LU101451B1 - Manufacturing process of micro- and nanostructured patterns - Google Patents

Abstract

The present invention relates to a method of manufacturing micro- and nanostructured patterns comprising the spraying of an aerosol of metallic nanoparticles or of metal oxide (s) through at least one mask, a device for manufacturing micro patterns and nanostructures implementing said method, the use of said device to manufacture various types of coatings, in particular of a hydrophobic nature, and micro- and nanostructured patterns obtained according to said method.

Description

© 1: Description LU101451 Title of the invention: process for manufacturing micro- and nanostructured units The present invention relates to a process for manufacturing micro- and nanostructured units comprising the spraying of an aerosol of metallic nanoparticles or of oxide (s ) metallic (s) through at least one mask, a device for the manufacture of micro- and nanostructured patterns implementing said method, the use of said device to manufacture various types of coatings, in particular of a hydrophobic nature, and micro- patterns and nanostructures obtained according to said process.

Surface texturing at the micro- and / or nanometric scale consists in modifying the topography of an initially flat surface, in order to create patterns (studs, holes, grooves, etc.) in a more or less regular way, thus conferring on said surface new functionalities such as, for example, properties of hydrophobicity or superhydrophibicity, making the surface self-cleaning, anti-fouling, or protecting it from contact with corrosive solutions; optical properties (modification of the reflection or absorption of light to obtain anti-reflection properties or specific coloring); tribological properties (modification of the friction between two sliding surfaces to reduce wear, improvement of lubrication, feeling of softness on contact with the skin); biological properties (modification of the capacity of cell adhesion to a substrate for the de-fouling of surfaces), etc ... As examples of superhydrophobic surfaces offered by nature itself, mention may be made of the surface of the leaves of lotus formed by micro- and nano-texturations (called papillae) covered with wax which makes it superhydrophobic and self-cleaning.

Drops of water run off the lotus leaves without ever wetting them and carry with them the dust and particles present.

This is then referred to as the “lotus effect” phenomenon, which is the generic term used to qualify the biomimicry of the superhydrophobia of certain plants [Neinhuis et al., Annals of Botany, 1997, 79, 667-677] such as the lotus. (Nelumbo sp), the leaves of which exhibit this characteristic.

Other plants, such as the leaves of nasturtium (Tropaeolum), cabbage, reed (Phragmites), taro (Colocasia esculenta) or columbine, and

Ç 2; certain animals (for example ducks, more particularly their feathers), LU101451 in particular insects, show the same “lotus effect” phenomenon. The functionalities generated depend on the morphology of the patterns, their organization, their size, and the pitch of the network.

Today, surface texturing is mainly applied to semiconductor materials in the field of electronics (eg microelectromechanical systems, magnetic hard disks), in particular in order to reduce friction by reducing the contact surface, and to polymer materials. . The first superhydrophobic products were marketed in the early 2000s, such as a self-cleaning facade paint sold under the trade name Lotusan®, self-cleaning glasses marketed by the company Ferro GmbH and installed in optical sensors located at toll booths on German motorways, or anti-corrosion protective coatings for buildings sold under the trade name Protectosil® by the company Evonik.

Surface texturing is of great interest to the transport sector, particularly aeronautics and maritime, with respect to resistance to fouling, resistance to corrosion, etc. In particular, reducing friction would improve aero- or hydro-dynamism and significantly reduce fuel consumption. The main existing techniques for carrying out surface micro- and / or nanotexturing are based on material removal. They include lithography, laser ablation, wet or dry etching, and electroplating of metal. In particular, lithography requires a large number of steps such as the deposition of a photosensitive resin on the surface of the substrate to be structured, the deposition of a mask, irradiation at a given wavelength, chemical development to reveal the patterns in the resin, the etching or the deposition of a metal in the areas of the surface left free in order to obtain the desired patterns on the surface, and finally the elimination of the remaining resin. In addition, this method is complex to implement and expensive. Laser ablation involves removing material using a laser beam. This method can therefore pose heating problems. Wet or dry etching consists of etching a surface

. 3; covered with a mask.

The attack can be carried out by wet route, in particular by LU101451 using an aggressive chemical solution: or by physical route, called "dry", in particular by implementing an ion bombardment by means of an appropriate gas or electrons by means of a suitable plasma.

The physical route can prove to be difficult to implement industrially and costly.

As for the wet process, it can be accompanied by undesirable isotropic sub-etchings, and does not always make it possible to control the texturing.

Electroplating is a process of electrochemically adding material to a conductive substrate.

It is often accompanied by parasitic reactions (eg reduction of protons) which can weaken the deposits or modify its properties.

Furthermore, the morphology of the deposit is difficult to control.

Electroplating of metal is sometimes coupled with self-assembly techniques of nanoparticles by capillary action which allow better control of the order of patterns and minimize their defects.

Self-assembly is achieved by evaporation of a colloidal solution of nanoparticles on a substrate.

However, it requires pre-structuring of the substrate to locate the adsorption sites of the nanoparticles.

By way of example, US 2008/107876 A1 describes a method for the selective growth of zinc oxide microstructures comprising a step of applying an organic or inorganic material to a substrate, a step of forming a pattern having a predetermined and specific position and a predetermined interval on the substrate, using a lithography process or a physical or chemical etching technique, and a step of selectively growing zinc oxide microstructures at the position where the pattern is formed, in using different growth techniques such as hydrothermal synthesis, physical or chemical vapor deposition.

Therefore, at present, no technique meets the requirements of simple implementation, scalable, cost-saving and low impact on the environment.

Laser and lithographic techniques, widely used in research, are not economically viable when considering scaling up.

In addition, laser processes releasing thermal energy can damage the patterns.

Furthermore, the solutions proposed are not always satisfactory as regards the quality.

; of texturing, in particular the control of the geometry of the patterns such as the LU101451 control of uniform dimensions and / or a well-defined morphology.

Thus, the aim of the invention is to overcome all or part of the drawbacks of the prior art, and in particular to provide a method for manufacturing micro- and nanostructured patterns, which is simple, economical, can be used on a large scale, having a low environmental impact, and guaranteeing a good quality of surface texturing.

The first subject of the present invention is therefore a process for manufacturing micro- and nanostructured units, characterized in that it comprises at least the following steps: a) the preparation of an aerosol of metallic nanoparticles or of oxide (s) metallic (s), b) the spraying of the aerosol of nanoparticles through at least one mask, and c) the deposition of the nanoparticles on a surface of a substrate, and in that step a) is carried out by putting implementing a device for generating said aerosol comprising: a reaction chamber comprising at least a first inlet configured for the admission of a liquid composition comprising at least a first precursor of the nanoparticles, at least one second inlet configured for the admission of 'a gaseous composition comprising at least one carrier gas and at least one reactive gas, and at least one outlet configured to extract the nanoparticles from the reaction chamber, - a liquid injector connected to said first input ée, configured to inject or spray said liquid composition into the reaction chamber, and - a nanoparticle injector connected to said outlet of the reaction chamber, configured to inject or spray the nanoparticles, and - control means for controlling the injection or spraying of said liquid composition and / or said nanoparticles, step a) comprising the following substeps:

, al) the introduction of the liquid composition into the reaction chamber through said first inlet LU101451 by means of said liquid injector, a2) the introduction of the gaseous composition into the reaction chamber through said second inlet, a3) the reaction of the precursor of the nanoparticles with the reactive gas in the reaction chamber, to form the nanoparticles, and a4) the formation of an aerosol of the nanoparticles, by means of said nanoparticle injector. The process of the invention is simple, economical, it can be used on a large scale, it has a low environmental impact, and it guarantees a good quality of surface texturing. In particular, the various steps are carried out while avoiding any contact with the nanoparticles. Furthermore, the use of the mask makes it possible to form various micro- and nanostructured patterns on a surface of a substrate with well-defined dimensions and / or morphology.

In the invention, the expression “nanoparticles” means particles having at least one dimension less than approximately 100 nm, preferably particles having a dimension ranging from approximately 1 to 100 nm, particularly preferably ranging from 1 to 50 nm. approximately, and more particularly preferably ranging from 1 to 20 nm approximately.

Considering several nanoparticles according to the invention, the term "dimension" means the number-average dimension of all the nanoparticles of a given population, this dimension being conventionally determined by methods well known to those skilled in the art.

The size of the nanoparticles according to the invention can for example be determined by microscopy, in particular by scanning electron microscope (SEM), by transmission electron microscope (TEM), by DOSY NMR, or by dynamic light scattering.

The nanoparticles of the invention are preferably in the form of nanocrystals. In the invention, the expression "nanocrystalline" means a nanoparticle (as defined above) composed of atoms in a poly- or monocrystalline arrangement.

; The metal nanoparticles can be nanoparticles of at least one Lu101451 metal chosen from: Zn, Cu, Ag, Ru, Pt, Pd, Au, Ir, Sn, Fe, Co, Ni, and an alloy of at least one of the aforementioned metals.

The nanoparticles of metal oxide (s) can be nanoparticles of at least one metal oxide chosen from an oxide of: Zn, Sn, Cd, B, Al, Ga, In, Th, Ge, Ti, Zr, Hf, Sc, Y, Si, Bi, and lanthanide (eg

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). Step a) Thanks to the aerosol generator device used in step a), it is possible to control the size and the morphology of the nanoparticles that one wishes to obtain.

Sub-step a1) Sub-step a1) makes it possible to introduce the liquid composition into the reaction chamber through said first inlet, by means of said liquid injector.

The liquid composition comprises at least a first precursor of the nanoparticles The first precursor of the nanoparticles can be a precursor of at least one metal or of at least one metal oxide, in particular comprising at least one metal chosen from Zn, Cu, Ag , Ru, Pt, Pd, Au, Ir, Sn, Fe, Co, Ni, Cd, B, Al, Ga, In, Th, Ge, Ti, Zr, Hf, Sc, Y, Si, Bi, and a lanthanide (eg

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The first precursor of the nanoparticles can be liquid at room temperature (for example at 20-25 ° C approximately), or can be dissolved in a solvent at room temperature.

The solvent can be any solvent which dissolves the first precursor of the nanoparticles, in order in particular to form the liquid composition at room temperature. The solvent can also dissolve the other compounds which are likely to be present in the liquid composition.

In the invention, the expression “precursor of the nanoparticles” means a reagent comprising at least one chemical element which constitutes the nanoparticles.

Said

. 7. first precursor of the nanoparticles is capable of reacting with the reactive gas LU101451 (sub-step a3)), in order to form the nanoparticles. The liquid composition can further comprise a stabilizing agent. The stabilizing agent makes it possible to stabilize the nanoparticles. I! generally makes it possible to stabilize the surface of the nanoparticles and usually represents an organic molecule which binds to the surface of the nanoparticles and thus avoids the aggregation and / or the agglomeration and / or the coalescence of the nanoparticles. The stabilizing agent controls the morphology of the nanoparticles during step a), while preventing their agglomeration, and allows the cohesion or structuring of the nanoparticles during step c).

Any stabilizing agent known to those skilled in the art which is liquid at room temperature or can be dissolved in the liquid composition at room temperature, and which interacts by physisorption or chemisorption with the nanoparticles (or at least with the first precursor of nanoparticles) can be used in the method of the invention.

Advantageously, the stabilizing agent can be chosen from amines, such as, for example, primary amines, acids such as, for example, carboxylic acids, thiols, phosphorus derivatives and basic ethers, and preferably chosen from amines.

As examples of amines, mention may be made of aliphatic amines, particularly preferably saturated aliphatic amines, and more particularly saturated aliphatic amines having from 6 to 20 carbon atoms.

The liquid composition can further comprise at least a second precursor of the nanoparticles (which is different from the first precursor as defined above). Said second precursor of the nanoparticles is capable, just like the first precursor of the nanoparticles, of reacting with the reactive gas, in order to form the nanoparticles.

A second precursor of nanoparticles is generally used if nanoparticles of a mixture of at least two different metals, or a mixture of at least two oxides of different metals are prepared.

. The aerosol generator device implementing step a) can include in Lu101451 in addition to a reservoir T 'configured to contain the liquid composition as defined in the invention.

The tank T 'can be a Fisher-Porter type tube.

The tank T 'can be connected by a pipe or a supply line to the first inlet of the reaction chamber.

In one embodiment, step a) comprises, before sub-step a1), a sub-step a0) of preparing the liquid composition and introducing said composition into the tank T *. The tank T 'is preferably connected to a tank T? configured to contain pressurized gas.

The gas from tank T? pressurizes the tank T 'to a pressure p! The pressure at the first inlet of the reaction chamber is then equal to P *. The pressurized gas can be argon, helium or dinitrogen.

Pressurization means can be used, in order to allow precise control of the thrust pressure of the liquid composition.

Advantageously, the pressure P ′ is at least 0.5 bar above atmospheric pressure (ie at least 1.5 bar), and more particularly ranges from approximately 1 bar above atmospheric pressure to About 5 bars above atmospheric pressure.

The control means of the aerosol generator device supply control signals AO and Aa intended respectively to control the opening and closing of the injectors of liquid and of nanoparticles.

The control signals are preferably binary logic control signals.

Control means such as an injection control unit can be used.

The injection control unit can control the flow rate (or pulse train) of the liquid injector and / or the nanoparticle injector.

. 9, The flow rate (or the pulse train) can be defined by the following injection parameters Lu101451: the injection frequency (in hertz, Hz) and / or the duration of the injector opening (in milliseconds, ms ). In a particular embodiment, the duration of opening of the liquid injector and / or the frequency of injection of the liquid injector connected to the first inlet of the reaction chamber configured to inject or spray the liquid composition in the reaction chamber, can be set so that the entire amount of liquid composition is introduced into the reaction chamber. Advantageously, during substep a1), the liquid injector has an opening time ranging from about 1 ms to about 20 ms, and preferably from about 1 ms to about 10 ms. During sub-step a1), the liquid injector has an injection frequency ranging from about 1 Hz to about 50 Hz, and preferably from about 1 Hz to about 5 Hz. The injection of liquid is from about 1 Hz to about 50 Hz. periodic preference (ie pulsed).

Sub-step a2) Sub-step a2) makes it possible to introduce the gaseous composition into the reaction chamber through said second inlet. The gas composition comprises at least one carrier gas and at least one reactive gas.

The reactive gas can be chosen from reducing gases and oxidizing gases.

More particularly, the reactive gas can be water vapor, oxygen, carbon dioxide, carbon monoxide, hydrogen, ammonia or arsenic trihydride.

In one embodiment, the reactive gas is capable of reacting with the first precursor of the nanoparticles (and the second precursor of the nanoparticles if there is one), to form the nanoparticles (sub-step a3)), as soon as said reactive gas is contacted with the liquid composition in the reaction chamber.

The reactive gas can be a precursor of nanoparticles or can be different from a precursor of nanoparticles. In other words, when the reactive gas is a precursor of nanoparticles, it contains at least one chemical element which will constitute said nanoparticles. When the reactive gas is different from a

. 10, a precursor of nanoparticles, it does not contain any chemical element which will LU101451 constitute the nanoparticles obtained according to the process of the present invention. The embodiment according to which the reactive gas is a precursor of the nanoparticles is particularly suitable if nanoparticles of a mixture of at least two different above-mentioned metals, or of a mixture of at least two oxides of different above-mentioned metals are prepared. One of the aforementioned metals can thus be supplied by the reactive gas and another of the aforementioned metals can be supplied by the first precursor of the nanoparticles as defined in the invention. The aerosol generator device may further comprise a reservoir T * configured to contain the gaseous composition.

The T ° tank can be connected by a pipe or a supply line to the second inlet of the reaction chamber.

The T ° reservoir can be a Fisher-Porter type tube. The T ° tank can be connected to a T * tank configured to contain the carrier gas. Carrier gas from tank T * pressurizes tank T? at a pressure P *. The pressure at the level of the second inlet of the reaction chamber is then equal to P °, preferably such that P *> P *.

The carrier gas can be a gas inert to the reagents used in step a), such as argon, helium or dinitrogen.

In one embodiment, step a) further comprises, before sub-step a2), a sub-step a1 ′) of preparing the gas composition and introducing said gaseous composition into the tank T *.

During the sub-step a1 ′), the carrier gas present in the tank T * can be introduced into the tank T ° containing the reactive gas.

The introduction of the carrier gas into the T ° tank can be carried out by any means. More specifically, the carrier gas is introduced continuously into the T ° tank. A pressure and / or flow regulator can be placed between the T * and T ° tanks. {

'Advantageously, the pressure P * is at least equal to the pressure P' minus 0.5 bar, LU101451 and preferably ranges from approximately 0.5 bar above atmospheric pressure to approximately 4.5 bar above atmospheric pressure.

In a preferred embodiment of the invention, the reactive gas of the gaseous composition is obtained from a liquid reactant. In other words, the liquid reactant is capable of producing the reactant gas directly, when the appropriate temperature and pressure conditions are implemented.

In this embodiment, the precursor of the nanoparticles is preferably a precursor of nanoparticles of metal oxide (s), such as for example an organometallic compound.

In this embodiment, the T ° reservoir is configured to contain the liquid reagent and transform the liquid reagent into reactive gas.

The liquid reagent can be water in the liquid state. Thus, the reactive gas produced from water in the liquid state is water vapor.

In a particularly preferred embodiment, during the sub-step at '), the pressure of the pressure regulator arranged between the tanks T * and T ° during the introduction of the carrier gas into the tank T ° can be controlled so as to converting liquid reagent to reactive gas.

Thus, during sub-step a1 ′), the reactive gas is produced in situ in the tank T * from the liquid reagent, and the carrier gas from the tank T * is introduced into the tank T °, in order to form the composition sparkling.

In a particular embodiment, the aerosol generator device may further comprise a heating device connected to the tank T * for heating the liquid reagent in the tank T °, and triggering the conversion of said liquid reagent into reactive gas during the process. sub-step a1 ').

The heater can heat the liquid reagent to a temperature of from about 70 ° C.

In another embodiment, no conversion of a liquid reactant to a reactant gas is required. Therefore, the liquid reagent is not present in the T ° reservoir.

; In this embodiment, the T ° tank can be connected to a T ° LU101451 tank configured to contain the reactive gas. The reactive gas can then be hydrogen, oxygen, ammonia or arsenic trinhydride.

Therefore, during the sub-step a1 ’), the reactive gas from the tank T ° and the carrier gas from the tank T * are both introduced into the tank T °, in order to form the gas composition.

The introduction of the reactive gas from the tank T ° into the tank T * can be carried out by any means. More specifically, the reactive gas is introduced continuously into the T ° tank. A pressure and / or flow regulator can be placed between the T ° and T ° tanks.

Sub-steps a1) and a2) can be concomitant.

Sub-step a3) During sub-step a3), nanoparticles are obtained by reaction of the first precursor of said nanoparticles, and of the second precursor of said nanoparticles if it exists, with the reactive gas of the gaseous composition.

The reactive gas is thus capable of reacting with the first and the second precursors of the nanoparticles, to produce the nanoparticles.

Step a) is versatile, and depending on the nature of the reactive gas and of the nanoparticle precursors, different types of reactions can be implemented.

Sub-step a3) can be chosen from chemical reactions involving hydrolysis, oxidation, reduction or an acid-base reaction.

As examples of such chemical reactions, mention may be made of: - reactions of coordination complexes (ie organometallic or inorganic compounds), with water, dioxygen or dihydrogen, - reactions of compounds comprising at least one element from column 13 of the periodic table of chemical elements with a gaseous hydride comprising at least one element from column 15 of the periodic table of chemical elements making it possible to form nanoparticles of at least one following metal: Zn, Cu, Ag,

. Ru, Pt, Pd, Au, Ir, Sn, Fe, Co, Ni or at least one of the following metal oxides: Zn, Sn, LU101451 Cd, B, Al, Ga, In, Th, Ge, Ti, Zr , Hf, Sc, Y, Si, Bi, and lanthanide, - reactions of silica precursors with ozone, water or dioxygen, - reactions of cobalt precursors with dioxygen or water .

Examples of chemical reactions involving the reaction of an organometallic compound with water are described in application FR2853307. Examples of chemical reactions involving the reaction of a compound comprising at least one element from column 13 of the periodic table of chemical elements with a gaseous hydride comprising at least one element from column 15 of the periodic table of chemical elements are described in FR2969137 .

During sub-step a3), the pressure P in the reaction chamber is generally at most equal to the pressure P *. According to a particularly preferred embodiment of the invention, sub-step a3) is a chemical reaction involving the reaction of an organometallic compound with water. Therefore, the first precursor of nanoparticles is an organometallic compound and the reactive gas is water vapor. The reaction results in nanoparticles of at least one metal oxide as defined in the invention.

The organometallic compound can be a coordination complex containing at least one organic group linked to at least one metal atom via a carbon atom or a heteroatom of this organic group, said heteroatom being other than oxygen, in particular chosen from N , P, As, Si, S, Se, and Te.

The organometallic compound is reactive with water and is converted upon exothermic hydrolysis to a metal oxide when contacted with steam as a reactive gas.

The organometallic compound can comprise at least one metal chosen from Zn, Sn, Cd, B, Al, Ga, In, Th, Ge, Ti, Zr, Hf, Sc, Y, Si, Bi, and lanthanide (eg Ce, Pr , Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu).

As examples of organometallic compounds which can be used in step a) of the process of the invention, mention may be made of coordination complexes

. 14; comprising at least one metal chosen from Zn, Sn, Cd, B, Al, Ga, In, Th, Ge, Ti, Zr, LU101451 Hf, Sc, Y, Si, Bi, and lanthanide (eg Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), and at least one organic group selected from amide, alkyl, aryl, alkene, alkyne and silyl groups, said organic group being bonded to said metal by a carbon atom or a heteroatom of this organic group, said heteroatom being other than oxygen, in particular chosen from N, P, As, Si, S, Se, and Te. The organic alkene, silyl and alkyl groups are preferred. Examples of organometallic compounds are Zn (CeH411) 2, commonly referred to as ZnCy2 or zinc bis (cyclohexyl), [Sn (N (CHz) z) z]>, dicyclopentadienyl tin Sn (CsHs) 2, indium cyclopentadienyl In (CsHs), {Fe [N (SiMe3) a] a}, {Co [N (SiMe3) 2] z}, [Ni (COD) z], Ru (COD) (COT), [Cu (iPr- Me-AMD)]>, hexamethyldisiloxane Si20 (CHz) s, or tetraethoxysilane Si (OEt) ,.

The liquid composition injected into the reaction chamber therefore comprises said organometallic compound as the first precursor of the nanoparticles.

The solvent of the liquid composition can be a non-aqueous solvent, in particular in order to dissolve said organometallic compound at room temperature, more particularly when the organometallic compound used in substep at) is solid at room temperature.

Such non-aqueous solvents can be chosen from alkanes (e.g. pentane, heptane or cyclohexane), toluene, and a mixture thereof.

When the organometallic compound used in substep a1) is liquid at room temperature, a solvent is not required. Such an organometallic compound can be hexamethyldisiloxane, or tetraethoxysilane.

In a preferred embodiment, the molar concentration of the organometallic compound in the liquid composition ranges from about 0.001 mol / l to about 1 mol / l, and preferably from about 0.01 mol / l to about 0.1 mol / l.

When the first precursor is an organometallic compound, the liquid composition preferably further comprises a stabilizing agent as defined in the invention.

; The stabilizing agent is preferably a saturated aliphatic amine, more LU101451 preferably having from 6 to 20 carbon atoms, such as hexadecylamine, dodecylamine, or octylamine.

The molar ratio of the stabilizing agent to the organometallic compound can range from about 0.01 to about 5, and preferably from about 0.1 to about 2. In the liquid composition, the stabilizing agent can represent from 1 at approximately 30% by mass, and preferably from 5 to 20% by mass approximately, relative to the total mass of the organometallic compound.

The sub-steps a1), a2) and a3) can be concomitant.

Sub-step a4) On leaving the nanoparticle injector, the nanoparticles are in the form of an aerosol.

In the invention, the expression “nanoparticle aerosol” means that the nanoparticles are in suspension in a gas phase (under optimal conditions) or form a mixture of nanoparticles and liquid droplets in a gas phase (under less optimal conditions. ). The aerosol generator device, and in particular the outlet of said nanoparticle injector, can be connected to an injection chamber, in particular so as to implement step b) in said injection chamber .

In other words, the aerosol of nanoparticles formed during substep a4) is directed during the following step b) into the injection chamber by means of said nanoparticle injector.

Preferably, the aerosol generator device used in step a) is not connected to an evaporation chamber.

The injection chamber, at the inlet, has a pressure P; preferably ranging from 10 ° to approximately 1 bar.

The entrance to the injection chamber is located after the exit of the aerosol generator device, and before the mask, relative to the trajectory of the nanoparticles.

, 16. In sub-step a4), the nanoparticles optionally dispersed in an LU101451 mixture of gas and / or liquid phase are expelled or extracted from the reaction chamber, in particular towards the injection chamber.

In a particular embodiment, the duration of opening of the nanoparticle injector and / or the injection frequency of the nanoparticle injector connected to the outlet of the reaction chamber, configured to inject or spray the nanoparticles, can be parameterized so that the sub-step a3) is complete (ie that the first precursor of the nanoparticles, and the second precursor of the nanoparticles if it exists, are completely consumed in order to form the nanoparticles). Advantageously, during sub-step a4), the nanoparticle injector has an opening time ranging from about 1 ms to about 20 ms, and preferably from about 1 ms to about 10 ms.

In a preferred embodiment, the ratio of the duration of opening of the nanoparticle injector to the duration of opening of the liquid injector is greater than or equal to 2, particularly preferably greater than or equal to 4, and more particularly preferably greater than or equal to 5, when the pressure at the outlet of the nanoparticle injector of the device as defined in the invention or in the injection chamber connected to the reaction chamber of the device such as defined in the invention is equal to atmospheric pressure.

In another embodiment, the ratio of the opening time of the nanoparticle injector to the opening time of the liquid injector is greater than or equal to 1, when the pressure at the outlet of the injector nanoparticles of the device as defined in the invention or in the injection chamber connected to the reaction chamber of the device as defined in the invention is below atmospheric pressure.

During sub-step a4), the nanoparticle injector preferably has an injection frequency ranging from approximately 0.1 Hz to approximately 50 Hz, particularly preferably approximately 0.5 Hz to approximately 10 Hz, and more particularly preferably from about 1 Hz to about 5 Hz.

. The device used in step a) can be any conventional direct liquid injection LU101451 device such as that marketed by the company Kemstream under the reference "Atokit KF50 Direct Injection Atomizer". The sub-steps a1), a2), a3) and a4) can be concomitant.

Step b) During step b), the aerosol of nanoparticles is sprayed through a mask.

Through the use of a mask, various and mastered patterns can be deposited on the surface of the substrate.

Step b) is preferably carried out in the injection chamber.

The injection chamber may include an element configured to direct the aerosol towards the mask such as a cone shaped element.

The mask can be directly connected to the element configured to direct the aerosol.

The injection chamber can be connected to a deposition chamber, in particular to allow the implementation of the following step c).

The aerosol of nanoparticles passes through the mask, preferably by virtue of a pressure difference between the injection chamber and the deposition chamber.

In one embodiment, the deposition chamber, at the outlet, has a pressure Pa such that Py <Pi, and preferably Py <P i. The pressure P; in bar is that at the inlet of the injection chamber.

The exit from the injection chamber is located after the substrate, relative to the path of the nanoparticles.

According to a particularly preferred embodiment of the invention, the pressure P; in bar at the inlet of the injection chamber and the pressure Pa in bar at the outlet of the deposition chamber are such that the P / P ratio; ranges from 1 to 5 × 10 ° approximately, and preferably from 10 ° to 10 * approximately.

The mask can include or be made of a metallic material such as aluminum, stainless steel, titanium, or anodized aluminum.

The mask may have one or more openings, preferably multiple LU101451 openings. The openings are preferably of millimeter or micrometric size. In particular, the openings can have at least one dimension, and preferably a diameter, ranging from about 10 to about 500 µm.

The openings of the mask can have any geometric shape (point or continuous), in particular circular, rectangular, square, triangular, elliptical, rectilinear, of the honeycomb type, in the form of a network of lines, of the type zig-zag, etc ...

The openings can be evenly distributed or randomly distributed over the mask, and preferably evenly distributed. The average distance between two adjacent openings is preferably at least 10 µm, and particularly preferably at least 100 µm. The average distance can reach several centimeters. This thus makes it possible to form substantially identical patterns uniformly distributed over the surface of the substrate. The number of openings in the mask generally corresponds to the number of micro- and nanostructured patterns that one wishes to deposit on the surface of the substrate. The mask can include a hundred to several hundred openings. The mask can have any general shape, such as for example a circular, rectangular, square, or triangular shape. Preferably, the mask has a thickness of from about 0.5mm to about 1cm. According to a preferred embodiment of the invention, the mask is in the form of a (circular) disc with a thickness ranging from 0.5 mm to about 5 mm. According to a particularly preferred embodiment of the invention, the mask is a shower electrode, for example such as those conventionally used in a plasma reactor, also called “injection shower”. A shower electrode is usually used as a gas distribution shower in a plasma reactor, in order to diffuse gases and obtain an optimal flow. The shape and dimensions of the mask, and the shape and dimensions of the apertures of the mask make it possible to control the shape, distribution and dimensions of the micro- and nanostructured patterns deposited on the surface of the substrate.

; 19; The invention is not limited to the use of a single mask. For example, steps LU101451 b) and c) can be repeated with a new mask having a different shape and / or dimensions. In one embodiment of the invention, the injection chamber may comprise means intended to move the mask during steps b) and c) along a given path with respect to the substrate which remains fixed. This thus makes it possible to deposit micro- and nanostructured patterns according to a specific geometry. Step c) During step c), the nanoparticles are deposited on the surface of the substrate in order to form micro- and nanostructured patterns.

Steps b) and c) can be concomitant. The pressure Pq at the outlet of the deposition chamber preferably ranges from approximately 10 ° to 1 bar, particularly preferably from approximately 102 to 10 mbar, and more particularly preferably from approximately 0.5 to 3 mbar. Thanks to this pressure, the deposition of micro- and nanostructured units (e.g. accumulation of material) is optimized. The micro- and nanostructured units preferably have a height relative to the surface of the substrate on which they are deposited of at least approximately 10 nm, preferably ranging from approximately 100 nm to approximately 1000 μm, and particularly preferably ranging from about 10 µm to about 500 µm.

The ratio of the height of a pattern to the surface of the substrate, to the distance between two patterns can vary from 10 "to 10? approximately, preferably from 10 ° to 10 "approximately, and particularly preferably from 0.5 to 1.5 approximately. Said ratio is more particularly preferably equal to approximately 1.

The patterns can be shaped like a pyramid, a dune or a spot.

The mask is preferably placed at a distance from the surface of the substrate of at most approximately 10 cm, and particularly preferably ranging from 0.5 to 5 cm approximately.

The units obtained can have a hydrophobic or superhydrophobic character, in particular having a contact angle ranging from about 80 ° to about 150 °.

The units are preferably micro- and nanostructured units.

. Thanks to the micro- and nanostructured patterns obtained according to the process of the invention, it LU101451 is possible to manufacture self-cleaning coatings, anti-frost coatings, anti-corrosion coatings, anti-fog glasses, anti- windshields. rain, breathable and stain resistant clothing, anti-humidity paints, anti-bacterial, anti-fouling or anti-bio-fouling coatings, optical filters, self-healing or aging-resistant coatings, etc. The substrate is preferably placed in the deposit room.

The substrate can include or be made of a metallic material such as aluminum or a metal alloy such as stainless steel; one or more glasses such as silica; sapphire; a composite material such as thermoplastic polymers loaded with carbon fibers; one or more transparent plastics; one or more polymeric materials such as polyurethane, polycarbonate, or poly (vinyl butyral); of fabric: or of a lignocellulosic material such as wood.

The substrate can be of rigid or flexible structure, in particular in the form of a flexible sheet.

When the substrate is of flexible structure, it can be deposited on a substrate holder of rigid structure.

According to one embodiment of the invention, the substrate can be a flat substrate or can comprise at least one flat surface on which the micro- and nanostructured patterns are deposited.

In one embodiment of the invention, the deposition chamber may comprise means intended to move the substrate during steps b) and c) along a given path with respect to the mask which remains fixed.

This thus makes it possible to deposit micro- and nanostructured patterns according to a specific geometry.

The method may further comprise the reiteration of steps a), b) and c) with another precursor of the nanoparticles (different from the first and second precursors as defined in the invention), in order to form micro- and nanostructured units comprising at least two different metals or two oxides of different metals or a mixture of oxides of metals and metals.

| 21. The method may further comprise a step d) of post-treatment such as an LU101451 heat treatment, assisted by plasma or photo-assisted.

The second object of the invention is a device for manufacturing micro- and nanostructured patterns implementing a method as defined in the first object of the invention, characterized in that it comprises:

a device for generating an aerosol of nanoparticles comprising: a reaction chamber comprising at least one first inlet configured for the admission of a liquid composition, at least one second inlet configured for the admission of a gaseous composition, and at least one outlet configured to extract nanoparticles from the reaction chamber, * a liquid injector connected to said first inlet, configured to inject or spray said liquid composition into the reaction chamber, * a nanoparticle injector connected to said outlet of the reaction chamber, configured to inject or spray the nanoparticles,

* control means for controlling the injection or spraying of said liquid composition and / or said nanoparticles, * a reservoir T 'configured to contain the liquid composition, and * a reservoir T ° configured to contain the gaseous composition, - a injection chamber comprising at least one mask, and

a deposition chamber comprising a substrate intended to receive the nanoparticles forming micro- and nanostructured patterns.

The device for generating an aerosol of nanoparticles and its elements may be as defined in the first subject of the invention.

The injection chamber and its elements can be as defined in the first subject of the invention.

The deposition chamber and its elements can be as defined in the first subject of the invention.

Thanks to the device of the invention, micro- and nanostructured units can be obtained in a controlled manner, avoiding any manipulation of the nanoparticles and / or

. contact with said nanoparticles.

This thus makes it possible to reduce | 101451 substantially environmental impact of said method, and to ensure good safety for manipulators and users during the implementation of the method, while ensuring good control of the geometry of the desired patterns such as control of uniform dimensions and / or of a well-defined morphology.

The third object of the invention is the use of a device as defined in the second object of the invention for manufacturing self-cleaning coatings, anti-frost coatings, anti-corrosion coatings, anti-fog glasses, anti-fog windshields. - rain, breathable and anti-stain clothing, anti-humidity paints, anti-bacterial, anti-fouling or anti-bio-fouling coatings, optical filters, self-healing or aging-resistant coatings.

The device can in particular be used in the fields of construction, transport (automotive, aeronautics), energy, and / or medical applications.

A fourth subject of the invention is micro- and nanostructured patterns, characterized in that they are obtained according to a process as defined in the first subject of the invention.

In a preferred embodiment, the units are made of zinc oxide.

According to a preferred embodiment of the invention, the patterns have a height of 100 µm.

In a preferred embodiment, the distance between two patterns is 1 cm.

The patterns may be in the shape of a "pyramid" preferably having a base with a circumference of at most 700 µm.

Brief Description of the Drawings The accompanying drawings illustrate the invention: [Fig. 1] FIG. 1 represents an example of a device for generating an aerosol of nanoparticles according to the invention. [Fig. 2] FIG. 2 represents an example of a device for manufacturing micro- and nanostructured patterns according to the invention. [Fig. 3] FIG. 3 represents an example of micro- and nanostructured units obtained according to the process of the invention.

Other characteristics and advantages of the present invention will become apparent in the light of the description of non-limiting examples of the method according to the invention given with reference to the figures, LU101451.

Examples Figure 1 shows an example of an aerosol generator device of nanoparticles 1A according to the invention.

The device for generating an aerosol of nanoparticles 1A comprises: * a reaction chamber 2 comprising a first inlet 3 configured for the admission of a liquid composition 4 comprising at least a first precursor of the nanoparticles, a second inlet 5 configured for the 'admission of a gaseous composition 6 comprising at least one carrier gas and at least one reactive gas, and an outlet 7 configured to extract the nanoparticles 8 from the reaction chamber 2, * a liquid injector 9 connected to said first inlet 3 , configured to inject or spray said liquid composition 4 into reaction chamber 2, * a nanoparticle injector 10 connected to said outlet 7 of reaction chamber 2, configured to inject or spray nanoparticles 8, and * control means 11 to control the injection or spraying of said liquid composition 4 and / or said nanoparticles 8. The device for generating an aerosol of nanoparticles 1A co It furthermore takes a reservoir 12 (as reservoir T *) configured to contain the liquid composition 4 and connected by a pipe or a supply line 13 to the first inlet 3 of the reaction chamber 2. The reservoir 12 is connected. to a reservoir 14 (as reservoir T?) containing argon (as pressurized gas), in order to allow the introduction of argon through the upper part of the reservoir 12. The device generating an aerosol of nanoparticles 1A further comprises a reservoir 15 (as a T ° reservoir) configured to contain the gaseous composition, said reservoir 15 being connected by a pipe or a supply line 16 to the second inlet 5 of the reaction chamber 2 Reservoir 15 is connected to reservoir 17 (as reservoir T *) configured to contain argon (as carrier gas).

, The device for generating an aerosol of nanoparticles 1A also comprises a LU101451 heating device 18 connected to the reservoir 15 to heat the liquid reagent (water) in the reservoir 15 and trigger the conversion of said liquid reagent into reactive gas (water vapor ). FIG. 2 represents an example of a device 1 for manufacturing micro- and nanostructured patterns according to the invention.

In device 1, the device for generating an aerosol of nanoparticles 1A, and more particularly the outlet of the nanoparticle injector 10 of said device 1A, is connected to an injection chamber 1B which is itself connected to a chamber deposit 1C.

In the injection chamber 1B, a mask 19 is arranged so that the nanoparticle aerosol generated by means of the nanoparticle injector 10 can pass through said mask 19. Finally, at a certain distance from the mask 19, a substrate 20 placed in the deposition chamber 1C makes it possible to deposit the nanoparticles in micro- and nanostructured patterns.

The device used in the examples detailed below is a direct liquid injection device marketed by the company Kemstream under the reference “Atokit KF50 Direct Injection Atomizer”. Example 1 In a glove box, a zinc precursor [Zn (CeH41) 2] (186 mg, 0.8 mmol) and dodecylamine (DDA, 15 mg, 0.08 mmol) is dissolved in 15 ml of pentane in a Fisher-Porter tube 12 of an aerosol generator device 1A, in order to form the liquid composition 4. The liquid composition 4 is injected into the reaction chamber 2 through a first inlet 3 by means of a liquid injector 9 and with the help of a pressurized argon tank 14 brought to a pressure of 1.5 bar above atmospheric pressure (ie

P * = 2.5 bar). Special care is taken to avoid contact of reagents with ambient air by purging all connected lines with argon.

Liquid injection is performed with an injection frequency of 1 Hz and an opening time of 5 | 30 ms controlled by an injection control unit 11. In parallel, water vapor (reactive gas) is introduced into the reaction chamber 2 via a second inlet 5 while bubbling argon (carried carrier gas. at 1 bar above

, atmospheric pressure, i.e.

P ° = 2 bar) in a Fisher-Porter Tube 15 LU101451 containing 5 ml of water (liquid reagent). The temperature of the water in the Fisher-Porter Tube 15 is controlled by a heater 18 which allows more or less water vapor to be formed.

The temperature of the heating device 18 is set at 40 ° C. Nanoparticles of zinc oxide are then formed in the reaction chamber 2 by hydrolysis of the organometallic zinc complex during its contact and reaction with water vapor. .

The contact time between the water vapor and the zinc precursor is controlled by means of the nanoparticle injector 9. The injection of nanoparticles 10 is carried out with an injection frequency of 1 Hz and an opening time of. 5 ms controlled by the injection control unit 11. An aerosol of ZnO nanoparticles was obtained at the outlet of the nanoparticle injector 10 and directed by means of a conical element towards a mask 19 in a chamber of injection 1B.

The pressure in the reaction chamber 2 is equal to 0.5 bar above atmospheric pressure, ie approximately 1.5 bar.

The pressure P; at the inlet of the injection chamber 1B is equal to 0.5 bar above atmospheric pressure, ie approximately 1.5 bar.

The mask 19 used is a metal mask comprising 600 holes with a diameter of 600 μm each.

It is in the form of a disc with a diameter of 300 mm with a thickness of 1 mm.

After the aerosol has passed through the mask 19, the nanoparticles are deposited in the deposition chamber 1C on a stainless steel substrate 20 of dimensions 1 cm x 1 cm.

The distance between the mask 19 and the substrate 20 is 1 cm.

The pressure Pa at the outlet of the deposition chamber 1C is equal to 1 mbar.

Following the deposition of the nanoparticles, patterns in the shape of a "pyramid" as represented in FIG. 3 were obtained. FIG. 3 shows an image by electron microscopy of one of the "pyramid" patterns obtained, the base of which is approximately 50 μm. and the height 100 µm thus showing microstructuring (Figure 3a). Furthermore, at higher magnification, | (Figure 3b) we can distinguish more anarchic geometric patterns of the order of 500 nm showing nanostructuring.

The combination of these two types of micro- and

; nanostructuring of the patterns impart roughness to the surface and therefore its LU101451 hydrophobic properties.

The hydrophobic nature of the deposition carried out (wettability) was observed by rapid imaging coupled with the deposition of a drop of water where it is observed that the drop is evacuated from the surface (equivalent to the lotus effect observed on leaves plants).

Claims (1)

| 27 Claims LU101451 [Claim 1] Process for manufacturing micro- and nanostructured units, characterized in that it comprises at least the following stages: a) the preparation of an aerosol of metal nanoparticles or of metal oxide (s) ( s) (8), b) spraying the aerosol of nanoparticles (8) through at least one mask (19), and c) depositing nanoparticles (8) on a surface of a substrate (20), and in that step a) is carried out by implementing a device for generating said aerosol (1A) comprising: - a reaction chamber (2) comprising at least a first inlet (3) configured for the admission of a liquid composition (4) comprising at least a first precursor of the nanoparticles, at least a second inlet (5) configured for the 'admission of a gas composition (6) comprising at least one carrier gas and at least one reactive gas, and at least one outlet (7) configured to extract the nanoparticles (8) from the reaction chamber, - A liquid injector (9) connected to said first inlet (3), configured to inject or spray said liquid composition (4) into the reaction chamber (2), and - a nanoparticle injector (10) connected to said outlet (7) of the reaction chamber (2), configured to inject or spray the nanoparticles (8), and - control means (11) for controlling the injection or spraying of said liquid composition (4) and / or said nanoparticles (8), step a) comprising the following substeps: a1) introducing the liquid composition (4) into the reaction chamber (2) through said first inlet (3), by means of said injector of liquid (9), a2) introduction of the gas composition (6) into the reaction chamber (2) through said second inlet (5), a3) reacting the precursor of the nanoparticles with the reactive gas in the reaction chamber (2) to form the nanoparticles (8), and TN 28 a4) aerosol formation of nanoparticles (8) by means of said LU101451 nanoparticle injector (10). [Claim 2] Method according to claim 1, characterized in that the aerosol generator device (TA) is connected to an injection chamber (1B), so as to implement step b) in said chamber. injection (1B), and the injection chamber (1B), at the inlet, has a pressure P; ranging from 10 ° to 1 bar. [Claim 3] A method according to claim 2, characterized in that the injection chamber (1B) is connected to a deposition chamber (1C), in order to allow the implementation of the following step c), and the deposition chamber (1C) at a pressure Py such that P; = Pa. [Claim 4] Method according to any one of the preceding claims, characterized in that the nanoparticles (8) are nanoparticles of metal oxide (s) of at least one metal oxide chosen from an oxide of: Zn, Sn, Cd, B, Al, Ga, In, Th, Ge, Ti, Zr, Hf, Sc, Y, Si, Bi, and lanthanide. [Claim 5] A method according to any one of the preceding claims, characterized in that the liquid composition (4) further comprises a stabilizing agent selected from amines, acids, thiols, phosphorus derivatives and basic ethers. [Claim 6] A method according to any one of the preceding claims, characterized in that, during sub-step a1), the liquid injector (9) has an opening time ranging from 1 ms to 20 ms. [Claim 7] A method according to any one of the preceding claims, characterized in that, during sub-step a1), the liquid injector (9) has an injection frequency ranging from 1 Hz to 50 Hz. [Claim 8] A method according to any one of the preceding claims, characterized in that, during substep a4), the nanoparticle injector (10) has an opening time ranging from 1 ms to 20 ms. [Claim 9] Method according to any one of the preceding claims, characterized in that, during sub-step a4), the nanoparticle injector (10) has an injection frequency ranging from 0.1 Hz to 50 Hz . [Claim 10] A method according to any one of the preceding claims, characterized in that the first precursor of the nanoparticles . 29 L is an organometallic compound, the reactive gas is water vapor and the LU101451 sub-step a3) is a chemical reaction involving the reaction of said organometallic compound with water to lead to nanoparticles of at least one metal oxide (8). [Claim 11] A method according to claim 10, characterized in that the organometallic compound is a coordination complex comprising at least one metal selected from Zn, Sn, Cd, B, Al, Ga, In, Th, Ge, Ti, Zr , Hf, Sc, Y, Si, Bi, and lanthanide, and at least one organic group selected from amide, alkyl, aryl, alkene, alkyne and silyl groups, said organic group being bonded to said metal through a carbon atom or a heteroatom of this organic group, said heteroatom being other than oxygen. [Claim 12] A method according to any one of the preceding claims, characterized in that the mask (19) has several openings of millimeter or micrometric size. [Claim 13] A method according to any one of the preceding claims, characterized in that the micro- and nanostructured units have a height relative to the surface of the substrate (20) on which they are deposited of at least 10 nm. [Claim 14] A method according to any one of the preceding claims, characterized in that the mask (19) is placed at a distance from the surface of the substrate (20) of at most 10 cm. [Claim 15] Device (1) for manufacturing micro- and nanostructured patterns implementing a method as defined in any one of the preceding claims, characterized in that it comprises: | - a device for generating an aerosol of nanoparticles (1A) comprising: * a reaction chamber (2) comprising at least a first inlet (3) | configured for the admission of a liquid composition (4), at least one second inlet (5) configured for the admission of a gaseous composition (6), and at least one outlet (7) configured to extract nanoparticles (8) of the reaction chamber (2), * a liquid injector (9) connected to said first inlet (3), configured to inject or spray said liquid composition (4) into the reaction chamber (2), , 30, * a nanoparticle injector (10) connected to said output (7) of the LU101451 reaction chamber (2), configured to inject or spray the nanoparticles (8), * control means (11) to control the 'injection or spraying of said liquid composition (4) and / or said nanoparticles (8), * a reservoir T' (12) configured to contain the liquid composition (4), and * a reservoir T ° (15) configured for contain the gaseous composition (6), - an injection chamber (1B) comprising at least one mask (19), and - a deposition chamber (1C) comprising a substrate (20) intended to receive the nanoparticles (8) forming micro- and nanostructured patterns. [Claim 16] Use of a device as defined in claim 15, for manufacturing self-cleaning coatings, anti-frost coatings, anti-corrosion coatings, anti-fog goggles, anti-rain windshields, breathable and anti-corrosion clothing. -stains, anti-humidity paints, anti-bacterial, anti-fouling or anti-bio-fouling coatings, optical filters, self-healing or aging-resistant coatings. [Claim 17] Micro- and nanostructured patterns, characterized in that they are obtained according to a process as defined in any one of claims 1 to 14.