EP3099631A1 - Structure photonique de surface en materiau refractaire et son procede de realisation - Google Patents
Structure photonique de surface en materiau refractaire et son procede de realisationInfo
- Publication number
- EP3099631A1 EP3099631A1 EP15708294.2A EP15708294A EP3099631A1 EP 3099631 A1 EP3099631 A1 EP 3099631A1 EP 15708294 A EP15708294 A EP 15708294A EP 3099631 A1 EP3099631 A1 EP 3099631A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- textured surface
- microstructures
- substrate
- needles
- microstructure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 239000011819 refractory material Substances 0.000 title claims description 15
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- 238000001312 dry etching Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 229910018503 SF6 Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 5
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 5
- 230000007423 decrease Effects 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 150000001247 metal acetylides Chemical class 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
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- 229910000640 Fe alloy Inorganic materials 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000001652 electrophoretic deposition Methods 0.000 claims description 3
- 238000005188 flotation Methods 0.000 claims description 3
- 229910001026 inconel Inorganic materials 0.000 claims description 3
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- 239000011368 organic material Substances 0.000 claims description 3
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- 239000002356 single layer Substances 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000001074 Langmuir--Blodgett assembly Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000002310 reflectometry Methods 0.000 description 25
- 230000000873 masking effect Effects 0.000 description 18
- 239000011324 bead Substances 0.000 description 16
- 230000003287 optical effect Effects 0.000 description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 239000011733 molybdenum Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 9
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- 238000010849 ion bombardment Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
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- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
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- 239000010931 gold Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 239000010944 silver (metal) Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/10—Details of absorbing elements characterised by the absorbing material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/60—Details of absorbing elements characterised by the structure or construction
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Definitions
- the present invention generally relates to a textured surface structure for refractory photonic structures, particularly for solar thermal absorbers.
- Solar absorbers are widely used in the solar thermal field where they absorb visible solar radiation and re-emit very little infra-red radiation.
- the invention relates to the structuring of a refractory material, it also relates to the production of photonic crystals on high temperature materials.
- the present invention can also be used to produce optical structures of photovoltaic cells, for example on metal electrodes.
- selectivity means that the reflectivity of the material is very different in the wavelength range of visible and infra-red. In the visible, a very low reflectivity is sought while a very high reflectivity is sought in the field of infrared.
- JP2011047304 describes a structure for photonic applications such as solar heat absorbers, operable at high temperatures, comprising a thermally stable substrate having a pitch surface, and a set of microstructures called “needles”. substantially pyramidal forms, and of the order of one micron, these microstructures being distributed on the face of the substrate in a bidimensional periodic pattern and in one piece with the substrate.
- each "needle” has on each of its faces the smallest needles of the order of one nanometer.
- WO2012 / 057073 discloses a structure for photonic applications such as solar heat absorbers, operable at high temperatures, comprising a thermally stable substrate and having a planar surface, and a set of texturing microstructures of substantially pyramidal shapes, such microstructures being distributed on the face of the substrate in a two-dimensional periodic pattern and in one piece with the substrate.
- CN 103 151 397 discloses a structure for photonic applications such as solar thermal absorbers, comprising a ceramic, glass or polymer substrate for example, and having a planar surface, a conductive film deposited on the substrate and including balls. of copper sulphide forming a set of texturing microstructures, and carrying nanoscale copper sulphide needles to form cactus-shaped microstructures.
- WO2013 / 171286 discloses a solar cell having a surface made of a first material, the optical device having a non-periodic nanostructure formed in the surface, said nanostructure comprising a plurality of conical shaped structures. Said cones are non-periodically distributed on the surface and have random distribution heights, at least a portion of the conical shaped structures having a height greater than or equal to 100 nm.
- This document also describes a method of manufacturing a non-periodic nanostructured surface on a solar cell, said method comprising the steps of: using a surface comprising SiC or GaN; forming a thin layer of mask material on at least a portion of the substrate; treating the thin layer to form nanoids of thin-film material; etching the SiC or GaN by substantially anisotropic etching and simultaneously etching at least a portion of the thin film mask material to form a non-periodic nanostructure.
- the nanostructure comprises a plurality of conical shaped surface structures having a random height distribution, at least a portion of the structures having a height greater than or equal to 100 nm.
- the object of the invention is to provide surface photonic structures of refractory material with an innovative geometry to obtain a wavelength selectivity, adapted to solar thermal absorbers, and compatible with a low-cost industrial manufacturing process, can be implemented on a large scale over a large area and compatible with refractory materials at high temperatures.
- the subject of the invention is a textured surface structure for photonic structures, in particular for solar thermal absorbers, capable of operating at high temperatures, comprising a substrate consisting of a thickness of a first material thermally stable and having a flat or curved surface, and a set of texturing microstructures, characterized in that each microstructure is formed by a mat of needles extending parallel to each other, made in the first material, and arranged on and in one piece with the substrate, and
- the microstructures are distributed on the face of the substrate in a two-dimensional periodic pattern.
- the textured surface structure comprises one or more of the following characteristics, taken alone or in combination:
- the first material has a columnar microstucture
- each microstructure has a maximum height located in a central zone of the microstructure and decreases globally from the central zone to the edge of the microstructure;
- the envelope surface of the needles forming each microstructure has a peripheral flank generally having the shape of a truncated cone, a truncated pyramid, a prism, or a cylinder.
- the arrangement of the microstructures on the exposure face of the substrate is made in the form of a tessellation of elementary microstructure networks, the elementary networks having the 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 between them;
- the height of the needles is less than or equal to 300 nm, preferably less than or equal to 200 nm,
- the size of the base of the needles is less than or equal to 100 nm, preferably less than or equal to 50 nm; the height H of the microstructures is substantially identical, and less than or equal to 300 nm, preferably less than or equal to 200 nm, the size L of the base of the microstructures is substantially identical, and between 100 nm and 10 ⁇ m, preferably between 400 and 6O0nm;
- the microstructures each comprise a substantially identical number of needles of between 10 and 10,000;
- the contours of the bases of the microstructures are substantially identical and included in the assembly formed by ellipses and circles;
- the first material is included in the group consisting of the metals Mo, W, Ta Cu, Al, Ni, Pt, Rh, Ag, Au, the nitrides of the same metals, and the carbides of the same metals.
- the subject of the invention is also a method for producing textured surfaces for photonic structures, in particular for solar thermal absorbers, capable of operating at high temperatures, comprising
- a first step of providing a substrate consisting of a thickness of a first optically reflective material and thermally stable, and having a planar or curved exposure face,
- each microstructure being formed by a carpet of needles extending relative to each other, made in the first material, and arranged on and in one piece with the substrate, or being compact with an overall cone shape, and
- microstructures being distributed on the face of the substrate in a bidimensionnei periodic pattern.
- the textured surface manufacturing method comprises one or more of the following features, taken alone or in combination:
- the first step is: depositing a columnar material on a second support material
- the second support material being comprised in the assembly formed by metal materials such as iron alloys in particular steels, nickel alloys especially inconels, aluminum alloys, ceramic materials such as carbide, silicon, as well as organic materials, especially polymers;
- the second step comprises the successive steps consisting in a third step of depositing a compact monolayer of particles into a third material on the surface of the substrate, and
- etching by a dry etching process the substrate on the exposure side side through interstices existing between the particles, the third material being included in the silica (Si0 2 ) assembly, polystyrene (PS) or any other material in the form of beads of required size;
- 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 0, the flotation transfer technique , the technique of dynamic and mobile thin end flow, or by a deposition technique involving exclusively particles in colloidal solution comprised in the assembly formed by the electrophoretic deposition, the horizontal deposition by evaporation of a film, the deposition by evaporation of a bath, the deposition by vertical shrinkage. a submerged substrate and horizontal deposition by forced removal of the nip;
- the dry etching process implemented in the fourth step (210) is an ionic reactive etching using a gas mixture of sulfur hexafluoride (SF 6 ) and oxygen (0 2 ) in a ratio of 5/3;
- the etching rate of the refractory material Vmat and the etching rate V by particles are greater than 50 nm per minute, and the etching selectivity Sg, defined, corresponds to the ratio of the etching rate of the refractory material to the etching speed of the particles; particles, is between 1 and 10;
- the manufacturing method defined above comprises a seventh particle removal step performed after the fourth step.
- Figure 1 is a scanning electron microscope view of a first embodiment of a textured surface structure of the invention
- Figure 2 is a scanning electron micrograph view of a second embodiment of a textured surface structure of the invention.
- Fig. 3 is an atomic force microscopy view of the first embodiment of the textured surface of Fig. 1 showing the arrangement of the microstructures in a hexagonal mesh network;
- FIG. 4 is a comparative view of optical performance in the reflectivity range between the surface structure of FIG. 1 and FIG. structuring and a classical structure with simple dendritic structuring without modulation microstructure;
- Figure 5 is a view of the optical characterization reflectivity terrme of the surface structure of Figure 1 double structuring;
- Figure 6 is a view of a model representative of a dual pattern of the textured surface of Figure 1 for simulating the optical performance of said textured surface;
- FIG. 7 is a comparative view of the simulated optical performance in reflectivity range on the model of FIG. 6 for two values of needle width and actual optical performance in terms of reflectivity of the actual surface structure of the FIG. 1 double structuring;
- Fig. 8 is a flowchart of a method of manufacturing a textured surface structure of Figs. 1 and 2 according to a first embodiment
- Fig. 9 is a flowchart of a second embodiment of a method of manufacturing the textured surface structure of Figs. 1 and 2;
- Figure 10 is a view of the dry etching mechanisms implemented in the manufacturing processes of Figures 8 and 9;
- FIG. 11 is a scanning electron microscopic view of a textured surface with micrometric solid conical structures obtained with one of the methods of FIGS. 8 and 9, set in a particular manner;
- Fig. 12 is a comparative view of optical reflectivity performance between two surface structures of Fig. 11 obtained for two different sizes of masking beads and conventional unstructured material;
- FIG. 3 is a comparative view of the performances in terms of the wavelength rejection of the surface structures obtained with the methods of FIGS. 8 and 9.
- the rejection corresponds to the wavelength range in which the reflectivity varies greatly from FIG. 'a value low at short wavelengths to a high value at long wavelengths.
- a textured surface structure 2 for photonic structures in particular for solar heat absorbers, able to operate at high temperatures, comprises a substrate 4, consisting of a thickness of a first optically reflective material and thermally stable, for example molybdenum, and having a face 6, flat or curved, exposure to light, for example solar.
- a substrate 4 consisting of a thickness of a first optically reflective material and thermally stable, for example molybdenum, and having a face 6, flat or curved, exposure to light, for example solar.
- the textured surface structure 2 also comprises an assembly 8 of texturing microstructures 10.
- Each texturing microstructure 10 is formed by a carpet 12 of needles 14 extending parallel to each other, made in the first material, arranged on and in one piece with the substrate 4.
- Needlesles Elements in the form of a thin rod of circular cross section, ovoid, polygonal or the like.
- the texturing microstructures are distributed over the face 6 of the substrate in a two-dimensional periodic pattern.
- the first material is a columnar material
- the envelope surface 18 of the needles 14 forming each microstructure 10 has a maximum height H located in a central zone 20 of the microstructure 10 and decreases globally from the central zone towards the edge 22 of the microstructure 10.
- the envelope surface 18 is conventionally defined as a convex regular surface containing the peaks of the needles.
- the envelope surface 18 of the needles 14 forming each microstructure 10 has a peripheral flank 24 having generally the shape of a truncated cone, a truncated pyramid, a prism, a cylinder.
- Figure 1 which is an enlarged view of several microstructures 10 allows to determine the main characteristics.
- the thin surface The terms of the degree of spatial resolution, that is to say, the nanometric scale, can be seen as the product of convolution of the surfaces of two structures at two different scales, one micron and the other nanometer.
- the first surface is the surface of a portion of an ellipsoid of revolution whose large dimension corresponds to the radius of masking particles which are used as masks in the manufacturing processes of Figures 8 and 9, and which are arranged along the exposure face according to a compact hexagonal network. All the vertices of the needles are located on this first surface.
- the large size L corresponding to the diameter of the masking particles when the processes of Figures 8 and 9 are implemented is here equal to 540nm, but could be different, for example between 100nm and 1000nm.
- the small dimension of the ellipse is here 300nm but could be different, for example between 50 and 500nm.
- the second smaller scale surface is that corresponding to the needles whose width is here 50nm +/- 20nm and the height h is between 0 and 200nm, the vertices arriving on the previous structure.
- needles 34 of the same microstructure 40 are interconnected by walls 42 into open or closed chains.
- needles 44 of the same microstructure 50 are grouped into cyclic chains forming tubes 54.
- the arrangement of the microstructures 10, 40, 50 on the exposure face 6 of the substrate 4 is in the form of a tessellation of elementary arrays 60, 70 of microstructures,
- the elementary arrays 60, 70 have the same mesh pattern included in the set formed by the hexagonal meshes, the square meshes, the triangular meshes, and are characterized by a degree of compactness of the microstructures between them.
- the microstructure network is also compact with hexagonal mesh, but the microstructures 40, 50 differ from those of FIGS. 1 and 3 in that they are interconnected by walls 42 in open or closed chains.
- the height h of the needles varies within the same microstructure, being lower or equal to 300 nm, preferably less than or equal to 200 nm.
- the size of the needle base is less than or equal to 100 nm, preferably less than or equal to 50 nm.
- the height H of the microstructures is substantially identical, and less than or equal to 1000 nm, preferably less than or equal to 200 nm.
- the size L of the base of the microstructures is substantially identical, and between 100 nm and 10 ⁇ m, preferably between 400 and 600 nm.
- the microstructures each comprise a substantially identical number of needles between 10 and 10,000.
- the contours of the bases of the microstructures are substantially identical and included in the assembly formed by ellipses and circles.
- the first material is included in the set formed by the metals Mo, W, Ta, Cu, Al, Ni, Pt, Rh, Ag, Au, the nitrides of the same metals, and the carbides of the same metals.
- the optical reflectivity performances of the textured surface structure 2 of FIG. 1 with double structuring according to FIG. the invention, and a conventional structure with simple dendritic structuring without modulation microstructure are separated.
- a first curve 102 is the reflectivity evolution curve for the double-structured surface structure as a function of the exposure wavelength expressed in nanometers.
- the textured surface is obtained by etching a molybdenum film through a self-organized ball mat. It therefore has a set of microstructures arranged in a hexagonal network whose characteristic dimension is related to that of the size of the masking beads of the carpet. To this large-scale micrometric structure is added or superimposed a smaller scale structure whose origin comes from the differential etching of the deposited molybdenum columns. This double structuring allows an excellent optical performance with an absorption greater than 95% in the visible and a high reflectivity in the infra-red sought to obtain a low emissivity.
- a second curve 104 is the evolution curve of the reflectivity for a non-selective absorbing surface, obtained by etching a molybdenum film without a ball mat, as a function of the exposure wavelength expressed in nanometers.
- the solar spectrum 108 and the reflectivity curve 106 of the double-structured surface described in FIG. 4 are represented on the same graph.
- the double structured surface has an absorption greater than 92% for the solar spectrum of wavelengths between 300nm and 1000nm.
- Figure 6 a representative model of a double patterning of the textured surface of Figure 1 for simulating the optical performance of said textured surface is provided.
- the simulated structures consist of nano-needles 112 in molybdenum having a profile 114 of sinusoidal longitudinal section of 20nm width at half-height convoluted with a trapezoidal structure 118 of larger size 120 equal to 500 nm.
- the right portion 122 of FIG. 4 represents a mapping of the electric field intensity when a plane electromagnetic wave arrives on the simulated doubly structured surface.
- the first simulated reflectivity curve 142 describes the evolution of the reflectivity calculated on the basis of the double structuring model described in FIG. 8 as a function of the exposure wavelength when the width of the needle at half height is equal to 60 nm.
- the second simulated reflectivity curve 142 describes the evolution of the reflectivity, calculated on the basis of the double structuring model described in FIG. 8 as a function of the exposure wavelength when the width of the mid-needle height is equal to 30 nm.
- the agreement of the simulation curves 142, 144 with the experimental curve 102 shows that the microstructures of FIG. 1 can also be represented by nano-needles whose vertices arrive on a trapezoidal shape with a width of approximately 500 nm corresponding to the size of the masking beads and height of the order of 250nm.
- the simulation carried out according to a two-dimensional model does not involve a particular arrangement 0 according to the third additional three-dimensional axis. This means that the compact hexagonal arrangement in the plane of the face of exposure of the microstructures of size corresponding to the masking beads is only a particular case. Thus, other arrangements are quite possible with the same level of performance.
- a textured surface fabrication method 202 for photonic structures as described for example in Figures 1 to 3 comprises a set of steps 204, 206, 208, 210, 212.
- This method is particularly suitable for the manufacture of solar thermal absorbers, the manufactured textured surface being able to operate at high temperatures.
- a substrate is provided, consisting of a thickness of a first optically reflective material and thermally stable, and having a planar or curved exposure face.
- a set of texturing microstructures is realized.
- Each microstructure is formed by a mat of needles extending parallel to each other, made in the first material, and arranged on and in one piece with the substrate, or is compact with an overall cone shape.
- microstructures are distributed over the exposure face of the substrate in a two-dimensional periodic pattern.
- the first step 204 consists of:
- a dense material that is to say having a visible dense microstructure on a layer of the deposit observed in scanning electron microscopy on the scale of the thickness of the layer
- forming the first material on a second material support or polishing a face of a solid material, that is to say a polycrystalline material obtained by any other technique that the deposition of the material on a support, previously supplied and forming the first material.
- the second support material is comprised in the assembly formed by metallic materials such as iron alloys, in particular steels, nickel alloys, especially inconels, aluminum alloys, but also ceramic materials such as aluminum alloy. silicon carbide as well as organic materials, in particular polymers, or any other material that can serve as a support.
- the first material is for example molybdenum but may also consist of other materials such as W, Cu, Ni, Pt, Rh, or Ag, Au, or composite materials such as nitrides or metal carbides.
- the support material or the first material when used as a bulk material will preferably be polished to obtain roughness of less than 0.1 micron or less prior to the structuring process.
- the second step 206 comprises a third step 208 and a fourth step 210, executed successively.
- a compact monolayer of masking particles of a third material is deposited on the surface of the substrate, the third 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.
- the substrate is etched by a dry etching process on the side of the exposure face through interstices existing between the particles,
- a reduction in the size and shape of the particles by dry etching is implemented.
- a surface manufacturing method 302 textured for photonic structures as described for example in Figures 1 to 3 comprises a set of steps 204, 306, 208, 210, 312.
- the first step 204 of the method 302 of Figure 9 is identical to the first step of the method 202 of Figure 8.
- the second step 306 of the method 302 of FIG. 9 comprises, like the method 202 of FIG. 8, the third step 208 and the fourth step 210.
- the second step 306 of the method 302 of Figure 9 differs from the method 202 of Figure 8 in that it comprises a sixth step 312, interposed between the third step 208 and the fourth step 210, in which a reduction of the The size and shape of the particles by dry etching is implemented without interaction with the dry etching of the substrate.
- the manufacturing methods 202, 302 include a seventh particle removal step 314 performed after the fourth step 210.
- the seventh step 314 is to clean the textured surface by plunging it into a bath éthano! in the presence of ultrasound for at least 5 minutes.
- 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 particle deposition techniques in a compact film is the set formed by the method of transferring a monofilm of compacted particles onto a moving carrier liquid, the Langmuir Biodgett technique, the Langmuir Shaefer technique, the surface vortical method, the flotation transfer technique, the dynamic and mobile thin laminar flow technique.
- the second family of deposition of particles in a compact film is the assembly formed by the electrophoretic deposition, the horizontal deposition by evaporation of a film, the deposition by evaporation of a bath, the deposition by vertical withdrawal of a submerged substrate and the horizontal deposition by forced removal of the contact line.
- the deposited masking beads are preferably in SiO 2, but may be of a different nature as long as the main parameters of the etching are respected.
- the dry etching process implemented in the fourth step 210 is, for example, an ionic reactive etching using a gaseous mixture of sulfur hexafluoride (SFe) and oxygen (O 2 ) in a ratio of / 3.
- gases capable of selectively etching the material with respect to the beads may also be used.
- the etching rate of the refractory material Vmat and the etching rate V by particles are greater than 50 nm per minute, and the etching selectivity Sg, defined as the ratio of the speed for etching the refractory material on the etching rate of the particles, is between 1 and 10.
- RIE reactive ion etching reactor
- a substrate temperature equal to 20 ° C.
- etch chemistries may be used, particularly fluorochemicals.
- FIG. 10 the various dry etching mechanisms used in the manufacturing processes of FIGS. 8 and 9 are described.
- the ions originating from the SF 6 plasma frontally attack the surface of the substrate, which is accessible through the passage interstices, in a non-selective and anisotropic manner. existing between the masking beads.
- the effectiveness of the attack is even higher than the access to the surface of the material through the carpet of balls is easy.
- the ion bombardment etching of the substrate surface can be accompanied by an etching of ion masking masking surface masking, erosion of the surface of the masking beads having an effect on the velocity of the masking balls. engraving.
- the first mechanism known as "ion bombardment" is at the origin of the modulating form at the micrometric scale of the microstructures.
- the species originating from the SFe 02 plasma chemically and selectively etch the joints present between the columnar structures of the molybdenum constituting the substrate.
- the second mechanism of "chemical etching” is at the origin of the second structure in needles or tubes at the nanoscale.
- a textured surface 372 with micrometric solid cone structures 374 is illustrated by a scanning microscope view.
- This textured surface 372 was obtained with one of the methods of FIGS. 8 and 9, adjusted in a particular manner, using beads 1 micron in diameter.
- FIGS. 8 and 9 makes it possible to obtain the double structures as those described in FIGS. 1 to 3, but it is also an industrial process for obtaining solid conical structures on molybdenum-type refractory materials.
- a first curve 402 represents the evolution of the reflectivity as a function of the exposure wavelength for a conventional unstructured surface.
- Second, third curves 404, 406 represent revolution of the reflectivity as a function of the exposure wavelength of textured surfaces according to solid conical structures as in FIG. 11 and obtained for two different, respectively equal, sizes of masking beads. at 1 micron and 540nm.
- a first curve 422 represents the evolution of the reflectivity as a function of the exposure wavelength for a conventional unstructured surface.
- a second curve 424 represents the evolution of the reflectivity as a function of the exposure wavelength of a textured surface according to the invention for a SF 6 / O 2 ratio of 5: 0 (pure SF 6 ). .
- Third and fourth curves 426, 428 represent the evolution of the reflectivity as a function of the exposure wavelength of textured surfaces according to solid conical structures as in FIG. 11 and obtained for two different sizes of masking beads, respectively equal to 1 micron and 540nm.
- the rejection wavelength that is to say the wavelength at which the reflectivity rises, depending on the conditions of the process and especially the size of the wavelengths. deposited particles.
- Figure 13 shows the adjustment of this wavelength between 900 and 1400nm.
- the surface structures of the invention described above may be covered with layers of materials such as Si0 2 or others to improve their optical performance by acting as anti-reflective layers, or their aging resistance.
- selective solar absorbers systems comprising selective absorbers of shapes, for example flat or cylindrical,
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Abstract
Description
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FR1450748A FR3016875B1 (fr) | 2014-01-30 | 2014-01-30 | Structure photonique de surface en materiau refractaire et son procede de realisation. |
PCT/IB2015/050615 WO2015114519A1 (fr) | 2014-01-30 | 2015-01-27 | Structure photonique de surface en materiau refractaire et son procede de realisation |
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FR3055706B1 (fr) * | 2016-09-05 | 2018-09-07 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Surface optique antireflet, structuree et a grande duree de vie, et son procede de realisation |
FR3075332B1 (fr) * | 2017-12-14 | 2020-04-03 | News | Absorbeur de rayonnements solaires, systeme et procede associe |
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KR100898470B1 (ko) * | 2004-12-03 | 2009-05-21 | 샤프 가부시키가이샤 | 반사 방지재, 광학 소자, 및 표시 장치 및 스탬퍼의 제조 방법 및 스탬퍼를 이용한 반사 방지재의 제조 방법 |
US20090020924A1 (en) * | 2007-02-21 | 2009-01-22 | Iowa State University Research Foundation, Inc. | Drying-mediated self-assembly of ordered or hierarchically ordered micro- and sub-micro scale structures and their uses as multifunctional materials |
US7846750B2 (en) | 2007-06-12 | 2010-12-07 | Guardian Industries Corp. | Textured rear electrode structure for use in photovoltaic device such as CIGS/CIS solar cell |
WO2010065635A2 (fr) * | 2008-12-02 | 2010-06-10 | Massachusetts Institute Of Technology | Structures coniques métalliques à sous-longueur d'onde comme absorbeur solaire sélectif |
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FR2948039B1 (fr) | 2009-07-17 | 2011-11-25 | Commissariat Energie Atomique | Procede pour la texturation de revetements type dlc, et revetements type dlc ainsi textures |
JP5465952B2 (ja) * | 2009-08-26 | 2014-04-09 | スタンレー電気株式会社 | 太陽熱集熱板、その製造方法及び太陽熱発電システム |
FR2954590B1 (fr) | 2009-12-23 | 2012-07-13 | Commissariat Energie Atomique | Procede de fabrication d'une electrode a nanostructures metallique et dielectrique pour le filtrage colore dans une oled et procede de fabrication d'une oled. |
WO2012057073A1 (fr) * | 2010-10-25 | 2012-05-03 | シャープ株式会社 | Organe collecteur de chaleur solaire et son procédé de fabrication |
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WO2015114519A1 (fr) | 2015-08-06 |
FR3016875A1 (fr) | 2015-07-31 |
FR3016875B1 (fr) | 2016-03-04 |
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