Process for forming a metallic coating from a metallization solution

Abstract

A method for forming a metallic coating from a metallization solution, wherein the metallization solution comprises at least one metal ionic precursor, at least one structuring liquid, and at least one driving liquid, wherein the at least one metal ionic precursor comprises at least one metal cation and at least one counterion, the at least one structuring liquid serves to dissolve the at least one metal ionic precursor in the metallization solution, the at least one driving liquid serves to nebulize the metallization solution; and wherein the method comprises: applying the metallization solution to a substrate, and exposing the metallization solution to a plasma under atmospheric conditions, thereby obtaining the metallic coating.

Description

Technical field of the invention

[0001] The invention relates to a method for forming a metallic coating from a metallization solution, a metallization solution and a metallic coating. Background of the invention

[0002] Thin polycrystalline metallic coatings, or films, are components used in many applications, such as catalytic surfaces, electrolyzers, batteries, solar cells, fuel cells, electronic devices, touchscreens, and others. Currently, the field of surface metallization, or metallic coatings, is dominated by electroplating or vapor deposition processes, as described by Jiri George Drobny in "4 - Processing Techniques for Thermoplastic Elastomers" in the "Handbook of Thermoplastic Elastomers (Second Edition)," William Andrew Publishing, 2014, pages 33–173, ISBN 9780323221368, https: / / doi.org / 10.1016 / B978-0-323-22136-8.00004-1. These techniques require high material costs, expensive equipment, and, in many cases, generate chemical waste.

[0003] US patent application 2023 / 0220230 A1 describes a metallic coating as a conductive laminate with a specific volume resistivity and excellent heat dissipation properties. The conductive laminate comprises a base material and a conductive ink film (a metallization solution) on the base material. The conductive ink is an ink containing metal particles, a metal complex, or a metal salt. The metal particle ink is, for example, an ink composition obtained by dispersing metal particles in a dispersion medium. The dispersion medium includes, for example, 2-propanol, propylene glycol monomethyl ether, and ethylene glycol monopropyl ether. An example of the metal salt is silver nitrate. US 2023 / 0220230 A1 further describes a method for producing the metallic coating as a conductive ink film using the metallization layer.For example, the conductive ink film is produced by applying the conductive ink to the base material and then firing the applied ink. The conductive ink film can be produced by repeatedly applying and firing the conductive ink.

[0004] European patent EP 3 887 463 B1 describes a method for growing a transparent, conductive metal layer as a metallic coating on a substrate. The method comprises applying a crystal growth ink to the surface of the substrate. The crystal growth ink contains a metal ion precursor as a metallization solution. The method further comprises plasma irradiation of the substrate to cause the growth of a crystalline metal framework on the substrate. The irradiation is carried out based on a set of predefined exposure parameters. EP 3 887 463 B1 further describes that the irradiation of the substrate is carried out in a vacuum chamber to cause the growth of the crystalline metal framework, i.e., the layer, on the substrate. In other words, the method according to EP 3 887 463 B1 is a chamber-based, non-atmospheric plasma process.The irradiation step in EP 3 887 463 B1 is carried out at a gas flow rate of 20 SCCM to 50 SCCM, i.e. 0.02 to 0.05 litres / minute, and for an irradiation time of between 2 minutes and 15 minutes, i.e. 120 seconds and 900 seconds.

[0005] International patent application WO 2015 / 071746 A1 describes a method and apparatus for generating a plasma under atmospheric pressure and at low temperatures. The method comprises passing a process gas in the flow direction through a tube channel made of dielectric material and having an inlet and an outlet section at atmospheric pressure, and positioning a first and a second coaxial pair of electrodes in contact with the outer surface of the tube channel. The first pair of electrodes is positioned upstream of the second pair of electrodes with respect to the flow direction of the gas within the tube channel and is connected to a high-frequency generator. The second pair of electrodes is connected to a radio frequency (RF) generator. The high-frequency generator generates a filamentary plasma within the tube channel that extends at least as far as the second pair of electrodes.The radio frequency generator generates a second RF plasma. The method further comprises directing the RF and filamentary plasma out of the tube channel through the outlet section, wherein these plasmas contain at least one neutral gas with a temperature of no more than 100 °C at the outlet. Summary of the invention

[0006] This disclosure describes a method for forming a metallic coating from a metallizing solution or liquid.

[0007] The metallization solution or liquid comprises at least one metal ion precursor, at least one structuring liquid, and at least one driving liquid. The term "metallization solution" refers to an ink formulation, an ink composition, or an ink.

[0008] The at least one metal ion precursor is a solid. The metal ion precursor comprises at least one metal cation and at least one counterion.

[0009] The term "structuring liquid," i.e., a stabilizing liquid, serves to dissolve the at least one metal ion precursor in the metallization solution. The at least one structuring liquid can improve the solidification of the metallization solution. It can also promote crystallization, i.e., crystal formation, of the metallization solution. The at least one structuring liquid can also change the shape of the crystals in the metallization solution.

[0010] The term “driving fluid” is used to atomize the metallization solution, i.e. the ink, preferably via an atomization generator.

[0011] The process involves applying the metallization solution to a substrate and exposing the metallization solution to a plasma under atmospheric conditions, thereby forming the metallic coating.

[0012] In one aspect, the metallization solution has a layer thickness on a substrate, and the metallization solution is applied to the substrate such that the layer thickness of the metallization solution is at most 2 mm.

[0013] In one aspect, the metallization solution may comprise the at least one metal ionic precursor in a concentration between 0.01 wt.% and 30 wt.% relative to the at least one structuring liquid and the at least one driving liquid. The at least one structuring liquid and the at least one driving liquid contain solvents that are substantially rapidly decomposed under atmospheric plasma conditions, i.e., the metallization solution is converted into the metallic coating when it interacts with the plasma under atmospheric conditions. The conversion from the metallization solution to the metallic coating is completed, for example, in less than 10 seconds. The at least one structuring liquid and the at least one driving liquid are substantially nebulized.

[0014] The term "nebulization" encompasses both aerosolization and evaporation. Aerosolization means suspending particles and / or droplets in a gas stream. Evaporation refers to the phase transition of an element from the liquid to the gaseous phase.

[0015] The term "nebulization generator" refers to a system consisting of an aerosol generator, an evaporation generator, or a combination thereof. The aerosol generator is, for example, a nebulizer, but this is not a limitation of the invention. The evaporation generator is, for example, a bubble atomizer or a bubble-based chemical vapor generator, but this is not a limitation of the invention.

[0016] In one aspect, the at least one structuring liquid can be a solvent. The solubility of the at least one metal ion precursor in the solvent is at least 15 mg / ml at 25°C, preferably at least 50 mg / ml at 25°C, more preferably at least 100 mg / ml at 25°C.

[0017] In one aspect, the at least one driving fluid may be selected from one of the solvents having a dynamic viscosity of 0.5 mPa.s to 5 mPa.s at 25°C.

[0018] In one aspect, the at least one metal cation can be selected from one of the following groups: Au, Ag, Pt, Pd, Cu, Ti, Nb, Ni, Co, Ru, Ir, and Rh, depending on the use, i.e., the end application, of the metallic coating. In another aspect, the at least one metal cation is Ag and / or Cu to obtain a conductive metallic coating. In another aspect, the at least one metal cation is Au and / or Pt for use in sensing applications and / or catalytic activities, such as in the hydrogen oxidation reaction, the oxygen reduction reaction, and CO2 fixation. In another aspect, the at least one metal cation is Pd to obtain a metallic coating for use in electroplating as a starting layer. In another aspect, the at least one metal cation is Ti and / or Nb to obtain a metallic coating for use in dielectric applications.

[0019] The step of “applying the metallization solution to the substrate” refers to depositing or printing the metallization solution onto the substrate.

[0020] The use of a plasma in the exposure step allows a chemical reaction to occur between the metallization solution and the plasma without exposing the substrate surface to high temperatures. Exposure to high temperatures could otherwise damage the substrate surface or the underlying layers, especially in multilayer substrates.

[0021] The step of exposing the metallization solution to the plasma under atmospheric conditions requires a significantly high gas flow rate. However, this high gas flow rate can be compensated for by a significantly short exposure time. In other words, generating a plasma under atmospheric conditions requires a higher plasma concentration than under vacuum conditions. Plasma generation under atmospheric conditions occurs faster than under vacuum conditions.

[0022] The process can be used to create fine structures in the metallic coating, i.e., structures in the range of tenths of a micrometer. The process may involve printing the fine structures with a high-precision printer, e.g., one with an accuracy of 20-30 micrometers. The creation of the fine structures demonstrates that the process enables spatial control, i.e., it can be precisely controlled.

[0023] In one aspect, the application of the metallization solution to the substrate is performed using a first machine, e.g., a printer. The exposure of the metallization solution to the plasma under atmospheric conditions is performed using a second machine, e.g., an atmospheric plasma generator. The process is referred to as a two-step process.

[0024] In another aspect, the method comprises nebulizing the metallization solution, exposing the metallization solution to the plasma under atmospheric conditions, and applying the resulting nebulized metal to the substrate.

[0025] In another aspect, the nebulization step and the exposure step are performed in the nebulization generator, so that the metallic coating is obtained in a single production step. In other words, the nebulization generator enables both nebulization of the metallization solution and exposure of the metallization solution to the plasma under atmospheric conditions. The process is referred to as a one-step process.

[0026] In one aspect, the two-step process enables more precise application of the metallization solution compared to the one-step process. In another aspect, the one-step process enables the metallization solution to be applied to significantly larger surfaces of the substrate compared to the two-step process. The one-step process is also more easily scalable than the two-step process. Furthermore, the one-step process enables the formation of a metallic coating on three-dimensional (3D) substrates and does not require flat, two-dimensional substrates. Both the one-step and two-step processes are significantly faster compared to electroplating and vapor deposition techniques. Description of the characters Fig. Figure 1 shows a flow diagram describing a process for forming a metallic coating from a metallizing solution. Fig. Figure 2 shows one aspect of obtaining a metallic coating. Fig. Figure 3 shows another flow chart describing the process for forming the metallic coating from the metallization solution. Fig. Figure 4 shows another aspect of obtaining the metallic coating. Fig. Figure 5 shows an image of platinum (Pt) on an electrolyzer. Fig. Figure 6 shows an image of Pt islands on an electrolyzer. Fig. Figure 7 shows an image of the obtained metallic coating 20, consisting of gold (Au) and palladium (Pd) on a silicon substrate. Detailed description of the invention

[0027] The invention is described below with reference to the drawings. It is to be understood that the embodiments and aspects of the invention described herein are merely examples and do not limit the scope of the claims in any way. The invention is defined by the claims and their equivalents. It is to be understood that features of one aspect or embodiment of the invention may be combined with features of another aspect or other embodiments of the invention.

[0028] In a first aspect, a metallization solution 10 is described in this document. The metallization solution 10 comprises at least one metal ion precursor, at least one structuring liquid, and at least one driving liquid. The at least one metal ion precursor comprises at least one metal cation and at least one counterion. The at least one structuring liquid serves to dissolve the at least one metal ion precursor in the metallization solution 10. The at least one driving liquid serves to nebulize the metallization solution 10.

[0029] In one aspect, the metal cation is a positively charged ion. The counterion is, in one aspect, an ion with a charge equal to but opposite to that of the cation—in other words, an anion. In another aspect, the at least one counterion is a ligand. In another aspect, the counterion is an organic ligand.

[0030] In one aspect, the metal cation is stabilized by the ligand, forming an organometallic complex, such as a salt. The salt comprises coordination bonds. In another aspect, the metal cation is stabilized by the anion, forming a salt with ionic bonds.

[0031] In one aspect, the metal cation is selected from one of the following metals: Au, Ag, Pt, Pd, Cu, Ni, Co, Zn, In, Ti, V, Mn, Fe, Cr, Zr, Nb, Mo, W, Ru, Rh, Ca, Re, Os, Ir, Al, Ga, Sn and Sb. In another aspect, the metal cation is selected from one of the following metals: Au, Ag, Pt, Pd, Cu, Ti, Nb, Ni, Co, Ru, Ir and Rh.

[0032] In another aspect, the counterion is selected from the group consisting of one of the following: M(NO3)n, M(SO4)n, MCln, HmMCln+m and MN, where "M" is a metal atom or metal alloy having a valence of "n", H is hydrogen, NO3 is nitrate, SO4 is sulfate, Cl is chloride, "N" includes alkyl, aryl, acetyl, carbonyl, carboxyl, cyclopentadienyl, phenyl, biphenyl, pyridine, bipyridine, aromatic, cyano, amide and other organic groups and "m" is the valence of the counterion. In another aspect, the at least one counterion is selected from the group consisting of M(NO3)n, HmMCln+m, and MN, where "M" is a metal atom with a valence of "n," H is hydrogen, NO3 is nitrate, "N" includes oxalate, hydroxide, ketone, carboxyl, lactone, and "m" is the valence of the counterion. In another aspect, the at least one counterion is selected from the group of salts, e.g., H2PtCl6, when the metal cation consists of Pt.

[0033] In one aspect, the at least one structuring liquid is a solvent.

[0034] In another aspect, the solubility of the metal ion precursor in the solvent is at least 15 mg / ml at room temperature, i.e., 25°C. In another aspect, the solubility of the metal ion precursor in the solvent is at least 50 mg / ml at room temperature. In another aspect, the solubility of the metal ion precursor in the solvent is at least 100 mg / ml at room temperature.

[0035] In a further aspect, the concentration of the metal ionic precursor is at most 25 wt.% with respect to the metallization solution 10. In a further aspect, the concentration of the metal ionic precursor is between 1 and 15 wt.% with respect to the metallization solution 10. In a further aspect, the concentration of the metal ionic precursor is between 5 and 10 wt.% with respect to the metallization solution 10.

[0036] The structuring fluid can be selected from one of the following groups: glycols, glycol ethers, glycol esters, carbonate esters, water, ketones, sulfoxides and their derivatives or a combination thereof.

[0037] In one aspect, the driving fluid is selected from one of the following groups: solvents having a dynamic viscosity between 0.5 mPa.s and 5 mPa.s at 25 °C.

[0038] In another aspect, the driving fluid is selected from one of the following groups: alcohol, cyclic alcohols, toluene, dioxane, ethylamines, glycol ethers, acetonitrile and their derivatives or a combination thereof.

[0039] In a further aspect, the concentration of the structuring liquid is between 3 wt% and 40 wt% with respect to the metallization solution 10, and / or the concentration of the driving liquid is between 60 wt% and 97 wt% with respect to the metallization solution 10.

[0040] In another aspect, the metallization solution 10 comprises at least one additive selected from one of the following groups: organic molecules, polymers, conductive polymers, carbon nanotubes (CNTs), densifying agents, and surfactants.

[0041] Fig. 1 shows a flow diagram of a process for forming a metallic coating 20 from the metallization solution 10 on a substrate 30.

[0042] In one aspect, the substrate 30 is selected from one of the following groups: two-dimensional (2D) or three-dimensional (3D) substrates. In another aspect, the substrate 30 is selected from one of the following groups: polyimide (PI), woven textile, polyethylene terephthalate (PET), filter substrate, plastic substrate, metal nonwoven substrate, aluminum base substrate, ceramic substrate, glass substrate, and metal mesh substrate. In one aspect, the aluminum base substrate is an aluminum foil. In another aspect, the metal mesh substrate is a titanium mesh substrate.

[0043] The procedure according to Fig. 1 comprises applying the metallization solution 10 to the substrate 30 in an application step S100, such that the metallization solution 10 has a thickness on the substrate 30, wherein the thickness of the metallization solution 10 on the substrate 30 is at most 2 mm. The method further comprises the exposure step S200, in which the metallization solution 10 is exposed to a plasma 50 under atmospheric conditions, thereby forming the metallic coating 20 in the achievement step S400.

[0044] A thickness of the metallization solution 10 greater than 2 mm has adverse effects. The plasma 50 does not penetrate the metallization solution 10. The metallization of the metallic coating 20 is uneven.

[0045] The application S100 includes drop coating, spray coating, dipping, inkjet printing, aerosol spraying, aerosol jet printing, spin coating, or screen printing. In another aspect, the application S100 is a deposition of the metallization solution 10 onto the substrate 30.

[0046] S100 can be applied using application devices such as a nozzle, an inkjet printer or an aerosol jet printer.

[0047] In one aspect, the thickness of the metallization solution 10 on the substrate 30 is less than 2 mm and, for example, less than 0.5 mm.

[0048] In one aspect, the exposure step S200 is carried out with a device according to the international patent application WO 2015 / 071746 A1, which, however, does not limit the invention.

[0049] In one aspect, the exposure step S200 is carried out at a gas flow rate, i.e., an exposure gas flow rate, of at least 0.5 liters / minute, and / or for an exposure time of at most 3600 seconds, and / or at a power of at most 3000 watts (W), and / or at a plasma radio frequency (RF) between 50 Hz and 5 GHz.

[0050] In another aspect, the exposure step S200 is performed at a gas flow rate of at least 1 liter / minute, and / or for an exposure time between 1 and 120 seconds, and / or at a power between 5 W and 100 W, and / or at a plasma radio frequency (RF) between 1 kHz and 1 GHz. In one aspect, the exposure time is sufficiently short to form substantially a single spot. In other words, the term "a single spot" means that the nozzle is stationary and the metallization solution 10 is applied to the substrate at a single spot. The term "the exposure time is sufficiently short" means that the exposure time can be less than 1 second and results in metallization of the metallization solution on the substrate.

[0051] The values ​​of gas flow rate, exposure time, power and plasma depend on the type of substrate 30, the composition of the metallization solution 10 and the equipment used for applying S100 the metallization solution 10.

[0052] In one aspect, plasma 50 is a plasma consisting of partially ionized gas. The partially ionized gas is not in thermodynamic equilibrium. A radio frequency (RF) plasma is a partially ionized gas that is not in thermodynamic equilibrium. The partially ionized gas can exist at relatively low temperatures, for example, below 120°C.

[0053] In one aspect, the plasma 50 is selected from one of the following groups: argon (Ar), nitrogen, oxygen, hydrogen, air, helium, neon, xenon, ammonia, ethane (C2H6), carbon dioxide, carbon monoxide, methane (CH4), propane (C3H8), silane (SiH4), nitrogen dioxide, nitric oxide, or a combination thereof.

[0054] The at least one metal ion precursor reacts with the plasma 50 under atmospheric conditions during exposure step S200, in which the metallization solution 10 is exposed to the plasma 50, resulting in an electrochemical reduction of the at least one metal ion precursor. A large portion, i.e., at least 95%, of the structuring liquid and the driving liquid evaporates during the electrochemical reduction. The metal ions of the metal ion precursor absorb electrons from the plasma 50 and are converted into metal atoms. The absorption and conversion processes occur simultaneously. The metal atoms aggregate to form the metallic coating 20, which adheres to the substrate 30, similar to physical vapor deposition (PVD).

[0055] The metallic coating 20 formed thereby is, in one aspect, a polycrystalline metal layer, ie, a film.

[0056] In one aspect, the metallic coating 20 has a thickness between 2 nm and 500 nm. In another example, the metallic coating 20 has a thickness between 2 nm and 100 nm.

[0057] In one aspect, the polycrystalline metal film adheres to at least a portion of a surface 35 of the substrate 30. In another aspect, the polycrystalline metal layer is a partial layer. In other words, the partial layer is a layer comprising metal nanoislands and / or particles, for example, to maximize the metal surface area or other parameters. In another aspect, the metallic coating 20 is not fully formed and / or does not fully adhere to the surface 35 of the substrate 30. In another aspect, the metallic coating 20 covers only a portion of the surface 35 of the substrate 30.

[0058] In another aspect, the polycrystalline metal layer is a layer of separate particles, i.e., individual particles.

[0059] In another aspect, the metallic coating 20 comprises metal oxides. The metal oxides are selected from one of the following groups: silver oxide, copper oxide, nickel oxide, zinc oxide, indium oxide, titanium oxide (TiO2), iron oxide, zirconium oxide, niobium oxide, niobium pentoxide (Nb2O5), osmium oxide, iridium oxide, ruthenium oxide, rhodium oxide, aluminum oxide, tin oxide, and antimony oxide. In one aspect, the metal oxides are selected from TiO2 and Nb2O5, so that the metallic coating 20 has specific dielectric parameters.

[0060] In one aspect, the thickness, uniformity, and topology of the metallic coating 20 depend on the composition of the metallization solution 10. In another aspect, the thickness, uniformity, and topology of the metallic coating 20, i.e., the polycrystalline metal film, can be controlled by the gas flow rate, exposure time, power, and / or plasma frequency (RF). The thickness, uniformity, and topology of the polycrystalline metal film can be controlled by the gas flow rate required to drive the metallization solution 10 through the plasma 50 under atmospheric conditions.

[0061] In another aspect, the metallic coating 20 has a surface resistivity of at least 1 ohm / sq and / or a dielectric constant at 25°C of at least 20. In another aspect, the metallic coating 20 has a surface resistivity of at least 4 ohm / sq and / or a dielectric constant at 25°C of at least 35. In another aspect, the metallic coating 20 has a surface resistivity of at least 5 ohm / sq.

[0062] In one aspect, the metallic coating 20 is used in antibacterial applications, electronic applications, catalytic applications, or energy applications. In one aspect, the metallic coating 20 is used as a biological sensor, as part of a bioelectronic sensor, for the fabrication of electrolyzers, for the fabrication of energy storage devices such as fuel cells, as part of a porous transport membrane, as a starting layer for future chemical or electroplating metal deposition, or as part of a solar cell device.

[0063] Fig. 2 shows an achievement stage S400 in which the metallic coating 20 is obtained. Fig. 2 shows the exposure step S200, in which the metallization solution 10 is exposed to the plasma 50 under atmospheric conditions.

[0064] Fig. 3 shows another flow diagram of a process for forming the metallic coating 20.

[0065] The method further comprises, in a nebulization step S50, nebulizing the metallization solution 10. The method further comprises, in an exposure step S200, exposing the metallization solution 10 to the plasma 50 under atmospheric conditions, so that a nebulized metal 15 is formed. The term "nebulized metal" refers to a metal in aerosol and / or vapor form. The method further comprises, in an application step S100, applying the nebulized metal 15 to the substrate 30, thereby obtaining the metallic coating 20 in an achievement step S400.

[0066] The nebulisation S50 is selected in one aspect from one of the following methods: aerosolisation and / or evaporation.

[0067] In one aspect, nebulization S50 is performed at a nebulization gas flow rate of at least 0.01 liters / minute, and / or exposure S200 is performed for an exposure time of at most 3600 seconds, and / or at a power of at most 3000 watts (W), and / or at a plasma radio frequency (RF) between 50 Hz and 5 GHz. In another aspect, nebulization S50 is performed at a nebulization gas flow rate of at least 0.1 liters / minute, and / or exposure S200 is performed for an exposure time between 1 and 120 seconds, and / or at a power between 5 W and 100 W, and / or at a plasma radio frequency (RF) between 1 kHz and 1 GHz.

[0068] Fig. Figure 4 shows another view of the achievement stage S400 for obtaining the metallic coating 20. Fig. 4 shows an aerosol and / or vapor 45 generated by the nebulizer 40 from the metallization solution 10. The aerosol and / or vapor 45 is further exposed to the plasma 50 S200, so that the nebulized metal 15 is formed and subsequently applied to the substrate 30 S100, thereby obtaining the metallic coating 20 S400.

[0069] In a further aspect, the method is adapted to roll-to-roll production. In application step S100, the metallization solution 10 is applied to the substrate 30 in the roll-to-roll production line using a high-precision deposition process. In a further aspect, the high-precision deposition process is inkjet printing. Examples

[0070] The following are some non-limiting examples of the deposition of a metallic coating 20, i.e., polycrystalline metal thin films, using different methods and with different properties.

[0071] Example I. A metallization solution 10 comprises a metal ion precursor of silver nitrate (AgNO3) with a concentration of 17 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol and propylene glycol (ratio 1.2:1) as the structuring liquid and a mixture of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (ratio 1.5:1) as the driving liquid. The metallization solution 10 is applied to a two-dimensional (2D) substrate 30 made of polyimide (PI) in application step S100. The PI substrate 30 is then exposed to a plasma 50 of pure argon (Ar) gas under atmospheric conditions by means of an atmospheric plasma nozzle in exposure step S200, as in Fig. 2. Exposure S200 occurs at a plasma radio frequency (RF) of 13.56 MHz, a power of 50 watts (W), a gas flow rate of 5 liters / minute, and an exposure time of 10 seconds. The resulting metallic coating 20 is a bonded, conductive polycrystalline silver layer. The specific surface resistance of the metallic coating 20 is 1 ohm / sq.

[0072] Example II. A metallization solution 10 comprises a metal ion precursor of AgNO3 with a concentration of 3 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises ethylene glycol monopropyl ether as the structuring liquid and a mixture of ethanol and propylene glycol monomethyl ether acetate (ratio 1:1.2) as the driving liquid. The metallization solution 10 is then nebulized (aerosolized) in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized S50 at an aerosol (nebulization) gas flow rate of 0.2 liters / minute. The metallization solution 10 is exposed to a plasma 50 of pure Ar gas under atmospheric conditions in the exposure step S200, as in Fig. 4. The exposure S200 occurs at a plasma RF frequency of 12 MHz, a power of 20 W, a gas flow rate of 10 liters / minute, and an exposure time of 4 seconds. The metallization solution 10 is then applied S100 to a substrate 30 made of a woven textile. The resulting metallic coating 20 is a woven textile coated with a distribution of silver nanoparticles. The resulting metallic coating 20 exhibits an antibacterial effect.

[0073] Example III. A metallization solution 10 comprises a metal ion precursor of AgNO3 with a concentration of 14 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises ethylene glycol monopropyl ether as the structuring liquid and a mixture of propylene glycol monomethyl ether and n-propanol (ratio 1.5:1) as the driving liquid. The metallization solution 10 is then nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized S50 at an aerosol (nebulization) gas flow rate of 0.3 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of pure Ar gas under atmospheric conditions, as in Fig. 4. The metallization solution 10 is applied to a 2D polyethylene terephthalate (PET) substrate 30. Exposure S200 is performed at a plasma RF frequency of 12 MHz, a power of 25 W, a gas flow rate of 8 liters / minute, and an exposure time of 3 seconds. The resulting metallic coating 20 is a bonded, conductive polycrystalline silver layer. The specific surface resistivity of the resulting metallic coating 20 is 5 ohms / sq.

[0074] Example IV. A metallization solution 10 comprises a metal ion precursor of hydrogen (tetrachloridoaurate) (H[AuCl4]) with a concentration of 12 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol and propylene glycol (ratio 1:1.1) as the structuring liquid and a mixture of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (ratio 2:1) as the driving liquid. The metallization solution 10 is applied to a 2D substrate 30 made of polyimide (PI) in application step S100. The PI substrate 30 is then exposed to a plasma 50 of pure argon (Ar) gas under atmospheric conditions by means of an atmospheric plasma nozzle in exposure step S200, as in Fig. 2. Exposure S200 occurs at a plasma radio frequency (RF) of 13.56 MHz, a power of 30 watts (W), a gas flow rate of 7 liters / minute, and an exposure time of 15 seconds. The resulting metallic coating 20 is a bonded, conductive polycrystalline gold layer. The specific surface resistivity of the resulting metallic coating 20 is 4 ohms / sq.

[0075] Example V. A metallization solution 10 comprises a metal ion precursor of H[AuCl4] with a concentration of 2.5 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol monopropyl ether and water (ratio 3:1) as the structuring liquid and a mixture of ethanol and propylene glycol monomethyl ether acetate (ratio 1:1.3) as the driving liquid. The metallization solution 10 is then nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized S50 at an aerosol (nebulization) gas flow rate of 0.22 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of pure argon (Ar) gas under atmospheric conditions, as in Fig. 4. The metallization solution 10 is applied to a substrate 30 made of a two-dimensional (2D) filter substrate. The exposure S200 is carried out at a plasma RF frequency of 13.56 MHz, a power of 22 W, a gas flow rate of 7 liters / minute, and an exposure time of 5 seconds. The resulting metallic coating 20 is a filter substrate coated with a distribution of gold nanoparticles. The resulting metallic coating 20 exhibits a catalytic effect and can be used as a simple biological sensor.

[0076] Example VI. A metallization solution 10 comprises a metal ionic precursor of hexachloroplatinic(IV) acid (H2[PtCl6]) at a concentration of 1.0 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises ethylene glycol as the structuring liquid and a mixture of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (ratio 1.2:1) as the driving liquid. The metallization solution 10 is then nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized S50 at an aerosol (nebulization) gas flow rate of 0.3 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of pure argon (Ar) gas under atmospheric conditions, as in Fig. 4. The metallization solution 10 is applied to a plastic substrate 30. The exposure S200 occurs at a plasma RF frequency of 13.56 MHz, a power of 25 W, a gas flow rate of 8 liters / minute, and an exposure time of 10 seconds. The resulting metallic coating 20 is a plastic substrate coated with a distribution of platinum nanoparticles. The resulting metallic coating 20 exhibits a strong catalytic effect, for example, in the degradation of hydrogen peroxide (H2O2).

[0077] Example VII. A metallization solution 10 comprises a metal ionic precursor of hexachloroplatinic(IV) acid (H2[PtCl6]) with a concentration of 23 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol and propylene glycol (ratio 1:1.3) as the structuring liquid and a mixture of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (ratio 1.2:1) as the driving liquid. The metallization solution 10 is applied to a 2D substrate 30 made of polyimide (PI) in application step S100. The PI substrate 30 is then exposed to a plasma 50 of pure argon (Ar) gas under atmospheric conditions by means of an atmospheric plasma nozzle in exposure step S200, as in Fig. 2. Exposure S200 occurs at a plasma radio frequency (RF) of 13.56 MHz, a power of 45 watts (W), a gas flow rate of 7 liters / minute, and an exposure time of 5 seconds. The resulting metallic coating 20 is a bonded, conductive polycrystalline platinum layer. The specific surface resistance of the metallic coating 20 is 5 ohms / sq. The resulting metallic coating 20 can be used as part of a bioelectronic sensor.

[0078] Example VIII. A metallization solution 10 comprises a metal ion precursor of H2[PtCl6] with a concentration of 27 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol monopropyl ether and water (ratio 2:1) as the structuring liquid and a mixture of propylene glycol monomethyl ether and n-propanol (ratio 1:1.3) as the driving liquid. The metallization solution 10 is then nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized S50 at an aerosol (nebulization) gas flow rate of 0.25 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of pure Ar gas under atmospheric conditions, as in Fig. 4. Exposure S200 occurs at a plasma RF frequency of 13.56 MHz, a power of 22 watts (W), a gas flow rate of 10 liters / minute, and an exposure time of 5 seconds. The metallization solution 10 is then applied to a metal fleece substrate 30. The resulting metallic coating 20 is a metal fleece substrate coated with a complete continuous layer of platinum, with each metal fiber being individually coated. The resulting metallic coating 20 can withstand harsh chemical conditions and can be used in the manufacture of electrolyzers or fuel cells as part of a porous transport membrane.

[0079] Fig. Figure 5 shows an image of the obtained metallic coating 20 from Example VIII. Fig. Figure 5 shows the resulting metallic coating 20, consisting of a platinum layer in an electrolyzer. The image in Fig. 5 was imaged with a Zeiss Gemini scanning electron microscope at a magnification of 3,500 under a voltage of 5 kV and an InLens detector.

[0080] Example IX. A metallization solution 10 comprises a metal ion precursor of H2[PtCl6] with a concentration of 12 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol and water (ratio 1:1) as the structuring liquid and a mixture of propylene glycol monomethyl ether acetate and n-propanol (ratio 1:1.5) as the driving liquid. The metallization solution 10 is then nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized S50 at an aerosol (nebulization) gas flow rate of 0.22 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of pure argon (Ar) gas under atmospheric conditions, as in Fig. 4. Exposure S200 occurs at a plasma RF frequency of 12 MHz, a power of 25 watts (W), a gas flow rate of 8 liters / minute, and an exposure time of 7 seconds. The metallization solution 10 is then applied to a metal mesh substrate 30. The resulting metallic coating 20 is a metal mesh substrate coated with platinum (Pt) droplets or nanoislands. The resulting metallic coating 20 exhibits a catalytic effect and can be used in the fabrication of energy storage devices.

[0081] Fig. Figure 6 shows an image of the obtained metallic coating 20 from Example IX. Fig. Figure 6 shows the resulting metallic coating 20, consisting of Pt droplets / nanoislands in an electrolyzer. The image from Fig. 6 was acquired with a Zeiss Gemini scanning electron microscope at a magnification of 4,000 under the conditions of 5 kV and an InLens detector.

[0082] Example X. A metallization solution 10 comprises a metal ion precursor of palladium(II) nitrate (Pd(NO3)2) at a concentration of 8 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises propylene carbonate and γ-butyrolactone (ratio 20:1) as structuring liquid and 1,4-dioxane as driving liquid. The metallization solution 10 is then nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized S50 at an aerosol (nebulization) gas flow rate of 0.22 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of pure argon (Ar) gas under atmospheric conditions, as in Fig. 4. Exposure S200 occurs at a plasma RF frequency of 13.56 MHz, a power of 20 watts (W), a gas flow rate of 8 liters / minute, and an exposure time of 3 seconds. The metallization solution 10 is then applied S100 to a plastic substrate. The resulting metallic coating 20 is a plastic substrate coated with a continuous, uninterrupted layer of palladium. The metallic coating 20 can be used as a starting layer for future electroplating or chemical metal deposition.

[0083] Example XI. A metallization solution 10 comprises a metal ionic precursor of copper(II) nitrate (Cu(NO3)2) with a concentration of 23 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises propylene glycol as a structuring liquid and n-propanol as a driving liquid. The metallization solution 10 is applied to a 2D substrate 30 made of polyethylene terephthalate (PET) in application step S100. The PET substrate 30 is then exposed to a plasma 50 made of 98% argon (Ar) and 2% hydrogen (H2) gas under atmospheric conditions by means of an atmospheric plasma nozzle in exposure step S200, as in Fig. 2. Exposure S200 occurs at a plasma RF frequency of 13.56 MHz, a power of 35 watts (W), a gas flow rate of 5 liters / minute, and an exposure time of 2 seconds. The resulting metallic coating 20 is a bonded, conductive polycrystalline copper layer. The surface resistivity of the metallic coating 20 is 1 ohm / sq. The metallic coating 20 can be used as part of a solar cell device.

[0084] Example XII. A metallization solution 10 comprises a metal ion precursor of Cu(NO3)2 with a concentration of 17 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises ethylene glycol as the structuring liquid and a mixture of n-propanol and toluene (ratio 3:1) as the driving liquid. The metallization solution 10 is then nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized in S50 at an aerosol (nebulization) gas flow rate of 0.25 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of 98% Ar and 2% H2 under atmospheric conditions, as in Fig. 4. Exposure S200 occurs at a plasma RF frequency of 13.56 MHz, a power of 22 watts (W), a gas flow rate of 10 liters / minute, and an exposure time of 2 seconds. The metallizing solution 10 is then applied to a plastic substrate. The resulting metallic coating 20 is a plastic substrate coated with a complete, continuous layer of copper. The surface resistivity of the metallic coating 20 is 2 ohms / sq. The metallic coating 20 can be used as part of a solar cell device.

[0085] Example XIII. A metallization solution 10 comprises a mixture of two metal ion precursors: H[AuCl4] with a concentration of 9 wt.% and Pd(NO3)2 with a concentration of 12 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol, propylene carbonate, and γ-butyrolactone (ratio 6:18:1) as the structuring liquid and 1,4-dioxane as the driving liquid. The metallization solution 10 is applied to a two-dimensional (2D) silicone substrate 30 in application step S100. The silicone substrate 30 is then exposed to a plasma 50 of pure argon (Ar) gas under atmospheric conditions by means of an atmospheric plasma nozzle in exposure step S200, as in Fig. 2. Exposure S200 occurs at a plasma RF frequency of 13.56 MHz, a power of 40 watts (W), a gas flow rate of 4 liters / minute, and an exposure time of 10 seconds. The resulting metallic coating 20 is a bonded conductive polycrystalline layer of gold and palladium.

[0086] Fig. Figure 7 shows an image of the obtained metallic coating 20 from Example XIII. Fig. Figure 7 shows the resulting metallic coating 20, consisting of the gold and palladium layer on the silicon substrate 30. The image in Fig. 7 was recorded with a Zeiss Gemini scanning electron microscope at a magnification of 620,000 under a voltage of 5 kV and an InLens detector. The inset diagram on the right side of Fig. Figure 7 is an energy dispersive spectroscopy (EDS) spectrum of the same sample, recorded at a magnification of 12,000 under a voltage of 10 kV with an SE2 detector. It shows peaks for Au, Pd, and the silicon substrate 30.

[0087] Example XIV. A metallization solution 10 comprises a mixture of two metal ion precursors: Pd(NO3)2 at a concentration of 1.3 wt.% and AgNO3 at a concentration of 13 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol monopropyl ether, propylene carbonate, and γ-butyrolactone (ratio 15:23:1) as the structuring liquid and a mixture of 1,4-dioxane and n-propanol (ratio 1.5:1) as the driving liquid. The metallization solution 10 is then nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized in S50 at an aerosol (nebulization) gas flow rate of 0.2 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of pure Ar gas under atmospheric conditions, as in Fig. 4. Exposure S200 occurs at a plasma RF frequency of 13.56 MHz, a power of 25 watts (W), a gas flow rate of 8 liters / minute, and an exposure time of 4 seconds. The metallization solution 10 is then applied to a plastic substrate. The resulting metallic coating 20 is a plastic substrate coated with a complete, uninterrupted layer of silver and palladium.

[0088] Example XV. A metallization solution 10 comprises a metal ion precursor of bis(ammonium lactato)dihydroxide titanium with a concentration of 13 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol and water (ratio 1:3) as the structuring liquid and n-propanol as the driving liquid. The metallization solution 10 is applied to a 2D substrate 30 made of aluminum (Al) in the application step S100. The Al substrate 30 is then exposed to a plasma 50 made of pure oxygen gas under atmospheric conditions by means of an atmospheric plasma nozzle in the exposure step S200, as in Fig. 2. Exposure S200 occurs at a plasma RF frequency of 13.56 MHz, a power of 40 watts (W), a gas flow rate of 8 liters / minute, and an exposure time of 15 seconds. The resulting metallic coating 20 is a titanium layer with a high dielectric constant.

[0089] Example XVI. A metallization solution 10 comprises a metal ionic precursor of niobium oxalate with a concentration of 9 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of propylene glycol, oxalic acid, and water (ratio 1:2:6) as the structuring liquid and n-propanol as the driving liquid. The metallization solution 10 is applied to a 2D substrate 30 made of aluminum (Al) in the application step S100. The Al substrate 30 is then exposed to a plasma 50 of pure oxygen gas under atmospheric conditions by means of an atmospheric plasma nozzle in the exposure step S200, as in Fig. 2. Exposure S200 occurs at a plasma RF frequency of 13.56 MHz, a power of 45 watts (W), a gas flow rate of 10 liters / minute, and an exposure time of 10 seconds. The resulting metallic coating 20 is a niobium oxide layer with a high dielectric constant.

[0090] Example XVII. A metallization solution 10 comprises a metal ionic precursor of niobium oxalate with a concentration of 14 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol, oxalic acid, and water (ratio 1:3:8) as a structuring liquid and n-propanol as a driving liquid. The metallization solution 10 is applied to a 2D substrate 30 made of aluminum (Al) in application step S100. The Al substrate 30 is then exposed to a plasma 50 of 95% argon (Ar) and 5% hydrogen (H2) gas under atmospheric conditions by means of an atmospheric plasma nozzle in exposure step S200, as in Fig. 2. Exposure S200 is performed at a plasma RF frequency of 13.56 MHz, a power of 45 watts (W), a gas flow rate of 10 liters / minute, and an exposure time of 12 seconds. The resulting metallic coating 20 is a niobium layer with a high dielectric constant.

[0091] Example XVIII. A metallization solution 10 comprises a metal ionic precursor of hexachloroiridium(IV) acid (H2[IrCl6]) at a concentration of 2 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol and water (ratio 1:2) as the structuring liquid and n-propanol as the driving liquid. The metallization solution 10 is then nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized S50 at an aerosol (nebulization) gas flow rate of 0.18 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of 95% argon (Ar) and 5% hydrogen (H2) gas under atmospheric conditions, as in Fig. 4. Exposure S200 occurs at a plasma RF frequency of 15 MHz, a power of 30 watts (W), a gas flow rate of 10 liters / minute, and an exposure time of 4 seconds. The metallization solution 10 is then applied to a substrate 30 made of a titanium mesh. The resulting metallic coating 20 exhibits a catalytic effect and can be used in the manufacture of energy storage devices.

[0092] Example XIX. A metallization solution 10 comprises a metal ion precursor of rhodium(III) nitrate (Rh(NO3)3) at a concentration of 4 wt.% relative to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol and water (ratio 1:1) as the structuring liquid and a mixture of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (ratio 1.5:1) as the driving liquid. The metallization solution 10 is then nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized in S50 at an aerosol (nebulization) gas flow rate of 0.2 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of 95% argon (Ar) and 5% hydrogen (H2) gas under atmospheric conditions as in Fig. 4. Exposure S200 occurs at a plasma RF frequency of 20 MHz, a power of 28 watts (W), a gas flow rate of 8 liters / minute, and an exposure time of 3 seconds. The metallization solution 10 is then applied to a substrate 30 made of a titanium mesh. The resulting metallic coating 20 exhibits a catalytic effect and can be used in the manufacture of energy storage devices.

[0093] Example XX. A metallization solution 10 comprises a mixture of two metal ionic precursors: dihexachloroplatinic(IV) acid (H2[PtCl6]) with a concentration of 17 wt.% and hexachloroiridium(IV) acid (H2[IrCl6]) with a concentration of 2 wt.% with respect to the metallization solution 10. The metallization solution 10 comprises a mixture of ethylene glycol and water (ratio 1:1) as the structuring liquid and a mixture of propylene glycol monomethyl ether and n-propanol (ratio 1:1.6) as the driving liquid. The metallization solution 10 is nebulized in the nebulization step S50 using an aerosol (nebulization) generator 40. The metallization solution 10 is nebulized S50 at an aerosol (nebulization) gas flow rate of 0.22 liters / minute. The metallization solution 10 is exposed in the exposure step S200 to a plasma 50 of 95% argon (Ar) and 5% hydrogen (H2) gas under atmospheric conditions as in Fig.4. Exposure S200 occurs at a plasma RF frequency of 18 MHz, a power of 28 watts (W), a gas flow rate of 9 liters / minute, and an exposure time of 6 seconds. The metallization solution 10 is then applied to a titanium mesh substrate 30 in application step S100. The resulting metallic coating 20 exhibits a catalytic effect and can be used in the manufacture of energy storage devices. Reference symbol: 10 Metallization solution 15 Misty Metal 20 Metallic coating 30 Substrat 35 Surface 40 fog generator 45 Aerosol and / or vapor 50 plasma 100 device QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] US 2023 / 0220230 A1

[0003] EP 3 887 463 B1

[0004] WO 2015 / 071746 A1 [0005, 0048] Cited non-patent literature

[0000] Jiri George Drobny in "4 - Processing Techniques for Thermoplastic Elastomers" in the "Handbook of Thermoplastic Elastomers (Second Edition)", William Andrew Publishing, 2014, pages 33-173, ISBN 9780323221368, https: / / doi.org / 10.1016 / B978-0-323-22136-8.00004-1

[0002]

Claims

[1] A method for forming a metallic coating (20) from a metallization solution (10), wherein the metallization solution (10) comprises at least one metal ion precursor, at least one structuring liquid and at least one driving liquid, wherein the at least one metal ionic precursor comprises at least one metal cation and at least one counter ion, the at least one structuring liquid serves to dissolve the at least one metal ionic precursor in the metallization solution (10), the at least one driving liquid serves to atomize the metallization solution (10); and wherein the method comprises: applying (S100) the metallization solution (10) to a substrate (30), and exposing (S200) the metallization solution (10) to a plasma (50) under atmospheric conditions, whereby (S400) the metallic coating (20) is obtained. [2] The method according to claim 1, wherein the metallization solution (10) on the substrate (30) has a thickness, and the application (S100) of the metallization solution (10) to the substrate (30) is carried out such that the thickness of the metallization solution (10) is at most 2 mm. [3] The method according to claim 1 or 2, wherein the exposure (S200) is carried out at a gas flow rate of at least 0.5 litres / minute; and / or for an exposure time of at most 3600 seconds; and / or with a power of at most 3000 watts (W); and / or at a plasma radio frequency (RF) between 50 Hz and 5 GHz. [4] A method according to any one of the preceding claims, wherein the metallization solution (10) is exposed to a plasma (50) selected from one of the following groups: argon (Ar), nitrogen, oxygen, hydrogen, air, helium, neon, xenon, ammonia, ethane (C2H6), carbon dioxide, carbon monoxide, methane (CH4), propane (C3H8), silane (SiH4), nitrogen dioxide, nitrogen monoxide or a combination thereof. [5] Method according to one of the preceding claims, further comprising nebulizing (S50) the metallization solution (10) before application (S100). [6] A method according to any one of the preceding claims, wherein the method comprises the steps in the following order: atomizing (S50) the metallization solution (10); Exposing (S200) the metallization solution (10) to the plasma (50) under atmospheric conditions, thereby (S250) obtaining a nebulized metal (15); and Applying (S100) the atomized metal (15) to the substrate (30), whereby (S400) the metallic coating (20) is obtained. [7] A method according to claim 5 or 6, wherein the nebulizing (S50) is selected from one of the following methods: aerosolization and / or evaporation. [8] Method according to one of claims 5 to 7, wherein the nebulisation (S50) is carried out at a nebulisation gas flow rate of at least 0.01 litres / minute; and / or the exposure (S200) is carried out at a plasma gas flow rate of at least 0.5 litres / minute; and / or for an exposure time of not more than 3600 seconds; and / or with a power of not more than 3000 watts (W); and / or at a plasma radio frequency (RF) between 50 Hz and 5 GHz. [9] Method according to one of claims 5 to 8, wherein the nebulisation (S50) is carried out with a nebulisation gas flow rate of at least 0.1 litres / minute; and / or the exposure (S200) is carried out with a plasma gas flow rate of at least 2 litres / minute; and / or for an exposure time between 1 and 120 seconds; and / or at a power between 5 W and 100 W; and / or at a plasma radio frequency (RF) between 1 kHz and 1 GHz. [10] Method according to one of the preceding claims, wherein at least one metal cation is selected from one of the following groups: Au, Ag, Pt, Pd, Cu, Ti, Nb, Ni, Co, Ru, Ir and Rh; and the at least one counterion is selected from the group consisting of M(NO3)n, HmMCln+m and MN, where "M" is a metal atom having a valence of "n", H is hydrogen, NO3 is nitrate, "N" comprises an oxalate, hydroxide, ketone, carboxyl, lactone, and "m" is the valence of the counterion. [11] A process according to any one of the preceding claims, wherein the at least one metal ionic precursor has a concentration of at most 25 wt% with respect to the at least one structuring liquid and the at least one driving liquid, preferably between 1 and 15 wt%, and more preferably between 5 and 10 wt% with respect to the at least one structuring liquid and the at least one driving liquid. [12] Method according to one of the preceding claims, wherein the at least one structuring liquid is a solvent, and the solubility of the at least one metal ionic precursor in the solvent is at least 15 mg / ml at 25 °C, preferably at least 50 mg / ml at 25 °C, more preferably at least 100 mg / ml at 25 °C. [13] A method according to any one of the preceding claims, wherein the at least one structuring liquid is selected from one of the following groups: glycols, glycol ethers, glycol esters, carbonate esters, water, ketones, sulfoxides and their derivatives or a combination thereof. [14] A method according to any one of the preceding claims, wherein the at least one driving liquid is a solvent having a dynamic viscosity of 0.5 mPa·s to 5 mPa·s at 25°C. [15] A process according to any one of the preceding claims, wherein the at least one driving liquid is selected from one of the following groups: alcohols, cyclic alcohols, toluene, dioxane, ethylamines, glycol ethers, acetonitrile and their derivatives or a combination thereof. [16] Method according to one of the preceding claims, wherein the structuring liquid is present in a concentration between 3 wt% and 40 wt% with respect to the metallization solution (10); and / or the driving liquid is present in a concentration between 60 wt% and 97 wt% with respect to the metallization solution (10). [17] Method according to one of the preceding claims, wherein the substrate (30) is selected from a two-dimensional (2D) or a three-dimensional (3D) substrate, in particular from polyimide (PI), woven textile, polyethylene terephthalate (PET), filter substrate, plastic substrate, metal fleece substrate, aluminum base substrate, preferably aluminum foil, ceramic substrate, glass substrate and metal mesh substrate, preferably titanium mesh. [18] Method according to one of the preceding claims, wherein the metallization solution (10) comprises at least one additive selected from one of the following groups: organic molecules, polymers, conductive polymers, carbon nanotubes (CNT), densifying agents and surfactants. [19] Metallic coating (20) obtained by the method of any one of the preceding claims, wherein the metallic coating (20) is a polycrystalline metal layer. [20] Metallic coating (20) according to claim 19, wherein the metallic coating (20) has a thickness between 2 nm and 500 nm, preferably between 2 nm and 100 nm. [21] Metallic coating (20) according to claim 19 or 20, comprising metal oxides, wherein the metal oxides are preferably selected from one of the following groups: silver oxide, copper oxide, nickel oxide, zinc oxide, indium oxide, titanium oxide, iron oxide, zirconium oxide, niobium oxide, osmium oxide, iridium oxide, ruthenium oxide, rhodium oxide, aluminum oxide, tin oxide and antimony oxide, preferably titanium dioxide (TiO2) and niobium pentoxide (Nb2O5). [22] Metallic coating (20) according to one of claims 19 to 21, wherein the metallic coating (20) has a specific surface resistance of at least 1 Ω / □, preferably at least 4 Ω / □, particularly preferably at least 5 Ω / □; and / or a dielectric constant at 25 °C of at least 20, preferably of at least 35. [23] Use of the metallic coating (20) according to any one of claims 19 to 22 in an antibacterial application, electronic application, catalytic application or energy application. [24] Use of the metallic coating (20) according to any one of claims 19 to 23 as a biological sensor, as part of a bioelectronic sensor, for the production of electrolyzers, for the production of energy storage devices, preferably fuel cells, as part of a porous transport membrane, as a starting layer for future chemical or galvanic metal depositions or as part of a solar cell device. [25] Metallization solution (10) comprising at least one metal ionic precursor, at least one structuring liquid and at least one driving liquid, wherein the at least one metal ionic precursor comprises at least one metal cation and at least one counter ion; the at least one structuring liquid serves to dissolve the at least one metal ionic precursor in the metallization solution (10); and the at least one driving liquid serves to atomize the metallization solution (10), wherein preferably the at least one structuring liquid is a solvent and the solubility of the at least one metal ionic precursor in the solvent is at least 15 mg / ml at 25 °C; and / or wherein preferably the driving liquid is a solvent with a dynamic viscosity of 0.5 mPa·s to 5 mPa·s at 25 °C. [26] Metallization solution (10) according to claim 25, wherein at least one metal cation is selected from one of the following groups: Au, Ag, Pt, Pd, Cu, Ti, Nb, Ni, Co, Ru, Ir and Rh; and the at least one counterion is selected from the group consisting of M(NO3)n, HmMCln+m and MN, where "M" is a metal atom having a valence of "n", H is hydrogen, NO3 is nitrate, "N" comprises an oxalate, hydroxide, ketone, carboxyl, lactone and "m" is the valence of the counterion. [27] Metallization solution (10) according to claim 25 or 26, wherein the at least one metal ionic precursor has a concentration of at most 25 wt% with respect to the at least one structuring liquid and the at least one driving liquid, preferably between 1 wt% and 15 wt%, particularly preferably between 5 wt% and 10 wt% with respect to the at least one structuring liquid and the at least one driving liquid. [28] Metallization solution (10) according to one of claims 25 to 27, wherein the at least one structuring liquid is a solvent and the solubility of the at least one metal ionic precursor in the solvent is at least 50 mg / ml at 25 °C, preferably at least 100 mg / ml at 25 °C. [29] Metallization solution (10) according to one of claims 25 to 28, wherein the at least one structuring liquid is selected from one of the following groups: glycols, glycol ethers, glycol esters, carbonate esters, water, ketones, sulfoxides and their derivatives or a combination thereof. [30] Metallizing solution (10) according to one of claims 25 to 29, wherein the at least one driving liquid is selected from one of the following groups: Alcohols, cyclic alcohols, toluene, dioxane, ethylamines, glycol ethers, acetonitrile and their derivatives or a combination thereof. [31] Metallization solution (10) according to one of claims 25 to 30, wherein the structuring liquid is present in a concentration between 3 wt% and 40 wt% with respect to the metallization solution (10); and / or the driving liquid is present in a concentration between 60 wt% and 97 wt% with respect to the metallization solution (10). [32] Metallization solution (10) according to one of claims 25 to 31, further comprising at least one additive selected from one of the following groups: organic molecules, polymers, conductive polymers, carbon nanotubes (CNT), densifying agents and surfactants.

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