Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
  • C03C11/005—Multi-cellular glass ; Porous or hollow glass or glass particles obtained by leaching after a phase separation step
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/31—Pre-treatment
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/32—After-treatment
  • C03C2218/328—Partly or completely removing a coating
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
  • G02B2207/101—Nanooptics

Definitions

• TITLE METHOD OF MANUFACTURING A STRUCTURE WITH NANOPARTICLES ON A TEXTURED SURFACE AND SUCH A STRUCTURE WITH NANOPARTICLES
• the invention relates to a method of manufacturing a structure comprising nanoparticles on a textured surface as well as such a structure.
• the silver layer is deposited by magnetron sputtering at thicknesses between 10 and 80 nm and dewetting is induced by annealing at 400 ° C for 2 hours in an oven.
• the nanoparticles have a diamond shape with a spherical part emerging from the cavities and a frustoconical part in the cavities.
• the size distribution is narrower than on a flat substrate. For example, for hollows 80nm deep, 215nm wide, and with a deposited silver thickness of 30nm, particles of 150nm height are obtained and the diameter is characterized by a distribution having a peak at 215nm and a width at mid. height of approximately 90nm.
• the invention aims at an alternative manufacturing process, industrially feasible on large surfaces, in a reliable and reproducible manner, by keeping the control of the size, of the size dispersion, of the surface density of the nanoparticles, by adjusting them as required. as needed.
• the first subject of the invention is for this purpose a process for manufacturing nanoparticles, in particular plasmonic nanoparticles, on a textured surface comprising, in this order: - the surface nanotexturing of a first layer made of a first material, in particular transparent (solid material or coating deposited on a support in particular transparent, dielectric in particular inorganic such as glass or polymer), in particular which is inorganic or containing a source of an inorganic material, first layer in particular with a thickness E0 of at least 10nm and preferably at most 500nm or 300nm or 200nm if as a layer (coating) on a support, the surface thus nanotextured being provided with a plurality of disjoint (and three-dimensional) nanocavities of nanometric width WO (preferably taken at the surface of the nanocavity, at the high level), in particular of nanometric HO height (preferably from the lowest point of the nanocavity), and even of nanometric length LO in particular with an aspect ratio W0 / L0 of
• nanometric width W1 (with the narrowest distribution of widths possible if necessary) in particular of nanometric height H1 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 a normal top view, in particular circular or of circular type , the nanoparticles being in said nanocavities, optionally under flush, flush with or emerging from said nanocavities, in particular one or more nanoparticles per nanocavity.
• the first material being a material capable of demixing, preferably amorphous, in particular a mixture of oxides, or of chalcogenides or a metal or a metal alloy or a mixture of oxide (s) and a metal, the surface nanotexturing being obtained from the following steps in this order:
• the first layer comprising nanodrops of a phase (preferably amorphous) called Pg (in another phase called a preferably amorphous matrix), disjoint nanodrops, for example emerging at the surface, of nanometric width preferably of at most 300nm or 200nm, said first demixed material being inorganic
• the dewetting - in the solid state (preferably) or in the liquid state - is carried out at a temperature T2 below T1, in particular T1-T2 above 50 ° C or at least 100 ° C.
• Phase separation surface nanostructuring offers multiple advantages over prior art nanoprinting surface structuring.
• Nanotexturing by phase separation results in a nanostructure with nanocavities in the range of tens to a few hundred nanometers. This makes it possible to control the size of the nanoparticles obtained by dewetting which are preferentially placed in the nanocavities.
• the size of the nanocavities is adjustable (by adjusting the composition of the first material and / or the time / temperature of the heat treatment or even the temperature ramp / and even by adjusting the thickness in the case of a first non-massive 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 size distribution of nanoparticles smaller than what is obtained by dewetting on a flat substrate (all other things being equal).
• inorganic material capable of demixing there may be mentioned: mixture of oxides, chalcogenides or mixture of metals and / or alloys or oxide (s) and phase Pg metal.
• the invention makes it possible in particular to obtain nanoparticles with modular sizes (in particular diameter, in particular average) of between 10 and 200 nanometers or even from 20 to 150nm or 100nm (which can be used on the surface or covered), with a method of which all stages 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 light while modulating the plasmonic absorption of the particles.
• the second material is therefore chosen capable of dewetting on the first layer or on another layer and preferably capable of generating plasmonic objects.
• the phase separation makes it possible to generate in particular sizes of nanocavities between 10 and 300nm and even at most 200nm or 150nm.
• the nanodrops are typically circular in shape (on the surface).
• the size of the nanodrops will be dictated by:
• composition of the first material capable of demixing in particular the difference in composition between the Pg phase and the matrix
• the density of nanodrops decreases over time in favor of the size of the drops (it drops when the duration of the heat treatment increases) there is first a maximum density of small drops then a density which decreases with larger drops.
• the nanocavities do not occupy a regular position with a constant pitch but are distributed aperiodically.
• T2 is chosen low enough so as not to deform the nanocavities or deform the first material and the possible underlying support if the first material is in a thin layer.
• a T2 float glass is at most 500 ° C or 650 ° C with a heat treatment time of less than 15, 10, 5 minutes.
• Tg + 150 ° C for a period of at most 5 minutes.
• the demixing dome delimits the thermodynamically stable region (miscible mixture) from the regions of immiscibility. Within this dome there are three regions, one in the center called spinodal, the other two at the edges called binodal. In the early stages, spinodal decomposition gives rise to 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.
• Phase separation can be:
• - a by nucleation growth leading directly to the coexistence of at least a first phase (in particular amorphous and / or of glass, of oxides) and a second phase (in particular of amorphous and / or of glass, of oxides) which is the so-called Pg, simple to perform, - b) or else 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 of glass, of oxides) and a second phase (in particular amorphous and / or glass, oxide) and a so-called secondary phase separation (at T1) leads to the coexistence of a third phase (in particular amorphous and / or glass, of 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 Pg phase,
• 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.
• a final droplet structure conventionally 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.
• a phase rich in network modifier for example barium
• the phase rich in network forming agent such as silica
• the heat treatment can preferably be subsequent to the formation of the first layer or take place during the formation of the first layer, which is a solid material or a coating deposited on a support (in particular inorganic and / or transparent, in particular glass) in particular coating with a thickness E0 of at least 10 nm after deposition.
• a support in particular inorganic and / or transparent, in particular glass
• the nanodrops may emerge on the surface and / or immersed in the first layer of the first demixed material, the method preferably comprises a step of partial removal of the first layer capable of making the submerged nanodrops open, possibly the step of removing the material.
• phase Pg is an extension of said partial withdrawal.
• said removal of the nanodrops and / or said partial removal step is preferably by a liquid route, in particular chemical attack, dissolution, or by a dry route, in particular by plasma etching (fluorinated, etc.).
• the duration of the elimination and / or partial withdrawal can preferably be at most one day, one hour or even at most 30, 10, 5 minutes.
• the elimination as the heat treatment can be done when the first layer scrolls, mobile in translation.
• the first layer is for example on a conveyor.
• the heat treatment provision can be made for the heat treatment to be followed by rapid cooling, in particular quenching (gas or cold air blowing, immersion for example in water, in particular for the first metal material) in particular of at most 15min, 5min, 1min, 30s (in order to freeze the nanodrops to the width, the desired size).
• quenching gas or cold air blowing, immersion for example in water, in particular for the first metal material
• the duration of the heat treatment is no more than 15min, 5min, 1 min in order in particular to easily integrate it into an industrial line
• heat treatment being chosen from annealing, annealing with quenching, rapid annealing treatments, in particular using a flame, a plasma torch or laser radiation.
• the heat treatment can be carried out during the movement, in particular horizontal and / or in translation of said first material, for example a glass or a coating in particular of glass (or of oxides) on a support (in particular transparent, inorganic in particular glass) in particular on a conveyor (rollers, glass moving in translation) for example of an industrial line.
• a glass or a coating in particular of glass (or of oxides) on a support in particular transparent, inorganic in particular glass
• a conveyor rollerers, glass moving in translation
• the heat treatment is carried out for example:
• a heating element on the side or even on the rear face of the first layer preferably, or on the side or even the front surface with the nanodrops, without sticking to the surface
• a heating element for example a heating plate, a heating network
• the first layer is a coating deposited on a support (in particular transparent, in particular inorganic in particular glass, or polymer), optionally by heating the support during a deposition to form the first layer (liquid route, in a frame of PVD etc).
• a support in particular transparent, in particular inorganic in particular glass, or polymer
• T1 liquid route, in a frame of PVD etc.
• the heat treatment can be a conventional treatment by placing the first layer in an annealing furnace or be localized, creating heating at the surface of the first layer, for example irradiation by laser beam or by ions or electrons.
• the heat treatment can be flash and not damage the underlying support if the first material is a deposit (the first layer is a deposit).
• the heat treatment does not exceed 15 min to increase the rate in an industrial line.
• T1 is preferably less than 1000 ° C or even 750 ° C.
• T1 can be between 580 ° C and 750 ° C typically for a glass and be followed by a toughening operation.
• the annealing treatment is generally carried out in a furnace, respectively quenching or annealing.
• the entire substrate is brought to a high temperature, at least 300 ° C in the case of annealing, and at least 500 ° C, or even 600 ° C, in the case of quenching.
• the rapid annealing is preferably carried out using a flame, a plasma torch or laser radiation.
• a relative movement is created between the substrate and the device (flame, laser, plasma torch).
• the device is fixed, and the coated substrate (support with first layer) scrolls past the device so as to treat its surface.
• the temperature of the substrate is generally at most 100 ° C, or even 50 ° and even 30 ° C during processing.
• Each point of the thin layer (first layer) is subjected to the rapid annealing treatment for a period generally less than or equal to 1 second, or even 0.5 second.
• the rapid annealing heat treatment is preferably carried out using laser radiation emitting in the infrared or the visible.
• the wavelength of the radiation is preferably in a range ranging from 530 to 1200 nm, or from 600 to 1000 nm, in particular from 700 to 1000 nm, or even from 800 to 1000 nm.
• Laser diodes are preferably used, emitting for example at a wavelength of the order of 808 nm, 880 nm, 915 or even 940 nm or 980 nm. In the form of diode systems, very high powers can be obtained, making it possible to reach surface powers at the level of the coating to be treated of greater than 20 kW / cm 2 , or even 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.
• each line is preferably disposed perpendicular to the direction of travel of the substrate, or disposed obliquely.
• the different lines can process the substrate simultaneously, or in a time-shifted manner. The important thing is that the entire surface to be treated is.
• the substrate can thus be set in motion, in particular in translational movement facing the fixed laser line, generally below, but possibly above, the laser line. This embodiment is particularly valuable for continuous processing.
• the substrate can be fixed and the laser can be mobile.
• the difference between the respective speeds of the substrate and of the laser is greater than or equal to 1 meter per minute, or even 4 and even 6, 8, 10 or 15 meters per minute, in order to ensure a high processing speed.
• the substrate can be set in motion using any mechanical conveying means, for example using strips, rollers or trays in translation.
• the conveyor system makes it possible to control and regulate the speed of movement.
• the laser can also be set in motion to adjust its distance from the substrate, which can be useful especially when the substrate is curved, but not only.
• the laser radiation device for said heat treatment can be integrated into a layer deposition line, in particular a first glass layer, for example a magnetic field assisted cathode sputtering deposition line (magnetron process), or a chemical deposition line.
• a layer deposition line in particular a first glass layer
• magnetic field assisted cathode sputtering deposition line magnet process
• chemical deposition line in vapor phase (CVD), in particular assisted by plasma (PECVD), vacuum or atmospheric pressure (APPECVD).
• CVD vapor phase
• PECVD assisted by plasma
• APPECVD vacuum or atmospheric pressure
• said heat treatment can be chosen from the toughening, annealing and rapid annealing treatments, in particular using a flame , a plasma torch or laser radiation.
• the first layer can be chosen transparent (for example solid glass or glass on glass). The size of the nanocavities can make it possible to remain transparent.
• transparency is meant in the visible and / or infrared (near infrared, far infrared, etc.).
• the first layer of material capable of demixing may be a solid material or is a coating on a support having sufficient thermal resistance at T1 (free from significant deformations at T1), it comprises the formation of said coating by deposition at a temperature less than or equal to T1 or accompanied by heating of the support or of the surface at T1 creating said phase separation during said deposition.
• the first layer may be a transparent coating (colorless or tinted) on a transparent support (colorless or tinted), in particular inorganic and / or dielectric, in particular glass.
• the method can then comprise the formation of the first layer including:
• liquid deposition such as sol-gel, for example by spray
• PVD physical vapor phase
• magnetron sputtering with optional radiofrequency or evaporation in particular from a ceramic or oxide target (s) or even from a metal alloy target optionally (if necessary) in reactive spraying (oxygen with rare gas such as argon),
• this can be an electrolytic deposit.
• the first material capable of demixing preferably comprises:
• the Pg phase can preferably be in a silica-based matrix (second phase).
• the first material capable of demixing may be a chalcogenide or preferably silicate, borate or borosilicate glass, in particular with a network former (silicon and / or boron) and at least one network modifier chosen in particular from an alkali metal oxide.
• RO alkaline earth metal R2O, an element oxide 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), solid or in a layer on a support (transparent and / or dielectric, preferably made of glass).
• a glass preferably silicate, borate or borosilicate
• solid or in a layer on a support transparent and / or dielectric, preferably made of glass.
• Demixing in a glass takes place when it undergoes heat treatment with T1 which is below the critical demixing temperature while allowing atomic mobility, whether diffusive or hydrodynamic in nature.
• silicate, borate or borosolicate glasses it is preferable to avoid (or with a weight content of less than 1% of the total weight) the oxide of lead, cadmium or mercury. It is preferred to avoid (or with a weight content of less than 1% of the total weight) oxides of transition metals from column 5 to 11 of the Periodic Table of the Elements.
• Glass in particular silicate, borate or borosolicate, may include dopants (rare earths) or any other element which does not adversely affect demixing.
• phase separation is known in alloys, the article entitled “phase separation in metallic glasses” by DH Kim et al., Progress in Materials Science (2013), pages 1103-1172, Elservier edition lists different glass compositions. metallic giving rise to demixing at the nanometric scale.
• the method can comprise the formation of the first layer which is a coating of oxides or of glass oxide (s) (in particular silicate, borate or borosilicate) on a support (transparent and / or dielectric, for example a glass) for example.
• oxides or of glass oxide (s) in particular silicate, borate or borosilicate
• a support transparent and / or dielectric, for example a glass
• formation by sol gel route from precursors of an oxide or of several oxides (in particular of silica and / or boron oxide), and also of alkali oxide RO, alkaline earth oxide R2O, of element columns 4 and 12) or with any other source of oxides (salts, powder, acid, etc.).
• Organometallics are used in particular as precursor.
• Silica can be obtained using silane, tetraethoxysilane (TEOS), or even hexamethyldisiloxane (HDMSO), optionally using an accelerator such as triethylphosphate.
• TEOS tetraethoxysilane
• HDMSO hexamethyldisiloxane
• boric acid As a precursor for boron, boric acid can be chosen.
• NA 2 OB 2 O-S1O 2 N BS
• Na20 sodium acetate in solution
• the first material solid or coating on a preferably transparent and dielectric support, in particular made of float glass in particular
• silicate glass is silicate glass.
• the silica (S1O2) content by weight is at least 20 or 40% of the total weight and even at least 50%, 55%, 65% and even at most 80%.
• the B 2 O 3 content is zero or less than the silica content, and preferably less than 20%.
• the weight content of B 2 O 3 + S1O 2 can be at least 40%, 55%, 65% and even at most 95%, 80%.
• the first material solid or coating on a preferably transparent and dielectric support, in particular made of float glass in particular
• the content by weight 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 at most 20%.
• the first material (solid or coating on a preferably transparent and dielectric support, in particular made of float glass in particular) is borosilicate glass.
• the content by weight 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%.
• the chemical composition of the first layer can comprise (or consist of) at least one oxide of at least one of the 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: K 2 0 0-25 %
• PbO 0-40% - and even one or more oxides (preferably at most 3 in all) can be added or substituted:
• first, or second or third above-mentioned compositions it is preferable to avoid (or with a weight content of less than 1% of the total weight) the oxide of lead, cadmium or mercury. It is preferred to avoid (or with a weight content of less than 1% of the total weight) 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 less than 1% by weight.
• compositions can comprise dopants (rare earths) or any other element which do not interfere with demixing.
• dopants rare earths
• Corning 7070 glass a lithium potassium borosilicate
• an example is described in the publication by Wheaton et al. Entitled “Evaluation of phase separation in glass with the use of atomic force microscopy", Journal of Non Crystalline solids 353 (2007) pages 4767-4778.
• binary systems Na2 ⁇ D - S1O2 For a first layer of solid glass or thin layer, there may be mentioned binary systems Na2 ⁇ D - S1O2.
• An example is described in the publication by Utsuno et al. Entitled “Phase separation of Na 2 0-Si0 2 films prepared by sputtering” journal of non crystalline solids (2004) pages 337-340.
• first solid glass layer or thin layer For a first solid glass layer or thin layer, mention may be made of Si0 2 -BaO binary systems. An example is described in the publication by Seward et al entitled “Development of Two-Phase Structure in Glasses", with special reference to the System BaO-Si0 2. " Journal of the American Ceramic Society, 1968, 51, pages 634-643 . If the first layer is deposited cold, there is no phase separation, this is created by the heat treatment at T1 for example during heating from 580 ° C or 700 ° C followed by quenching operation.
• Nanocavities have, for example, a circular or almost circular perimeter on the surface.
• 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 nanocavity coverage rate can be at most 60%, 50% or 40% and at least 5%, 10% to 15%, preferably 15% to 40%.
• the filling rate of nanocavities with 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).
• the dewetting is in the solid state and of one or more metals.
• the dewetting is carried out for example in an oven, in particular under a controlled atmosphere (neutral gas, oxidizing atmosphere).
• the material capable of dewetting is a material having a low energy of adhesion 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
• the material capable of dewetting is a material having a low energy of adhesion 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
• it can be for example:
• a metal used alone or as a mixture, alloy, 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 germanium doped manganese
• 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 April 2019 pages 320-327.
• Dielectric glass metasurfaces are poorly absorbent, and have a high refractive index, which makes it possible to modulate the propagation of light efficiently.
• the dewetting can be solid, in particular a metal or a metal alloy.
• the deposit to form the second layer can be:
• PVD physical in vapor phase
• magnetron sputtering with optional radiofrequency or evaporation in particular from a ceramic or oxide target (s) or even from a metal alloy target in reactive oxygen sputtering with rare gas (such as argon)
• the deposit to form the second layer can be directly on said first layer, (the second material being directly in contact with said first layer), the nanoparticles are then in the nanocavities in contact with the first layer, preferably one by one. nanocavity.
• the method comprises after said removal and before the deposition of the second material the formation of another layer, by depositing on said nanotextured surface, in another preferably dielectric material distinct from said first demixed material, the dewetting being on said other layer.
• the other layer may have a distinct affinity for said first material and / or a distinct functionality, in particular capable of modifying the environment of the nanoparticles, in particular the refractive index (and therefore the plasmonic response).
• the other layer can also change the crystallinity and wetting properties.
• the other material is inorganic and even transparent (metal oxy and / or nitride, silicon, or glass, for example with a composition different from glass with nanocavities).
• the other layer is, for example, of nanometric thickness E2 less than HO, thus partially filling said nanocavities.
• E2 is at most 20nm.
• the nanocavities thus coated with the other layer preferably remaining of nanometric width (measured at the surface) preferably at most 300nm or 200nm, in particular the nanoparticles in the nanocavities being in contact with the other layer.
• nanometric width measured at the surface
• the second material is a layer directly deposited on the first material or on another layer if we want to modify the dewetting conditions or to provide functionality to the final product for example can be an alkali barrier layer etc.
• the deposition of the other layer can be consistent, in particular physical vapor deposition, such as magnetron sputtering.
• the first layer is preferably made of glass, the other material is an oxide, or nitride or oxynitride layer, crystallized or amorphous, in particular ZnO, TiN.
• This other layer in particular crystalline or amorphous oxide, can be:
• This other layer can have optical functionality, to adjust an optical response.
• This other layer can be dielectric.
• the method can comprise the deposition of a preferably inorganic overcoat on the nanoparticles (in contact with the other material or the first material) in particular the deposit is compliant, in particular a physical vapor deposition such as magnetron or liquid sputtering.
• All of the above layers can be used for the other material.
• it may be made of a material identical or similar to said other material.
• the overlay material (essentially) is inorganic and even transparent (metal oxy and / or nitride, silicon, or glass, for example of composition different from glass with nanocavities).
• This overcoat in particular crystallized or amorphous oxide, can be: - ZnO (crystallized oxide)
• This overlayer can be dielectric.
• This other layer can have an optical functionality, to adjust an optical response, in particular in an identical material. (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, predominantly larger than the nanoparticles in the nanocavities of nanometric size and preferably (if necessary) the method comprises the removal of all or part of the nanoparticles between the nanocavities by action mechanical such as brushing, crumpling, etc.
• the first layer may be a coating on a glass, in particular float glass and the method may include bending during said heat treatment and / or lamination after said removal and / or assembly in double or triple glazing .
• the invention also relates to a structure obtained in particular by the method described above comprising:
• 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 occupancy rate of the nanoparticles in the nanocavities being d 'at least 40% or even at least 80%, the nanoparticles being of width W1 (in particular average) of at most 300nm, 200nm or 150nm and preferably at least 10 or 20nm.
• second material preferably plasmonic, in particular inorganic and / or dielectric, in particular metallic or oxide
• At least one of the following characteristics can also be provided:
• the filled nanocavities comprise a single nanoparticle
• the nanocavities have a width of at most 300nm and even at most 200nm or 150nm and preferably at least 20nm - 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 at most 200nm or 150nm and even at least 10nm or 20nm ,
• the distribution profile (in number) of the width of the nanocavities is a (bell-shaped) curve comprising a vertex corresponding to a D0 value of at most 300nm or even at most 200nm or 150nm or 100nm and 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 vertex (the highest if several vertices or a single vertex, in particular bell-shaped) corresponding to a D1 value of at most 300nm or even at most 200nm or 150nm or 100nm and at least 10 or 20nm
• the distribution profile (in number) of the diameter of the nanoparticles in the nanocavities is a curve comprising a vertex (main, the highest if several vertices or a single vertex, in particular bell-shaped) corresponding to a value D1 in particular of at plus 300nm or even at most 200nm or 150nm or 10Onm and at least 10nm or 20nm and with a width at mid-height of at most 60nm or at most 50nm (and possibly at least 10nm) in particular for D1 of at most 100nm or at most 75nm
• the structure comprises said nanoparticles in the nanocavities (of a given material, preferably plasmonic, in particular inorganic and / or dielectric, in particular metallic or oxide) and optionally nanoparticles (in particular of said given material) between the nanocavities, at least 80% or even at least 90% of nanoparticles on the nanotextured surface are in the nanocavities and less than 10% or 5% or 1% of nanoparticles are between the nanocavities (high level of the nanotextured surface) and in particular the nanoparticles between the nanocavities are of average width greater than (average) width in nanocavities
• the first layer is in particular demixed glass, coated on a support or solid.
• the nanoparticles are plasmonic and / or metallic or dielectric, in particular inorganic, in particular metallic or oxides.
• the nanocavities are distributed aperiodically.
• the distance between two neighboring nanocavities on average is at least 0.5W0 or at least W0
• the nanoparticles have a width W1 between the mean width ⁇ 30% or even ⁇ 20% or even ⁇ 15% the surface of the first layer, preferably made of 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 crystalline or amorphous layer, in particular a ZnO, TiN layer.
• the nanoparticles are covered with a dielectric layer (inorganic) in particular thickness sufficiently small to conform (to undulate), for example a layer of oxide, or nitride or oxynitride, of at least one silicon metal in particular SiN, SiO, TiOx.
• a dielectric layer inorganic in particular thickness sufficiently small to conform (to undulate)
• oxide, or nitride or oxynitride of at least one silicon metal in particular SiN, SiO, TiOx.
• the nanocavity width distribution profile can be a (bell-shaped) curve with a vertex corresponding to an OD value of at most 300nm or even at most 200nm or even 150nm or 100nm and at least 10nm or 20nm .
• This profile can be almost symmetrical.
• DO corresponds to the mean value of the width of the nanocavities.
• the diameter distribution profile of nanoparticles in nanocavities can be a curve with a main vertex (bell-shaped) corresponding to a D1 value of at most 300nm or even at most 200nm or even 150nm or 100nm and at less 10 or 20nm. This profile can be almost symmetrical.
• D1 corresponds to the mean value of the diameter of the nanoparticles in the nanocavities.
• nanoparticles (of said same second material) have been greatly reduced or eliminated between the nanocavities. This makes it possible to control (tighten) the size distribution of the nanoparticles.
• the distribution profile of the diameter of the nanoparticles in the nanocavities and between the nanocavities can be an envelope which convolves two bell curves or even a double bell curve (visible) with a vertex corresponding to a D1 value. at most 300nm or even at most 200nm or even 150nm or 100nm and at least 10 or 20nm and another peak with a peak corresponding to a value D2 greater than D1.
• FIG. 1 schematically shows the different stages of manufacturing a nanostructured product carrying a set of nanoparticles in nanocavities according to the invention.
• FIG. 2 diagrammatically represents for a binary mixture the demixing dome, separating the region where the mixture of two liquids is miscible from the region of immiscibility. Inside this dome we find 3 regions (a) and (c) the growth nucleation domains, binodal, and (b) the spinodal decomposition domain
• Figure 3a is an AFM (atomic force microscopy) image of a nanostructured surface according to the invention with nanocavities.
• Figure 3b is an SEM (scanning electron microscopy) image of a nanostructured surface according to the invention with nanocavities and carrying nanoparticles according to the invention in and outside the nanocavities.
• Figure 3b is an SEM image of a reference planar surface (for comparative purposes) carrying nanoparticles.
• Figure 3c shows a set of curves C1, C2, C2R corresponding respectively to:
• Figure 3d is an SEM image of the nanostructured surface according to the invention with nanocavities according to the invention and carrying nanoparticles in and outside the nanocavities.
• Figure 3e is an SEM image of the nanostructured surface according to the invention with nanocavities according to the invention and carrying nanoparticles only in the nanocavities after removal of the surface particles by wiping.
• Figures 4a, 4b (tilted), 4c (slice) are SEM images of this layer with a nanostructured surface according to the invention with nanocavities according to the invention and carrying nanoparticles in and outside the nanocavities.
• Figure 4a is an SEM image of a reference flat surface (for comparative purposes) carrying nanoparticles.
• Figure 4d shows a set of curves C3, C3R corresponding respectively to:
• FIGS. 5a to 8a are AFM images of various nanostructured surfaces according to the invention with nanocavities according to the invention.
• FIGS. 5b to 8b are SEM images of these nanostructured surfaces with nanocavities and carrying nanoparticles according to the invention in and outside the nanocavities.
• Figure 5'b is an SEM image of a reference planar surface (for comparison) carrying nanoparticles.
• Figure 5c shows a set of curves according to the invention C4, C5, C6, Cl, and a C4R curve corresponding respectively to:
• Figure 5d shows a set of curves according to the invention C4, C5, C6, Cl, and a C4R curve corresponding respectively to:
• Figures 9a to 12a are SEM images of various nanostructured surfaces with nanocavities and carrying nanoparticles according to the invention in and outside the nanocavities.
• Figure 13 shows a set of curves F1, F2, F3, F4, corresponding respectively to:
• Figure 1 shows schematically the different stages of manufacturing a nanostructured glass product carrying a set of nanoparticles in nanocavities according to the invention.
• step 2 annealing at high temperature (T1) to obtain a demixed material 1 'with nanodrops 2' in a die 2
• step 3 elimination of the nanodrops to obtain the emerging nanocavities 3 on the then nanostructured surface 11 - step 4): deposit of a thin layer 4 in a second material capable of dewetting on the nanostructured surface 11
• step 5 annealing for dewetting of said second material 4, forming nanoparticles in nanocavities 5 and outside 5 ’
• step 6) possible removal of the nanoparticles which are not in the nanocavities, for example by wiping.
• a support is obtained with a thin layer capable of demixing or a solid material capable of demixing is used.
• Step 1 deposition by magnetron sputtering (RF) from a ceramic target to form a thin glass composition Si02-B203-BA0 layer (80- 10- 10% by weight of oxide)
• - 2nd step annealing at 950 ° C in an oven, for a given time, at ambient atmosphere to obtain phase separation of the glass -
• Step 3 pulping (including solution [30 units of HOF / 1 part HNO 3 (68%) / 1.5 HF units (40%)] diluted 6 times in deionized water DI) and 3min immersion to obtain the nanostructuring of the surface.
• Step 4 magnetron deposition of given thickness silver - Step 5: Annealing 400 ° C for 2 hours in the ambient atmosphere dewetting money
• the system After heat treatment, the system separated into two phases: one rich in silica, either as a lattice former and the other rich in barium, or as a lattice modifier. This last phase is therefore less polymerized and it is possible to remove it preferentially by acid treatment
• Figure 2 shows schematically 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 region of immiscibility. Inside this dome we find 3 regions (a) and (c) the growth nucleation, binodal domains, and (b) the spinodal decomposition domain
• the matrix M and the phase Pg are identified in regions a) and c)
• Example No. 1 The thickness of the glass layer on amorphous silica is 50nm and the annealing for the phase separation is 8h. We deposit 10nm of money. A reference example was also produced without texturing the thin layer of glass.
• FIG. 3a is an AFM image of the nanostructured surface with nanocavities 3 on the surface 11.
• FIG. 3b is an SEM image of the nanostructured surface 11 according to the invention with nanocavities and carrying nanoparticles 5 in and outside 5 ' nanocavities.
• Figure 3'b is an SEM image of the reference flat surface 11 (for comparative purposes) carrying 50 nanoparticles.
• Figure 3c shows a set of curves C1, C2, C2R corresponding respectively to: - the distribution (normalized, in number) of the diameter of the nanocavities of the nanostructured surface, which is a bell-shaped C1 curve exhibiting a peak with a vertex corresponding to a given nanocavity width OD less than 50nm, of about 30nm, with a width at mid-height of about 13nm - the distribution of the diameter of the nanoparticles on the nanostructured surface, which is a C2 double-bell curve showing a first peak or main peak (the highest and narrow) with a vertex corresponding to a diameter D1 here less than OD, about 26nm with a width at mid-height of about 18nm followed by a second peak (wider and less high) with a vertex corresponding to a diameter D'1 greater than OD, of about 105nm - the distribution of the diameter of the nanoparticles on the flat reference surface which is a bell-shaped C2
• Figure 3d is another SEM image of the nanostructured surface 11 with nanocavities and carrying 5 nanoparticles in the nanocavities and outside the 5 'nanocavities.
• FIG. 3e is an SEM image of the nanostructured surface 11 with nanocavities and only carrying nanoparticles 5 in the nanocavities after removal of the large particles at the surface by wiping.
• the thickness of the glass layer on the silicon wafer is 100nm and the annealing for phase separation is 15min. We deposit 15nm of money.
• a reference example was also produced without texturing the thin layer of glass.
• Figures 4a, 4b (in tilt), 4c (in slice) (with higher magnification) are SEM images of this layer with nanostructured surface 11 with nanocavities and carrying 5 nanoparticles in nanocavities and 5 'nanoparticles outside nanocavities.
• Figure 4'a is an SEM image of a flat reference surface 11 '(for comparative purposes) carrying nanoparticles 50.
• Figure 4d shows a set of curves C3, C3R corresponding respectively to:
• the distribution of the diameter of the nanoparticles on the nanostructured surface which is a double bell curve C2 exhibiting a first main peak (the highest and narrow) with a vertex corresponding to a diameter D1 of approximately 50nm with a width at mid-height of about 42nm followed by a second peak (wider and less high) with a peak corresponding to a diameter D'1 of about 130nm
• the distribution of the diameter of the nanoparticles on the flat reference surface which is a bell-shaped C2R curve exhibiting a (single) peak with a vertex corresponding to a given width D2 of approximately 165nm.
• This example illustrates the influence of the size of the nanocavities for a given thickness on the size, the density of the nanoparticles.
• the thickness of the glass layer on the silicon wafer is 100nm. We deposit 15nm of money. A reference example was also produced without texturing the thin layer of glass.
• Substrates having different sizes of nanocavities are produced by varying the duration of the heat treatment, respectively 1 minute, 15 minutes, 4 hours and 20 hours.
• Figures 5a to 8a are AFM images of various (four in number) nanostructured surfaces according to the invention with nanocavities (5a) 1min, (6a) 15min, (7a) 4h and (8a) 20h.
• Nanocavities occupy an aperiodic position and do not form a structured network of constant pitch. It is observed that the density of nanocavities decreases when the size of the nanocavities increases. This is explained by the fact that the growth of the drops rich in barium which are at the origin of these nanocavities is similar to an Ostwald ripening mechanism. There is therefore conservation of matter and the increase in the size of the drops implies that they are more distant from each other. In the following table 1 we also define the relation to the close neighbors of each nanocavity, the density of nanocavities [Table 1] The minimum size corresponds for a given hole to the distance from its closest neighbor, which is on average 41 nm for the first image.
• the averaged size says that for a given hole, its neighbors are on average at 60 nm.
• the maximum size says that it is possible to find mesas up to 10Onm in size between neighboring nanocavities.
• the same silver thickness of 15nm was deposited on the five different substrates (including the flat substrate).
• Figures 5b to 8b are SEM images on these various nanostructured surfaces with nanocavities and carrying nanoparticles in and outside the nanocavities.
• Figure 5'b is an SEM image of a reference flat surface glass thin layer 11 (for comparison) carrying 50 nanoparticles.
• Figure 5c shows a set of curves C4, C5, C6, C7, C4R corresponding respectively to: the distribution of the diameter of the nanoparticles on the first nanostructured surface, which is a double-bell curve C4 exhibiting a first peak or main peak ( highest and narrow) with a vertex corresponding to a diameter D1 followed by a second peak (wider and less high) with a vertex corresponding to a diameter D'1 - the distribution of the diameter of the nanoparticles on the second nanostructured surface, which is a C5 double bell curve presenting a first peak (the highest and narrow) with a vertex corresponding to a diameter D1 with a width at mid-height followed by a second peak (wider and less high) with a vertex corresponding to a diameter of 1 - the distribution of the diameter of the nanoparticles on the third nanostructured surface, which is a curve C6 exhibiting a peak (the highest and narrow) with a vertex corresponding to a diameter D1 with
• the error bars correspond to the width at half height of the modal distribution of nanoparticles for the main peak (nanoparticles in nanocavities) and for the second peak (nanoparticles between nanocavities).
• the hatched area corresponds to the non-recentered mid-height width of the particle distribution on the flat reference surface.
• D1 is approximately 22nm with a width at mid-height of approximately 27nm, D’1 is approximately 125nm.
• D1 is approximately 54nm with a width at mid-height of approximately 32nm, D’1 is approximately 130nm.
• D1 is approximately 72nm with a width at mid-height of approximately 43nm, D’1 is approximately 130nm.
• D1 is approximately 100nm with a width at mid-height of approximately 46nm, D'1 is approximately 150nm.
• the diameter of the n a n o particles on the upper textured surface excluding nacavities remains close to that of the particles on a flat surface.
• the size of the silver nanoparticles is smaller for textured surfaces than for the flat surface coated with the same thin layer of glass (same composition, same density, same surface energy).
• the distribution is bimodal.
• the peak of the small particles is controllable because the size of the nanocavities of the substrate is controllable.
• the average size of silver nanoparticles increases from about 25nm to 50nm.
• the following example aims to show the influence of silver thickness for a given distribution of nanocavities.
• the thickness of the glass layer on the silicon wafer is 100nm and the annealing for phase separation is 15 min.
• a reference example was produced without texturing the thin layer of glass.
• Figures 9a to 12b are SEM images of various nanostructured surfaces with nanocavities and carrying 5 nanoparticles in nanocavities and 5 'nanoparticles outside nanocavities.
• Figure 13 thus shows a set of curves F1, F2, F3, F4, corresponding respectively to:
• a double-bell curve F2 presenting a first peak or main peak (the highest and narrow) with a vertex corresponding to a diameter D1 with a width at mid-height followed by a second peak (wider and less high) with a vertex corresponding to a diameter D'1
• the distribution of the diameter of the nanoparticles from a dewetting of a layer of the third thickness, of 20nm on the same nanostructured surface which is a double-bell F3 curve presenting a first peak or main peak (the highest and narrow) with a vertex corresponding to a diameter D1 with a width at mid-height followed by a second peak (wider and less high) with a vertex corresponding to a diameter D'1
• the distribution of the diameter of the nanoparticles from a dewetting of a layer of the fourth thickness, of 25nm on the same nanostructured surface which is a double-bell F4 curve presenting a first peak or main peak (the highest and narrow) with a vertex corresponding to a diameter D1 with a width at mid-height followed by a second peak (wider and less high) with a vertex corresponding to a diameter D'1.
• the error bars correspond to the width at half the height of the distribution.
• the hatched zone corresponds to the non-recentered mid-height width of the distribution of nanocavities (top of the main peak and of the second peak).
• D1 is approximately 30nm with a width at mid-height of approximately 18nm, D’1 is approximately 90nm.
• D1 is approximately 56nm with a width at mid-height of approximately 30nm, D'1 is approximately 136nm.
• D1 is approximately 53nm with a width at mid-height of approximately 50nm, D'1 is approximately 140nm.
• D1 is approximately 50nm with a width at mid-height of approximately 50nm, D’1 is approximately 170nm.
• Figure 14 shows the evolution of particle diameters on the surface outside nanocavities and in nanocavities as a function of the thickness of silver deposited.
• the modal diameter of the nanocavities is approximately 36nm (corresponding to a heat treatment of 15min).
• the diameter of particles on the surface increases with thickness in a manner similar to dewetted particles on a flat surface. Their diameter is still slightly smaller and we can think that the nanocavities constrain the size.
• the diameter of the nanoparticles inside the nanocavities increases with the thickness in a similar way to the other two populations of particles.
• the size of the particles in the nanocavities stagnates.
• the limit value corresponds to the edge of the gray zone in FIG. 14, which represents the modal diameter of the nanocavities widened from the width to mid-height of their distribution.
• the particle size is limited by the diameter of nanocavities for a range of thicknesses or particles do not form bridges between nanocavities.
• the diameter would increase as the particles begin to form a continuum between several nanocavities. There is therefore an optimum thickness so that the silver nanoparticles remain disjoint. It should also be noted that this ' limit thickness from which the diameter of the nanocavities limits the growth of the particles lodged therein depends on the size of these nanocavities.
• the surface energy of the substrate and the thickness of silver constitute the two levers for modulating the distribution of dewetted nanoparticles.
• a new parameter on which it is possible to play is the surface texturing.
• a bimodal distribution is then obtained and particles of very small sizes compared to those usually obtained.
• this modulation is more effective if we deposit a lower thickness to a critical size from which the particles are no longer impacted by the texturing. This critical thickness depends on the size of the nanocavities of the textured surface.
• the composition of the glass used for the thin layer can be modified, here it is a borosilicate of Ba, but all that is needed is a glass (borosilicate of Na, of Ca, etc ...) or any other material which allows phase separation.
• the method of depositing the glass in a thin layer can change, here we use the magnetron RF deposit, but the possibility of liquid deposition.
• the substrate itself could give rise directly to phase separation (for example sodium borosilicate composition of the Vycor or Pyrex type).
• the glass composition of the thin film can be adapted to have a lower critical phase separation temperature and therefore to reduce the necessary annealing temperature.
• the metal suitable for dewetting here is silver, other metals are possible in particular copper, gold, aluminum, or even a dielectric.
• the metal layer is deposited by magnetron but another method of obtaining thin layers such as evaporation can be used. A deposit on the nanotextured surface leaving nanocavities is possible.
• the heat treatment in the examples is in an oven but it is also possible to use a rapid annealing treatment, in particular by means of a laser.

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