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    • 专利摘要:
    An antireflection optical surface, with visible and near infrared absorption, comprises a substrate (4) made of SiC silicon carbide material and a set (8) of microstructures (10, 12, 14, 16, 18, 20, 22) lining an exposure face (6) of the substrate (4). Each microstructure (10, 12, 14, 16, 18, 20, 22) is formed by a single protuberance disposed on and in one piece with the substrate (4). The microstructures (10, 12, 14, 16, 18, 20, 22) have the same shape and dimensions, and are distributed on the face (6) of the substrate (4) in a two-dimensional periodic pattern, and the shape of each microstructure (10, 12, 14, 16, 18, 20, 22) is smooth and regular with a radius of curvature that varies continuously from the top of the microstructure to the face (6) of the substrate (4).
    公开号:FR3055706A1
    申请号:FR1658238
    申请日:2016-09-05
    公开日:2018-03-09
    发明作者:Emmanuel Ollier；Nicolas Dunoyer
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    Holder (s): COMMISSIONER OF ATOMIC ENERGY AND ALTERNATIVE ENERGIES Public establishment.
    Extension request (s)
    Agent (s): MARKS & CLERK FRANCE General partnership.
    FR 3 055 706 - A1 (54) ANTI-REFLECTIVE OPTICAL SURFACE, STRUCTURED REALIZATION.
    ©) An anti-reflective optical surface, with absorption in the visible and near infrared range, comprises a substrate (4) made of a material based on silicon carbide SiC and a set (8) of microstructures (10, 12, 14, 16, 18, 20, 22) of texturing lining an exposure face (6) of the substrate (4).
    Each microstructure (10, 12, 14, 16, 18, 20, 22) is formed by a single protuberance disposed on and in one piece with the substrate (4).
    The microstructures (10, 12, 14, 16, 18, 20, 22) have the same shape and the same dimensions, and are distributed over the face (6) of the substrate (4) according to a two-dimensional periodic pattern, and
    The shape of each microstructure (10, 12, 14, 16, 18, 20, 22) is smooth and regular with a radius of curvature which varies continuously from the top of the microstructure to the face (6) of the substrate (4 ).
    AND A LONG LIFETIME, AND ITS METHOD OF

    ANTI-REFLECTIVE, STRUCTURED AND LONG-LASTING OPTICAL SURFACE AND METHOD FOR THE PRODUCTION THEREOF
    The present invention relates to an anti-reflective surface structured on a material based on silicon carbide SiC. .
    The present invention relates in particular to an optical surface with high absorption in the visible range and with reduced emissivity which can serve as a solar absorber.
    The present invention also relates to a ceramic solar absorber of the silicon carbide type, used on a solid material of silicon carbide SiC or as an absorbent layer of SiC deposited on the surface of another material, for example steel, constituting by example a solar receiver. This is the main application of this invention.
    The solar absorbers known to date use silicon carbide structured in volume or surfaces structured in a material different from silicon carbide or interference deposits obtained from materials different from silicon carbide.
    A first document by F. Gomez-Garcia, entitled "Thermal and hydrodynamic behavior of ceramic volumétrie absorbers for central receiver solar power plants: A review", published in Ftenewable and Sustainable Energy Fteviews 57 52016), 648-658, describes a solar absorber made of silicon carbide structured in its volume in the form of a porosity in which the solar radiation is partially trapped.
    A second document, the article by YM Song et al., Entitled "Antireflective grassy surface on glass substates with self masked dry etching", published in Nanoscale Research Letters 2013, 8: 505, describes the principle of a plasma etching process. which by its chemistry generates micro-masking, which micro-masking slows down the etching of the substrate material in places. The result is a microstructure with relatively high aspect ratios which reduce the reflectivity of the surface. The approach described in this document only concerns glass and cannot be directly applied to silicon carbide. The structures produced here by this process are of sizes smaller than that produced in our patent proposal.
    A third document, the article by J. Cai et al., Entitled “Recent advances in antireflective surfaces based on nanostructure arrays”, published in Royal Society of Chemistry ©, Material Horizons 2015, 2, pages 37-53, describes a first process allowing pseudoperiodic structures to be produced, this time on silicon carbide SiC for lighting applications by LED light emitting diodes (in English Light Electroluminescent Diode). The conical structures obtained by this process are produced by etching through a metal mask obtained by dewetting thin layers. The reflectivity at 6 degrees of incidence over the spectral range from 390 to 785 nm is reduced from 20.5% to 1.62%. The same article mentions a second process for producing microstructures by plasma etching of a silicon Si substrate through a mask of polystyrene beads. This second method is limited here to the etching of a silicon substrate and does not describe the development of a shape of the microstructures which is particularly resistant to oxidation.
    Like the third document, patent application WO 2013/171274 A1, forming a fourth document, describes a micro-masking etching process, the micro-masking being carried out by dewetting of metals, and describes a micro-surface. structured on substrates of silicon carbide SiC or gallium nitride GaN to obtain an anti-reflective function. This microstructured surface manufacturing process is carried out by plasma etching through metal nano-islands from 10 to 380nm in diameter and separation distances. The islands are made of metals including silver, platinum, aluminum, palladium. The base of the cones is less than 400nm. According to a first production process, the gold nanano-islands are formed from annealing for three minutes at 650 ° C. with a layer of gold of thickness 3 to 11 nanorreters. According to a second production process, the nanos islands are formed from 33 minutes annealing at 650 ° C on a layer of gold 13 to 21 nanometers thick. The characteristic dimensions of the microstructures obtained are thus small, less than a hundred nanometers. In addition, the use of metal is generally not recommended in the manufacture of semiconductor devices for reasons of contamination and modification of carrier mobility. In addition, this metal dewetting technique is sensitive to the types of materials used for the substrate, to their monocrystalline or polycrystalline nature, as well as to the surface roughness of the substrate, which we seek to avoid.
    Like the third document, patent application WO 2015/114519 A1, forming a fifth document, describes a method for structuring molybdenum using plasma etching of a molybdenum substrate through a mask of silica beads. or polystyrene. The microstructures obtained described are for example of pyramidal shape, and have sharp edges, promoting the wear of the micro-structured surface when it is subjected to a corrosive environment. The aim is to improve the performance of the molybdenum absorbers thus obtained, in particular their lifetime when these surfaces are subjected to a high temperature and an oxidizing environment such as air. In fact, these molybdenum surfaces exhibit poor temperature resistance in air due to its oxidation.
    The technical problem is to provide anti-reflective optical surfaces for solar absorbers which have both a high absorption capacity for solar radiation and a resistance of this capacity at high temperature and in an oxidizing medium such as air.
    To this end, the subject of the invention is an anti-reflective optical surface, with absorption in the visible and near infrared range, in particular for solar thermal absorbers, capable of operating at high temperatures, and comprising a substrate, consisting of a thickness of a first material based on silicon carbide SiC, and having a flat face or exposure curve, and a set of texturing microstructures lining the face. The anti-reflective optical surface is characterized in that each microstructure is formed by a single protuberance produced in the first material, arranged on and in one piece with the substrate, and the microstructures have the same shape and same dimensions, and are distributed over the face of the substrate in a two-dimensional periodic pattern, and the shape of each microstructure is smooth and regular, having a single apex and a radius of curvature which varies continuously from the apex of the microstructure to the face of the substrate.
    According to particular embodiments, the anti-reflective optical surface comprises one or more of the following characteristics:
    the first material based on silicon carbide is silicon carbide SiC monocrystalline or polycrystalline, or silicon carbide SiC monocrystalline or polycrystalline, enriched in silicon in the form of islands of silicon Si;
    .- the surface of each microstructure has the same maximum height h located in a central zone and corresponding to the height of the microstructure and decreases from the top towards an edge B of a base of the microstructure;
    .- the surface of each microstructure comprises part of the surface of a spherical, elliptical or parabolic cap;
    .- each microstructure has substantially the same base diameter d greater than or equal to 0.3 pm and less than or equal to 5 pm, preferably between 0.5 pm and 2 pm, and the same maximum height h of each microstructure is greater or equal to 0.5 times the base diameter d and less than or equal to 1.5 times the base diameter d;
    .- the radius of curvature of each microstructure is greater than or equal to 0.1 pm and distributed around a central value of radius of curvature between 0.25 pm and 1 pm;
    the arrangement of the microstructures on the exposure face of the substrate is produced in the form of a tiling of elementary networks of microstructures, the elementary networks having the same pattern of mesh included in the assembly formed by the hexagonal meshes, square meshes, triangular meshes, and being characterized by a degree of compactness of the microstructures therebetween.
    The subject of the invention is also a solar absorber comprising an optical surface as defined above.
    The invention also relates to a method for manufacturing an anti-reflective optical surface, in particular for solar thermal absorbers, capable of operating at high temperatures. The manufacturing process includes a first step of providing a substrate, consisting of a thickness of a first material based on silicon carbide SiC, and having a planar or curved exposure face. The manufacturing process is characterized in that it further comprises a second step, executed following the first step, consisting in producing a set of texturing microstructures, lining the face, each microstructure being formed by a single protuberance produced in the first material, and arranged on and in one piece with the substrate, and the microstructures having the same dimensions, being distributed on the face of the substrate in a two-dimensional periodic pattern, and the shape of each microstructure being smooth and regular by having a single apex and a radius of curvature which varies continuously from the apex to the face.
    According to particular embodiments, the method for manufacturing an anti-reflective optical surface comprises one or more of the following characteristics:
    .- the first step consists either in supplying monocrystalline or polycrystalline silicon carbide SiC, or either in providing monocrystalline or polycrystalline silicon carbide SiC, enriched in silicon in the form of islands of silicon Si;
    .- the first step consists either in isostatic compression of a silicon carbide powder SIC, or either in growing polycrystalline silicon carbide SiC, or either in growing monocrystalline silicon carbide SiC, or either in infiltrating high temperature silicon in a porous carbon matrix;
    .- the second step comprises the successive steps consisting in: in a third step depositing a compact monolayer of particles in a second material on the surface of the substrate, and in a fourth step etching by a dry etching process the substrate on the side of the exposure face through interstices existing between the particles, the second material being included in the assembly formed by silica (SiO 2 ), polystyrene (PS) or any other material in the form of beads of required size;
    .- a reduction in the size and shape of the particles by dry etching is implemented, either in a fifth step carried out during the fourth step at the same time as the dry etching of the substrate, or in a sixth fifth step interposed between the third step and the fourth step;
    .- the deposition of the compact film of particles used during the third step is carried out either by a deposition technique involving the air / liquid interface to order the particles included in the assembly formed by the Langmuir Blodgett technique , the Langmuir Shaefer technique, the surface vortic method, the flotation transfer technique, the dynamic and mobile thin laminar flow technique, or by a deposition technique involving exclusively particles in colloidal solution included in the assembly formed by electrophoretic deposition, horizontal deposition by evaporation of a film, evaporation deposition of a bath, deposition by vertical withdrawal of an immersed substrate and horizontal deposition by forced withdrawal from the contact line;
    the dry etching process implemented in the fourth step is reactive ion etching using a gaseous mixture of sulfur hexafluoride (SF 6 ) and dioxygen (O 2 ) in a ratio of 5/3;
    the etching speed of the substrate material Vsub and the etching speed V by particles, the etching selectivity Sg, defined as the ratio of the etching speed of the substrate to the etching speed of the particles, and the etching time are adjusted from so as to consume all the particles and avoid the creation of sharp edges on the surface of the substrate;
    the manufacturing process includes a seventh step of removing particles carried out after the fourth step.
    The invention will be better understood on reading the description of several embodiments which will follow, given solely by way of example and made with reference to the drawings in which:
    .- Figure 1 is a view by scanning electron microscopy of a first embodiment of an anti-reflective optical surface, microstructured according to the invention, made of polycrystalline silicon carbide SiC, obtained by plasma etching through a mask self-organizing beads with a diameter of 1 micron (pm);
    .- Figure 2 is a sectional view in the direction of their height and passing their vertices of three adjacent microstructures of the anti-reflective optical surface of Figure 1;
    .- Figure 3 is a view by scanning electron microscopy of a second embodiment of an anti-reflective optical surface, microstructured according to the invention, made of silicon carbide enriched in poly-crystalline silicon SiCSi, obtained by plasma etching with through a mask of self-organizing beads of 0.5 micron (pm) diameter;
    Figure 4 is a general flow chart of a process for manufacturing a textured optical surface of Figures 1 to 3 according to a first embodiment;
    Figure 5 is a flowchart of a second embodiment of a method for manufacturing the textured surface structure of Figures 1 to 3;
    Figure 6 a view of a main mechanism of dry etching implemented in the manufacturing processes of Figures 1 to 3;
    Figure 7 is a view of the reflectivity spectra, measured in the visible and infrared domains for the anti-reflective optical surface of the second embodiment of Figure 3;
    Figure 8 is a comparative view of the reflectivity spectra measured in the visible and infrared domains for the anti-reflective optical surfaces of the first and second embodiments of Figures 1 and 3;
    FIG. 9 is a view of a surface of silicon carbide SiC, different from that of the invention, having parasitic microstructures and obtained by plasma etching in the absence of the use of a mask of self-silica beads organized;
    Figure 10 is an optical view to scale of a portion of an anti-reflective surface of silicon carbide enriched SiCSi according to the second embodiment of Figure 3, obtained after solar illumination at 745 W / m 2 concentrated with a concentration factor 1000 in a concentration spot of 10 mm in diameter and a rise in temperature in this spot to 676 ° C;
    FIG. 11 is an optical view to scale, similar to that of FIG. 7, of a portion of a surface of molybdenum Mo, nano-structured according to the method of the aforementioned patent application WO 2015/114519 A1, and obtained after solar illumination under 810 W / m2 concentrated with a concentration factor 1000 in a concentration spot of 10 mm in diameter and reaching a temperature in this spot of 582 ° C;
    Figure 12 is a view of the reflectivity spectra of an SiCSi enriched silicon carbide absorber, the surface of which is structured according to the second embodiment of Figure 3, the spectra being measured before and after exposure to concentrated solar radiation by a Fresnel lens with 1000 magnification and dimensions 33x33 cm2 under 900 W / m2 of incident solar radiation;
    FIG. 13 is a view of the reflectivity spectra in the visible and infrared domains of an absorber of silicon carbide enriched SiCSi, the surface of which is structured according to the second embodiment of FIG. 3, the spectra being measured at different times during aging in air at a temperature of 1000 ° C;
    FIG. 14 is a view of the evolution of the solar absorption of a solar absorber made of enriched silicon carbide SiCSi, the exposure surface of the absorber being structured according to the second embodiment of FIG. 3 and exposed in air at a temperature of 1000 ° C;
    FIG. 15 is a view of the evolution over time of the solar absorption of two samples of a solar absorber made of silicon carbide SiC, manufactured according to the same manufacturing process, the exposure surface of the absorber being structured according to the first embodiment of Figure 1 and exposed to air at different temperatures;
    Figure 16 is a view by scanning electron microscopy of the technical effect of the uneven or irregular shape and the small size of the parasitic microstructures of Figure 9 on the aging performance of the micro-structured surface in terms of modifications of the shape and size of the microstructures, aging in air being visualized after 250 hours at a permanent temperature of 1000 ° C;
    Figure 17 is a view by scanning electron microscopy of the technical effect of the regular shape and size of the microstructures of a surface according to the invention of Figures 1 and 3 on the aging performance of the micro-structured surface in terms of modifications to the shape and size of the microstructures, aging in air being visualized after 250 hours at a permanent temperature of 1000 ° C;
    The invention relates to the geometry of the structuring of materials based on silicon carbide and to its production methods which make it possible to increase the absorption of solar radiation in a predetermined wavelength range and to have available at the same time of an extremely resistant solution, in terms of a high stability of the shapes and dimensions of the microstructures, at high temperature and in corrosive medium, for example an oxidizing medium such as air.
    According to FIG. 1, an anti-reflective optical surface 2, with absorption in the visible and near infrared domain, in particular for thermal solar absorbers, capable of operating at high temperatures, comprises a substrate 4, consisting of a thickness e of a first material based on silicon carbide SiC of the first type, that is to say polycarbonate silicon carbide SiC, and having a flat or curved face 6, of exposure to light, solar for example.
    The anti-reflective optical surface 2 also includes a set 8 of microstructures 12, 14, 16, 18, 20, 22, 24 for texturing lining the face 6 of exposure of the substrate.
    Here, only seven texturing microstructures 10, 12, 14, 16, 18, 20, 22, 24 have been designated by a reference numeral for the sake of simplification of the description.
    Each texturing microstructure 12, 14, 16, 18, 20, 22, 24 is formed by a single protuberance made of the first material, placed on and in one piece with the substrate 4.
    The microstructures 12, 14, 16, 18, 20, 22, 24 have the same shape, with local variations in materials or processes, and the same dimensions; they extend parallel at least locally with respect to each other in a local direction, perpendicular to the exposure face 6, here solar, at the location of each microstructure 12, 14, 16, 18, 20, 22, 24.
    The microstructures 12, 14, 16, 18, 20, 22, 24 are distributed on the solar exposure face 6 of the substrate 4 according to a two-dimensional periodic pattern 32. Here, the shape of the two-dimensional periodic pattern 32 is for example compact hexagonal.
    The shape of each microstructure 12, 14, 16, 18, 20, 22, 24 is smooth and regular by having a single apex, 42, 44, 46, 48, 50, 52, 54 and a radius of curvature which varies continuously from the top of the microstructure 12, 14, 16, 18, 20, 22, 24 to the exposure face 6 of the substrate 4.
    According to FIG. 2, a profile 62 of partial section of the assembly 8 of the microstructures, here the three microstructures 24, 12, 18, aligned and adjacent to each other, and of the substrate 4 in support, comprises a contour line 66 continues exposure surface 6.
    According to Figures 1 and 2, the surface of each microstructure 12, 14, 16, 18, 20, 22, 24 has the same maximum height h, located in a central area surrounding its apex and corresponding to the height of microstructure 12 , 14, 16, 18, 20, 22, 24, and decreases from the top to an edge B of a base of the microstructure 12, 14, 16, 18, 20, 22, 24.
    The texturing microstructures 12, 14, 16, 18, 20, 22, 24 are obtained in this example by plasma etching through a mask of self-organizing beads having a diameter equal to one micron. The diameter d of a microstructure located respectively below each ball is here correlatively about 1 micrometer and the top of the shape of each microstructure 12, 14, 16, 18, 20, 22, 24 can be described here by a hemisphere or a rounded cone or the top of a parabola.
    Here and preferably, all the adjacent microstructures are joined at their edges at the level of the exposure face, and their junction surface has a point or a line of discontinuous curvature.
    As a variant, the adjacent microstructures are not contiguous at their edges at the level of the exposure face, and the junction curve of each microstructure with the exposure face has a discontinuous line of curvature.
    As a variant, the adjacent microstructures are not contiguous at their edges at the level of the exposure face, and on a neighborhood of the junction curve of each microstructure with the exposure face, the curvature is continuous.
    Diameters of 0.5 micron can be used and produce an optical performance similar to that obtained with a diameter of 1 micron. The arrangement of the microstructures 12, 14, 16, 18, 20, 22, 24 in the local plane of the structured surface is periodic like the arrangement of the ball mat used, the periodic pattern of the arrangement being preferably hexagonal compact but could be different.
    According to Figure 1 which is a perspective view from above of the selective anti-reflective optical surface 2, it clearly appears that the two-dimensional periodic pattern 32 is compact hexagonal and that the network of microstructures thus formed is a compact network with hexagonal mesh.
    According to FIG. 3 and a second embodiment of the invention, an anti-reflective optical surface 102 is structured and produced this time in a material based on silicon carbide SiC of the second type SiSiC which, like the anti-reflective surface of FIG. 2 comprises silicon carbide SiC, but which is enriched in silicon Si by presenting islets of silicon Si. This second type of material SiSiC is for example obtained by the formation of a porous carbon material from 'a pyrolysis then an infiltration of a silicon precursor is carried out at high temperature to form the silicon carbide compound SiSiC. In the case of this second type of material, the structure obtained is analogous to that obtained for the silicon carbide SiC of the material of the first type of FIG. 1 and results in a compact hexagonal arrangement of structures which can be described by a form of parabolic domes or rounded cones, or even hemispheres whose diameter here is 0.5 micron.
    Here in Figure 3, two areas of the substrate 104 material and microstructures 108 resting on the exposure face 106 of the substrate 104 are shown partially. A first zone 152 in silicon carbide SiC is illustrated in the upper left corner of FIG. 3 and a second zone 154 in silicon Si is illustrated in the lower right corner of FIG. 3, which second zone 154 forms an island of silicon Si in the substrate 104.
    It should be noted that the residues of silica beads visible on the top of certain microstructures 108 are not part of said microstructures and that these residues of beads will have disappeared at the end of the manufacturing process due to their consumption by the etching process.
    In general, an anti-reflective optical surface according to the invention, with absorption in the visible and near infrared range, in particular for solar thermal absorbers, capable of operating at high temperatures, comprises a substrate, consisting of a thickness of a first material based on silicon carbide SiC, and having a plane or curved exposure face, and a set of texturing microstructures lining the exposure face.
    Each microstructure is formed by a single protuberance made of the first material, arranged on and in one piece with the substrate. The microstructures have the same shape and same dimensions, and are distributed on the face of the substrate in a two-dimensional periodic pattern, and the shape of each of each microstructure is smooth and regular, having a single apex and a radius of curvature which varies continuously from the top of the microstructure to the face of the substrate.
    The first material based on silicon carbide is included in the assembly formed by the monocrystalline silicon carbide SiC, the polycrystalline silicon carbide, the monocrystalline or polycrystalline silicon carbide SiC, enriched in silicon in the form of islands of silicon Si.
    In particular, the surface of each microstructure comprises part of the surface of a spherical or elliptical or parabolic cap.
    In general and independently of the embodiment of the selective anti-reflective optical surface, each microstructure has substantially the same base diameter d greater than or equal to 0.3 μm and less than or equal to 5 μm, preferably between 0.5 μm and 2 pm, and the same maximum height h of each microstructure is greater than or equal to 0.5 times the base diameter d and less than or equal to 5 times the base diameter d.
    The radius of curvature p of each microstructure is greater than or equal to 0.1 μm and distributed around a central value p 0 of radius of curvature between 0.25 μm and 1 μm.
    In general, the arrangement of the microstructures on the exposure face of the substrate is carried out in the form of a tiling of elementary networks of microstructures, the elementary networks having the same mesh pattern included in the assembly formed by the meshes. hexagonal, square meshes, triangular meshes, and being characterized by a degree of compactness of the microstructures therebetween.
    According to FIG. 4 and a first embodiment, a method 202 for manufacturing the texturing of the anti-reflective optical surfaces as described for example in FIGS. 1 to 3 comprises a set of steps 204, 206, 208, 210, 212.
    This process is particularly suitable for the manufacture of solar thermal absorbers, the textured surface produced being able to operate at high temperatures and / or under an oxidizing environment such as air.
    In a first step 204, a substrate is provided, consisting of a thickness of a first material based on silicon carbide SiC, thermally stable and having a flat or curved exposure face.
    In a second step 206, executed following the first step 204, a set of texturing microstructures lining the face of the substrate is produced.
    Each microstructure is formed by a single protuberance made of the first material, and arranged on and in one piece with the substrate.
    The microstructures have the same shape and the same dimensions, and are distributed over the exposure face of the substrate in a two-dimensional periodic pattern.
    The shape of each microstructure is smooth and regular with a unique apex and a radius of curvature that varies continuously from the apex of the microstructure to the face of the substrate.
    The first step 204 consists:
    either to supply monocrystalline or polycrystalline silicon carbide SiC, or either to provide monocrystalline or polycrystalline silicon carbide SiC, enriched in silicon in the form of islets of silicon Si.
    In particular, the first step 204 consists of:
    either isostatic compression of a silicon carbide powder SIC, or either to grow polycrystalline silicon carbide SiC, or either to grow monocrystalline silicon carbide SiC, or either to infiltrate silicon at high temperature in a porous carbon matrix.
    The second step 206 comprises a third step 208 and a fourth step 210, executed successively.
    In the third step 208, a compact monolayer of masking particles made of a second material is deposited on the surface of the substrate, the second material being included in the assembly formed by silica (SiO 2 ), polystyrene (PS) or any other material in the form of balls of required size.
    In the fourth step 210, the substrate is etched by a dry etching process on the side of the exposure face through gaps existing between the particles,
    During the fourth step 210, that is to say at the same time as the dry etching of the substrate, in a fifth step 212 a reduction in the size and the shape of the particles by dry etching is implemented.
    According to FIG. 5 and a second embodiment derived from the first embodiment, a method 302 of manufacturing an anti-reflective optical surface, textured for, for example, for solar thermal absorbers and as described for example in FIGS. 1 to 3, includes a set of steps 204, 306, 208, 210, 312.
    The first step 204 of method 302 of FIG. 5 is identical to the first step of method 202 of FIG. 4.
    The second step 306 of the method 302 of FIG. 5 comprises, like the method 202 of FIG. 4, the third step 208 and the fourth step 210.
    The second step 306 of the method 302 of FIG. 5 differs from the method 202 of FIG. 4 in that it comprises a sixth step 312, interposed between the third step 208 and the fourth step 210, in which a reduction in size and of the shape of the particles by dry etching is implemented without interaction with the dry etching of the substrate.
    According to Figures 4 and 5, the manufacturing methods 202, 302 comprise a seventh step 314 of removing the particles, carried out after the fourth step 210. For example, the seventh step 314 consists in cleaning the textured surface by immersing it in a bath ethanol in the presence of ultrasound for at least 5 minutes.
    According to Figures 4 and 5, the deposition of the compact film of particles implemented during the third step 208 is carried out, either by a deposition technique of a first family involving the air / liquid interface to order the particles , or by a deposition technique of a second family involving exclusively particles in colloidal solution.
    The first family of techniques for depositing particles into a compact film is the assembly formed by the method of transferring a monofilm of compacted particles onto a moving carrier liquid, the technique of
    Langmuir Blodgett, the Langmuir Shaefer technique, the surface vortic method, the float transfer technique, the dynamic and mobile fine laminar flow technique.
    The second family of deposition of particles in a compact film is the assembly formed by electrophoretic deposition, horizontal deposition by evaporation of a film, deposition by evaporation of a bath, deposition by vertical withdrawal of a substrate submerged and horizontal deposition by forced withdrawal from the contact line.
    The masking beads deposited are preferably made of SiO 2 , 10 but may be of a different nature as long as the main parameters of the etching are respected.
    The parameters applied to carry out the ball deposits when the method used is the method of transferring a monofilm of compacted particles onto a moving carrier liquid and when a textured surface of Figures 1 to 3 is produced are described below in the following table 1.
    Settings Applied value Min Max Diameter ofparticles ofsilica 1pm or 540nm 0.01 pm 10pm Solvent Butaniol Concentration 35g / l 10g / I 50g / l Carrier liquid Deionized water Carrier liquid flow 400 ml / min 100 ml / min 1000ml / min Particle injection rate 0.5 ml / min 0.01 l / min 3 ml / min Pulling speed 1 cm / min 0.1 cm / min 10 cm / min
    Table 1
    According to FIGS. 4 and 5, the dry etching process implemented in the fourth step 210 is, for example, reactive ion etching using a gaseous mixture of sulfur hexafluoride (SF 6 ) and dioxygen (O 2 ) in a 5/3 report. Other gases capable of selectively etching the material with respect to the balls may also be used.
    In general and independently of the dry etching process used, the etching speed of the substrate material Vmat and the etching speed V by particles are greater than 50 nm per minute, and the etching selectivity Sg, defined as the ratio of the etching speed of the substrate material on the etching speed of the particles, is between 0.5 and 10.
    When a textured surface of Figures 1 to 3 is manufactured, the dry etching process described below can be used. This engraving process implements:
    - SiO 2 silica beads of 530nm or 1 μm deposited colloidally with flotation of a compact monolayer of beads on a solvent and transfer to the substrate to be textured,
    - a reactive ion etching type reactor RIE (known in English as Reactive Ion Etching),
    - a generator at a frequency of 13.56 GHz,
    - a mixture of SF 6 and O 2 gases,
    - flows of 5sccm for SF 6 and 3sccm for O 2 ,
    - a pressure of 25mT,
    - a power of 0.25W / cm 2 (20W on a sole with a diameter of 10cm), and
    - a substrate temperature equal to 50 ° C.
    The time of the etching process depends on the type of material used for the substrate and the diameter of the beads used.
    When balls with a diameter of 530 nm are used, the time of the etching process is equal to 600 s for a substrate material of first type SiC, and equal to 480 s for a substrate material of second type SiSiC.
    In the case of a silica ball with a diameter of 1 micron, the time of the etching process is multiplied by 2 compared with the balls of diameter 530nm, or for example 1200s for a substrate of the first SiC type.
    The conditions of the etching processes defined above are conditions optimized for obtaining the selectivity (ratio of the etching speeds between the mask of silica beads and the material to be etched of the SiC or SiSiC type) making it possible to achieve a ratio of form of microstructures, defined as the ratio of their height to their width, of about 1, that is to say between 0.3 and 5.
    Other etching chemistries can be used, in particular fluorochemicals.
    According to FIG. 6, a dry etching mechanism known as “ion bombardment” is implemented in the manufacturing processes of FIGS. 4 and 5.
    According to this mechanism represented by the arrows 322, 324, 326, the ions coming from the plasma of SF 6 attack frontally in a rather selective and anisotropic manner the surface of the substrate which is accessible through the interstices of passage existing between the masking balls. The easier the attack is, the easier it is to access the surface of the material through the bead mat. In FIG. 6, the lengths of attack arrows 322, 324, 326, proportional to the intensity and the effectiveness of the plasma attack decrease from a point 330 of the surface of the substrate to "open sky" to go to a contact point 332 of the masking ball 328. In a related manner, the etching by ion bombardment of the surface of the substrate is accompanied by an etching of the masking by ion erosion of the surface of the masking balls, the erosion of the surface of the masking balls having an effect on the etching speed. This so-called “ion bombardment” mechanism is responsible for the shape of the microstructures described in Figures 1 to 3.
    Thus, the process of Figures 4 and 5 makes it possible to obtain the structures like those described in Figures 1 to 3.
    The reflectivity spectra obtained from the selective anti-reflective optical surfaces described in particular in FIGS. 1 to 3 are similar to the spectrum 402 illustrated in FIG. 7, measured for a structuring of a SiSiC material. The reflectivity, measured in the visible and near infrared range, that is to say for the wavelengths between 0.3 and 2.5 microns, is greatly reduced, which therefore allows the realization of an efficient solar absorber.
    The spectrum measurements were carried out on the same SiSiC textured surface sample by a first measuring device which provided a first spectrum curve 404 in the visible range, and by a second measuring device which provided a second curve 406 spectrum in the infrared range.
    According to FIG. 7, the reflectivity spectra 404, 406 in the visible and infrared domains show their difference in reflectivity, a low reflectivity or high absorption for a thick non-transparent medium being observed in the visible domain, and a relatively high reflectivity or low. emissivity according to Kirschoff's law being observed in the infrared IR range. Here, a solar absorption of 95.9% and an emissivity at 500 ° C of 67% are measured.
    According to Figure 8, the reflectivity spectra of optical surfaces using SiC and SiSiC materials before and after structuring are collected.
    A first spectrum 414 illustrates the evolution of the reflectivity, expressed as a percentage on a linear scale, as a function of the wavelength, expressed in micron on a logarithmic scale, for a non-textured or smooth raw optical surface made of silicon carbide .
    A second spectrum 416 illustrates the evolution of the reflectivity as a function of the wavelength for an anti-reflective optical surface SiC made of silicon carbide, the anti-reflective optical surface SiC being textured with a mask of self-organizing beads of diameter 0.5 microns (pm).
    A third spectrum 418 illustrates the evolution of the reflectivity as a function of the wavelength for a raw non-textured or smooth optical surface made of silicon carbide enriched in silicon SiSiC.
    A fourth spectrum 420 illustrates the evolution of the reflectivity as a function of the wavelength for an SiSiC anti-reflective optical surface made of silicon carbide enriched in silicon, the SiSiC anti-reflective optical surface being textured with a mask of self-organizing beads of diameter. 0.5 microns (pm).
    The comparison of the second and fourth spectra 416, 420, with the first and third spectra 414, 418, show the strong decrease in reflectivity and therefore of improvement of the absorption in the visible and near infrared domain for the two types of materials (SiC, SiSiC) based on silicon carbide.
    It should be noted that the manufacturing method according to the invention which uses dry etching has a particular technical effect when the use of a bead mask during the etching step is omitted. In fact, as shown in FIG. 9, without a mask of beads, a parasitic micro-masking with small dimensions appears on the optical surface based on silicon carbide due to the deposition of carbon, this micro-masking being linked to the deposition of carbonaceous molecules originating from the gas. etching and by-products of the etching reaction. This micro-masking has the effect of creating a mat 432 of parasitic microstructures 434 in the form of needles of a hundred nanometers width at most on the optical surface 442 thus obtained.
    Conversely, in the case of the presence of silica used in the self-organizing beads of the mask provided in the manufacturing process according to the invention, oxygen present in the composition of the beads is released during etching and modifies the composition of the reaction products by avoiding the accumulation of carbon on the surface of the substrate and thus avoids parasitic micro-masking. This then results in the compact hexagonal structure of smooth domes which will have good resistance to oxidation.
    The structures of the anti-reflective optical surfaces as described in Figures 1 to 3 or obtained by the manufacturing processes described in Figures 4 to 6 are very suitable for solar absorbers and have the double advantage of a very good absorption capacity of the solar radiation and excellent resistance to oxidation in air or other oxidizing medium.
    According to Figure 10, an optical view of a sample 452 of an anti-reflective surface of silicon carbide enriched SiSiC according to the second embodiment of Figure 3, obtained after solar illumination at 745 W / m 2 concentrated with a factor of concentration 1000 in a spot of concentration 454 of 10 mm in diameter and a rise in temperature in this spot at 676 ° C., shows that the structure of the surface produced on the silicon carbide enriched in silicon SiSiC shows no deterioration after exposure under high solar concentration in air at nearly 700 ° C. The concentration spot cannot be distinguished in this view from the rest of the surface of the sample.
    Conversely and according to FIG. 11, an optical view, similar to that of FIG. 10, of a sample 462 of a surface of molybdenum Mo, nano-structured according to the method of the aforementioned patent application WO 2015 / 114519 A1, and obtained after solar illumination at 810 W / m2 concentrated with a concentration factor 1000 in a 464 concentration spot 10 mm in diameter and reaching a temperature in this spot of 582 ° C, shows that the nanostructured molybdenum material oxidizes on the surface in the concentration spot 464, distinguishable in FIG. 11 by a lighter shade, and deteriorates very strongly in air.
    The structure of the anti-reflective optical surface 452 according to the second embodiment of FIG. 3 has better resistance to oxidation than that of the nanostructured molybdenum of FIG. 11 which exhibits cracks and delaminations under the effect of its oxidation in air.
    According to Figure 12, a first spectrum 472 and a second spectrum 474 of reflectivity of an SiSiC enriched silicon carbide absorber whose surface is structured according to the second embodiment of Figure 3 are illustrated. The first and second spectra 472, 474 are respectively the spectra measured before and after exposure to concentrated solar radiation by a Fresnel lens of magnification 1000 and dimensions 33x33 cm2 under 900 W / m2 of incident solar radiation.
    The first and second spectra 472, 474 confirm the very good resistance to oxidation of the absorbers structured according to the invention, the two reflectivity spectra before and after the sun exposure being superimposable.
    According to FIG. 13, reflectivity spectra, 481,482, 483, 484, 485, 486, 487, 488, measured in the visible and infrared domains of an enriched silicon carbide SiCSi absorber whose surface is structured according to the second embodiment of Figure 3, is illustrated. The spectra 481, 482, 483, 484 in the visible range, respectively the spectra 485, 486, 487, 488 are measured at different respective times, 0 hours, 3 hours, 15 hours, 25 hours, during aging under air at a temperature of 1000 ° G
    FIG. 13 confirms the integrity of the absorbers structured according to the invention for extremely high aging temperatures of the order of 1000 ° C., in air, with spectra in the visible range 481,
    482, 483, 484 and in the infrared range 485, 486, 487, 488 unchanged between 0 and 25 hours.
    According to FIG. 14, the temporal evolution 492 of the measured solar absorption of a solar absorber made of enriched silicon carbide SiSiC, the exposure surface of which is structured according to the second embodiment of FIG. 3 is illustrated, aging taking place at a temperature of 1000 ° in air. It appears that the solar absorption and through it the reflectivity parameter remains almost unchanged over time for extreme temperatures and confirms the excellent performance in service life of the absorbers structured according to the invention.
    According to FIG. 15, the time evolution 502 of the measured solar absorption of two samples of a solar absorber made of silicon carbide SiC whose exposure surface is structured according to the first embodiment of FIG. 1, is illustrated , the two samples being exposed to air for three high temperatures equal to 800 ° Q 1000 ° C and 1200 ° C.
    A first set 504 and a second set 506 of measurement data relate respectively to the first and second samples for a temperature of 800 ° C.
    A third set 508 and a fourth set 510 of measurement data relate to the first and second samples for a temperature of 1000 ° C.
    A fifth set 512 and a sixth set 514 of measurement data relate to the first and second samples for a temperature of 1200 ° C.
    The first, second, third, fourth, fifth, sixth data sets 504, 506, 508, 510, 512, 514 confirm excellent resistance to oxidation under high temperature air of the solar absorber for the SiC material structured according to the invention, for example with spherical or paraboloid domes of 0.5 micron or 1 micron in diameter. The absorption performance is here maintained above 95% over time, independently of the extreme high temperatures considered here for aging.
    These excellent lifetime properties are obtained thanks to the intrinsic resistance of silicon carbide to oxidation but also to the particular forms of structures produced according to the invention.
    In fact, as shown in FIG. 16, the uneven or irregular shape and the small size of parasitic microstructures 552, such as those of FIG. 9 and representative of the state of the art, are clearly modified during aging after 250 hours in air at a permanent temperature of 1000 ° C while being totally oxidized by an oxide layer of relatively large dimension.
    Conversely, as shown in Figure 17, the regular shape (spherical, softened conical, parabolic) and the relatively large size of the microstructures of a surface according to the invention of Figures 1 and 3, allow microstructures 562 to retain substantially the same shape and size by being slightly oxidized on the surface. Thus the optical property of low reflectivity / high absorption is preserved in extreme conditions of temperature and oxidizing medium.
    The possible applications of the invention relate in particular to:
    .- selective solar absorbers, .- systems comprising selective absorbers of for example planar or cylindrical shapes.
    权利要求:
    Claims (17)
    [1" id="c-fr-0001]
    1- Anti-reflective optical surface, with absorption in the visible and near infrared range, in particular for solar thermal absorbers, capable of operating at high temperatures, and comprising a substrate (4; 104), consisting of a thickness d '' a first material based on silicon carbide SiC, and having a flat face (6; 106) or exposure curve, and a set (8) of microstructures (10, 12, 14, 16, 18, 20, 22 ; 108) of texturing lining the face (6; 106), said anti-reflective optical surface being characterized in that each microstructure (10, 12, 14, 16, 18, 20, 22; 108) is formed by a single protuberance produced in the first material, arranged on and in one piece with the substrate (4; 104), and the microstructures (10, 12, 14, 16, 18, 20, 22; 108) have the same shape and same dimensions, and are distributed on the face (6; 106) of the substrate (4; 104) in a two-dimensional periodic pattern, and the shape of each a microstructure (10, 12, 14, 16, 18, 20, 22; 108) is smooth and regular by having a single apex and a radius of curvature which varies continuously from the apex of the microstructure (10, 12, 14, 16, 18, 20, 22; 108) to the face (6; 106) of the substrate (4; 104).
    [2" id="c-fr-0002]
    2- anti-reflective optical surface according to claim 1, in which the first material based on silicon carbide is monocrystalline or polycrystalline silicon carbide SiC, or monocrystalline or polycrystalline silicon carbide SiC, enriched in silicon in the form of Si silicon islands.
    [3" id="c-fr-0003]
    3- anti-reflective optical surface according to any one of claims 1 to 2, in which the surface of each microstructure (10, 12, 14, 16, 18, 20, 22; 108) has the same maximum height h located in a central zone and corresponding to the height of the microstructure (10, 12, 14, 16, 18, 20, 22; 108) and decreases from the top towards an edge B of a base of the microstructure (10, 12, 14, 16, 18, 20, 22; 108).
    [4" id="c-fr-0004]
    4- Anti-reflective optical surface according to any one of claims 1 to 3, in which the surface of each microstructure (10, 12, 14, 16, 18, 20, 22; 108) comprises part of the surface of a cap spherical, elliptical or parabolic.
    [5" id="c-fr-0005]
    5- anti-reflective optical surface according to any one of claims 1 to 4, in which each microstructure (10, 12, 14, 16, 18, 20, 22; 108) has substantially the same base diameter d greater than or equal to 0 , 3 pm and less than or equal to 5 pm, preferably between 0.5 pm and 2 pm, and the same maximum height h of each microstructure (10, 12, 14, 16, 18, 20, 22; 108) is greater or equal to 0.5 times the base diameter d and less than or equal to 1.5 times the base diameter d.
    [6" id="c-fr-0006]
    6- anti-reflective optical surface according to any one of claims 1 to 5, in which the radius of curvature of each microstructure (10, 12, 14, 16, 18, 20, 22; 108) is greater than or equal to 0.1 pm and distributed around a central value of radius of curvature between 0.25 pm and 1 pm.
    [7" id="c-fr-0007]
    7- Anti-reflective optical surface according to any one of claims 1 to 6, in which the arrangement of the microstructures (10, 12, 14, 16, 18, 20, 22; 108) on the exposure face of the substrate is produced in the form of a tiling of elementary networks (60; 70) of microstructures, the elementary networks having a same mesh pattern included in the assembly formed by the hexagonal meshes, the square meshes, the triangular meshes, and being characterized by a degree of compactness of the microstructures with one another.
    [8" id="c-fr-0008]
    8- Solar absorber comprising an anti-reflective optical surface defined according to one of claims 1 to 7.
    [9" id="c-fr-0009]
    9- Method for manufacturing an anti-reflective optical surface, in particular for solar thermal absorbers, capable of operating at high temperatures, said manufacturing process comprising a first step (204) consisting in providing a substrate, consisting of a thickness of a first material based on silicon carbide SiC, and having a planar or curved exposure face, characterized in that it further comprises a second step (206; 306), executed following the first step , consisting in producing a set of texturing microstructures, lining the face, each microstructure being formed by a single protuberance produced in the first material, and arranged on and in one piece with the substrate, and the microstructures having the same and same dimensions, being distributed over the face of the substrate in a two-dimensional periodic pattern, and the shape of each microstructure being smooth and even by having a single apex and a radius of curvature which varies continuously from the apex to the face.
    [10" id="c-fr-0010]
    10- A method of manufacturing an anti-reflective surface according to claim 9, wherein the first step (204) consists of:
    either to supply monocrystalline or polycrystalline silicon carbide SiC, or either to provide monocrystalline or polycrystalline silicon carbide SiC, enriched in silicon in the form of islets of silicon Si.
    [11" id="c-fr-0011]
    11- A method of manufacturing an anti-reflective surface according to any one of claims 9 to 10, in which the first step (204) consists of:
    either isostatic compression of a silicon carbide powder SIC, or either to grow polycrystalline silicon carbide SiC, or either to grow monocrystalline silicon carbide SiC, or either to infiltrate silicon at high temperature into a porous carbon matrix.
    [12" id="c-fr-0012]
    12- A method of manufacturing an anti-reflective surface according to any one of claims 9 to 11, wherein the second step (206; 306) comprises the successive steps consisting in a third step (208) depositing a compact monolayer of particles in a second material on the surface of the substrate, and in a fourth step (210) etching by a dry etching process the substrate on the side of the exposure face through interstices existing between the particles, the second material being included in the assembly formed by silica (SiO 2 ), polystyrene (PS) or any other material in the form of beads of required size.
    [13" id="c-fr-0013]
    13- A method of manufacturing an anti-reflective surface according to claim 12, wherein a reduction in the size and shape of the particles by dry etching is implemented, either in a fifth step (212) performed during the fourth step ( 210) at the same time as the dry etching of the substrate, ie in a sixth fifth step (312) interposed between the third step (208) and the fourth step (210).
    [14" id="c-fr-0014]
    14- A method of manufacturing an anti-reflective surface according to any one of claims 12 to 13, wherein the deposition of the compact film of particles used during the third step (208) is carried out either by a deposition technique involving the air / liquid interface to order the particles included in the set formed by the Langmuir Blodgett technique, the Langmuir Shaefer technique, the vortic surface method, the flotation transfer technique, the flow technique dynamic and mobile thin laminar, either by a deposition technique involving exclusively particles in colloidal solution included in the assembly formed by electrophoretic deposition, horizontal deposition by evaporation of a film, deposition by evaporation of a bath, the deposition by vertical withdrawal of a submerged substrate and the
    5 horizontal deposition by forced withdrawal of the contact line.
    [15" id="c-fr-0015]
    15- A method of manufacturing an anti-reflective surface according to any one of claims 12 to 14, wherein the dry etching process implemented in the fourth step 10 (210) is a reactive ion etching using a gas mixture of sulfur hexafluoride (SF 6 ) and dioxygen (O 2 ) in a ratio of 5/3.
    [16" id="c-fr-0016]
    16- A method of manufacturing an anti-reflective surface according to claim 15, wherein
    The etching speed of the substrate material Vsub and the etching speed V by particles, the etching selectivity Sg, defined as the ratio of the etching speed of the substrate to the etching speed of the particles, and the etching time are adjusted so as to consume all the particles and avoid the creation of sharp edges on the surface of the
    20 substrate.
    [17" id="c-fr-0017]
    17- A method of manufacturing an anti-reflective surface according to any one of claims 12 to 16, comprising a seventh step (314) of particle removal performed after the fourth step (210).
    1/12
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    引用文献:
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    法律状态:
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    2018-03-09| PLSC| Publication of the preliminary search report|Effective date: 20180309 |
    2018-09-28| PLFP| Fee payment|Year of fee payment: 3 |
    2019-09-30| PLFP| Fee payment|Year of fee payment: 4 |
    2021-06-11| ST| Notification of lapse|Effective date: 20210506 |
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    FR1658238A|FR3055706B1|2016-09-05|2016-09-05|ANTIREFLECTIVE, STRUCTURED AND HIGHLY LIFETIME OPTICAL SURFACE, AND METHOD FOR CARRYING OUT THE SAME|
    FR1658238|2016-09-05|FR1658238A| FR3055706B1|2016-09-05|2016-09-05|ANTIREFLECTIVE, STRUCTURED AND HIGHLY LIFETIME OPTICAL SURFACE, AND METHOD FOR CARRYING OUT THE SAME|
    US15/694,690| US20180067235A1|2016-09-05|2017-09-01|Structured antireflection optical surface having a long lifetime and its manufacturing method|
    EP17188969.4A| EP3290966A1|2016-09-05|2017-09-01|Anti-reflective optical surface, structured and with long durability, and method for manufacturing same|
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