of the spray (size of the droplets, speed of drainage, speed of the reaction, etc.). For example, adding neutral polymer (s) (i.e. not reacting with the reaction partners) in the solvent can increase the viscosity of the solvent.
• reaction partners any type of chemical entity, atom or molecule, capable of binding to another chemical entity, atom or molecule, identical or different, optionally dissolved in one or more solvents.
• reaction partners of a polymeric nature is understood to mean any organic or non-organic macromolecule constituted by a repeated sequence of identical or different units or monomers, all of which are linked together by covalent bonds.
• controlled thickness it is understood that the thickness of the film is controlled by the sputtering parameters on the substrate.
• a "thin film” according to the present invention is to be distinguished from a liquid film of the present invention. Indeed, a thin layer is preferably free of solvent, unless the latter is involved in the very structure of said thin layer.
• the thin layer is a compact, polycrystalline and / or amorphous layer, which is advantageously free of defects and homogeneous thickness.
• inorganic thin films with variable porosity and degree of crystallinity.
• organic thin films hybrid (organic / inorganic), mineral or nanoparticles.
• free surface it is understood that it is the bare surface of the substrate, that is to say the surface of said substrate can be covered by a liquid film and then a thin layer according to the invention by evaporation / crystallization / precipitation of at least one of the solvents / products contained in the film.
• substrate denotes a solid support on which at least one thin layer according to the invention will be deposited.
• This support can be of any kind, that is to say natural or synthetic, organic, inorganic or inorganic, crystalline, polycrystalline and / or amorphous.
• the substrate may be in motion relative to the spray jets and be micro-agitated by ultrasound.
• polymeric nature according to the present invention is well known to those skilled in the art as being applicable to generally organic or semi-organic substances characterized by the repetition of one or more types of monomeric units.
• the embodiment of the process according to the invention is firstly determined by the choice of the reaction partner (s).
• a particular embodiment according to the present invention the reactants leading to the product to be deposited by physical or physicochemical interaction ⁇ chemical.
• any physical or physico-chemical technique applicable in this case and known to those skilled in the art can be used for the formation of the thin layer. Additional manipulation could consist in the use of laser technology, or in the use of strong magnetic and / or electric fields, the piezoelectric effect, ultrasound, the application of an electrospray, electrochemistry, microwaves, or a simple heat treatment, for example.
• a gas such as nitrogen or an inert gas such as Argon in carrying out the process whether as a carrier gas in the spray, or simply in the chamber where the spray is done, or both.
• a gas such as nitrogen or an inert gas such as Argon
• deposit films according to the present invention by the use for example of ultrasonic nozzles.
• the present invention can be carried out under ambient atmosphere. It is of course also possible to use an oxidizing, reducing or reactive gaseous atmosphere in the implementation of the process of the present invention.
• reaction partner any reaction partner according to the physicochemical and / or physical technique applied.
• Another advantageous method according to the present invention relates to the reaction partners, which reaction partners lead to the product (s) to be deposited by chemical reaction.
• Another advantageous process according to the present invention concerns reaction partners comprising a mineral, inorganic, organic or nanoparticle and two solvents, the first of which is a solvent of said product and the second and a non-solvent of said product.
• At least one of the reaction partners of the process according to the invention is of inorganic nature.
• reaction partners of the process according to the invention are aqueous solutions of complementary inorganic cations and anions.
• a particular embodiment of the process of the present invention is the crystallization of a salt, thus composed of an anion and a cation. It is possible to form this salt from two different pairs of dissolved salts by spraying two separate solutions each containing one of the two salt pairs. The reaction therefore produces a compound that crystallizes according to the equation:
• the pairs (Ani / Cati), (An 2 / Cat 2 ) and (An 2 / Cati) are in solution, while (Ani / Cat 2 ) precipitates or crystallizes, thus forming the thin layer on the surface of the support. Couples in solutions are removed from the surface of the substrate at the same time as the solvent (s), so in most cases by drainage.
• one of the reaction partners of the process according to the invention is a small organic molecule, a polymer or a nanoparticle, with the exception however of the case where two reaction partners of polymer nature, each of identical chemical nature, interact by electrostatic interactions (1 polyanion and 1 polycation) and are deposited by simultaneous sputtering, and also excluding the case where all the reaction partners are deposited by alternating sputtering, except for the case where the two partners are of inorganic nature.
• small organic molecule it is understood molecules whose molecular masses are less than 2000 g. mol -1 and having several sites of interactions (hydrogen bonds, electrostatic interactions, etc.)
• the origin of the polymer may be natural or synthetic.
• the polymer may be organic or semi-organic, of indefinite size or defined, of small size, that is to say of a molecular weight of up to 2000 g. mol -1 , or of a larger size, that is to say of a molecular weight greater than 2000 g. mol -1 .
• the polymer may be a chain of amino acids that form a peptide, a chain of sugars that forms a polysaccharide, a DNA or RNA fragment, a polyacrylate, a polystyrene, the cellulose or a derivative (methyl hydroxypropylcellulose). , for example), etc.
• the compound contains an organic fragment (thus hydrocarbon), and another inorganic part. This is the case of organic complexes of iron and inorganic or metallic nanoparticles, for example.
• the interaction between the reaction partners is advantageously controlled by determining at least one of the following adjustment parameters:
• the following spray nozzles are used:
• gas pressure between 0.1 and 10 bar, preferably between 0.5 and 5 bar, more preferably between 1 and 3 bar,
• Flow rate of the sprayed solutions of between 0.1 and 30 mL / min, preferably between 1 and 25 mL / min, more preferably between 2 and 21 mL / min, more preferably between 3 and 19 mL / min.
• the spraying parameters depend inter alia on the nozzles used.
• the nozzle models mentioned above which have been used in laboratory-scale reactors must be adapted to each case.
• the spray nozzle sizes on an industrial scale are likely to be different from those used at the laboratory scale, the person skilled in the art will be able to adapt the spray parameters in each case.
• the preferred embodiments of the present invention regarding the sputtering criteria are of course applicable to other embodiments of the other technical criteria of the present invention.
• the spraying of the different liquids against said substrate in the process according to the invention can be carried out alternately or simultaneously.
• the spraying of the different liquids on said substrate in the process according to the invention is carried out alternately, only when the reaction partners are of complementary inorganic natures.
• the surface of the substrate and the spray nozzles are relatively movable relative to each other, so as to ensure the deposition of the thin layer on the entire substrate and to improve homogeneity of the thin layer.
• the alternating or simultaneous spraying operation is followed by a heat treatment.
• the spraying according to the present invention can be carried out continuously or it can be interrupted without affecting the integrity of the thin layer obtained at the end of the process. Indeed, it has been noticed that an interruption of the deposit does not influence the growth of the thin layers.
• the same thicknesses of thin layers are obtained, whether said thin layers are produced in a single step or in several steps, the important thing being that the cumulative spraying time is constant, even if the thin layer is dried after each step. This is true for both polymeric, organic and inorganic base coatings. This is a proof of the robustness of the process according to the invention.
• the droplets can meet while they are still suspended in the gas that carries them and / or the space that contains them and coalesce at that moment, or coalesce when they meet the support or the liquid film already formed on the support.
• the mixing which takes place during this coalescence makes it possible to obtain a liquid film of extreme homogeneity in the distribution of the reaction partners, allowing an optimization of the reactions which take place in said film.
• the interest of the present invention lies in the use of small droplets and a thin liquid film to allow rapid mixing of the reaction partners in the liquid film by rapid diffusion (the diffusion and mixing rate are a function inverse of the size of the droplets and the thickness of the liquid film) leading to the growth of the thin layer.
• the melting of the individual droplets with the liquid film leads to a rapid mixing of the solutions containing the reaction partners within the liquid film.
• a continuous renewal of the liquid film is achieved by the present invention.
• the nature of the screen can be in any type of material and any form possible.
• the opening of the additional screen, between the nozzle (s) and the point of overlap of the spray jets, is calibrated.
• the screen can be interposed between the nozzle (s) and the point of recovery of the spray jets by any movement whatsoever.
• the additional screen is inserted between the nozzle (s) and the point of overlap of the spray jets by a rotary movement.
• the screen is said to be rotatable in this particular embodiment.
• the additional screen is inserted between the nozzle (s) and the point of overlap of the spray jets by lateral linear movement on a slide system for example.
• the screen is therefore linear in this particular embodiment. It may be advantageous during the spraying according to the method of the invention to interpose an additional rotary screen between the nozzle (s) and the start point of overlap of the spray jets.
• Said plate on which are sprayed jets of liquid reagents, can be positioned and oriented in any way so as to achieve a thin layer.
• Said plate can be positioned vertically so that the surplus of reaction liquid and / or solvent (s) flow as and when spraying according to the method of the present invention.
• Said plate can also be inclined more or less strongly with respect to the vertical.
• the inclination of said plate with respect to the vertical axis is low for rapid thin film formation reactions or possibly not requiring additional treatment, that is to say at an angle between 0 ° and 45 ° with respect to the vertical axis.
• the inclination of said plate relative to the horizontal axis is low for slow reactions or requiring additional treatment (for example by laser technology), that is to say at an angle between 0 ° and 45 ° to the horizontal axis.
• Air flow control control of the thickness of the liquid film
• the thickness of the formed film is directly related to the imposed air flow.
• spraying an air flow intended to control the thickness of the liquid film that forms in contact with the free surface of the substrate intended to control the thickness of the liquid film that forms in contact with the free surface of the substrate.
• the homogeneity of the film thickness is also influenced by the liquid flow, the nature of the substrate, the viscosity of the liquid (concentration) and the positioning of the nozzles.
• a mono-compound sprayer for example spraying a single liquid under pressure
• a multi-compound sprayer for example a chemical compound in solution in a solvent medium
• a nebulizer involving the spraying of a gas and a liquid
• the quality of the spray and therefore of the liquid film obtained is also determined by the positioning of the nozzles of the sprayers (covering of the spray jets).
• the nozzles are arranged in such a way that the spray jets reach the surface of the substrate in a direction substantially orthogonal to the latter.
• gas pressure between 0.1 and 10 bar, preferably between 0.5 and 5 bar, more preferably between 1 and 3 bar,
• flow rate of the sprayed solutions of between 0.1 and 30 ml / min, preferably between 1 and 25 ml / min, more preferably between 2 and 21 ml / min, more preferably between 3 and 19 ml / min,
• Spray gas used compressed air or nitrogen.
• the spraying parameters depend inter alia on the nozzles used.
• the nozzle models mentioned above which have been used in laboratory-scale reactors must be adapted to each case.
• the sizes and characteristics of the spray nozzles on an industrial scale are probably different from those used at the laboratory scale, the person skilled in the art will be able to adapt the spray parameters in each case.
• the thickness of the film obtained in contact with the free surface of the substrate according to the method of the present invention may be between about ten nanometers and several hundred microns.
• the liquid film obtained in contact with the free surface of the substrate according to the process of the present invention is of a controlled thickness typically between 0.1 ⁇ m and 100 ⁇ m, more advantageously between 0.1 and 50 ⁇ m, even more advantageously between 0.5 and 5 ⁇ m.
• the film obtained in contact with the free surface of the substrate according to the method of the present invention has a substantially constant thickness.
• the thickness of the thin layer obtained by elimination (evaporation or drainage) of the solvent (s) contained in the film and / or the crystallization / precipitation of the products obtained in the film, in contact with the surface free of the substrate according to the method of the present invention may be between a few nanometers and several hundred microns.
• a particularly important technical criterion in understanding the process according to the invention thus relates to the solubility of the thin layer.
• the solubility of the deposited thin film material is lower than the solubility of the reaction partners in the liquid spray solutions.
• the solubility of the material constituting the thin layer is lower than that of the reaction partners. So the material will settle progressively on the surface of the substrate more easily than the reaction partners individually and increase the thickness of the thin layer as a function of the spraying time (simultaneous spraying) or the number of spraying cycles (alternating spraying).
• a thin layer of different inorganic crystals selected from, for example, calcium phosphate, calcium fluoride, calcium oxalate, Prussia, silver chloride, iron phosphate, copper sulphide (CuS), zinc sulphide (ZnS), cadmium sulphide, indium sulphide, tin sulphide, lead sulphide , arsenic sulphide, antimony sulphide, molybdenum disulfide, manganese sulphide, iron sulphide (FeS 2 ), cobalt sulphide, nickel sulphide and lanthanum sulphide, selenide copper (Cu 2 Se), silver selenide, zinc selenide, antimony selenide, indium selenide, cadmium selenide, bismuth selenide, lanthanum selenide, copper tellurate, cadmium tellurate, indium tellurate, lanthan
• the deposited thin film furthermore comprises a substance of interest that can be used in catalysis, optics, optoelectronics, or else having magnetic properties, such as mineral salts containing iron.
• the deposited thin film further comprises a substance of interest, in particular of a therapeutic nature or for transfection, chosen from antibiotics, anti-inflammatories, antibacterials, anticancer drugs, DNA, RNA and plasmids for example.
• a substance of interest in particular of a therapeutic nature or for transfection, chosen from antibiotics, anti-inflammatories, antibacterials, anticancer drugs, DNA, RNA and plasmids for example.
• the surface of the substrate to be coated is made adhesive.
• said surface is rendered adhesive by functionalization, for example by adsorption of PEI, by surface nucleation or by mineralization of said substrate.
• the term "substrate” denotes a solid support on which at least one thin layer according to the invention will be deposited.
• This support may be of any kind, that is to say natural or synthetic, organic, inorganic or inorganic, crystalline, polycrystalline and / or amorphous.
• the substrate in the process according to the invention, is a bio-material.
• the bio-material is preferably an implant.
• the inorganic layers made by the method according to the present invention can have different applications: magnetic coatings, layers having mechanical properties, manufacture of layers for optics (for reflective or anti-reflective coatings, photovoltaic cells, for example), in micro- electronic (layers of insulators, semiconductors and conductors of integrated circuits), storage and production of energy (photovoltaic cells), biotechnology (biological microsensors, biochips, biocompatible materials %), micro and nanotechnologies (mechanical sensors and chemical, microfluidic, actuators, detectors, adaptive optics, nanophotonics, etc.), etc.
• Figure 1 side view of an embodiment of the spray according to the present invention.
• FIG. 2 Schematic representation of the simultaneous spraying system according to the invention used for the deposition of different thin layers from two reaction partners of the same nature or of a different nature (inorganic / inorganic, polymer / polymer, polyelectrolyte / small oligo-ion) and polyelectrolyte / nanoparticle).
• On the right are images of thin layers deposited on silicon plates (40mm x 40mm) whose colors are generated by optical interference indicating the quality and homogeneity of the thin films obtained.
• the silicon wafers were rotated slowly to improve the homogeneity of the liquid films / thin films in each case.
• Figure 3 Micrographs of thin films of calcium fluoride obtained by simultaneous spraying; (A) 1 second on a "Formvar" support, analyzed by TEM (upper half of the image) and electron diffraction (lower half of the image); (B) 10 S and (C) 40 S on a silicon plate analyzed by atomic force microscopy, topography (upper frame of the image) and line profile (lower frame of the image). The scanned surfaces are 5 ⁇ m x 5 ⁇ m and the scale of the Z axis is 400 nm; (D) 1 min, (E) 5 min and (F) 10 min on a glass substrate, analyzed by scanning electron microscopy, top view (upper half of the image) sectional view (lower half of the picture) . Scale bars from (D) to (F) are 2ym.
• FIG. 4 Variation of the thickness of a thin layer of calcium fluoride, obtained by simultaneous spraying of solutions of calcium chloride (10 -2 mol / l) and sodium fluoride (2.10 -2 mol / l) according to spray time, measured by ellipsometry.
• the dotted line serves as a guide for the eyes.
• Figure 5 Thicknesses of a thin layer of calcium fluoride, obtained for spraying times ranging from 0 to 10 minutes, measured by scanning electron microscopy. Points D, E and F correspond to the thin layers of Figure 2D, 2E and 2F.
• the dotted line serves as a guide for the eyes.
• the dotted line serves as a guide for the eyes.
• the polycrystalline nature of the thin layer obtained makes said thin layer appear white in reflected light.
• the image at the bottom right corresponds to the plate obtained after 60 seconds of spraying.
• NB at the bottom of the exposed plate, the black mark is due to the clamp holding said plate during spraying.
• Figure 7 Eliptical thicknesses of a thin layer of calcium oxalate, obtained by simultaneously spraying solutions of calcium chloride (2.10 -1 mol / L) and sodium oxalate (10 ⁇ 2 mol / L), in depending on the spray time.
• the dotted line serves as a guide for the eyes.
• the image at the bottom right corresponds to the plate obtained after 40 seconds of spraying.
• NB at the bottom of the exposed plate, the black mark is due to the clamp holding said plate during spraying.
• FIG. 8 Eliptical thicknesses of a thin layer of iron (III) hydrogen phosphate, obtained by simultaneously spraying solutions of iron (III) chloride (2.5 ⁇ 10 -2 mol / l) and of ammonium hydrogen phosphate (3, 75.10 " mol / L), depending on the spraying time
• the dotted line serves as a guide for the eyes.
• FIG. 9 Eliptical thicknesses of a thin layer of silver chloride, obtained by simultaneously spraying solutions of silver nitrate (10 -2 mol / L) and sodium chloride (10 -2 mol / L), according to FIG. spray time.
• the dotted line serves as a guide for the eyes.
• FIG. 10 UV-visible spectrum of a thin layer of silver chloride obtained by simultaneously spraying solutions of silver nitrate (10 -2 mol / L) and sodium chloride (10 -2 mol / L) after 3 minutes of spraying.
• the peak at about 270 nm corresponds to AgCl.
• the image at the top right corresponds to a quartz plate covered with the thin layer of AgCl after 3 minutes of spraying.
• the polycrystalline nature of the thin layer obtained makes said thin layer appear white in reflected light.
• NB at the bottom of the exposed plate, the black mark is due to the clamp holding said plate during spraying.
• FIG. 11 UV-visible spectrum of a thin layer of Prussian blue, obtained by simultaneously spraying solutions of iron (II) chloride (3.10 -3 mol / L) and potassium hexacyanoferrate (III) (3.10 - 3 mol / L), depending on the spraying time.
• the spectrum shows an increase in the absorbance of the thin layer with the growth of said thin layer.
• the growth of the thin layer increases steadily with the spraying time.
• the discontinuity of the curves obtained at around 790 nm corresponds to the automatic change of filters in the spectrophotometer.
• the image at the top and in the center of the figure corresponds to a plate coated with a thin layer after 5 minutes of spraying NB: below of the exposed plate, the black mark is due to the clamp holding said plate during spraying.
• Figure 12 Thickness variations of a thin layer, obtained by simultaneously spraying polyethylene glycol (0.5 mg / mL) and poly (acrylic acid) (PAA) solutions (0.5 mg / mL) at pH 2 , measured by ellipsometry as a function of the cumulative spraying time.
• the construction of the thin layer is based on the formation of hydrogen bonds between the two polymers.
• Figure 13 Ellipsometric thicknesses of a thin layer of PAH / hexacyanoferrates (III) of potassium as a function of the spraying time.
• concentrations of the spray solutions simultaneously were 1 mg / mL PAH and 3.10 -2 mol / L for potassium hexacyanoferrate (III).
• the dotted line serves as a guide for the eyes.
• Figure 14 Ellipsometric thicknesses of a thin layer of PAH / oxalate, obtained by simultaneous spraying of PAH (1 mg / mL) and oxalate ( 10-1 mol / L) solutions, as a function of the spraying time.
• the dotted line serves as a guide for the eyes.
• Figure 16 Ellipsometric thicknesses of a thin layer of PAA / spermine, obtained by simultaneous spraying of solutions of spermine (8.66 ⁇ 10 -3 mol / L) and PAA (0.5 mg / mL) at pH 7.5, depending on the spraying time.
• the dotted line serves as a guide for the eyes.
• Figure 17 Ellipsometric thicknesses of a thin layer of PAH / cyclodextrin sulfate, obtained by simultaneous spraying of PAH solutions (0.5 mg / mL) and of sodium salt of cyclodextrin sulfate (4.55 ⁇ 10 ⁇ 3 mol / L) at pH 7.5, depending on the spraying time.
• the dotted line serves as a guide for the eyes.
• FIG. 18 Ellipsometric thicknesses of thin PAH / sodium citrate layers, obtained by simultaneous spraying of solutions of PAH (0.5 mg / mL) and citric acid (14.56 ⁇ 10 -3 mol / L) at pH 7, depending on the spraying time.
• the different colors represent different spray intervals between ellipsometry measurements.
• the curve shows that sprays made at different time intervals have no significant influence on the final thickness of the thin layer.
• the final thickness of the thin layer is dependent on the total spraying time.
• the dotted line serves as a guide for the eyes.
• Figure 19 The images A, B, C, D, E and F obtained by atomic force microscopy comprise two parts: the topographies (above) and the profile lines (below) of thin layers obtained by simultaneous spraying according to the present invention:
• PDADMAC Polydiallyl Dimethyl Ammonium Chloride
• PAA PAA
• E Polydiallyl Dimethyl Ammonium Chloride
• F Polydiallyl Dimethyl Ammonium Chloride
• the scanned surfaces are 12 ym x 12 ym.
• the scale bars are 2.5 ⁇ m.
• the thin layers of (A), (B), (C), (E) and (F) were scraped in order to Properly determine their height profile and exact thickness.
• the Y axis is between 0 and 120 nm for (A), (B) and (C) and between 0 and 400 nm for (D), (E) and (F).
• Figure 20 Thin layers prepared by simultaneous spraying of PAH (1 mg / mL, M w ⁇ 15000 g / mol) and 0.02 mol / L of citrate (B, D) and a mixture of citrate and glutaraldehyde (GA) (A, C) with final concentrations of 0.02 mol / L each.
• A, B thin layers before immersion in NaCl.
• C, D thin layers after immersion of the lower part of each plate, in 0.5 mol / L of NaCl for 1 minute.
• the thin layer prepared in the absence of glutaraldehyde (D) was completely dissolved while the formation of the citrate / GA thin layer did not dissolve. This demonstrates crosslinking during spraying and formation of the thin layer.
• the citrate / GA thin layers remain intact even in a salt solution overnight.
• NB the imperfection at the top of the layer (D) is an artifact due to the handling of the plate during soaking in the saline solution.
• Figure 21 Ellipsometric thicknesses of a thin layer of PAH / gold nanoparticles / sodium citrate as a function of time.
• the dotted line serves as a guide for the eyes.
• the following solutions were sprayed simultaneously: 1) PAH (1 mg / mL, M w ⁇ 15000 g / mol) and 2) gold nanoparticles (12 nmol / L, average size of nanoparticles 13 nm, nanoparticles prepared by reduction of citrate by adding 70 mL of 38.8.10 ⁇ 3 mol / L of sodium citrate solution to 700 mL of HAUCI 4 solution at 1.10 "3 mol / L).
• Figure 22 UV-visible spectrum of a thin layer PAH / citrate, obtained by simultaneous spraying for 5 minutes, containing gold nanoparticles on a glass plate. The presence of gold nanoparticles in the thin layer is confirmed by the strong plasmon absorption band centered at about 650 nm.
• Figure 23 a) Schematic representation of the alternating sputtering system according to the invention used for the deposition of purely inorganic AB thin layers from 2 complementary salts A and B. b) Image of a thin layer of calcium phosphate obtained after 75 spraying cycles on a 1.5 cm x 5.0 cm silicon wafer. Because of its polycrystallinity and its nanoporous morphology, the coating appears white in reflected light.
• Figure 24 ad) Scanning electron micrographs showing a top view of a thin layer of CaF 2 obtained at different stages of growth of the alternately sputtered thin layer.
• the number of spraying cycles for each sample are as follows: 3 (a), 10 (b), 50 (c) and 200 (d).
• the scale bar represents 10 ym.
• eh) electron micrographs and diffraction patterns were obtained by transmission electron microscopy of CaF 2 crystals after 1 cycle (e, f) and 3 cycles (g, h) of spraying.
• the scale bars represent 100 nm for the image (e) and 200 nm for the image (g).
• Figure 25 ad) Scanning electron micrographs showing a top view of a thin layer of CaHPO 4 obtained at different stages of growth of the alternately sprayed thin film.
• the number of spray cycles for each sample are: 3 (a), obtained 10 (b), 50 (c) and 200 (d).
• the scale bar represents 10 ym.
• eh) electron micrographs and diffraction patterns were by CaF 2 crystal transmission electron microscopy after 1 cycle (e, f) and 3 cycles (g, h) of spraying.
• the scale bars represent 100 nm for the image (e) and 200 nm for the image (g).
• Figure 26 Scanning electron micrographs showing a side view of a thin layer composed of CaF 2 (ad) and CaHPO 4 (eh) at different stages of growth of the alternately sprayed thin layer, ik) Evolution the thickness of CaF 2 (i), CaHPO 4 (j) and CaC 2 O 4 (k) films as a function of the number of spray cycles.
• the thicknesses were at the same time by atomic force microscopy (scratching of the coating, blue circles) and scanning electron microscopy (red circles).
• the number of spraying cycles for each sample are as follows: (a), 50 (b, e), 100 (c, f), 150 (g) and 200 (d, h).
• the scale bars represent 5 ym for (ad) and 100 ym for (eh).
• Figure 27 Scanning electron micrographs showing a top view (ad) and a cross section (eh) of a thin layer composed of CaC 2 O 4 at different stages of growth of the alternately sputtered thin layer.
• the number of spraying cycles for each sample are as follows: (a, e), 50 (b, f), 100 (c, g) and 200 (d, h).
• the scale bars represent 10 ⁇ m for top views and 5 ⁇ m for cross sections.
• FIG. 28 Evolution of the absorbance measured at 200 nm as a function of the spraying time for thin films of CaF 2 (a), CaC 2 O 4 (b) and CaHPO 4 (c) after 5 (O), ( ⁇ ), 15 ( ⁇ ) and 20 ( ⁇ ) cycles.
• the curves show that in two cases (a, b) there are curves with a plateau and in one case (c) there is a curve with a maximum. This indicates that it is necessary to optimize the spraying time depending on the reaction partners to be able to build a thin layer (case (a) and (b): above a spray time of 1-2 seconds the construction is independent of the spraying time, and case (c): the construction depends on the spraying time, the thin layer dissolves beyond the maximum spraying time).
• Figure 29 Scanning electron micrograph showing a top view of a CaHPC film after 100 spraying cycles.
• the scale bar represents 100 ym.
• Figure 30 is a schematic representation (left) and a photograph (right) of the enclosure used to work under an inert atmosphere.
• the present invention has already been used to produce thin organic, inorganic, mineral, hybrid or nanoparticle-containing layers. For all these cases, it was possible to manufacture very homogeneous thin layers for which the thicknesses could be varied as a function of the spraying time (simultaneous spraying) or as a function of the number of spraying cycles (alternating spraying).
• the reagents used were obtained from Sigma Aldrich, Fluka, Carlo Erba Reagents and Merck.
• the glass, quartz and silicon plates were obtained from Fisher Bioblock Scientific (France), WaferNet Inc. (USA) and Thuet B. (France).
• Ultrapure water having a resistivity of 18.2 M ⁇ .cm, was obtained from reverse osmosis water with a Milli-Q Gradient system from Millipore. The water was directly used after purification.
• the size and electron diffraction of the nanocrystals were determined by transmission electron microscopy (EM, Phillips, CM200) used in "low-dose” mode at a 200kv acceleration voltage, equipped with a digital apparatus (Gatan, Orius 1000). The resolution of the microscope was 0.2 nm. The acquisition and processing of the images was done with the software "Digitalmicrograph software”.
• the Z sections of the samples were obtained by breaking the glass substrates coated with a thin layer.
• the UV-visible absorbance spectra of the examples below were carried out on a device of the type: Varian Cary 500 Scan.
• the variations in intensity of the baseline are due to the scattering of light by the crystals within inorganic thin layers, which makes it possible to follow the evolution of the growth of said thin layers.
• the ellipsometry measurements of the examples below were made with a "PLASMOS SD 2300" type device operating at a wavelength of 632 nm and at an angle of 70 °.
• the given thicknesses are all derived from an average of 10 measurements made at different locations of the coated plate.
• Example 1 Development of the technical characteristics of simultaneous spraying to obtain a coating.
• the silicon wafers were cleaned by immersing them successively for one hour in a mixture of methanol and hydrochloric acid (50:50) and one hour in a concentrated sulfuric acid solution, followed by an abundant rinsing in water. ultra-pure before use.
• the gas under pressure has been produced by various means:
• the solutions were sprayed simultaneously on the substrates with a circular or vertical movement, in order to improve the homogeneity.
• the solution flow rate was 13 ⁇ 2 mL / min and 19 ⁇ 2 mL / min respectively for the positively or negatively charged compounds, with a gas pressure of 2 bar,
• the flow rates of the solutions were 12 ⁇ 1 mL / min for the two solutions respectively, with a gas pressure of 2 bar,
• the flow rates of solution of the two compounds was 6 ⁇ 1 mL / min with a gas pressure of 3 bars in the case of the airbrushes of Aztek, and 13 ⁇ 2 mL / min and 19 ⁇ 2 mL / min for positively and negatively charged compounds respectively with a gas pressure at 2 bars, in the case of airbrushes from Paasche.
• AuNPs gold nanoparticle
• citrate with glutaraldehyde citrate solution flow rates were 6 ⁇ 1 mL / min and poly (allylamine) hydrochloride flux (PAH) ) was 3 ⁇ 1 mL / min, with gas pressure at 3 bar.
• PAH poly (allylamine) hydrochloride flux
• the simultaneous spraying technique according to the invention can for example be applied to the spraying of inorganic / inorganic solutions (case A), polymer / polymer (case B), polyelectrolytes / small oligo-ions (case C) and polyelectrolytes / nanoparticles (case D).
• Example of application of case B polyethylene oxide (0.5 mg / mL, M w ⁇ 50,000 g / mol, with stabilizers) and polyacrylic acid (0.5 mg / mL, M w ⁇ 100,000, 35% by weight in water ) at pH 2.
• the plates (A, B, C, D) of Figure 2 were obtained on silicon plates (40 mm x 40 mm) in slow rotation (10 and 1250 rpm) to improve the homogeneity of the films / layers thin in each case. Rapid rotation of the supports is also possible (tested up to 15000 rev / min). The color shades were obtained by optical interference indicating the quality and homogeneity of the thin films obtained.
• Example 3 Obtaining Inorganic Thin Films by Simultaneous Spraying
• the process according to the invention is well suited to obtaining a thin layer of calcium fluoride according to the following equation:
• Table 2 Assignment of experimental dh, k, i values obtained from transmission electron diffraction data for samples of incomplete CaF2 coatings after 1 second spraying. Comparison with the values of the literature clearly shows that the composition of the thin layer is CaF2.
• the method according to the invention has also been tested and approved in obtaining inorganic thin layers of calcium hydrogen phosphate (CAHPC) of calcium oxalate (4 CaC20), of iron hydrogenphosphate (Fe 2 (HP0 4) 3), Prussian blue (Fe 4 [Fe (CN) 6 ] 3) and silver chloride (AgCl).
• CAHPC calcium hydrogen phosphate
• Fe 2 (HP0 4) 3 iron hydrogenphosphate
• Prussian blue Fe 4 [Fe (CN) 6 ] 3
• silver chloride AgCl
• Example 4 Obtaining an Inorganic Thin Layer by Alternate Spraying
• the process involves spraying compound A for 2 seconds and then compound B for 2 seconds and this spraying cycle can be repeated n times to form the thin layer (A / B) n .
• obtaining a thin layer of calcium fluoride is carried out by simultaneously spraying solutions of calcium chloride (2.10 -2 M) and sodium fluoride (2.10 -2 M) using a manual pump sprayer (Roth, flow rate 0.6 mL / s).
• Scanning electron microscopy revealed that the growth of a thin film begins with the formation of nanocrystals which increase in number and size with the number of spray cycles until the surface is completely covered ( Figure 24 ad). Then, the growth of the thin layer takes place in the direction normal to the layer. Transmission electron microscopy and electron diffraction have shown that the smallest crystals, monocrystalline, become polycrystalline ( Figure 24 eh). In the case of CaF2, dense polycrystalline thin layers are obtained.
• Alternating sputtering has also been tested and approved for obtaining inorganic thin films of calcium hydrogen phosphate (CaHPO 4 ) and calcium oxalate (CaC 2 O 4 ).
• CaHPO 4 calcium hydrogen phosphate
• CaC 2 O 4 calcium oxalate
• growth of the thin layer occurs by nucleation of small additional polycrystalline crystals rather than growth of crystals ( Figure 25 and 27).
• porous polycrystalline thin films are obtained in the case of CaHPO 4 and CaC 2 O 4 .
• the properties of the layers can be controlled by the molar mass of the constituents.
• Example 6 Thin Films of Polyelectrolyte Complexes / Small Oligo-ions by Simultaneous Spraying
• Thin films obtained by simultaneous spraying of PAH and sodium citrate dissolve rapidly when immersed in NaCl solutions at ionic strengths above 0.15M, opening up possibilities for use as materials or trigger release systems.
• the rapid degradation of such thin layers can easily be avoided and controlled by crosslinking; for example by heating at 130 ° C for a few hours in an oven or for a few minutes with a heat gun.
• This allows a partial crosslinking by formation of amide bonds by reaction of the carboxylic acid groups of the citrates with the amino groups of PAH, in a manner similar to the case described with the thin layers obtained by the "LbL" type technique.
• the simultaneous spraying technique according to the process of the present invention allows in situ chemical thin layer crosslinking by adding reactive compounds to the sprayed solutions.
• the addition of glutaraldehyde to the citrate solution leads to the development of a network of covalent bonds by the Schiff basic formation.
• Such coatings do not dissolve in 0.5 mol / L NaCl solution even for a long period of time (see Fig. 20).
• the two-nozzle simultaneous spraying process can be extended to a so-called "multi-nozzle” process (greater than 2), allowing the consecutive application of 2 different pairs of complementary reaction partners by simultaneous sputtering making it easy to produce laminated thin layers and thus incorporating different materials and therefore different functionalities (thin layers of the sandwich type).
• multi-nozzle a so-called "multi-nozzle” process (greater than 2), allowing the consecutive application of 2 different pairs of complementary reaction partners by simultaneous sputtering making it easy to produce laminated thin layers and thus incorporating different materials and therefore different functionalities (thin layers of the sandwich type).
• the combination of several deposition methods, for example LbL and simultaneous sputtering also makes it possible to obtain layered multimaterial layers.

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