EP4334261A1

EP4334261A1 - Method for manufacturing a demixed-layer system, and demixed-layer system of this kind

Info

Publication number: EP4334261A1
Application number: EP22727957.7A
Authority: EP
Inventors: Jean-Thomas FONNE; Barbara BOUTEILLE; Emmanuelle GOUILLART; Ekaterina Burov; Damien VANDEMBROUCQ
Original assignee: Saint Gobain Glass France SAS; Centre National de la Recherche Scientifique CNRS; Compagnie de Saint Gobain SA
Current assignee: Saint Gobain Glass France SAS; Centre National de la Recherche Scientifique CNRS; Compagnie de Saint Gobain SA
Priority date: 2021-05-03
Filing date: 2022-05-02
Publication date: 2024-03-13
Also published as: WO2022234224A1; FR3122419B1; FR3122419A1

Abstract

The invention relates to a method for producing a demixed-layer system, in particular of glass, using a flash thermal treatment by irradiation. The invention also relates to a demixed-layer system obtained in this way.

Description

DESCRIPTION

TITLE: METHOD FOR MANUFACTURING A MIXED LAYER SYSTEM AND SUCH A MIXED LAYER SYSTEM

The invention relates to a method for manufacturing a demixed layer system as well as such a demixed layer system.

The obtaining of phase separation of a thin layer giving a nanotexturing of the surface of the glass layer is known from Jean-Thomas Fonné's doctoral thesis "Diffusion and phase separation in thin layers of silicates deposited by sputtering » Pierre and Marie Curie University, 2017.

This process for obtaining a demixed glass layer comprises the deposition by magnetron sputtering of a thin layer of Si02-Ba0-B203 followed by heat treatment in an oven, typically between 500°C and 1200°C from 5 minutes to several hours, to obtain phase separation.

The invention is aimed at an alternative manufacturing process that is more compatible with industrial requirements.

The invention also aims to broaden the range of possible products.

The invention proposes for this purpose as a first object a method of manufacturing a demixed layer system comprising in this order:

- the supply of a coated substrate comprising a substrate (preferably transparent, in particular dielectric, in particular inorganic in particular mixture of oxides, of glass in particular of oxides or even organic in particular polymer) comprising at least a first layer in a first material (preferably transparent in particular which is inorganic or containing a source of an inorganic material), first layer in particular with a thickness E0 of at least 10 nm and preferably of at most 500 nm or 300 nm or 200 nm, in particular first layer obtained by physical vapor deposition (in particular sputtering) or liquid (sol-gel, etc.) rather than by chemical vapor deposition CVD, the first material preferably being amorphous, in particular a mixture of oxides (in particular glass), or a mixture of oxide(s) and a metal, a mixture of chalcogenides (chalcogenide glass) or a metal alloy,

- a heat treatment of the first layer (over all or part of its thickness) leading to a phase separation of the first layer (over all or part of its thickness), then called the demixed layer (in particular liquid phase separation, in particular if the first material is a glass, the temperature reached in the first layer being above the glass transition temperature).

The heat treatment according to the invention is obtained by irradiating the coated substrate with a beam (continuous or pulsed, beam taken in the broad sense) of electromagnetic radiation, in particular from 250 nm to 15 μm, in particular laser (radiation emitting in the infrared, ultraviolet, or visible) or flash lamp (in the infrared in particular) or electronics (in particular the first material, metal or a metal alloy) or ions, for a duration of at most 1s, better still at most 10ms or 5ms, the coated substrate absorbing said beam (thus, at least a fraction of the thickness of the coated substrate, including or not including the substrate itself, absorbing said beam).

The heat treatment is preferably subsequent to the formation of the first layer rather than during the formation of the first layer.

The fact of producing a thin layer demixed on the substrate by flash treatment rather than a massive (“bulk”) substrate demixed by flash treatment makes it easier to adjust the composition of the first layer capable of demixing.

The flash treatment process by laser beam in particular offers a significant productivity gain compared to conventional heat treatment such as quenching (~a few minutes or hours) used in an industrial line.

The method of treatment by laser beam in particular is compatible with the dimensions of “large size” substrates (glazing, etc.) in particular of “jumbo” size (6 m×3 m) emerging from the float processes.

The method of treatment by laser beam in particular can be carried out industrially in a reliable and reproducible manner, keeping control over the type of phase separation, by adjusting the parameters of the method according to needs. Preferably, the substrate is not tempered and the heat treatment is not tempering, so a cutting step can be provided at any stage of manufacture after the heat treatment (before or after selective elimination of a phase, or after formation of (nano)interconnected network or (nano)plots or (nano)cavities or (nano)particles in (nano)cavities). The variation of one or more parameters of the beam, in particular laser or flash lamp (in particular power, or even choice of wavelength and/or even focusing plane for the laser) makes it possible in particular to explore phase separation ranges (size of (nano)structures in particular) much more easily than by varying the time and temperature parameters of conventional heat treatments in ovens. This flash treatment by laser beam in particular offers the possibility of obtaining new structures with conventional annealing, in particular by easily obtaining (nano)objects (drops/cavities/plots) of at most 200nm or less, in particular for maintain transparency.

The heat treatment can be localized, creating surface heating of the first layer, for example irradiation by laser beam or ions or electrons, "beam" of a flash lamp.

The treatment is not in particular a high-temperature heat treatment of the entire assembly consisting of the substrate and one or more layers; the substrate is therefore not heat treated by this flash treatment, as in the case of bending, quenching. Said heat treatment can be in particular by irradiation using laser radiation or a flash lamp.

Such lamps are usually in the form of sealed glass or quartz tubes filled with a rare gas, with electrodes at their ends. Under the effect of a short electrical pulse, obtained by discharging a capacitor, the gas ionizes and produces a particularly intense incoherent light. The emission spectrum generally includes at least two emission lines; it is preferably a continuous spectrum exhibiting an emission maximum in the near ultraviolet and extending up to the near infrared. The lamp is preferably a xenon or argon, helium or krypton lamp. The emission spectrum preferably comprises several lines, in particular at wavelengths ranging from 160 to 1000 nm. The radiation can come from several lamps arranged side by side, so as to treat a larger area simultaneously. All the lamps can in this case emit flashes simultaneously. The or each lamp is preferably arranged transversely to the longer sides of the coated substrate. The or each lamp has a length preferably of at least 1 m and even 3 m so as to be able to process large substrates. According to a second preferred embodiment, the electromagnetic radiation is laser radiation, in particular laser radiation in the form of at least one laser line.

The laser radiation is preferably generated by modules comprising one or more laser sources as well as shaping and redirection optics.

It is possible to create a relative movement between the coated substrate and the device which is in particular a laser or flash lamp. Generally, the device is fixed, and the coated substrate comes to scroll past the device so as to treat its surface. The temperature of the substrate (if it does not absorb the beam) can be at most 100° C., even 50° C. and even 30° C. during the heat treatment. The substrate is preferably a sheet of glass, glass-ceramic, or a polymeric organic material. It is preferably transparent, colorless (it can then be a clear or extra-clear glass) or colored, for example blue, green, gray or bronze. The glass is preferably of the silico-sodo-lime type, but it can also be of borosilicate or alumino-borosilicate type glass, in particular for high temperature applications (oven doors, fireplace inserts, fireproof glazing). The preferred polymeric organic materials are polycarbonate or polymethyl methacrylate or else polyethylene terephthalate (PET). The substrate advantageously has at least one dimension greater than or equal to 1 m, or even 2 m and even 3 m. The thickness of the substrate generally varies between 0.5 mm and 19 mm, preferably between 0.7 and 9 mm, in particular between 1 and 8 mm, or even between 4 and 6 mm. The substrate can be flat or curved, even flexible.

The laser radiation or flash lamp can for example emit in the infrared or the visible. If necessary, the surface power of the laser beam in particular is greater than 20 kW/cm ² , better still than 30 kW/cm ² .

The laser radiation preferably comes from at least one laser beam forming a line (called “laser line” in the remainder of the text) which simultaneously irradiates all or part of the width of the substrate. The in-line laser beam can in particular be obtained using high-power laser diode systems associated with focusing optics. The coated substrate can be moved, in particular by moving in translation opposite the fixed laser line, generally below, but optionally above the laser line. This embodiment is particularly valuable for continuous processing.

Alternatively, the substrate can be fixed and the laser can be mobile. Preferably, the difference between the respective speeds of the substrate and the laser is greater than or equal to 1 meter per minute, even 10 or 15 meters per minute, in order to ensure a high processing speed. The laser can also be set in motion so as to adjust its distance from the substrate, which can be useful in particular when the substrate is curved before the deposition of the first layer (preferably deposited by liquid route), but not only.

The laser radiation device for said heat treatment can be integrated into a line for depositing layers, in particular, of the first layer (and one or more layers, in particular for absorbing the beam), for example a line for depositing by sputtering assisted by magnetic field (magnetron process), or a line of chemical vapor deposition (CVD), in particular assisted by plasma (PECVD), under vacuum or under atmospheric pressure (APPECVD).

The phase separation can thus be obtained directly on an industrial line at the outlet of the deposition frame, in particular by spraying (coater) of the first layer (and other layers) thanks to the flash process, in particular laser heat treatment and no longer to post-temperature heat treatment at a transformer. With such a flash treatment the cooling is almost instantaneous.

The irradiation by laser beam or flash lamp is thus preferably carried out during the scrolling of the coated substrate, in particular (horizontal) scrolling in translation, in particular on a conveyor (with rollers, belts, with translation plates), in particular with a beam forming a laser line. The conveyor makes it possible to control and regulate the speed of movement. In particular, the running speed is preferably at least 1 m/min and better still at least 10 m/min. In particular, the laser beam (focused at the level of the plane of an absorption layer, for example) is in the form of a laser line simultaneously irradiating all or part of the width of the coated substrate, preferably scrolling across the entire width.

And in particular, the surface power of the beam and/or the running speed are adjusted according to the absorption of the coated substrate; the thickness and/or the composition of the layer and/or according to the desired morphology of the demixed layer.

The heat treatment is adapted according to the absorption capacity of the coated substrate:

- low absorbent coated substrate: high power and/or low speed

- highly absorbent coated substrate: low power and/or high speed.

The treatment (power and/or speed) is adapted to provide enough energy to obtain demixing, while avoiding delamination of the first layer.

Furthermore, power and/or speed can be finely adjusted to obtain the size and morphology of the desired structures. The higher the heating (temperature reached in the first high layer), the higher the size of the structures.

The phase separation can be a fraction of the first layer if the thickness of the layer is too great, especially when the heating created by the beam remains on the surface.

The choice of the composition of the first layer and therefore the shape of the demixing dome can make it possible to fix:

- the range of temperatures allowing the phase separation (and to determine the necessary beam with a possible absorption layer) - the final morphology obtained (droplets, dots or interconnected (nano)network, and the size of the structures), and therefore to optimize it for the flash treatment by laser beam in particular and/or to obtain the desired structures.

The thickness of the first layer can also be optimized to control the size of the (nano)structures obtained after the flash treatment by beam, in particular laser, in addition to the composition and the beam parameters (and running speed).

The invention is applicable to any glass (preferably oxide) giving rise to phase separation (silicate, borate, borosilicate of NaO, CaO, BaO (S1O ₂ -B ₂ O ₃ - BaO), etc. ...).

To obtain the optimal demixing by laser flash treatment, it is preferred a first composition material whose glass transition temperature Tg which is not too high. A first material of Tg <900°C or even <700°C is preferred.

The process can then comprise the formation of the first layer including:

- a liquid deposition, such as sol-gel, for example by spray

- or physics in the vapor phase (PVD) such as magnetron sputtering with optional radio frequency or evaporation, in particular from a ceramic target or oxide (s) or even from a metal alloy target possibly (if necessary) in reactive spraying (oxygen with rare gas such as argon)

- or even chemical vapor phase (CVD).

The first material capable of demixing is chosen from: a dielectric such as a chalcogenide glass, a mixture of a first oxide and at least one second oxide or of a metal or even a metal alloy.

The first material capable of demixing is for example a silicate, borate or borosilicate glass, in particular with a network former and at least one network modifier chosen in particular from: an alkali metal oxide; alkaline earth, an oxide of a column 4 and 12 element, including sodium borosilicate.

The method of deposition of glass, oxides in a thin layer can be a radio frequency magnetron deposition or with a doped ceramic target for deposition in continuous mode, or liquid / sol-gel deposition for example.

In order to deposit thin layers of glass by PVD deposition, solid glasses can be prepared beforehand which are shaped to obtain ceramic targets.

An example of reactive deposition with a metallic target is an Si-Ba target to obtain an SiC>2-BaO layer.

The first material capable of demixing preferably comprises: - a mixture of a first oxide and at least a second oxide or a metal or silicon "cluster",

- a glass of chalcogenide.

- a metal (with several phases) or a metal alloy.

The second phase can be in a first phase based on silica The first material capable of demixing can be a chalcogenide glass or preferably a silicate, borate or borosilicate glass, in particular with a network former (silicon and/or boron) and at least least one lattice modifier chosen in particular from an oxide of alkali RO, of alkaline earth metal R2O, an oxide of an element from columns 4 and 12 (in particular ZnO and Ti02).

An example of a first material capable of demixing can be a glass (preferably silicate, borate or borosilicate) in particular Si02-Ba0-B203, Si02-Na20-B2O3, or Si02-Ca0-B2O3·

Demixing in a glass takes place when it undergoes heat treatment below the critical demixing temperature while allowing atomic mobility, whether diffusive or hydrodynamic in nature.

For silicate, borate or borosilicate glasses, it is preferable to avoid (or with a weight content of less than 1% of the total weight) lead, cadmium or mercury oxide. It is preferred to avoid (or with a content by weight of less than 1% of the total weight) the oxides of transition metals from column 5 to 11 of the periodic table of the elements.

The glass, in particular silicate, borate or borosilicate, can comprise dopants (rare earths) or any other element which does not harm the demixing.

An example of a Na20-B ₂ 03-Si02 (N BS) system is described in the "Handbook of Sol Gel Science and technology Second edition volume" by Lisa Kelin and others, Springer, in the "borosilicate by sol gel method chapter" pages 621 to 665. As source of Na2<D can be used sodium acetate in solution.

The method may comprise the formation of the first layer which is a coating of oxides or glass of oxide(s) (in particular silicate, borate or borosilicate) on the substrate, for example by the sol-gel route, from precursors of an oxide or several oxides (in particular of silica and/or boron oxide), and also of alkaline oxide RO, alkaline earth metal R2O, element of columns 4 and 12) or with any other source of oxides (salts, powder, acid, etc.). In particular, organometallic precursors are used. The silica can be obtained using silane, tetraethoxysilane (TEOS), or even hexamethyldisiloxane (HDMSO), optionally using an accelerator such as triethylphosphate.

As a precursor for boron, boric acid can be chosen. In a first configuration, the first material (on a substrate preferably made of float glass in particular) is made of silicate glass. The weight content of silica (S1O2) is at least 20 or 40% of the total weight and even at least 50%, 55%, 65% and even at most 80%.

The B2O3 content is zero or less than the silica content, and preferably less than 20%. The weight content of B2O3 + S1O2 can be at least 40%, 55%, 65% and even at most 95%, 80%.

In a second configuration, the first material (on a substrate preferably made of float glass or polymer in particular) is made of borate glass. The weight content of B2O3 is at least 20% or 40% of the total weight and even at least 50%, 55%, 65% and even at most 90%, 80%. The silica content by weight is zero or less than the B2O3 content, and preferably by at most 20%.

In a third configuration, the first material (on a substrate preferably made of float glass in particular) is made of borosilicate glass.

The weight content of B2O3 is at least 20% of the total weight and even at least 40%, 55%, 65% and even at most 95%, 80%. The silica content by weight is at least 20% of the total weight and even at least 40%, 55%, 65% and even at most 95%, 80%. The content by weight of B2O3+S1O2 can be at least 40%, 55%, 65% and even at most 95%, 80%. And for the first or second or third configuration, the chemical composition of the first layer (on a substrate preferably of float glass or polymer in particular) may comprise (or consist of) at least one oxide of at least one of following alkali and alkaline-earth metal oxides (for example at most 3 or 2 of said oxides), varying within the weight limits (by weight of the glass) defined below:

_K2 0 0-25%

Rb ₂ 0 0-15%

Na ₂ 0 0-20% LI2O 0-20%

CS ₂ O 0-20%

BaO 0-45%

srO 0-40%

MgO 0-30% CaO 0-15% PbO: 0-40%

- and even one or the following oxides (preferably at most 3 in all) can be added or substituted:

- AI2O3: 0-35% - ZnO: 0-50%

- or even T1O2.

For the first, or second or third compositions mentioned above, it is preferred to avoid (or with a content by weight of less than 1% of the total weight) lead, cadmium or mercury oxide. It is preferred to avoid (or with a content by weight of less than 1% of the total weight) the oxides of transition metals from column 5 to 11 of the periodic table of the elements. In particular, this composition may not contain lead, mercury, cadmuim (and from column 5 to 11) or even other constituents or at less than 1% by weight.

One of the aforementioned compositions may include dopants (rare earths) or any other element that does not harm demixing.

For a first glass layer, mention may be made of Na2<D-S1O2 binary systems. An example is described in the publication by Utsuno and others entitled “Phase separation of Na ₂ 0-Si0 ₂ films prepared by sputtering” journal of non crystalline solids (2004 337-340. For a first glass layer, mention may be made of systems An example is described in Seward et al., “Development of Two-Phase Structure in Glasses”, with special reference to the BaO-Si0 ₂ System _.” Journal of the American Ceramic Society, 1968, 51, pages 634-643.

If the first layer is cold deposited, there is no phase separation, this is created by the heat treatment by flash irradiation. For a first layer of metal alloy, this may be an electrolytic deposit.

In one embodiment of the invention, during irradiation, the first layer which is inorganic (or containing a source of an inorganic material) in particular oxides, glass and/or the chosen inorganic substrate (in particular oxides, glass of oxides) absorbs said preferably laser beam or flash lamp. And in particular during irradiation, the first layer of oxides (of oxide glass) or the oxide substrate (of oxide glass) absorbs said preferably laser beam emitting in the ultraviolet at at most 400 nm or emitting (in the far infrared) from 8 to 12pm, like a CO2 laser with a wavelength of 10 to 11pm. A silicon substrate can absorb in the visible or the near infrared, for example 1 μm. In one embodiment of the invention, the substrate comprising at least one so-called absorption layer layer distinct from the first layer (distinct from the unmixed layer after heat treatment), which is an underlayer under the first layer (preferably on the same main face of the substrate, first layer in contact or not with the absorption layer) or an overlayer (possibly in contact with the atmosphere) on the first layer. And the absorption layer absorbs the preferably laser beam (or flash lamp) in particular at a wavelength of 400 nm to 2000 nm, even of 900 nm to 1100 nm and preferably of 950 to 1050 nm. In particular before the heat treatment (before the deposition of the first layer if the absorption layer forms an underlayer on the same face of the substrate) the method comprises the deposition in particular by physical vapor deposition or by liquid route of the layer of 'absorption.

The laser beam is preferably focused on the absorption layer, the absorption substrate or the first absorption layer.

The absorption is defined as being equal to the value of 100% from which the transmission and the reflection (spectral and diffuse) of the absorption layer are subtracted. It can in a known way be deduced from measurements carried out using a spectrophotometer equipped with an integrating sphere.

The absorption layer preferably absorbs at least 20% or 50% or 80% of the beam (in particular electromagnetic radiation) used during the heat treatment. Part of the energy is thus absorbed by the absorption layer and transferred to the first layer, by thermal diffusion. The absorption layer preferably transmits less than 80%, even less than 50% or even less than 20% of the beam (radiation).

Preferably, the absorption layer is on the same main face of the substrate as the first layer.

The laser beam in particular can be on the first layer side or on the opposite side. It is possible to carry out irradiation on the first layer side and on the opposite side (with two beams for simultaneous or successive irradiations or with one beam with successive irradiations).

To promote heating of the first layer, the distance (from surface to surface) between the absorption layer and the first layer is preferably at most 200 nm.

The first layer and/or the absorption layer, as well as possibly all the layers deposited on or under the first layer, are typically thin layers, in the sense that their thickness is generally from 0.5 nm to 10 μm, more generally from 1 nm to 1 μm and even at most 200 nm or 50 nm. The first layer (and even the possible absorption layer) preferably covers at least 50% or 90% or 100% of the surface of the substrate. The absorption layer can cover the same area as the first layer.

It is possible to desire uniformity of the structures sought or different structures from one zone to another of the coated substrate.

The substrate can be covered with one or more first layers capable of demixing (in identical or distinct first materials and/or of identical or distinct thickness) adjacent, disjoint or not. One or more adjoining absorption layers, disjoint or not, can be used

The device (line laser preferably) can irradiate one or certain zones of the first layer thanks to a system for masking the first layer or shaping the beam.

The absorption layer may be inorganic, in particular which contains a metal, which is a metal or a mixture of metals, an oxide and/or nitride of one or more metals, or be an organic-based layer.

In the case of an absorption layer deposited by sputtering, it is preferred that the thickness be at most 50 nm or 30 nm and better still at least 0.5 nm (depending on the power of the beam in particular).

In the case of an absorption layer deposited by liquid means, in particular an overlayer, in particular organic-based layer, in particular carbon, the thickness may be at least 0.5 μm, and even micron and at least more than 8pm or 10pm.

The absorption layer can thus contain an absorbent element which is a metallic element chosen from germanium, titanium, silver, tungsten, niobium, indium, tin, copper, molybdenum, zinc , zirconium, silicon, vanadium, aluminum, nickel, chromium, iron and gold, or the absorption layer is based on at least one metal chosen from germanium, molybdenum, titanium, zinc, zirconium, silver, indium, tin, nickel, chromium, niobium, vanadium, tungsten, copper, iron, silicon, gold.

The absorption layer can be an oxide and/or nitride layer of at least one aforementioned metal.

Preferably, the absorption layer may be at most 50 nm or 30 nm thick and better still at least 0.5 nm (depending on the power in particular) and based on:

- of zinc or tin, or based on zinc and tin

- of Ni, of Cr, or based on NiCr

- germanium, - indium or based on a mixture of indium and another metal, in particular based on indium and tin InSn

- titanium

- silver.

By "layer based on ..." within the meaning of the present invention, it should be understood that the layer comprises more than 50 atomic % of the material mentioned.

Within the meaning of the invention, the fact that the absorption layer or any other layer (first layer, etc.), obtained by sputtering, consists of one or more elements (metal, etc.) means that this or these elements represent 98 to 100% by weight of the target used to deposit the layer (and therefore of the layer thus deposited); it is not excluded that the layer may comprise one or more metallic elements, such as for example aluminum and/or antimony, as a dopant to improve the conduction of the target, or as an impurity.

After treatment, the metallic absorption layer can be at least partially oxidized. Mention may be made of ZnOx (removable by acid solution) and GeOx (removable by liquid route), SnZnOx, TiOx.

Oxidation leads to a partial loss of absorption during irradiation.

In one configuration, the absorption layer being an overlayer, the method comprises the removal of the absorption layer by liquid means (immersion, jet, use of a washing machine) and/or mechanical action (wiping, immersion and ultrasound, brushing with or without liquid), or even by additional heat treatment, possibly removal by liquid means (immersion, jet, use of a washing machine) using a sacrificial layer which can be eliminated by liquid means (immersion, jet, use of a washing machine) present between the first layer and the absorption layer.

In particular, the method comprises physical vapor deposition (in particular sputtering) of the sacrificial layer and/or of the absorption layer or liquid deposition.

Preferably, the duration of the withdrawal (elimination) of the absorption layer is preferably at most 10 min or 5 min or 1 min and even at a temperature of at most 50° C. (if by liquid route) or even at ambient temperature.

Water can be used, in particular ionized water between 20°C and 50°C.

The absorption layer can be eliminated by liquid means, in particular soluble or dispersible in aqueous or alcoholic solvents, in particular it is a layer of a metal such as zinc, magnesium, germanium, or molybdenum which oxidizes during the heat treatment, or a substoichiometric oxide of a metal such as zinc, magnesium, germanium, or molybdenum which oxidizes during heat treatment. To be easily soluble or dispersible, this layer (in particular overlayer) is preferably thin enough to oxidize over the entire thickness. Also, a thickness of at most 10 nm or 5 nm or 3 nm is preferred.

The absorption layer can be removable by a liquid route, in particular soluble or dispersible in aqueous or alcoholic solvents (preferably soluble in water), and can be an organic-based layer, in particular a radiation-absorbing agent which is for example a dye or pigment.

The radiation-absorbing agent (in particular at least 50% by weight) is dispersed in an organic matrix, preferably based on a water-soluble polymer, for example based on an acrylate polymer. The radiation-absorbing agent is preferably chosen from carbon particles, in particular particles of carbon black, graphite, graphene, carbon nanotubes, or mixtures thereof.

Pigments that absorb infrared radiation are in particular carbon black, carbon black, iron or chromium oxide, chromium spinels (for example FeCr ₂ Ü ₄ , MgCr ₂ C> ₄ , ZnC ^ Cu) or alternatively ytterbium salts. Pigments that absorb ultraviolet radiation are chosen in particular from metal salts, cerium oxide or sulphide. Dyes that absorb infrared radiation are chosen in particular from cyanine, metal complexes (Ni, Fe, Pt, Pd, etc.) with a dithiolene ligand, organometallic complexes of ytterbium. Dyes that absorb ultraviolet radiation are chosen in particular from rhodamine, phthalocyanine, coumarin and fluorescein.

The organic-based absorption layer can be deposited by various known techniques, such as deposition by coating, by spraying, by roller, by curtain, etc. It is understood that in the case of a removable organic-based layer by liquid route, some of its constituents such as pigments can remain insoluble in the solvent without harming the total elimination of said layer.

Under the absorption overlayer, in particular metal or metal oxides and/or nitrides, the preferably water-soluble sacrificial layer may be 0.5 to 50 nm thick, in particular:

- layer of zinc or magnesium oxide, or based on molybdenum or molybdenum oxide MoOx, germanium oxide GeOx, (depositable by spraying)

- chosen by metal halides and metal sulphates, materials of group I or VII, thus in particular Al2(SC>4)3 or NaCl or LiF or Nal or Csl (which are soluble in water and can be deposited by spraying) . Moreover, phase separation is known in alloys, the article entitled "phase separation in metallic glasses" by DH Kim and others, Progress in Materials Science (2013), pages 1103-1172, Elservier edition lists different glass compositions metals giving rise to demixing at the nanometric scale.

According to the invention, advantageously: the phase separation is by growth nucleation comprising a first phase, preferably amorphous, and at least one second phase possibly comprising disjoint drops, preferably amorphous,

- or the phase separation is by spinodal decomposition forming for example an interconnected (nano)network.

One application is to obtain by this process a demixed layer which has the anti-reflection function for a range of products whose substrate is a non-tempered glass.

Of course after the heat treatment the drops are solid just like the first phase.

In particular, the demixed layer comprises a first phase and a second phase in the form of disjoint drops (solid after the heat treatment), preferably amorphous, for example disjoint nanodroplets with a nanometric width of at most 300 nm, the method according to the invention comprises a selective phase elimination of the demixed layer, for example by a liquid route, in particular an acid solution, the selective elimination leading to:

- the surface texturing of the demixed layer, the surface thus textured being provided with a plurality of disjoint cavities of width W0 (in particular submillimetric, for example nanometric), in particular by elimination of the second phase

- the formation of a plurality of disjoint spots of width W0 (in particular submillimetric, for example nanometric), by elimination of the first phase, in particular spots distributed in an irregular, aperiodic manner.

Said selective elimination is preferably by liquid route, in particular chemical attack, dissolution, or by dry route, in particular by plasma etching. In the case of a glass layer, acid etching and fluorinated plasma etching are preferred.

The duration of elimination can preferably be at most a day, an hour or even 30, 10, 5 minutes.

Nanodrops are typically circular (on the surface) or oval in shape.

The size of the (nano)drops or (nano)plots will be dictated by:

- heat treatment - the composition of the first material capable of demixing (in particular the difference in composition between the first and second phases)

- the thickness of the first material suitable for demixing (if in a thin layer)

- the control of the environment which acts on the surface condition of the first material. In particular, the (nano)cavities or (nano)plots do not occupy a regular position with a constant pitch but are distributed aperiodically.

The disjoint pads can be of nanometric width WO (preferably taken from the surface of the nanocavity, at the top level), are in particular of nanometric height HO (preferably from the lowest point of the nanocavity), and even of LO nanometric length.

The drops (in particular nanodrops) can emerge on the surface and/or the drops (in particular nanodrops) are immersed in the demixed layer, the method then comprising a step of partial removal of the demixed layer capable of making the immersed nanodrops emerge (optionally the phase elimination step is an extension of said partial withdrawal).

Remember that there are different phase separation domains:

-domain of spinodal decomposition

- domain of decomposition by growth or binodal nucleation.

To illustrate the case of a binary mixture, the dome capable of demixing delimits the thermodynamically stable region (miscible mixture) from the regions of immiscibility. Inside this dome there are three regions, one in the center called spinodal, the other two on the edges called binodal. At the first moments, spinodal decomposition gives interconnected morphologies whereas a system whose phases separate by a nucleation-growth mechanism generally adopts a droplet morphology. The density of nanodrops can directly depend on the shape of the demixing dome which characterizes the first material.

The phase separation can be more precisely:

-a) by nucleation growth leading directly to the coexistence of at least a first phase (in particular amorphous and/or glass, oxides) and a second phase (in particular amorphous and/or glass, oxides), simple to achieve,

-b) or even the so-called primary phase separation (at T0> T1) leads by growth nucleation to the coexistence of at least a first phase (in particular amorphous and/or glass, oxides) and a second phase (in particular amorphous and/or glass, oxides) and a so-called secondary phase separation (at T1) leads to the coexistence of a third phase (in particular amorphous and/or glass, oxides) and fourth phase (in particular amorphous and/or glass, oxides) resulting from one of the first or second phases, the third phase being said phase with the drops .

-c) phase separation is by spinodal decomposition forming an interconnected (unstable) network possibly followed by fragmentation of said network to form said structure during heat treatment.

Indeed, a final structure in drops classically due to growth nucleation can also be observed by spinodal decomposition after fragmentation of one of the phases. This may be due to the high viscosity ratio between the two demixed phases. For example for a glass, a phase rich in network modifier (for example barium) being more fluid, it is more sheared than the phase rich in network former (such as silica) which leads to the fragmentation of the structure. bi-continuous and formation of nanodrops.

In the case of a mixture of at least three oxides for the first layer, it is possible to have a first phase which is a mixture of oxides or a single oxide and/or a second phase which is a mixture of oxides or a single oxide.

In one configuration, the surface texturing of the demixed layer leads to cavities which are nanocavities, the width WO being nanometric, and the method then comprises: - the formation, by depositing on the textured demixed layer, of a second layer at less coalescing and preferably at least percolating in a second inorganic material of nanometric thickness E1, preferably at most 150 nm and at most 50 nm in particular from 6 or 10 nm to 50 nm

- the formation, from dewetting of said second material, in particular solid or even liquid (such as glass at a temperature above Tg), of a multitude of disjoint nanoparticles in said nanocavities, the nanoparticles being of width W1 nanometric.

The process of treatment by beam in particular laser can be carried out industrially in a reliable and reproducible way, by keeping the control of the size of the structures (and even of the distribution of sizes), of the surface density of structures, by adjusting the process parameters depending on the needs.

The disjoint (and three-dimensional) nanocavities of nanometric width WO (preferably taken from the surface of the nanocavity, at the top level), are in particular of nanometric height HO (preferably from the lowest point of the nanocavity), and even of LO nanometric length. The nanocavities are in particular with an aspect ratio W0/L0 of at least 0.6, 0.8 or 0.9.

The disjoint (three-dimensional) nanoparticles are of width W1 nanometric (with the narrowest possible distribution of widths if necessary) in particular of height H1 nanometric in particular with a W1/H1 ratio ranging from 0.5 to 3 and even from 1 to 2 , width W1 for example determined in normal top view, in particular circular or of the circular type, the nanoparticles being in said nanocavities, possibly under flush, flush with or emerging from said nanocavities, in particular one or more nanoparticles per nanocavity.

It is known to produce metallic nanoparticles directly on the surface thanks to the solid state dewetting of silver. In the article entitled “Periodic Arrays of Diamond-Shaped Silver Nanoparticles: from scalable fabrication by template assisted Solid State Dewetting to Tunable Optical Properties” by Jacquet et al., Adv Funct Mater. 2019, 190119, p1 -14, silver nanoparticles are obtained by dewetting silver on a layer of silica sol gel textured by nanoimprinting,

Phase separation surface nanostructuring offers multiple advantages over prior art nanoimprint surface structuring. Nanotexturing by phase separation gives a nanostructure with nanocavities of the order of ten to a few hundred nanometers. This makes it possible to control the size of the nanoparticles obtained by dewetting which are placed preferentially in the nanocavities. The size of the nanocavities is adjustable (by adjusting the heat treatment / and even by varying the thickness of the first layer).

The size of the nanoparticles will depend on the size of the nanocavities and the dewetting (choice of the second material, thickness of the second material). In particular, it is possible to obtain a nanoparticle size distribution smaller than what is obtained by dewetting on a flat substrate (all other things being equal).

The invention makes it possible in particular to obtain nanoparticles with adjustable sizes between 10 and 200 nanometers (which can be used on the surface or covered), with a process in which all the steps can be carried out on a large scale. The advantage of controlling the diameter of the particles in this size range is in particular not to scatter the light while modulating the plasmon absorption of the particles.

The second material is therefore chosen capable of dewetting on the demixed layer or on another layer and preferably capable of generating plasmonic objects. Phase separation makes it possible in particular to generate sizes of nanocavities (or nanoplots) between 10 and 300 nm and even at most 200 nm or 150 nm.

T2 is chosen low enough not to deform the nanocavities or deform the first material and the substrate. For example for a float glass T2 is at most 500°C or 650°C. Generally for a float glass of given Tg, one can choose Tg+100°C for a duration for example of at most 15 or 5 minutes, or Tg+150°C for a duration of at most 5min.

The size of the nanocavities can make it possible to remain transparent in the visible and even in the infrared (near infrared or even far).

The size and arrangement of the nanocavities can be modulated.

The nanocavities have for example a circular or quasi-circular surface perimeter. The textured surface can be at least 20m ² . The textured surface can be all or part (at least 50%, 60%, 80%) of the total surface for example of a PLF.

The coverage rate of the nanocavities can be at most 60%, 50% or 40% and at least 5%, 10% to 15%, preferably from 15% to 40%. The degree of filling of the nanocavities by the nanoparticles can be at least 40%, 60%, 80%.

At least 40%, 60%, 80% of the nanocavities can each contain a single nanoparticle of said second material (with a sufficient deposited thickness of material capable of dewetting for example).

Preferably, the dewetting is in the solid state and of one or more metals.

Dewetting is carried out for example in an oven, in particular under a controlled atmosphere (neutral gas, oxidizing atmosphere).

For example, the material capable of dewetting is a material having a low adhesion energy with the glass (or underlying surface), preferably less than 0.8 J/m ² , or even less than or equal to 0, 4 J/m ² L Thus, it can be for example:

- of a metal, used alone or in a mixture, such as silver (adhesion energy of 0.35 J/m ^{2 )} , gold, tin, copper, aluminum or even Ni, or Pt, Ge, Fe, a gold-silver alloy, a doped silver, a manganese-doped germanium

- or more broadly, for example an inorganic material such as AgCl, MgF2, chalcogenide glass.

The dewetting can be in the liquid state, in particular a dielectric such as chalcogenide glass as for example described in the article entitled “Self assembly of nanostructured metasurfaces via templates fluid instabilities”, Nature nanotechnology, vol 14 avril 2019 pages 320-327. The glass dielectric metasurfaces are poorly absorbent and have a high refractive index, which makes it possible to modulate the propagation of light in an efficient manner.

The dewetting can be solid, in particular a metal or metal alloy.

The deposit to form the second layer can be:

- a cash deposit, such as silvering for cash

- or even physics in the vapor phase (PVD) such as magnetron sputtering with optional radio frequency or evaporation, in particular from a ceramic or oxide(s) target or even from a metal alloy target in reactive sputtering (oxygen with rare gas such as argon)

-or chemical vapor phase (CVD)

- electrolytic deposit

In addition, the deposit to form the second layer can be directly on said demixed layer (the second material being directly in contact with said demixed layer), the nanoparticles are then in the nanocavities in contact with the demixed layer, preferably one per nanocavity.

Or the method comprises, after said elimination and before the deposition of the second material, the formation of another layer, by deposition on said nanotextured surface, of another preferably dielectric material distinct from said first material of the demixed layer, the dewetting being on said another layer.

The other layer may have a distinct affinity from said first material and/or a distinct functionality in particular capable of modifying the environment of the nanoparticles, in particular the refractive index (therefore the plasmonic response). The other layer can also change the crystallinity and wetting properties.

Preferably, the other material (essentially) is inorganic and even transparent (oxy and/or metal nitride, silicon, or glass, for example with a different composition from glass with the nanocavities).

The other layer is for example of nanometric thickness E2 less than HO thus partially filling said nanocavities. For example E2 is at most 20nm.

The nanocavities thus coated with the other layer (at the bottom of the nanocavities, all or part of the walls) preferably remaining of nanometric width (measured at the surface) preferably of at most 300 nm or 200 nm, in particular the nanoparticles in the nanocavities being in contact with the other layer.

For instance :

- E2 is at most HO/5 and even at most H0/10. - and/or preferably HO (is at most 300nm, 200nm; 150nm, 50nm; 10Onm and at least 10nm.

The second material is a layer directly deposited on the first material or on another layer if one wants to modify the dewetting conditions or to bring a functionality to the final product for example can be a barrier layer to alkalines etc.

The deposition of the other layer can be consistent, in particular physical vapor deposition, such as magnetron sputtering.

The first layer (the demixed layer) is preferably glass, the other material is an oxide layer, or nitride or oxynitride, crystallized or amorphous, in particular ZnO, TiN.

This other layer, in particular crystallized or amorphous oxide, can be:

- ZnO (crystallized oxide) modifying surface energy and the layer of the second material coalesces at a lower thickness - TiN (amorphous) known to change the wetting of silver in particular

This other layer may have optical functionality, to adjust an optical response. This other layer can be dielectric.

To change the properties and/or also protect the nanoparticles, the method may comprise the deposition of a preferably inorganic overlayer on the nanoparticles (in contact with the other material or the first material) in particular the deposition is consistent, in particular a physical vapor deposition such as magnetron or liquid sputtering.

All of the above layers can be used for the other material. In particular, it can be made of a material that is identical or similar to said other material. Preferably, the overlayer material (essentially) is inorganic and even transparent, (oxy and/or nitride of metal, silicon, or glass, for example of difference in composition from glass with the nanocavities).

This overlayer, in particular crystallized or amorphous oxide, can be:

- ZnO (crystallized oxide) - TiN (amorphous) known to change the wetting of silver in particular.

This overlayer can be dielectric. This other layer can have an optical functionality, to adjust an optical response, in particular in a material identical (chemically and/or optically) or similar to said other material for complete encapsulation. The dewetting can also lead to particles on the surface between the nanocavities, mostly larger than the nanoparticles in the nanometric size nanocavities and preferably (if necessary) the method comprises the removal of all or part of the nanoparticles between the nanocavities by action mechanics such as brushing, scrunching...

The invention also relates to a demixed layer system obtained via the process described above comprising: the substrate coated with the demixed layer (in contact or not, in particular if under absorption layer) which comprises a first phase and a second phase in the form disjoint drops or comprises a first phase and a second phase which form an interconnected (nano)network.

The demixed layer has a free surface or is under an overlayer.

The invention also relates to a demixed layer system obtained via the process described above comprising the substrate coated with the demixed layer (in contact or not with the substrate, in particular if under absorption layer) which comprises a first phase, the demixed layer the surface texturing comprising a set of pads (nanoplots for example) or cavities (nanocavities for example) or the demixed layer comprising an interconnected network.

The demixed layer has a free surface or is under an overlayer.

As already described, the demixed layer, in particular transparent, can be an oxide or a mixture of oxides (two or more), in particular of glass, silicate, borate, borosilicate or a mixture of oxide(s) and a metal or of chalcogenide glass, and preferably the substrate is transparent, in particular glass or polymer.

As already described, the demixed layer system according to the invention may comprise the absorption layer, as an underlayer of the demixed layer or as an overlayer of the demixed layer, which is based on at least one metal, metal layer optionally partially oxidized or which is an oxide and/or nitride layer of one or more metals, the metal(s) preferably being chosen from germanium, molybdenum, titanium, zinc, magnesium, zirconium, silver, indium, tin, nickel, chromium, niobium, vanadium, tungsten, copper, iron, silicon, gold, zinc and tin mixture, indium and tin, nickel and chrome.

As already described, the demixed layer system according to the invention may comprise the absorption layer, preferably which is an overlayer on the demixed layer, the absorption layer is organic-based comprising a radiation-absorbing agent, in particular at based on carbon or dye particles. As already described, the demixed layer system according to the invention may comprise the absorption layer on the sacrificial layer (absorption layer for example in contact with the sacrificial layer), sacrificial layer on the demixed layer (sacrificial layer for example in contact with the demixed layer); the sacrificial layer is preferably a layer based on a zinc or magnesium oxide, or based on molybdenum or molybdenum oxide MoOx, a germanium oxide GeOx, or chosen from metal halides and sulphates metal, materials of group I or VII, and in particular Ah (S0 ₄ ) ₃ or NaCl or LiF.

The invention also relates to a demixed layer system obtained via the process described above comprising in this order on the substrate (in particular on the same main face:

- the possible absorption layer

- the inorganic demixed layer which is nanotextured on the surface with a surface provided with nanocavities of width WO of at most 300 nm and preferably of at least 10 nm,

- nanoparticles (in a given material called second material, preferably plasmonic, in particular inorganic and/or dielectric, in particular metallic or oxide), in particular of spheroidal shape, in the nanocavities, the nanoparticles having a width W1 preferably of at most 300nm or 200nm or 150nm and preferably at least 10 nm or 20nm, in particular at least 50% or even at least 80% of the nanoparticles in the nanocavities have a width of at most 300nm and even at most 200nm.

In addition, one or less of the following characteristics may be provided:

- the occupancy rate of the nanoparticles in the nanocavities is preferably at least 40% or even at least 80%,

- at least 80%, or 90% of the filled nanocavities comprise a single nanoparticle,

- at least 50% or even 80% or 90% or 100% of the nanocavities have a width of at most 300 nm and even at most 200 nm or 150 nm and preferably at least 20 nm

- at least 50% or even at least 80% or 90% of the nanoparticles in the nanocavities have a width (or a diameter) of at most 300nm and even of at most 200nm or 150nm and even of at least 10nm or 20nm ,

- the distribution profile (in number) of the width of the nanocavities is a (bell-shaped) curve comprising a peak corresponding to a D0 value of at most 300 nm or even of at most 200 nm or 150 nm or 100 nm and of at least 10nm or 20nm and in particular with a width at mid-height of at most 50nm - the distribution profile (in number) of the diameter of the nanoparticles in the nanocavities is a curve comprising a main peak (the highest if several peaks or single peak, in particular bell-shaped) corresponding to a D1 value of at most 300 nm or even of at most 200 nm or 150 nm or 100 nm and of at least 10 or 20 nm the first layer is in particular unmixed glass, as a coating on a support or solid.

- the particles are plasmonic.

- the nanocavities are distributed aperiodically.

- the distance between two neighboring nanocavities on average is at least 0.5W0 or at least W0.

- at least 50% or 80% of the nanoparticles have a width W1 between the mean width ±30% or even ±20% or even ±15%

- the surface of the demixed layer, preferably glass, is covered by another layer partially filling said nanocavities, the nanoparticles are in the nanocavities in contact with the other material, the other material is preferably an oxide layer, or of nitride or oxynitride, of at least one silicon metal, in particular a crystallized or amorphous layer, in particular a ZnO, TiN layer.

- the nanoparticles are covered with a dielectric layer (inorganic) in particular sufficiently small thickness to be conformal (to undulate), for example a layer of oxide, or nitride or oxynitride, of at least one silicon metal in particular SiN, SiO, TiOx.

Certain advantageous but non-limiting embodiments of the present invention are described below, which can of course be combined with each other if necessary. Figure 1 schematizes the different manufacturing steps of a demixed layer system in a first embodiment of the invention.

Figure 2 schematically represents for a binary mixture the demixing dome, separating the region where the mixture of two liquids is miscible from the immiscibility region. Inside this dome there are 3 regions (a) and (c) the growth, binodal nucleation domains, and (b) the spinodal decomposition domain.

Figure 3 is an SEM scanning electron microscopy image of the surface of a demixed layer system.

Figure 4 schematizes the different manufacturing steps of a demixed layer system in a second embodiment of the invention.

FIG. 5 diagrams the different manufacturing steps of a demixed layer system in a third embodiment of the invention. FIG. 6 diagrams the different manufacturing steps of a demixed layer system in a fourth embodiment of the invention.

FIG. 7 diagrams the different manufacturing steps of a demixed layer system in a fifth embodiment of the invention. Figure 8, Figure 9, Figure 10, Figure 11, Figure 12, Figure 13 are SEM images of the surface of demixed layer systems.

Figure 14 schematizes the different manufacturing steps of a nanostructured demixed layer system carrying a set of nanoparticles in nanocavities. FIG. 15 is an AFM atomic force microscopy image of a surface of a nanostructured demixed layer with nanocavities in a reference example from the applicant.

Figure 16 is an SEM image of a surface of a demixed nanostructured layer according to the invention with nanocavities and carrying nanoparticles inside and outside the nanocavities in a reference example of the Applicant.

Figure 1 schematizes the different manufacturing steps of a demixed layer system in a first embodiment of the invention.

A preliminary step is the supply or manufacture of a coated substrate 100 by deposition, in particular spraying or by liquid means, on a substrate 10 carrying a stack of layers comprising: a first layer of a first material 1, in particular amorphous, the composition of which allows a phase separation, surmounted by a sacrificial layer 2 which can be removed by the liquid route (for example soluble by a solvent, preferably aqueous, by immersion, by using a washing machine with a brush) and an absorption overlayer 3 absorbing a preferably electromagnetic radiation. There are then 3 steps:

Step 1) consists of a flash heat treatment in less than 1 s by radiation, preferably laser line, of a coated substrate 100a comprising the stack with the unmixed layer 1′ with a first phase 11 and a second phase 12 with ( nano)drops under the sacrificial layer and the overlayer. For example, the coated substrate is scrolled at at least 1 m per min (via a conveyor of an industrial line, for example with a spray deposition frame for layers 1 and/or 2 and/or 3) under a laser line of width for example sufficient to scan the width of the coated substrate and given surface power in W/mm with the laser line oriented perpendicular to the surface of the overlayer 3 and in the direction of this overlayer 3. The laser line is placed above the stack and the laser is oriented in the direction of the stack.

Step 2) consists of liquid removal of the sacrificial layer 2 and the overlayer 3 to obtain a coated substrate 100b comprising the substrate 10 with the demixed layer 1′ of free surface.

In a washing machine water hits the coated substrate which is horizontal or vertical and one or more brushes rub the coated substrate.

Optional step 3) consists of the selective elimination of the first phase, for example by acid attack, to obtain a coated substrate 100c comprising a substrate 10 carrying the second phase and which then forms a network of pads 12', for example distributed irregularly . The first phase can be the main phase.

Figure 2 schematically represents for a binary mixture the demixing dome (at a given critical temperature Te), separating the region where the mixture of two liquids is miscible from the immiscibility region. Inside this dome there are 3 regions (a) and (c) the growth, binodal nucleation domains, and (b) the spinodal decomposition domain

At T 1 temperature reached in the first layer, for example, the first and second phases M1 and M2 are identified in regions a) and c).

FIG. 3 is a front view SEM image of a demixed layer system 100b comprising a first phase 11 and a second phase 12 in the form of disjoint nanodroplets in an example 1 .

To do this, the first layer was deposited on a soda lime float glass (Planiclear glass from the applicant company) by magnetron (radio-frequency) sputtering from a ceramic target to form a thin layer of glass of composition S1O2-BaO- B2C>3 (35.5%-14.5%-50% by weight oxide). The thickness of the first layer (therefore of the demixed layer afterwards) is 200nm.

The sacrificial layer is a 20 nm germanium oxide layer deposited by magnetron sputtering in direct current mode from a germanium target under a reactive argon oxygen atmosphere and the absorption layer deposited by magnetron sputtering in direct current mode is a 6nm nickel chrome layer from a metal target. These sacrificial and absorption layers were removed by deionized water at 45° C. for a few minutes. The flash processing (a fraction of a second) was carried out with a running speed of 3m/min and a surface power of 17 kW/cm ² at a wavelength of approximately 1 μm. After heat treatment, the system separated into two phases: the second phase (nanodrops) is rich in silica, either in network former and the first phase rich in barium, or in network modifier. The first phase is therefore less polymerized and it is possible to remove it preferentially by acid treatment. For example, an H ₂ O/HNO ₃ (68%)/HF (40%)] solution diluted in deionized water for a few minutes is used.

The thin layer glass deposition method can change, for example with a doped ceramic target for direct current mode deposition.

Alternatively, a glass layer of Si0 ₂ -Ca0-B ₂ 0 ₃ or even Si0 ₂ -Na ₂ 0- B2O3· is chosen.

A preliminary step is the supply or manufacture of a coated substrate 200 by deposition, in particular spraying or by liquid means, on a substrate 10 carrying a stack of layers comprising: a first layer of a first material 1, in particular amorphous, the composition of which allows phase separation, surmounted by a sacrificial layer 2 which can be removed by the liquid route (for example soluble by solvent, preferably aqueous, by immersion, by using a washing machine with a brush) and an absorption overlayer 3 of preferably electromagnetic radiation.

There are then three steps.

Step 1) consists of flash annealing at less than 1s by preferably laser line radiation to obtain a coated substrate 200a comprising the stack with the demixed layer 1' with a first phase 13 and a second phase 14 with ( nano)drops, unmixed layer under sacrificial layer 2 and overlayer 3. The first phase may be the main phase.

For example, the coated substrate is scrolled at at least 1 m per min (via a conveyor of an industrial line, for example with a spray deposition frame for layers 1 and/or 2 and/or 3) under a laser line of width for example sufficient to scan the width of the coated substrate and given surface power with the laser line oriented perpendicular to the surface of the overlayer 3 and in the direction of this overlayer 3. The laser line is placed above the stack and the laser is oriented in the direction of the stack. Step 2) consists of liquid removal of sacrificial layer 2 and overlayer 3 to obtain a coated substrate 200b comprising substrate 10 with demixed free surface layer 1'.

The optional step 3) consists of the selective elimination of the second phase, for example by acid attack, to obtain a coated substrate 200c comprising a substrate 10 comprising the structured demixed layer 1′ which comprises the first phase 13 with a network of (nano)cavities 15 for example distributed irregularly and of substantially oval or round shape.

FIG. 5 diagrams the different manufacturing steps of a demixed layer system in a third embodiment of the invention.

A preliminary step is the supply or manufacture of a coated substrate 300 by deposition, in particular spraying or by liquid means, on a substrate 3' carrying a stack of layers comprising: a first layer of a first material 1, in particular amorphous, the composition of which allows phase separation,

The substrate 3′ is capable of absorbing radiation, preferably electromagnetic.

There are then two steps.

Step 1) consists of flash annealing at less than 1s by preferably laser line radiation to obtain a coated substrate 300a comprising the substrate 3' with the unmixed layer 1' with a first phase 11 and a second phase 12 with (nano)drops on the free surface. The first phase can be the main phase.

For example, the coated substrate is scrolled at at least 1 m per min (via a conveyor of an industrial line, for example with a sputtering deposition frame for layer 1) under a laser line of width, for example, sufficient to scan the width of the coated substrate and of given surface power with the laser line oriented perpendicular to the surface of layer 1 and in the direction of this layer 1. The laser line is placed above layer 1 and the laser is oriented in the direction of the layer 1.

Optional step 2) consists of the selective elimination of the first phase, for example by acid attack, to obtain a coated substrate 300b comprising the substrate 3' carrying the second phase and which then forms a network of pads 12', for example distributed irregularly.

FIG. 6 diagrams the different manufacturing steps of a demixed layer system in a fourth embodiment of the invention.

A preliminary step is the supply or manufacture of a coated substrate 400 by deposition, in particular spraying or liquid deposition, on a substrate 10 carrying a stack of layers comprising: a sub-layer 4 for absorption of radiation, preferably electromagnetic covered by a first layer of a first material 1 including amorphous whose composition allows phase separation.

There are then two steps.

Step 1) consists of flash annealing at less than 1s by preferably laser line radiation to obtain a coated substrate 400a comprising the substrate with the underlayer 4 and the unmixed layer 1' with a first phase 11 and a second phase 12 with (nano)drops. The first phase can be the main phase.

For example, the coated substrate is scrolled at at least 1m per min (via a conveyor of an industrial line, for example with a sputtering deposition frame for layers 1 and/or 4) under a laser line of sufficient width, for example to scan the width of the coated substrate and given surface power with the laser line oriented perpendicular to the surface of layer 1 and in the direction of this layer 1. The laser line is placed above this layer 1 and the laser is oriented towards this layer 1 .

Optional step 2) consists of the selective elimination of the first phase, for example by acid attack, to obtain a coated substrate 400b comprising the substrate 10 carrying the underlayer 4 and the second phase which then forms an array of pads 12 ' for example distributed irregularly.

FIG. 7 diagrams the different manufacturing steps of a demixed layer system in a fifth embodiment of the invention.

A preliminary step is the supply or manufacture of a coated substrate 500 by deposition, in particular spraying or liquid deposition, on a substrate 10 carrying a first layer 30 of a first material, in particular amorphous, the composition of which allows phase separation, first layer capable of absorbing radiation, preferably electromagnetic.

There are then two steps:

Step 1) consists of flash annealing in less than 1s by preferably laser line radiation to obtain a coated substrate 500a comprising the demixed layer 1′ with a first phase 11 and a second phase 12 with (nano)drops. The first phase can be the main phase.

For example, the coated substrate is scrolled at at least 1 m per min (via a conveyor of an industrial line, for example with a sputtering deposition frame for the layer 30) under a laser line of width, for example, sufficient to scan the width of the coated substrate and of given surface power with the laser line oriented perpendicular to the surface of the layer 30 and in the direction of this layer 30. Place the laser line above layer 30 and direct the laser towards layer 30.

Optional step 2) consists of the selective elimination of the first phase, for example by acid attack, to obtain a coated substrate 500b comprising the substrate 10, the layer 30 with the second phase which then forms an array of pads 12', for example distributed irregularly.

Figures 8-13 are six SEM images of the surface of six demixed layer systems 301a; 302a, 303a, 304a, 305a, 306a comprising a first removable phase 11 and a second phase 12 in the form of disjoint nanodroplets in examples numbered from 1' to 6'.

To do this, the first layer capable of demixing was deposited on a 250 μm silicon substrate by magnetron sputtering (radio-frequency) from a ceramic target to form a thin layer of glass of composition Si0 ₂ -Ba0-B ₂ C> ₃ (35.5%-14.5%-50% by weight of oxide. The thickness of the first layer (therefore of the demixed layer) is 100 nm.

The flash processing (a fraction of a second) was carried out with a frame rate and a given surface power at a wavelength of approximately 1 pm.

The data of examples 1' to 6' as well as of example 1 are recorded (for comparative purposes) in the following table 1. The estimated equivalent average diameter of the drops (on the surface), the standard deviation, and the density of the drops are calculated by image processing. [Table 1]

These results show that it is possible to greatly vary the structures obtained by phase separation and in particular their size or even their shape only by playing on the parameters of the laser. The slower the running speed of the line laser, and therefore the higher the temperature reached in the first layer, the larger the structures obtained.

It is possible to obtain droplets with an average equivalent diameter of less than 100 nm for the fastest laser processing speed from which phase separation is observed (7 m.min- ¹ ), down to droplets with an average diameter equivalent of the order of 500 nm for the slowest processing speed (4 m.min ^·1 ).

Figure 14 schematizes the different manufacturing steps of a nanostructured demixed layer system carrying a set of nanoparticles in nanocavities. A preliminary step already described in the previous embodiments is the manufacture of a coated substrate 600a by deposition, in particular spraying or liquid deposition, on a substrate 10 carrying a first layer of a first material, in particular amorphous, the composition of which allows phase separation and possibly an absorption layer as a sub-layer or as an over-layer (underlying a possible sacrificial layer between the first layer and the over-layer).

A next step already described in the previous embodiments consists of flash annealing in less than 1 s by preferably laser line radiation to obtain a coated substrate 600b comprising the demixed layer 1' with a first phase 16 and a second phase 114 with (nano)drops. The first phase can be the main phase.

For example, the coated substrate is scrolled at at least 1 m per min (via a conveyor of an industrial line, for example with a spray deposition frame for the layers) under a laser line of width, for example, sufficient to scan the width of the coated substrate and given surface power with the laser line oriented perpendicular to the free surface of the coated substrate and in the direction of the coated substrate. The laser line is placed above the coated substrate and the laser is directed in the direction of the coated substrate. Step 1) then consists of the selective elimination of the second phase, for example by acid attack, to obtain a coated substrate 600b comprising a substrate 10 comprising the structured unmixed layer 1 'which comprises the first phase 16 with a network of (nano)cavities 15 for example distributed irregularly and of substantially oval or round shape.

Step 2) consists of depositing a thin layer 40 of a second material 40 capable of dewetting on the nanostructured surface to obtain a coated substrate 600c of a material 41 covering the nanocavities

Step 3) consists of annealing for dewetting said second material 40, to obtain a coated substrate 600d comprising nanoparticles 5 in the nanocavities and nanoparticles 5' outside in the nanocavities 15 of the first phase 16 Step 4) consists of the possible removal of the nanoparticles which are not in the nanocavities, for example by scouring.

Figure 15 is an AFM image of a nanostructured surface with nanocavities

15 of a reference demixed layer system made by the Applicant.

To do this, a first layer was obtained by deposition by magnetron sputtering (radio-frequency) from a ceramic target to form a thin layer of glass of composition Si0 ₂ -Ba0-B ₂ C> ₃ (80%- 10%-10% by weight oxide). The thickness of the layer of glass on amorphous silica is 100 nm.

Heat treatment in an oven for 20 hours allowed phase separation After heat treatment, the system separated into two phases: the first phase

16 rich in silica, either as a network former and the second phase rich in barium, or as a network modifier. The second phase is therefore less polymerized and it is possible to preferentially remove it by acid treatment.

Dissolution by acid attack (solution containing 30 parts H ₂ 0 / 1 part HNO3 (68%) / 1.5 parts HF (40%) diluted in DI water) for 3 min made it possible to obtain the nanostructuring with the nanocavities.

This example of reference shows that to have large sizes of nanocavities the furnace implies long durations.

Figure 16 is an SEM image of a nanostructured surface with nanocavities and carrying 5 nanoparticles in the nanocavities and 5' nanoparticles outside the nanocavities.

A 15nm silver magnetron deposit was made on the nanostructured substrate of figure 15. Annealing at 400°C for 2 hours in an ambient atmosphere allows the dewetting of the silver On the surface of the demixed and textured glass layer, two populations of particles are therefore observed: large particles located on the substrate and small particles located inside the nanocavities. It is possible to modulate the size distribution of the particles by using a textured surface and thus to obtain smaller particles than on a flat surface.

The metal capable of dewetting is here silver, other metals are possible copper, gold, aluminum, or even a dielectric.

The metallic layer able to dewet is deposited by magnetron but another method of obtaining thin layers such as evaporation can be used. Covering the nanoparticles with an additional thin layer is possible. By using the flash heat treatment process, in particular line laser, it is possible to simplify the production of such a product.

Claims

1. Process for manufacturing a demixed layer system (100a to 600e) comprising:

- the supply of a coated substrate (10, 1, 2, 3, 4) comprising a substrate comprising at least a first layer (1, 1', 30) of a first material capable of demixing,

- a heat treatment of the first layer leading to a phase separation of the first layer, then called unmixed layer, characterized in that the heat treatment is obtained by irradiating the coated substrate with a beam of electromagnetic or electronic radiation or d ions, for a period of at most 1s, the coated substrate absorbing said beam.

2. A method of manufacturing a demixed layer system according to the preceding claim characterized in that the irradiation is carried out during the scrolling of the coated substrate, in particular horizontal, in translation, in particular with a beam forming a laser line.

3. A method of manufacturing a demixed layer system (300a, 500a) according to one of the preceding claims, characterized in that during irradiation, the first layer (30) which is chosen to be inorganic and/or the substrate ( 3′) which is chosen to be inorganic absorbs said beam, preferably laser or flash lamp, in particular first layer of oxides or oxide substrate absorbing said beam emitting in the ultraviolet in particular at 400 nm at most or emitting from 8 to 12 μm.

4. A method of manufacturing a demixed layer system (100a, 200a, 400a) according to one of the preceding claims, characterized in that the coated substrate comprising at least one layer called the absorption layer (3, 4) distinct from the first layer, which is an underlayer (4) under the first layer or an overlayer (3) on the first layer, during irradiation, the absorption layer absorbs the preferably laser beam in particular at a length of wave from 400nm to 2000nm, and even from 900nm to 110Onm.

5. A method of manufacturing a demixed layer system (100b, 200b) according to the preceding claim, characterized in that the absorption layer (3) being the overlayer (3), the method comprises removing the layer of absorption preferably eliminable by liquid route and/or by mechanical action, optionally removal using a sacrificial layer, between the first layer and the absorption layer, eliminable by liquid route.

6. A method of manufacturing a demixed layer system (100b to 600b) according to one of the preceding claims, characterized in that the demixed layer (3) comprising a first phase (11, 16) and a second phase (12, 14) in the form of disjointed drops, the method comprises selective phase elimination of the demixed layer (1, 1'), for example by liquid means, the elimination selective leading to:

- the surface texturing of the demixed layer (1'), the surface thus textured being provided with a plurality of disjoint cavities (15) of width WO, in particular by elimination of the second phase (14)

- or the formation of a plurality of disjoint studs (12') of width WO, by eliminating the first phase (11).

7. Method for manufacturing a demixed layer system (600d, 600e) according to the preceding claim, characterized in that the surface texturing of the demixed layer (1') leads to cavities which are nanocavities, the width WO being nanometric , and the method then comprises:

- the formation, by depositing on the demixed nanotextured layer (1'), of a second layer (40) at least coalescing and preferably at least percolating in a second inorganic material of nanometric thickness E1,

- the formation, from a dewetting of said second material, of a multitude of nanoparticles (5.5') disjointed in said nanocavities, the nanoparticles being of width W1 nanometric.

8. A method of manufacturing a demixed layer system (600d, 600e) according to claim 7 characterized in that the dewetting is liquid, in particular a chalcogenide glass, or solid, in particular a metal or metal alloy.

9. Demixed layer system (100a to 600a) obtained by the method according to one of claims 1 to 5 comprising the substrate coated with the demixed layer (1) comprises a first phase and a second phase in the form of disjoint drops or comprises a first phase and a second phase which form an interconnected network.

10. Demixed layer system (100b to 600e) obtained by the method according to one of claims 6 to 8 comprising the substrate coated with the demixed layer (1 ') comprises a first phase (11, 12), layer having a surface free or under an overlayer, the demixed layer has the surface texturing comprising a set of studs (12') or cavities (15) or the demixed layer comprising an interconnected network.

11 . Demixed layer system according to one of Claims 9 to 10, characterized in that the demixed layer (1'), in particular transparent, is an oxide or a mixture of oxides, in particular glass, silicate, borate, borosilicate or a mixture of oxide(s) and a metal or chalcogenide glass, and preferably the substrate is transparent, in particular glass or polymer.

12. System with a demixed layer (100a) according to one of claims 9 to 11, characterized in that it comprises an absorption layer, in the underlayer of the demixed layer or in the overlayer of the demixed layer, which is based at least one metal, metal layer optionally partially oxidized or which is an oxide and/or nitride layer of one or more metals, the metal or metals being preferably chosen from germanium, molybdenum, titanium, zinc, magnesium, zirconium, silver, indium, tin, nickel, chromium, niobium, vanadium, tungsten, copper, iron, silicon, gold, mixture of zinc and tin, indium and tin, nickel and chromium.

13. Demixed layer system (100a) according to one of claims 9 to 11 characterized in that it comprises an absorption layer, preferably which is an overlayer on the demixed layer, the absorption layer is based organic comprising an agent absorbing the beam, in particular based on pigments, or dye, in particular agent comprising carbon particles.

14. Demixed layer system (100a) according to one of claims 9 to 11 characterized in that it comprises an absorption layer on a sacrificial layer, sacrificial layer on the demixed layer; the sacrificial layer is preferably a layer based on a zinc or magnesium oxide, or based on molybdenum or molybdenum oxide MoOx, a germanium oxide GeOx, or chosen from metal halides and sulphates metallic, group I or VII materials, in particular Al ₂ (S0 ₄ ) ₃ OR NaCI or LiF.

15. Demixed layer system (600d, 600e) according to one of claims 10 to 13 characterized in that it comprises in this order on the substrate:

- the possible absorption layer

- the inorganic demixed layer which is nanotextured on the surface with a surface provided with nanocavities (15) with a width W0 of at most 300 nm and preferably of at least 10 nm,

- nanoparticles (5) in the nanocavities, the nanoparticles having a width W1 preferably of at most 300 nm and preferably of at least 10 nm, in particular at least 50% or even at least 80% of the nanoparticles in the nanocavities have a width of at most 300 nm and even at most 200 nm.