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
  • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
  • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
• • 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
  • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
• • 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
  • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
• • 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
  • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
  • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
  • C03C21/005—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to introduce in the glass such metals or metallic ions as Ag, Cu
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/02—Details
  • H01L31/0236—Special surface textures
• • 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
  • C03C2214/00—Nature of the non-vitreous component
  • C03C2214/08—Metals
• • 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
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/77—Coatings having a rough surface
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]

Definitions

• the present invention relates to the field of surface structuring and aims in particular at an ionic abrasion surface structuring method, a structured surface product and its uses.
• Characteristic techniques of small dimensions, in particular width or submicron period, the techniques of structuring are for the most part techniques using transfer masks for liquid or dry etching including lithographic techniques (optical lithography, electronic lithography ...) , used in microelectronics, or for (small) integrated optical components.
• the ionic abrasion generally under a wide, non-focused source, of typically low energy Ar + ions (typically between 200 and 2000 eV), is another large-area structuring technique which has the advantage of do not use masking.
• the present invention firstly relates to a high-performance method of manufacturing a structured product, especially glass, on a submicron scale and in line with industrial constraints: speed and simplicity of design (without the need for masking, in particular a step preferably), and / or adaptation to any size of surface, even the largest, and with flexibility and control over the type and / or size of patterns and their density.
• This process also aims to expand the range of structured products available including glass, in particular aims to obtain new geometries of new features and / or applications.
• the invention firstly proposes a surface structuring method that is to say forming at least one set of irregularities called patterns (generally of the same shape on average) with a submicron height and at least one sub-micron or sub-millimetric lateral dimension (called width) by ionic abrasion (involving elastic collisions of ions and atoms) with an ion beam (typically cations) possibly neutralized (typically by electrons ripped off) by the beam before impact with the material to be structured) which comprises the following steps:
• the molar percentage of oxide in the material being at least 40%, especially between 40 and 94%,
• the oxide and at least one species of nature distinct from the element or elements of the oxide, in particular more mobile than the oxide under ionic abrasion (and in the case of mixed oxide, more mobile than at least one oxide, especially the majority oxide), which is preferably a metal, the molar percentage of species (s) in the material ranging from 6% up to 50%, in particular ranging from 20% to 30% or even 40% and being lower than the percentage said oxide, species, with at least the majority of the species (or species), or even at least 80% or even 90%, having a greater characteristic dimension (called size) less than 50 nm, preferably less than or equal to at 25 nm, or even less than or equal to 15 nm,
• size characteristic dimension
• hybrid material being metastable before abrasion, that is to say kinetically stable under normal conditions of temperature and pressure and thermodynamically unstable under normal conditions of temperature and pressure, being in a local minimum potential energy, separated from the global minimum by a given activation energy Ea,
• the (pre) heating possible before abrasion the material in particular so as to reduce (without canceling) the activation energy up to a value E1 which is then brought by the abrasion (by an ad hoc selection of the energy of the ions of the beam and the flux), (possible heating because if Ea is too high, the kinetics of the aggregation of the mobile species of metal type is too slow compared to the abrasion speed of the hybrid material ), the (pre) heating and abrasion being spaced over time, the preheating possibly being replaced by a radiative treatment type IR,
• rare gas preferably Ar, or also Ne, Xe, Kr, and / or oxygen O 2 , nitrogen N 2 or carbon dioxide C0 2 ,
• the beam preferably having an energy of less than 5 keV, even less than or equal to 2 keV,
• the possible heating during the abrasion of the hybrid material in particular so as to reduce (without canceling) the activation energy.
• the oxide and mobile element will segregate if provided with the necessary energy by ionic abrasion
• the abrasion and the creation of the mask are simultaneous.
• the intrinsic properties of the material control the surface morphology created during etching.
• an abrasion speed which is sufficiently different from that of the oxide to increase the structuring speed, the difference (in absolute value) preferably being greater than 10%, preferably greater than 20%, even more preferably greater than 50%; (To thus select the species, it is possible to use, for example, known deposition rates, for example for magnetron sputtering).
• the species is in sufficient quantity on the large surface of abrasion to feed the masking and to obtain a sufficient density of grounds.
• the species is on a sufficient depth related to the desired depth of etching, to feed the masking during etching.
• the species is closely related to the oxide but is not miscible.
• the size of the species is limited for a homogeneous distribution of the species in the material and therefore a more homogeneous structure.
• the rate of the species in the oxide is measurable by microprobe or XPS
• the rate of the species can vary, for example with a concentration profile depending on the height of the structuring profile, and even the state of the metal.
• the class of oxide-metal hybrid materials judiciously selected according to the invention spontaneously creates a mask that is sufficiently dense, homogeneous and self-sustaining during ionic abrasion, giving access to one or more of the following characteristics:
• width W length L approximately or at least W greater than or equal to 0,3L under oblique incidence and 0,8L under normal incidence), relief oriented according to the angle of incidence,
• isotropic units that is to say without preferred direction (s) of orientation, typically the case at normal incidence or close to normal
• the height taken into account is the maximum height
• the width is measured at the base.
• the spacing D is the average distance between the centers of 2 adjacent patterns.
• the distances H, W, D can be measured by AFM, and / or SEM scanning electron microscopy.
• the averages are for example obtained on at least 50 patterns.
• the structured material has a set of patterns generally:
• average width W which may be less than 300 nm for optical applications in particular, even more preferentially less than 200 nm,
• average spacing D less than 300 nm, and even more preferably less than 200 nm.
• the aspect ratio (H / W) may be greater than 3.
• the density that is D / W, can depend on the height.
• width W is less than or equal to 5D, in particular less than
• the average standard deviation of height H, width W, may be less than 30%
• the average standard deviation of the spacing D may be less than 50% (for example at high temperature) or even less than 30%, even less than or equal to 10%.
• Structuring is not created by the physics of the ion / surface interaction
• the hybrid material may be termed metastable.
• metastability is the ability for a material to be kinetically stable but not thermodynamically stable. The transformation leading to the stable state is slow or even zero. If a physico-chemical system is represented by its potential energy, a metastable state will be characterized by a state that corresponds to a local minimum of potential energy. In order for the system to reach the state of the global energy minimum corresponding to the state of thermodynamic equilibrium, it must be supplied with a quantity of energy called activation energy Ea.
• the activation energy may depend on the manufacturing process. Structuring is not a consequence of the enrichment of the surface into one of the components, but is induced by the intrinsic metastability of the material. This metastability is controlled by the selection of the oxide, the mobile species.
• the hybrid material may consist essentially of mineral material.
• the hybrid material may comprise at least 70 mol% of the sum of the oxide and said metal.
• the hybrid material may contain other "neutral" elements for ionic abrasion (especially less than 30%).
• the structuring method according to the invention can be easily automated and associated with other transformations of the product.
• the process also simplifies the production chain.
• the process is suitable for the manufacture of large volume and / or large scale products, especially glass products for electronics, building or automotive, including glazing.
• the structuring method according to the invention also makes it possible to achieve characteristic magnitudes of ever smaller patterns on larger and larger surfaces, with tolerance to acceptable texturing defects, that is to say, not adversely affecting the desired performance.
• Ions can instantly provide sufficient energy for structuring (exceeding activation energy).
• the abrasion process also naturally creates a heating of the oxide up to about 80 ° C or even 100 ° C (depending on the energy and the flow), progressive heating, in a few minutes, which can be sufficient only to bring the activation energy or alternatively requires additional heating as already indicated then adjusting the temperature.
• the heating that may be necessary is greater if the chosen rate of the species is low.
• the temperature reached at the surface is variable depending on the hybrid material, the conditions of the structuring.
• the reference temperature is the temperature at the back of the material (opposite to the abraded surface)
• the temperature can also play a role on the structuring of the hybrid material according to the invention.
• the material is heated to a temperature greater than 50 ° C, or even greater than equal to 70 ° C, preferably greater than or equal to 100 or even 120 ° C, especially ranging from 150 ° C to 300 ° C before abrasion and / or during (all or part of) l 'abrasion.
• the species in a configuration with reliefs, by raising the temperature, the species forms larger aggregates (on the summits of the reliefs) which are more spaced so in particular one increases the height of reliefs and one increases the spacing between relief.
• heating temperature / energy input for reasons of energetic cost and / or resistance of the material or associated material (s), for example limited thermal resistance of an organic substrate carrying the hybrid material in a layer.
• the flux level can play a role in the structuring of a hybrid material according to the invention.
• the etching flux is greater than 0.01 mA / cm 2 , typically ranging from 0.05 to 0.3 mA / cm 2 or even above, especially greater than or equal to 0.4 mA / cm. 2 .
• a sufficient increase in flux makes it possible to reduce the structuring time, but can also modify the appearance of the structures formed as a rise in temperature (increase of the relief but decrease of the density).
• the energy of the incident ions can play a primordial role on the structuring of a hybrid material according to the invention.
• the effect of energy is complex. It will increase the rate of abrasion, but also the depth of penetration of ions which will allow the species to diffuse more efficiently in volume. We will have both an acceleration of the formation rate of structures, but also structures of greater width and height.
• the energy can be between 200 eV and 5000 eV, typically between 300 eV and 2000 eV, or preferably between 500 eV and 1000 eV.
• abrasion under vacuum is carried out, for example under a vacuum defined by a pressure of less than 10-7 mbar. It can act for example a thin film deposition frame.
• Said species has a lower abrasion rate than the oxide.
• the relief may in particular be punctual, in the form of a cone, in particular of maximum average lateral dimension, so-called length L, submicron, in particular with W greater than 0.3L under oblique incidence and at 0.8L, or even 0.9L under normal incidence. .
• the surface is not necessarily smooth and may already have a form of structuring.
• the species may be in optionally ionic form (thus oxidized) or not, may be diluted (isolated in the material) and / or in the form Aggregate preferably of (substantially) spherical shape.
• the incorporation of the species may be ion implantation (by ion bombardment), ion exchange, or incorporation of particles or growth in situ (from metal salts, etc.), as detailed later.
• the species is preferably chosen from at least one of the following species, in particular:
• Ag silver in particular for an optical function (absorption induced at the UV / visible boundary) and / or for catalysis, and / or antibacterial,
• Au gold for a grafting of biological molecules for sensors, for optics (non-linear), and / or antibacterial
• Lead Pb, Mo molybdenum may be omitted for environmental reasons.
• transition metals such as Ti, Nb, Cr, Cd, Zr (especially in silica), Mn are conceivable.
• the effective charge on the species is zero or less than 0.5 (known by EELS) to allow the species to aggregate.
• the oxide alone can be electrical insulator and the species can bring electrical conductivity properties.
• silica in particular, aluminum Al or boron B is preferably preferred since it integrates with the silica network and will not be easily aggregated.
• Transition metals or even some semi-metals are particularly preferred to earth alkalis or alkaline earths which have a too high abrasion rate.
• Li and Na are not suitable because they eject and do not aggregate (fast enough).
• the oxides can be further (sufficiently) transparent in the visible and even in a wider range to near or far IR or near UV depending on the intended applications.
• the mobile species does not aggregate (under normal conditions of temperature and pressure), but still has enough mobility under ionic abrasion to form the structures
• the oxide is preferably chosen from at least one of the following oxides: silica, alumina, zirconia, titanium oxide, cerium oxide, magnesium oxide, in particular a mixed oxide of aluminum and silicon, of zirconium and of silicon, titanium and silicon and preferably a glass
• the hybrid material may be first a glass, in particular silicocalcic, ionically exchanged, preferably with at least one of said species, ionic at the time of exchange, the following: silver, copper.
• the exchange depth is typically of the order of one micron or up to several tens of micrometers in depth.
• the distribution of the metal exchanged is therefore almost homogeneous in the abraded part of the material ( ⁇ 1 ⁇ ).
• Ion exchange is the ability of certain glass ions, particularly cations such as alkali ions, to be able to exchange with other ions with different properties.
• the ion exchange may be the exchange of certain ions of the glass by ions selected from, in combination or not, barium, cesium, thallium and preferably silver, copper.
• Silver is very mobile in the matrix and has a strong tendency to aggregate
• the ion exchange rate of the hybrid material is measurable by microprobe before and after structuring.
• Ion exchange is obtained by known techniques.
• the surface of the glass substrate to be treated in a bath of molten salts of the exchange ions, for example silver nitrate (AgNO 3 ), is placed at a high temperature between 200 and 550 ° C. and for a correspondingly long period of time. at the desired exchange depth.
• molten salts of the exchange ions for example silver nitrate (AgNO 3 )
• the glass in contact with the bath can advantageously be subjected to an electric field which is mainly a function of the conductivity of the glass and its thickness, and preferably varies between 10 and 100 V.
• the glass can then undergo another heat treatment, advantageously at a temperature between the exchange temperature and the glass transition temperature of the glass, in order to diffuse the ions exchanged in a direction normal to the face of the glass provided with the electrode, so as to obtain a gradient linear profile index.
• the chosen glass can be extraclair.
• Reference WO04 / 025334 can be referred to for the composition of an extraclear glass.
• a silicosodocalcic glass with less than 0.05% Fe III or Fe 2 O 3 .
• Saint-Gobain's Diamant glass, Saint-Gobain's Albarino glass (textured or smooth), Pilkington's Optiwhite glass, and Schott's B270 glass can be chosen.
• Ion exchange thus makes it possible to easily treat large areas, to be reproducible industrially. It allows to act directly and in a simple manner on the glass without the need to proceed to intermediate and / or complementary steps such as deposition of layers, etching.
• Ag + in glass as a replacement for Na + sodium ions is a function of the time during which the substrate is left in the bath.
• a layer of metallic silver may be deposited. It is deposited by magnetron, CVD, inkjet or silkscreen. An electrode layer is also deposited on the opposite side. The electric field is then applied between the silver layer and the metal layer. After the exchange, the electrode layer is removed by polishing or chemical bonding. The electric field applied between the metal layer or the bath, and the electrode, therefore generates the ion exchange.
• the ion exchange is carried out at a temperature between 250 and 350 ° C.
• the exchange depth is a function of the intensity of the field, the time during which the substrate is subjected to this field and the temperature at which the exchange is carried out.
• the field is between 10 and 100 V.
• a usual soda-lime glass such as Planilux glass from Saint-Gobain can be used.
• the size and depth of penetration of silver can be modified by changing the experimental conditions: increasing the time and temperature of the exchange gives larger particles to a greater depth and thus a more pronounced yellow coloration.
• the addition of an electric field during the exchange makes it possible to increase the depth of penetration without increasing the size of the particles.
• the depth of penetration can be adjusted so that it corresponds to the depth of the abrasion so that the yellow color disappears at the end of the abrasion or be slightly greater than a few ⁇ so that the yellow color is lower and therefore optically acceptable at the end of the abrasion.
• the structured exchanged glass can be monolithic, laminated, two-component. After structuring, the structured exchanged glass can also undergo various glass transformations: tempering, shaping, laminating, etc.
• the hybrid material may be in bulk or as an added layer on any substrate, thick or thin, planar or curved, opaque or transparent, mineral or organic.
• the layer of the hybrid structural material may be reported by gluing etc. or, preferably, be deposited on a particular glass substrate. This layer can be part of a stack of layers (thin) on the substrate, including glass.
• This layer of the hybrid structural material may preferably be transparent, have an optical index for example greater than that of a glass (typically around 1, 5).
• the layer of the structurable hybrid material can be deposited by any known deposition techniques directly on the substrate or on one or more functional layers (thin etc.) underlying.
• a functional (thin) layer for example a functional oxide layer such as a transparent conductive oxide (TCO) such as ⁇ (Indium Tin Oxide), ZnO, a mixed oxide or simple tin-based, indium or zinc or a photocatalytic layer (Ti0 2 anatase form for example).
• TCO transparent conductive oxide
• ⁇ Indium Tin Oxide
• ZnO Zinc Oxide
• Ti0 2 anatase form for example
• This layer of the hybrid material may advantageously be deposited on an alkali barrier layer (typically Si 3 N 4, SiO 2) to prevent the migration of the alkali ions from the glass to the layer during the various heat treatments (annealing or quenching ).
• an alkali barrier layer typically Si 3 N 4, SiO 2
• the substrate is not necessarily mineral and may be a plastic or a hybrid material, to obtain properties of flexibility and formatting inaccessible with glass substrates.
• the system used must have a low activation energy because no heat treatment above 300 ° C and most often 200 ° C is possible.
• the hybrid material may be a gel sol, mass or layer especially on transparent substrate, glass (mineral or organic). Gels have the advantage of being able to withstand even high heat treatments (eg type of operation (bending) hardening) and to resist UV exposure.
• high heat treatments eg type of operation (bending) hardening
• it is an oxide obtained by the sol-gel process from at least one of the following elements: Si, Ti, Zr, Al, V, Mg, Sn, and Ce and incorporating said metal or semi-metal in the form of (nano) particles, optionally precipitated, especially Ag, Cu, Au.
• the nanoparticles are preferably evenly distributed in the bulk material and / or the layer.
• the largest dimension of the particles is less than 25 nm and even more preferably less than 15 nm, and a shape ratio of less than 3 and preferably of spherical shape.
• the level of nanoparticles in the sol gel material is measurable by microprobe, XPS or EDX.
• Silica for example, has the advantage of being a transparent oxide, titanium oxide and zirconia to be high index.
• a silica layer typically has a refractive index of the order of 1.45
• a titanium oxide layer has a refractive index of the order of 2
• a zirconia layer has a refractive index of the order of 2.2.
• the layer may be essentially silica based in particular for its adhesion and its compatibility with a glass substrate.
• the precursor sol of the material constituting the silica layer may be a silane or a silicate.
• TEOS tetraethoxysilane
• lithium, sodium or potassium silicate for example deposited by "flow" coating ".
• the silica layer can thus be based on a sodium silicate in aqueous solution, transformed into a hard layer by exposure to a CO 2 atmosphere.
• the manufacture of a hybrid mass material by sol-gel process comprises, for example, the following steps:
• the manufacture of a layer of hybrid material by sol-gel process comprises for example the following steps:
• the choice of the colloidal suspension makes it possible to adjust, if necessary, the size of the particles inserted. As it is redispersed in the soil, care is taken to check the compatibility of the suspension with the soil to prevent the aggregation of the particles.
• the addition of the salt of the said metal is simpler and presented more often in the literature.
• water or low molecular weight alcohols having a low boiling point typically less than 100 ° C. are preferred to allow the good dissolution of the metal salt.
• the amount of nanoparticles present in the oxide / metal hybrids can be simply controlled by the synthesis conditions, and increases with the amount of metal introduced into the soil.
• hybrid metal / metal oxide material from the sol-gel process is very widely described in the literature.
• a large variety of metal / oxide pairs in the form of layers or massive materials has thus been synthesized.
• the metal particles are preferentially created in situ in the matrix by adding a salt of the corresponding metal and after reducing treatment (most often heat treatment or else a reducing agent: H 2 , hydrazine, etc.).
• mesoporous silica ie having a characteristic pore size of 3 -10 nm
• mesoporous silica ie having a characteristic pore size of 3 -10 nm
• Nickel nanoparticles have been obtained for optical applications by thermal treatment of nickel nitrate impregnated in a silica matrix in the publication entitled “Optical properties of sol-gel fabricated Ni / SiO 2 glass nanocomposites” (Yeshchenko OA et al. Journal of Physics and Chemistry of Solids, 2008, 69; 1615).
• Synthesis and characterization of tin oxide nanoparticles dispersed in monolithic mesoporous silica (YS Feng et al., Solid State Science, 2003 5, 729), Sn0 2 particles of 4-6 nm are obtained at 20 nm. % in mesoporous silica after heat treatment at 600 ° C.
• this sol gel method allows additional functionalization of the layer.
• the surface structured by said process can then be functionalized to obtain new wetting properties.
• This compound can be deposited on large surfaces (greater than m 2 ) of glass products or functional metal oxide layers, in particular textured products, and this after a possible deposition of a silica-based primer.
• the combination of this process and surface texturing gives superhydrophobic properties (lotus leaf type).
• the preferred deposition methods for the organic layers are dip coating (dip coating), or the spraying of the soil and the spreading of the drops by scraping or brushing or by heating as described in particular in the article entitled "Thermowetting structuring of the organic-inorganic hybrid materials »WS. Kim, K-S. Kim, Y-C. Kim, B-S Bae, 2005, Thin Solid Films, 476 (1), 181-184.
• the chosen method can also be a coating by spin-coating.
• This annealing may advantageously be coupled to the quenching step of the glass, which consists of heating the glass at high temperature (typically between 550 ° C. and 750 ° C.) and then cooling it rapidly.
• Said hybrid material may be a layer deposited by the physical vapor phase, typically by evaporation or by sputtering (especially magnetron) on a substrate, in particular transparent, glass, including by codeposition of the species (in the aforementioned list), such as copper, silver, or gold and the oxide in particular silica, zirconia, tin oxide, alumina, with a target of the oxide element and under an oxygen atmosphere, or with a target of said oxides
• Spraying will generally be preferred to evaporation due to a much higher deposition rate to make 100 nm or even micron layers faster.
• a deposition rate is generally close to 1 A min, with a maximum of 1 A / s, the magnetron deposition rates are typically between 1A / s and several tens of nm / s.
• SiO2-copper mixed layer deposition it would be possible either to use a codepot from a silicon and copper target, with the introduction of oxygen, or to directly use a copper target and a silica target.
• the substrate can be glass.
• glass substrate means both an inorganic glass (silicosodocalcique, borosilicate, vitroceramic, etc.) and an organic glass (for example a thermoplastic polymer such as a polyurethane or a polycarbonate).
• a substrate which, under normal conditions of temperature and pressure, has a modulus of at least 60 GPa for a mineral element, and at least 4 GPa for an organic element, is described as rigid.
• the glass substrate is preferably transparent, in particular having a global light transmission of at least 70 to 75%.
• an extra-clear glass is used, ie a glass having a linear absorption of less than 0.008 mm -1 in the wavelength spectrum from 380 to 1200 nm.
• the glass brand Diamant marketed by Saint-Gobain Glass is used.
• the substrate may be monolithic, laminated, two-component. After structuring, the substrate can also undergo various glass transformations: quenching, shaping, laminating, etc.
• the glass substrate may be thin, for example of the order of 0.1 mm for mineral glasses or millimeter for organic glasses, or thicker for example with a thickness greater than or equal to a few mm or even cm.
• a step of depositing a conductive, semiconductive and / or hydrophobic layer, in particular an oxide-based layer, may succeed to the first structuring.
• This deposit is preferably carried out continuously.
• the layer is for example metallic, silver or aluminum.
• a step of selective deposition of a conductive layer (in particular metal, based on oxides) on the structured surface, on or between patterns, for example dielectric or less conductive, can be advantageously provided.
• the layer for example metal, in particular silver or nickel, can be deposited electrolytically.
• the structured layer may advantageously be a layer (semiconductor) or a sol-gel type dielectric layer loaded with metal particles or a multilayer with a top layer of germination (seed layer in English) conductive.
• the chemical potential of the electrolytic mixture is adapted to make the deposit preferential in areas of high curvature.
• the structuring of the layer it is possible to envisage a transfer of the pattern network to the glass substrate and / or to an underlying layer, in particular by etching.
• the structured layer may be a sacrificial layer optionally partially or completely eliminated.
• Some areas of massive oxide or thin layer can be masked to avoid incorporating the mobile species or locally modify the incorporation conditions.
• the structured layer can also be used as a mask for an underlayer or the adjacent substrate
• the invention also covers a product with surface structuring, that is to say with a set of irregularities or patterns with a submicron height and at least one (sub) micronic lateral characteristic dimension, a hybrid solid material comprising
• the molar percentage of oxide in the material being at least 40%, especially between 40 and 94%,
• the molar percentage of species (s) in the material ranging from 6 mol% up to 50% and lower than the percentage of said oxide, with greater maximum characteristic dimension smaller than 50 nm obtainable by the process as described previously.
• the structured product can be for an application for electronics, building or automotive, or even for a microfluidic application
• optics in particular for LCD-type flat screen lighting or backlighting systems, in particular a light extraction means for an electroluminescent device, optical products for example intended for display screen, lighting, signage,
• the range of optical functionalities of nanostructured products is wide.
• the product may have at least one of the following characteristics:
• the pattern is a relief, in particular of maximum average lateral dimension, called length L, submicron, in particular with W greater than 0.3L under oblique incidence and 0.8L under normal incidence, the material being notably richer in mobile species in the summits of the reliefs, and on a thickness less than 10 nm, said superficial thickness,
• the pattern is a hole of height h, in particular of maximum average lateral dimension, called length L, submicron, in particular with W greater than
• the pattern is defined by a height H and a width W and a distance D between adjacent pattern
• the distance D being chosen less than 5 ⁇ in microfluidics or for wetting properties, at 2 ⁇ for infrared applications, at 500 nm, preferably at 300 nm, even more preferentially at 200 nm for optical applications or even widened to infrared (antireflection, light extraction, collection of light for photovoltaic or photocatalysis ...), the height H being preferably chosen to be greater than 20 nm, preferably greater than 50 nm, even more preferably greater than 100 nm for optical applications (visible and infrared), and greater than 70 nm, preferentially at 150 nm for the wetting properties (superhydrophobic or superhydrophilic),
• width W being chosen greater than D / 10, even more preferentially
• the pattern is defined by a height H and a width W and a distance D between adjacent pattern
• the distance D being chosen less than 5 ⁇ in microfluidic or for wetting properties, at 2 ⁇ for infrared applications,
• the height H being preferably chosen to be greater than 70 nm, preferentially at 150 nm for the wetting properties (superhydrophobic or superhydrophilic),
• width W being chosen greater than D / 10, even more preferentially at D / 5 and even more preferentially at D / 2.
• the abraded surface may form a substrate for the growth of a thin layer deposited under vacuum, the pattern is defined by a height H and a width W and a distance D between adjacent pattern:
• the distance D being chosen less than 200 nm, preferably between 200 nm and 100 nm, even more preferably at 50 nm,
• the height H being chosen preferably greater than 20 nm, preferably greater than 50 nm,
• width W being chosen greater than D / 10, even more preferentially at D / 5 and even more preferentially at D / 2.
• the relief can be particular punctual, cone-shaped.
• a thickness called superficial thickness typically from 2 to 10 nm.
• the recessed patterns it is possible to observe at the bottoms of the recesses an enrichment in said metal (over a thickness (less than the implantation wavelength of the beam ions, typically from 2 to 10 nm
• the presence of the reinforced metal zones can be made by known microscopic TEM, STEM techniques and / or by chemical mapping by known microscopic or spectrometric techniques STEM, EELS, EDX.
• the two main surfaces of said material may be structured with similar or distinct patterns, simultaneously or successively.
• the structured product may be a solar control and / or thermal control glazing used in a microfluidic application, an optically functional glazing, such as an antireflection, a reflective polarizer in the visible and / or infra-red, an element of forward light redirection including for liquid crystal display, light extraction means for organic or inorganic electroluminescent device, or superhydrophobic or superhydrophilic glazing.
• an optically functional glazing such as an antireflection, a reflective polarizer in the visible and / or infra-red
• an element of forward light redirection including for liquid crystal display, light extraction means for organic or inorganic electroluminescent device, or superhydrophobic or superhydrophilic glazing.
• FIGS. 1a-1d show a set of 4 AFM image projections of a hybrid silica / mass metal material structured at different times in a first embodiment of the invention.
• FIG. 2 shows schematically a sectional view of a structured glass product obtained according to the manufacturing process described in Figure 1 d.
• FIG. 3 represents a SEM image viewed from above of a hybrid silica / structured mass metal material obtained according to the manufacturing method described in FIG. 1 d.
• ⁇ 4a-4b Figures represent a set of two AFM image projections at different magnifications of a hybrid material silica / metal layer structured in a second embodiment of the invention.
• ⁇ 5a-5c represent a set of three AFM image projections at different magnifications of a hybrid material silica / copper structured layer in a third embodiment of the invention.
• FIG. 6 shows schematically a structured glass product obtained according to the manufacturing process described in Figure 5a.
• ⁇ 7a-7c are a set of three AFM image projections at different magnifications of a hybrid silica / copper material structured layer in a fourth embodiment of the invention.
• FIG. 8 shows an AFM image showing an example of a comparative control material hybrid silica / copper unstructured layer.
• FIG. 9 shows an AFM image showing an example of a hybrid material silica / copper structured layer in a fifth sample embodiment.
• FIG. 10 shows an AFM image showing an example of a hybrid material silica / copper layer structured in a sixth sample embodiment.
• Figure 1 1 shows an AFM image showing an example of a comparative control material hybrid silica / copper unstructured layer
• a first 2 mm thick silver glass was obtained after ion exchange from a Planilux ® glass from the company SAINT GOBAIN standard soda lime float glass.
• the glass is immersed in pure silver nitrate at 300 ° C for 2 hours.
• the resulting glass has a silver concentration profile of the surface up to several micrometers deep
• the silver thus penetrates to a depth of around 4 micrometers.
• the silver is probably present in the form of particles a few microns deep.
• the surface contains about 15% Ag in mol.
• the abrasion is in an ultrahigh vacuum pressure frame of 5.10 "8 mbar
• the ion beam Ar + energy 500eV was maintained at a flux of 0.09 mA / s.cm 2 .
• the AFM images of the surface of the silver glass show the appearance of a texturing composed of holes after abrasion. These holes, with a dense distribution and a few hundred nanometers in diameter appear after 30 minutes under the beam.
• FIGS. 1a-1d show a set of 4 AFM image projections of a hybrid silica / mass metal material structured at different times in a first embodiment of the invention.
• FIGS. 1 and 4 show the AFM images of a Planilux glass surface exchanged with silver after abrasion for 6, 12, 15, 30 minutes by an Ar + ion beam of energy 500 eV and maintained at a flux of 0. , 09 mA / s.cm 2 .
• the silver aggregates diffuses towards the surface and is abraded faster than silica. This high rate of abrasion of silver is also often observed in magnetron deposition.
• FIG. 2 diagrammatically represents a sectional view of a structured glass product obtained according to the manufacturing method described in FIG. 1 d, with 1: material not affected by ionic abrasion; 2: hollow; 3: zone rich in said species of metal type at the hollow; 10: structured surface.
• FIG. 3 represents a SEM image seen from above of a hybrid silica / structured mass metal material obtained according to the manufacturing method described in FIG. 1 d.
• FIG. 3 is a SEM image of a Planilux glass surface exchanged with silver after abrasion for 30 minutes by an Ar + ion beam of energy 500 eV and maintained at a flux of 0.09 mA / s. cm 2
• Planilux ® silver glass has been abraded. Holes of a few hundred nanometers in diameter formed during abrasion over the entire exposed beam surface. The holes obtained have a diameter W of 50 nm and a average height H of 20 nm. At the end of the abrasion, the yellow color is almost no longer visible on the sample.
• Planilux ® containing silver was abraded for different durations to determine the type of hole growth (Figure 1).
• a greater and / or faster structuring can be obtained by varying at least one of the following parameters: by increasing the amount of silver present in the glass, by heating during abrasion, by increasing the flux and / or ion energy, by modifying the incident ion.
• the silver glass obtained has no coloring unlike the Planilux ® .
• oxygen ions are more negatively charged than in Si0 2 because aluminum is more electropositive than silicon.
• the presence of alumina thus stabilizes the ionic form of the silver in the network and thus avoids the aggregation of metallic silver in the form of particles.
• the penetration depth of the silver is however greater because it is present up to 400 micrometers deep.
• the surface contains about 25% Ag 2 0.
• a second type of hybrid prepared by sol-gel was prepared and abraded.
• the sol-gel pathway consists of synthesizing an inorganic polymer, such as silica, at room temperature from organic precursors. In a first step, this precursor is placed in the presence of water to hydrolyze.
• the solution obtained (called sol) can be deposited on different substrates such as glass or silicon. During the deposition, the solvent of the solution evaporates until condensation of the hydrolysed precursor into an inorganic polymeric network
• the oxide gel obtained can be shaped, in particular in a thin layer, until complete condensation of the polymer.
• the deposition conditions make it possible to control the thickness. We can play in a very wide range on the layer size (from ten nanometers to a few microns).
• Other compounds may be added during the hydrolysis such as dyes, dopants, surfactants that confer porosity to the layer or organic compounds that will not be altered by the synthesis because it is carried out at room temperature.
• Silica layers of a few hundred nanometers thick containing 10 mol%. of silver were synthesized by sol-gel.
• the thickness of the sol-gel layer containing silver was measured by ellipsometry and is 250 ⁇ 20 nm.
• Sol-gel control layers of pure silica were synthesized under the same conditions as those containing silver.
• the silver or copper sols were deposited by spin-coating on the substrate (1000 rpm, 100 rpm for 2 min).
• the samples obtained were annealed overnight at 200 ° C. to remove the solvent remaining in the layer and initiate the condensation of the silica network. Heat treatment at higher temperature T reC uit (700 ° C) was applied. for the silver samples to finish the condensation and induce the formation of silver aggregates. Their heat treatment determines the oxidation state of silver. To obtain metallic silver, the annealing must take place between 500 ° C and 750 ° C.
• control layers before and after abrasion show little difference, regardless of the heat treatment imposed. They have a low roughness ( ⁇ 5 nm). These analyzes allow us to verify that no structuring takes place on pure silica. It is also a known result that the surface of silica, like other oxides relaxes after abrasion.
• the prereduced Tp layer cooked 700 ° C was structured under the effect of abrasion. Holes of a few tens of nanometers have formed and are distributed over the entire surface of the material, between the degassing bubbles.
• Figures 4a-4b show a set of 2 AFM image projections at different magnifications of a silica / metal hybrid material in a structured layer in a second embodiment of the invention.
• FIG. 4 shows the AFM images of the silver silica layers obtained by the sol-gel route described above and abraded at ambient temperature or at 200 ° C.
• the holes appear denser after abrasion to 200 ° C.
• the high temperature of the abrasion makes it possible to increase the diffusion and thus goes in the direction of the formation of larger aggregates.
• the holes are thus close together when one abrades at high temperature.
• FIGS. 5a-5c show a set of 3 AFM image projections at different magnifications of a structured layer silica / copper hybrid material in a third embodiment of the invention.
• the AFM images after abrasion at room temperature for 15 minutes of a layer of copper-doped silica obtained by sol-gel route are given in FIG. 5.
• the surface before abrasion is very slightly rough (-2 nm).
• the layer is homogeneous.
• Figure 6 shows schematically a structured glass product obtained according to the manufacturing method described in Figure 5a: 4: plot; 5: Zone rich in said species of metal type to the hollow. This zone can form a pure or almost pure taste in said metal type species; 10: structured surface.
• the abrasion temperature was increased to 200 ° C to accelerate diffusion.
• the abrasion time has been reduced to 10 min the size seems to have increased.
• FIGS. 7a-7c show a set of 3 AFM image projections at different magnifications of a structured layer silica / copper hybrid material in a fourth embodiment of the invention.
• the copper incorporated into the silica makes it possible to quickly obtain slightly structured surfaces after abrasion with pads approximately 10 nm high. Surfaces are more homogeneous than in the case of silver.
• the temperature treatment reduces the density of the pads and increases their size. The characteristic sizes are given in the following table: Temperature H nm D nm W nm
• a higher and / or faster structuring can be obtained by varying at least one of the following parameters: by applying a prior heat treatment, by increasing the amount of copper present in the glass, by heating during abrasion, increasing the flux and / or the energy of the ions, by modifying the incident ion.
• magnetron layer deposition is a common and well-controlled technique. Thanks to it, it is possible to form by coumble layers of submicron thickness see micron with a well controlled composition.
• the ionic abrasion and magnetron deposition can be done in the same vacuum chamber, which has great advantage in terms of time and cost of structuring.
• FIG. 8 shows an AFM image projection of a comparative control example of an unstructured layered silica / copper hybrid material.
• This is an AFM image of the magnetron-doped copper-doped silica layer after ionic abrasion at room temperature. At room temperature, no patterning was observed in AFM. The surface remains relatively rough, unlike a layer of pure silica which is smooth under ionic abrasion at normal incidence. The lack of structure may be due to insufficient mobility of copper in magnetron-deposited silica.
• the activation energy is too important a heat treatment is required, the heating temperature is all the greater as the rate will be low.
• Fig. 9 shows an AFM image projection of an example of a structured layer silica / copper hybrid material in a fifth embodiment of the sample.
• the temperature of the sample identical to that described in Figure 8 was raised to 175 ° C during abrasion.
• Fig. 10 shows an AFM image projection of an example of a structured layer silica / copper hybrid material in a sixth embodiment of the sample.
• the sample temperature identical to that described in Figure 8 was raised to 250 ° C during abrasion.
• FIG. 11 represents a projection of AFM images of a comparative control example of a hybrid silica / copper material in an unstructured layer.
• Figure 11 shows the area observed by AFM after abrasion at room temperature. Structural formation is not observed even with increasing temperature as in the previous examples. This illustrates that it is necessary to have a minimum amount of said metal element in the material.
• magnetron layer deposition followed by ionic abrasion has been demonstrated.
• layers with a higher copper concentration can be deposited.
• temperature has been demonstrated, which will not relax the surface but allow the formation of nanocones.
• the energy and flux of the incident ions can also be adjusted.

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