Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
  • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
  • B29C43/10—Isostatic pressing, i.e. using non-rigid pressure-exerting members against rigid parts or dies
  • B29C43/12—Isostatic pressing, i.e. using non-rigid pressure-exerting members against rigid parts or dies using bags surrounding the moulding material or using membranes contacting the moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
  • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
  • B29C35/0227—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using pressure vessels, e.g. autoclaves, vulcanising pans
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
  • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
  • B29C59/026—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing of layered or coated substantially flat surfaces
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
  • B29C43/32—Component parts, details or accessories; Auxiliary operations
  • B29C43/36—Moulds for making articles of definite length, i.e. discrete articles
  • B29C43/3642—Bags, bleeder sheets or cauls for isostatic pressing
  • B29C2043/3644—Vacuum bags; Details thereof, e.g. fixing or clamping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
  • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
  • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
  • B29C2059/023—Microembossing

Definitions

• the invention relates to a method of texturing a substrate of large area (of the order of at least m 2 ), based on the transfer of a micro-pattern (5 to 100 ⁇ ), meso- (1 5 ⁇ ) and / or nanoscopic (10 to 1000 nm) of a buffer (or mask) in a layer deposited on the surface of the substrate. (Nanoimprint lithography -NIL-, nanoimprint or embossing).
• Different methods can be used to transmit fluid pressure to the buffer and / or substrate. It may be a pressure vessel, a flexible membrane retranscribing the pressure of the fluid or pressurized fluid streams through openings disposed along the contact surface.
• the inventors have set themselves the goal of providing a method compatible with the glass industry and making it possible to achieve a perfectly regular texturing in depth, in patterns of a few tens to a few hundred nanometers for example, on a substrate of big surface.
• the invention which, accordingly, relates to a method of forming a texturing on a substrate, characterized in that it comprises the deposition of a deformable layer on the substrate,
• the texturing formed according to the invention is of dimensions between 10 nm and 100 ⁇ (depth of the valleys, height of the growths, width / diameter of the growths, width of the valleys ...), or even up to values of several centimeters: "Wall" of 10 ⁇ X 10 ⁇ X 4 cm.
• the texturing is capable of being formed, by this method, on surfaces of the order of at least one square meter, up to the dimensions of the glass sheet called Full Width Float (PLF), that is to say 3m X 6m in particular.
• PPF Full Width Float
• Deposition processes of the deformable layer on the substrate are not limited.
• a liquid deposit is used (laminar coating, spraying - spray-coating, tempering -dip-coating, and spin coating -spin coating).
• laminar coating the liquid precursors of the deformable layer form, at rest, a meniscus suspended from a slot from which they are extracted by displacement of this slot in a transverse position above the substrate.
• the girl pad is so called because it results from the molding of its material compared to a master. Its textured material can be polymer.
• the material of the pocket is non-permeable to air.
• the air of the chamber is discharged to a pressure at most equal to 0.5 bar or, in order of increasing preference, at 5 mbar, 2 mbar and 1 mbar.
• the air in the chamber is evacuated for fifteen minutes until a pressure of the order of 0.5 mbar is reached.
• the pouch is hermetically sealed before reintroducing the air into the enclosure.
• the sealed pouch is then placed in an autoclave which will make it possible to apply a pressure of between 0.5 and 8 bar and a temperature of between 25 and 400 ° C.
• the treatment in the autoclave can be between 15 minutes and several hours. These parameters must be adjusted according to the nature of the deformable layer.
• the objective here is to press the daughter pad against the initially deformable layer, sol-gel or other, while reticulating to make it indeformable. In this way, we print and freeze the pattern inscribed on the surface of the daughter pad in the layer deposited on the surface of the substrate. step Air sealing and evacuation is required to allow the transmission of fluid pressure to the buffer.
• the bag is pierced before it is opened and the daughter pad is removed from the surface of the substrate.
• the layer can then be subjected to a new heat treatment to densify, crystallize ( ⁇ 2 , ZnO) and improve its mechanical properties and / or to play on the hydrophilic / hydrophobic nature of its surface.
• the method of the invention does not require specific equipment (a bagging system and an autoclave). It is compatible with the devices commonly used in the glass industry, particularly for the lamination of windshields or for the manufacture of technical glazing such as laminated incorporating a liquid crystal film, of the type marketed by Saint-Gobain Glass under the registered trademark Privalite®.
• the method is compatible with the use of low cost buffers such as textured polymer sheets (produced by roll-to-roll in particular). Since the buffer is not destroyed during the process, it can be reused several times.
• the deformable layer is made of a thermally crosslinkable material, in particular a sol-gel material; having the advantage of leading to layers of high inorganic content that can withstand a quenching process of a glass sheet (constituting the substrate); mention may be made of silica, titanium oxide, zinc oxide or aluminum oxide, alone or as a mixture of several of them; a silica sol is advantageously obtained by hydrolysis of a sol-gel precursor, preferably methylethoxysilane; it is important to control the conditions of preparation of the sol-gel solution so that the layer remains deformable during the process; the deformable layer has a thermoplastic polymer matrix; mention may be made of poly (methyl methacrylate) (PMMA), polystyrene (PS), polycarbonate (PC), polyvinyl chloride (PVC), polyamide (PA), polyethylene (PE), polypropylene (PP), alone or in mixtures or copolymers of several of them;
• PMMA methyl methacrylate
• PS polys
• the precursors of the deformable layer comprise nanoparticles such as ⁇ 2 (in particular photocatalytic) or luminescent nanoparticles, for example CdSe, CdS, and / or organic and / or porogenic molecules of the latex type PMMA, PS, surfactant which, for certain d between them, are possibly intended to be eliminated before the final layer is produced; mention may be made of the incorporation of an inorganic component (nanoparticles) into a thermoplastic polymer matrix, to improve its thermal and mechanical resistance (impact resistance for example), or to adjust the optical properties of the textured layer or to provide it with a function;
• the textured face of the daughter pad is permeable to the air; contacting during the sealing step then requires no particular precaution to avoid the trapping of air bubbles between the coated substrate and the buffer; it may consist of an elastomeric polymer (PDMS, EVA, epoxy type) or glassy polymer or a copolymer;
• PDMS elastomeric polymer
• EVA epoxy type
• the textured face of the daughter pad is made of polymer or organic (polymer) -inorganic hybrid material, and the temperature in the autoclave is successively brought to a higher temperature, then lower than the glass transition temperature of this polymer material, or conversely ;
• the invention also aims to:
• a transparent assembly comprising a glass substrate coated with a textured layer, obtained by a process described above; the glass is in particular mineral, such as silicosodocalcique, float; -
• An application of a method described above, to obtain a substrate for the extraction, guiding or redirection of light for example, the fields of photovoltaics, daylighting (redirection of sunlight to the ceiling of a room by the appropriate texturing of a glazing), light extraction for OLED, polarizers;
• a superhydrophobic substrate is in particular feasible by covering the textured layer with a sol-gel overlay, for example consisting of a hydrophobic agent such as fluorinated silane, especially from known perfluoroalkylalkyl-trialkoxysilane precursors; the overlayer is advantageously very thin, of a thickness not exceeding a few nanometers - it is then sometimes referred to as monomolecular qualifier, thus not substantially modifying the geometry of the underlying texturing.
• a sol-gel overlay for example consisting of a hydrophobic agent such as fluorinated silane, especially from known perfluoroalkylalkyl-trialkoxysilane precursors
• the overlayer is advantageously very thin, of a thickness not exceeding a few nanometers - it is then sometimes referred to as monomolecular qualifier, thus not substantially modifying the geometry of the underlying texturing.
• Figure 1 shows a scanning electron microscope image showing the texture of the PET daughter plug used in Example 1 below.
• Figures 2a and b show scanning electron microscopy images of the embossed sample obtained in Example 1 below views, with respect to the embossed surface, from above (a) and in cross section (b).
• EXAMPLE 1 Transfer of a periodic network of micron-spherical half-spheres in a sol-gel silica layer.
• a silica sol is prepared from a methyltriethoxysilane mixture (marketed by Sigma Aldrich) / Acetic Acid (Prolabo) in a 45/55 mass ratio. The solution is stirred at room temperature for 12 hours.
• a PDMS buffer is produced by molding a periodic array of half-spheres obtained by an interferential lithography process. The diameter of the half-spheres is 3 ⁇ , the period is 5.5 ⁇ . The molding is carried out by casting a 10: 1 mixture of the two components (elastomer: catalyst) of SYLGARD® 184 SILICONE ELASTOMER KIT sold by Dow Corning by evacuating the residual air bubbles under vacuum and then crosslinking the elastomer at 80 ° C. for 4 hours.
• the sol is deposited by spin coating (2000 rpm, 1 min) on a 2 mm glass substrate of 10 ⁇ 10 cm 2 , marketed by Saint-Gobain Glass under the registered trademark Planilux®, the surface of which has been previously cleaned. by a Cerox® polishing.
• the layer is dried for 5 minutes at 50 ° C.
• the textured face of the PDMS buffer is contacted with the sol-gel silica layer.
• the samples are placed in a sealing bag and installed in a hermetic enclosure which is evacuated until a vacuum of 0.5 mbar is reached. At the end of the 20 minutes the pouch is sealed by heat sealing.
• the samples are then placed in the autoclave in which they simultaneously undergo a temperature rise up to 110.degree. C. and pressure up to 1.75 bar (5 min at 20.degree. C., raised to 60.degree. min, plateau at 60 ° C for 10 min, rise to 1 10 ° C in 5 min, plateau at 1 10 ° C for 20 min and drop to 35 ° C in 15 min, rise from 0 to 1, 75 bar in 5 min min, bearing at 1.75 bar for 40 min, down to 0 bar in 15 min).
• the samples are demolded cold.
• the transfer of the pattern into the sol-gel silica layer is characterized by
• EXAMPLE 2 Transfer of a periodic network of micron-spherical half-spheres in a layer of poly (methyl methacrylate).
• a PDMS buffer is produced by molding a periodic array of half-spheres obtained by an interferential lithography process.
• the diameter of the half-spheres is 3 ⁇ , the period is 5.5 ⁇ .
• the molding is carried out by casting a 10: 1 mixture of the two components (elastomer: catalyst) of SYLGARD® 184 SILICONE ELASTOMER KIT sold by Dow Corning by evacuating the residual air bubbles under vacuum and then crosslinking the elastomer at 80 ° C. for 4 hours.
• the PMMA solution is deposited by spin coating (2000 rpm, 1 min) on a 2 mm glass substrate 10 ⁇ 10 cm 2 marketed by Saint-Gobain Glass under the registered trademark Planilux®, the surface of which has been previously cleaned by Cerox® polishing.
• the textured face of the PDMS buffer is brought into contact with the PMMA layer.
• the samples are placed in a sealing bag and installed in a sealed chamber which is evacuated until a vacuum of 0.5mbar is reached. When the desired vacuum is reached, the bag is sealed by heat sealing.
• the samples are then placed in the autoclave in which they undergo an increase in pressure and temperature (5 min stage at 20 ° C, rise to 168 ° C in 10 min, 15 min plateau to 168 ° C and descent to 40 ° C in 30 min, rise from 0 to 1 bar in 5 min, 10 min to 1 bar, rise to 3 bar in 5 min, 30 min to 3 bar, down to 0 bar in 10 min).
• the pattern transfer in the PMMA layer is characterized by AFM. We find the hexagonal network of half-spheres. The patterns obtained are similar to those carried by the buffer: 3 ⁇ width, 1, 5 ⁇ height and a period of 5.5 ⁇ .
• EXAMPLE 3 Transfer of a periodic network of micron-spherical half-spheres in a poly (methyl methacrylate) -SiO2 hybrid layer.
• a suspension of silica nanoparticles (Nissan Chemical) in the MEK is added to the PMMA solution at a level of 20% by weight. The mixture is homogenized by magnetic stirring for 10 minutes.
• a PDMS buffer is produced by molding a periodic array of half-spheres obtained by an interferential lithography process. The diameter of the half-spheres is 3 ⁇ , the period is 5.5 ⁇ .
• the molding is carried out by casting a 10: 1 mixture of the two components (elastomer: catalyst) of SYLGARD® 184 SILICONE ELASTOMER KIT sold by Dow Corning by evacuating the residual air bubbles under vacuum and then crosslinking the elastomer at 80 ° C. for 4 hours.
• the solution of silica and PMMA particles is deposited by spin coating (2000 rpm, 1 min) on a 2 mm glass substrate 10 ⁇ 10 cm 2 marketed by Saint-Gobain Glass under the registered trademark Planilux®, whose surface has been previously cleaned by Cerox® polishing.
• the textured face of the PDMS buffer is brought into contact with the PMMA-S102 hybrid layer.
• the samples are placed in a sealing bag and installed in a sealed chamber which is evacuated until a vacuum of 0.5 is reached. mbar. When the desired vacuum is reached, the bag is sealed by heat sealing.
• the samples are then placed in the autoclave in which they undergo an increase in pressure and temperature (5 min stage at 20 ° C, rise to 168 ° C in 10 min, 15 min plateau at 168 ° C, descent to 40 ° C in 30 min, rise from 0 to 1 bar in 5 min, 10 min to 1 bar, rise to 3 bar in 5 min, 30 min to 3 bar and down to 0 bar in 10 min).
• the pattern transfer in the PMMA layer is characterized by AFM. We find the hexagonal network of half-spheres. The patterns obtained are similar to those carried by the stamp: 3 ⁇ width, 1, 5 ⁇ height and a period of 5 ⁇ m.
• EXAMPLE 4 Transfer of a semi-periodic network of nanometric spots in a sol-gel silica layer.
• a PDMS buffer is produced by molding a pseudo periodic array of studs obtained by an electronic lithography method coupled to a "step and repeat" method. The pads have a length of 1 .2 ⁇ , a width of 200 nm or 400 nm and a height of 350 nm.
• the molding is carried out by casting a 10: 1 mixture of the two components (elastomer: catalyst) of SYLGARD® 184 SILICONE ELASTOMER KIT sold by Dow Corning by evacuating the residual air bubbles under vacuum and then crosslinking the elastomer at 80 ° C. for 4 hours.
• the silica sol is deposited by spin coating (2000 rpm, 1 min) on a 2 mm glass substrate 10 ⁇ 10 cm 2 marketed by Saint-Gobain Glass under the registered trademark Planilux®, the surface of which has been previously cleaned by Cerox® polishing. The layer is dried for 5 minutes at 50 ° C.
• the textured face of the PDMS buffer is contacted with the sol-gel silica layer.
• the samples are placed in a sealing bag and installed in a hermetic enclosure which is evacuated until a vacuum of 0.5 mbar is reached. When the desired vacuum is reached, the bag is sealed by heat sealing.
• the samples are then placed in the autoclave in which they undergo a cycle of pressure and temperature rise (20 to 60 ° C rise in 5 min, 5 min plateau at 60 ° C, rise to 130 ° C in 5 minutes). min, stage of 25 min at 130 ° C, descent to 40 ° C in 20 min, rise from 0 to 2.5 bar in 5 min, 35 min stage at 2.5 bar, descent to 0 bar in 20 min) .
• the transfer of the pattern into the sol-gel silica layer is characterized by AFM.
• the patterns obtained are similar to those carried by the buffer. Plots of 200 nm and 400 nm in width are found, the length is 1 .2 ⁇ and the height of 350 nm.
• Example 5 Transfer of a semi-periodic network of lines in a silica layer from a PET buffer.
• the used dams are PET polymer films on which a coating has been deposited and then textured by roll-to-roll.
• the polymer films have a size of about 10 x 10 cm 2 ( Figure 1).
• the motive of these films was determined with the aim of giving them a "day ligthing" property while retaining the transparency of the PET.
• the surface of the PET film is thoroughly cleaned with alcohol and using sticky rollers (marketed by Teknek) to remove all traces of dust.
• the silica sol is deposited by spin-coating (2000 rpm, 1 min) on a 2 mm glass substrate 10 ⁇ 10 cm 2 marketed by Saint-Gobain Glass under the registered trademark Planilux®, the surface of which has been previously cleaned. by a Cerox® polishing. The layer is dried for 5 minutes at 50 ° C.
• the textured face of the PET pad is contacted with the sol-gel silica layer.
• the samples are placed in a sealing bag and installed in a sealed chamber which is evacuated until a vacuum of 0.5mbar is reached. When the desired vacuum is reached, the bag is sealed by heat sealing.
• the samples are then placed in the autoclave in which they undergo a cycle of rise in pressure and temperature (rise of 20 to 60 ° C in 5 min, step 5 min at 60 ° C, raised to 1 10 ° C in 5 min, level of 25 min at 1 10 ° C, descent to 40 ° C in 20 min; rise from 0 to 2 bar in 5 min, step of 35 min to 2 bar, descent to 0 bar in 20 min).
• the transfer of the pattern into the sol-gel silica layer is characterized by scanning electron microscopy. We find the network of pseudo-periodic lines with a period of 400 nm. The patterns obtained are similar to those carried by the buffer: 200 nm wide and 400 nm high.

Landscapes

• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Nanotechnology (AREA)
• Mechanical Engineering (AREA)
• Crystallography & Structural Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Health & Medical Sciences (AREA)
• Mathematical Physics (AREA)
• Theoretical Computer Science (AREA)
• Shaping Of Tube Ends By Bending Or Straightening (AREA)
• Casting Or Compression Moulding Of Plastics Or The Like (AREA)
• Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
• Surface Treatment Of Glass (AREA)
• Laminated Bodies (AREA)
• Application Of Or Painting With Fluid Materials (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Publications (1)

Family

ID=48577122

Family Applications (1)

Country Status (9)

Cited By (1)

Families Citing this family (8)

Citations (6)

Family Cites Families (9)

• 2012
  • 2012-05-14 FR FR1254373A patent/FR2990384B1/fr active Active
• 2013
  • 2013-05-14 US US14/401,363 patent/US9296132B2/en not_active Expired - Fee Related
  • 2013-05-14 WO PCT/FR2013/051048 patent/WO2013171420A1/fr not_active Ceased
  • 2013-05-14 EA EA201492087A patent/EA201492087A1/ru unknown
  • 2013-05-14 IN IN2198MUN2014 patent/IN2014MN02198A/en unknown
  • 2013-05-14 KR KR20147031601A patent/KR20150010726A/ko not_active Withdrawn
  • 2013-05-14 JP JP2015512106A patent/JP6141969B2/ja not_active Expired - Fee Related
  • 2013-05-14 CN CN201380024814.2A patent/CN104272187A/zh active Pending
  • 2013-05-14 EP EP13727285.2A patent/EP2850493A1/fr not_active Withdrawn

Patent Citations (6)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events