Method for producing a substrate by spraying particles onto a compact film of solid particles on a carrier liquid
10357799 ยท 2019-07-23
Assignee
Inventors
- Olivier DELLEA (La Talaudiere, FR)
- Philippe Coronel (Barraux, FR)
- Nicolas Dreuilles (Aussonne, FR)
- Pascal Fugier (Bernin, FR)
Cpc classification
B05D2451/00
PERFORMING OPERATIONS; TRANSPORTING
B05D2401/40
PERFORMING OPERATIONS; TRANSPORTING
B05D2451/00
PERFORMING OPERATIONS; TRANSPORTING
B05D1/20
PERFORMING OPERATIONS; TRANSPORTING
B05D2401/40
PERFORMING OPERATIONS; TRANSPORTING
International classification
B05D1/00
PERFORMING OPERATIONS; TRANSPORTING
B05D1/20
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A method for producing an assembly of particles bound by a substrate, including: making a compact film of solid particles floating on a carrier liquid, the solid particles potentially holding objects between them; spraying particles onto a face of the compact film opposite to the one immersed in a carrier liquid, to create a substrate-forming-skin adhering to the solid particles; and extracting an obtained assembly outside the carrier liquid.
Claims
1. A method for producing an assembly of particles, comprising: making a compact film of solid particles floating on a surface of a carrier liquid; spraying particles onto a first face of the compact film which is opposite to a second face of the compact film which is immersed in the surface of said carrier liquid, to create a substrate-forming skin adhering to the solid particles; and extracting the assembly of particles from said carrier liquid, the assembly of particles comprising a substrate provided by said substrate-forming skin, and said compact film of solid particles bound by said substrate, wherein the carrier liquid is located in a transfer area comprising an inlet of said solid particles and an outlet of solid particles, wherein the transfer area is continuously supplied with said solid particles through the inlet, and the extracting the assembly of particles, comprising the substrate provided by the substrate-forming skin and the compact film of solid particles bound by the substrate, is continuously performed through the outlet.
2. The method according to claim 1, wherein the spraying the particles is performed by vaporization of a liquid or by nebulization.
3. The method according to claim 1, wherein the particles sprayed during the spraying comprise polymerizable monomers.
4. The method according to claim 1, wherein the particles sprayed during the spraying comprise photopolymerizable monomers.
5. The method according to claim 1, wherein the making the compact film of solid particles on the carrier liquid is implemented by making said solid particles build up on a stop placed at the outlet of the transfer area.
6. The method according to claim 5, wherein the stop is a roller and the extracting comprises extracting the assembly of particles through the outlet of the transfer area by rotating the roller.
7. The method according to claim 1, further comprising implementing a tilted ramp for circulating said solid particles, connected to the inlet of the transfer area, and on which the carrier liquid circulates.
8. The method according to claim 1, wherein the spraying the particles is performed to obtain the substrate-forming skin having a plurality of areas with different characteristics.
9. The method according to claim 8, wherein the different areas of the substrate have different compositions.
10. The method according to claim 8, wherein the different areas of the substrate are obtained using one or more masks.
11. The method according to claim 1, wherein the substrate-forming skin is made from a composition comprising a polymerizable, photo-crosslinkable compound.
12. The method according to claim 1, wherein the substrate-forming skin is made from a composition comprising acrylonitrile.
13. The method according to claim 1, wherein the compact film of solid particles holds at least one object selected from among silicon chips, micro-batteries, components of organic electronics, metal elements, photovoltaic cells, cells, and micro-cells.
14. The method according to claim 1, wherein the substrate-forming skin is made to have an average thickness between 1 and 100 m.
15. A method for producing a device from at least two assemblies, each assembly being obtained by implementing a method according to claim 1, both assemblies being then superimposed.
16. The method according to claim 15, wherein the device is obtained from at least a first assembly and a second assembly superimposed and arranged in contact with each other, so that the first assembly comprises a substrate arranged between the compact film of solid particles of the first assembly and the compact film of solid particles of the second assembly, and so that the substrate comprises an electrically conductive area providing an electrical connection between electrically conductive parts of the compact films of solid particles of the first assembly and the second assembly.
17. The method according to claim 15, further comprising producing an optoelectronic device.
18. The method according to claim 1, wherein an average thickness of the substrate-forming skin corresponds to 50% to 99% of an average thickness of the assembly including the substrate and the film of solid particles bound by the substrate.
Description
(1) This description will be made with regards to the appended drawings among which:
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(11) With reference first to
(12) The facility 1 includes a device 2 for dispensing particles 4, the size of which can be between a few nanometers and several hundreds of micrometers. The solid particles, having preferably a spherical shape, can for example be silica particles. Other particles of interest can be made of metal or metal oxide such as Platinum, TiO.sub.2, of a polymer such as polystyrene or PMMA, or carbon, etc. As discussed above, the fibres also have a definite interest. To these examples can also be added the Janus-type particles, with two faces of distinct natures, and core-shell-type particles.
(13) More precisely, in the preferred embodiment, the particles are silica spheres with a diameter of about 1 m, stored in a solution in the dispensing device 2. The medium proportion is about 7 g of particles for 200 ml of solution, here butanol. Of course, for the sake of clarity, the particles represented in the figures assume a diameter greater than their real diameter.
(14) The dispensing device 2 has a controllable injection nozzle 6 with a diameter of about 500 m.
(15) The facility also includes a liquid conveyor 10, integrating a tilted ramp 12 for circulating the particles, and a substantially horizontal transfer area 14, or even having a slight tilting so as to promote the discharge of the facility when necessary. The top end of the tilted ramp is provided to receive the particles injected from the dispensing device 2. This ramp is straight, titled by an angle between 5 and 60, preferably between 10 and 30, enabling particles to be conveyed towards the transfer area 14. Moreover, a carrier liquid 16 circulates on this ramp 12, up to the transfer area. This liquid 16 can besides be recirculated using one or two pumps 18, between the transfer area 14 and the top end of the ramp. It is here preferably deionized water, on which the particles 4 can float. However, a new liquid can be favoured via an open circulation circuit. It can also be an association of several non-miscible liquids.
(16) The bottom end of this same ramp is connected to an inlet of the particle transfer area 14. This inlet 22 is located at an inflection line 24 marking the junction between the surface of the carrier liquid present on the tilting plane of the ramp 12, and the surface of the carrier liquid present on the horizontal part of the transfer area 14.
(17) The particle inlet 22 is spaced out from a particle outlet 26 using two side rims 28 retaining the carrier liquid 16 in the area 14. These rims 28, facing each other and at a distance from each other, extend parallel to a main flowing direction of the carrier liquid and of the particles in the facility, this direction being schematized by the arrow 30 in
(18) The bottom of the downstream part of the transfer area has a plate slightly tilted upstream with respect to the horizontal direction, for example by a value in the order of 5 to 10. It is the downstream end of this same plate 27, also referred to as a blade, which partly defines the particle outlet 26.
(19) The facility 1 is also provided with a stop 40 on which the solid particles are intended to build up to create their ordering. This stop preferably takes the shape of a roller 40 located at the particle outlet 26 of the transfer area 14. The axis 41 of the roller 40 is parallel to the outlet 26 of the area 14, near which this roller is located. Indeed, as detailed thereafter, the obtained assembly reaching the outlet 26 is provided to be easily transferred onto this roller 40, via a capillary bridge 42, also referred to as a meniscus, which connects it to the carrier liquid 16. Alternatively, the roller can be in direct contact with the transfer area, without departing from the scope of the invention. The above-mentioned capillary bridge is then no longer required.
(20) Here, the roller 40 can be freely rotating about its axis 41, or, more preferably, its rotation is restrained by an engine so as to avoid any risk of this roller rotating in the direction opposite to the normal direction for making the film.
(21) In the example shown in the figures, the width of the roller 40 corresponds to the width of the area 14 and of its outlet 26. It is a width L1 which also corresponds to the width of the film of solid particles intended to be obtained.
(22) Furthermore, at a downstream part of the transfer area 14, the facility comprises means 43 for vaporizing a liquid, the objective being to spray particles onto the obtained compact film before extraction outside the transfer area. To provide this vaporization of liquid, the means 43 can take the shape of a spray, also referred to as an aerosol spray, the objective of which is to ensure a spraying of fine droplets. Alternatively, projecting particles can be performed by nebulization, using means 43 then taking the shape of a nebulizer generally corresponding to an apparatus enabling a liquid to be transformed into a cloud of extremely fine particles (from a few micrometers to a few tens of micrometers), this cloud being also referred to as mist. This nebulization technique is also referred to as an atomization technique.
(23) A method for producing an assembly according to an embodiment will now be described with reference to
(24) First, the injection nozzle 6 is activated to start dispensing particles 4 onto the ramp 12. It consists in implementing an initial step of filling the transfer area 14, by the particles 4, with the carrier liquid 16 already at the level required in the area 14.
(25) During this initiating phase, the particles dispensed by the device 2 circulate on the ramp 12, and penetrate the area 14 in which they disperse, as schematized in
(26) As the particles 4 are injected on the ramp 12 and penetrate the transfer area 14, they abut against the roller 40 which remains static at this point, then the upstream front of these particles tends to shift upstream, in the direction of the inflection line 24. The injection of particles is continued even after this upstream front has exceeded the line 24, so that it raises on the tilted ramp 12.
(27) Indeed, it is provided that the upstream front of particles 54 raises on the ramp 12 so as to be located at a given horizontal distance d from the inflection line 24, as shown in
(28) At this moment, the solid particles 4 are ordered in the transfer area and on the ramp 12, on which they are automatically ordered, without any help, thanks in particular to their kinetic energy and to the capillary forces used at the time of the impact on the front 54. The ordering is such that the obtained compact film has a so-called hexagonal compact structure, in which each particle 4 is surrounded and contacted by six other particles 4 in contact with each other. It is then indifferently referred to as a compact film of particles, or a film of ordered particles.
(29) Once the ordered particles 4 forming the film cover the entire carrier liquid located in the transfer area 14, a step of spraying liquid particles onto the film is performed, using the spray 43. More precisely, as shown in
(30) This skin is made from a composition comprising a polymerizable, preferably photo-crosslinkable component, such as acrylonitrile in order to obtain a substrate material from the family of acrylics. Consequently, even if they are not represented, the facility comprises means for polymerizing the vaporized substance.
(31) Spraying is performed such that the sprayed particles remain on the face of the film located on the open air.
(32) This spraying technique makes it possible in particular to avoid the risks of destructuring the compact film, especially with respect to the solutions of prior art implementing a running outer substrate.
(33) In the described embodiment, the inlet 22 of the area 14 is continuously supplied with solid particles 4, whereas the extraction of the obtained assembly 50 downstream the spray 43 is also continuously performed through the outlet 26. Consequently, forming the skin 38 is performed upon the compact film passing under the spray 43, this film being preferably totally polymerized before extracting the assembly 50 outside the carrier liquid.
(34) In this respect, as schematized in
(35) During the running of the compact film in the transfer area, the injection of solid particles and the pulling speed of the assembly 50 are adjusted so that the front of particles remains in a substantially identical position. To do so, the flow rate of solid particles 4 can be in the order of 0.1 ml/min to several ml/min, whereas the linear speed of the assembly 50, also referred to as the pulling speed, can be in the order of a few mm/min to several hundreds of mm/min. As will be mentioned below, the supply with particles 4 can be temporarily stopped during the creation of patterns, or kept constant.
(36) Thus, the feature of the invention is to form the substrate whereas the film of ordered particles 4 is still located on the carrier liquid. This spraying technique enables low thicknesses of substrate to be obtained, while providing the adhesion to particles 4. As is schematized in
(37) To further broaden the spectrum of applications that can be considered, it is possible to create a compact film with different solid particles 4 in terms of dimensions and/or materials.
(38) For example, to obtain a heterogeneous film, dispensing particles of different natures in turn, which end up in the film with an order corresponding to the one in which they have been dispensed is enough. It is also possible to alternate between electrically insulated, electrically conductive, etc. solid particles 4.
(39) Another possibility consists in intervening directly within the compact film. By way of indicating example, as schematized in
(40) Depositing the polymerizable substance is performed for example using a dispensing nozzle or an ink-jet head (not shown). This distance as well as the other operations specific to this structuration of the film can be performed by stopping the advancement of the film as well as the dispense of particles 4.
(41) Upon contacting the particles, the substance 72 is able to adapt to the topography of the ordered film, and adheres to the particles 4 it covers. The polymerizable compound is for example a silicone resin, an epoxy resin, and/or a polyurethane resin. Polymerization is conventionally performed, for example thermally and/or optically, and occurs when the substance is still in the transfer area, before passing through the spray 43.
(42) The substance 72 is then as a liquid or a slurry, to which additives can possibly be added before its dispense.
(43) The substance 72, after being deposited on the film, adheres to the latter due to its composition.
(44) The following step (not shown) consists in moving the particles 4 surrounded by the patterns 70, and in placing in the recessed areas solid particles of different natures. Objects can also be placed in these recessed areas, without departing from the scope of the invention.
(45) Then, the structured film 4 passes under the spray 43 in order to be totally covered by the substrate 38.
(46) Incidentally, it is noted that the step of spraying particles can also be controlled so as to obtain a substrate-forming skin 38 having a plurality of areas of different characteristics, preferably to adapt to the solid particles 4 of the film which also have different natures.
(47) These areas have preferably different compositions as a function of the encountered needs. Other parameters can nevertheless evolve, such as the average thickness, the flexibility, the transparency, etc.
(48) Forming several areas is for example performed by spraying liquid particles having different compositions.
(49) Of course, these sprayings can be performed using one or more sprays, alternately or simultaneously, and with the compact film being stopped or running on the carrier liquid.
(50) As discussed above, differentiating areas within the substrate 38 is particularly interesting for producing a device 62 from at least two assemblies 50, each being obtained by implementing the method which has just being described, these two assemblies or more being superimposed after having been extracted from their respective transfer areas.
(51) An exemplary embodiment is shown in
(52) Consequently, the substrate 38 of the first assembly 50, the one under in the stacking, is interposed between the film of particles of the first assembly and the film of particles of the second assembly. This is in fact this substrate 38 which enables the adhesion between both superimposed assemblies 50 to be obtained.
(53) Moreover, appropriate connections can thus be made between both films 4, since the substrates become an integral part of the thus created devices 62.
(54) With this respect, it is noted that this aspect is also interesting to connect objects integrated into two directly consecutive assemblies. Thus, the invention provides the possibility to form compact films with particles holding objects between them, as will be described below.
(55) An exemplary embodiment is shown in
(56) More precisely, the depressed particles 4 located under each object 80 then define a break of level 82 with the other surrounding particles 4. Then these same surrounding particles sandwich the periphery of each object 80, thus making it possible to hold them in position with respect to each other, as well as with respect to the fixed structure of the transfer area.
(57) Each break of level 82 is preferably lower than the diameter of the particles 4, such that the depressed particles 4 are also kept and held by the surrounding particles. Nevertheless, when so-called heavy objects are put on the film, the surface of the liquid can be significantly deformed in a proportion equivalent to or even greater than the diameter of the particles. The most important thing is that the put object does not create a too significant discontinuity likely to lead to the tearing of the film of particles.
(58) Positioning the first objects, as well as the following objects, is preferably performed without stopping the stream of particles coming from the ramp 12, although it could be otherwise, without departing from the scope of the invention.
(59) The film 4 provided with the objects 80 then passes under the spray 43 so that the entirety is coated by the substrate 38.
(60) According to an alternative embodiment illustrated in
(61) It is indicated that several solutions are possible for depositing the objects 80. Among the preferred solutions, there is a solution consisting in providing one or more conveyors to convey these objects towards the transfer area.
(62) Each conveyor 67 is preferably parallel to the ramp 12, as shown in
(63) Incidentally, with this technique, it is not only possible to deposit the objects 80 on the film of particles 4 as shown in
(64) Whatever the chosen deposition technique, each object preferably has a large dimension greater than 0.2 cm and equal to or lower than L1, that is close to 30 cm. The thickness is between about a ten of micrometers and several tens of millimeters.
(65) Certain types of objects such as solar cells, micro-batteries and organic components have a simple square, rectangle or even disk shape, with a low thickness, and a surface area in the order of 0.1 to 100 cm.sup.2.
(66) These components can include pads or pins on the face in contact with the liquid or on the opposite face receiving the substrate, to connect them. Other types of objects, aiming for example for detecting elements, generating energy or even information transport, can have complex shapes, for example bent or helical parts.
(67) Besides, the ratio of the large dimension of the particles 4 to one of objects 80 accommodated in the film 4 is preferably between 10.sup.4 and 10.sup.8. Indeed, the large dimension of the particles is for example in the order of 1 nm to 500 m, whereas the objects can have a large dimension up to about 30 cm.
(68) The table below lists a few preferred examples for these objects.
(69) TABLE-US-00001 Field of Nature Dimensions application Polyethylene terephthalate PET: 3 4 cm.sup.2; thickness 250 m; PET: Organic (PET) with a structured gold 1.5 0.9 cm.sup.2; thickness 250 m, electronic layer at the surface Au: thickness 30 nm Glass with a photovoltaic 25 25 mm.sup.2; thickness 1.08 mm Photovoltaic cell at the surface cell Silicon chip 3 3 cm.sup.2; thickness 500 m Electronic 1 1 cm.sup.2; thickness 500 m Micro-battery on silicon 1 1 cm.sup.2; thickness 500 m Energy storage Bimetal material (e.g.: 3.5 2 cm.sup.2; thickness 140 m Thermal, zinc/copper) 5 1.6 cm.sup.2; thickness 200 m sensors 7 1.6 cm.sup.2; thickness 200 m
(70) Possible applications for the method which has just been described have been mentioned above.
(71) A particular exemplary production of an opto-electronic device 62 will now be described with reference to
(72) It is made by stacking three assemblies 50 each built according to the method specific to the present invention. The assemblies 50 are then superimposed as is shown in the right part in
(73) The three assemblies are respectively referred to as the upper assembly, the intermediate assembly and the lower assembly.
(74) The lower assembly 50 comprises a compact film of solid particles 4 which is structured in several ways. First, it comprises ordered solid particles 4 of different compositions, since clear beads 4 are electrically insulating whereas the slightly grey tinted beads are made of a different material, preferably metallic. Furthermore, the structuration of this film also comes from its integration of an object 80d, which is a photovoltaic cell surrounded by particles 4. This cell 80d has bonding pads directed upwards, and an opposite face directed downwards intended to constitute part of the outer surface of the final device 62.
(75) The substrate 38 of this lower assembly 50 also has differentiated areas. The clearest, referenced 38a, are of an electrically insulating material, and the darkest, referenced 38c and coating the pads 84 of the cell 80d, are electrically conductive. The intermediate grey tinted area 38b, covering the metal beads 4, is transparent to light.
(76) The intermediate assembly 50 comprises a compact film of solid particles 4 which is also structured in several ways. First, it comprises ordered solid particles 4 of different compositions, since the clear beads 4 are electrically insulating whereas the grey tinted beads are made of a different material, which is electrically conductive. Furthermore, the structuration of this film also comes from its integration of an object 80c, which is a photodiode surrounded by particles 4. This photodiode 80c has bonding pads 84 directed upwards, and an opposite face directed downwards intended to contact the light transparent area 38b of the substrate of the lower assembly. Similarly, the electrically conductive beads 4 are intended to contact the areas 38c covering the pads 84 of the photovoltaic cell 80d.
(77) The substrate 38 of this intermediate assembly 50 also has differentiated areas. The clearest, referenced 38a, are made of an electrically insulating material, and the darkest, referenced 38b and covering the pads 84 of the photodiode 80c as well as the conductive beads 4, are electrically conductive.
(78) The upper assembly 50 comprises a compact film of solid particles 4 which is also structured in several ways. First, it comprises ordered solid particles 4 of different compositions, since the clear beads 4 are electrically insulating whereas the grey tinted beads are made of a different material, which is electrically conductive. Furthermore, the structuration of this film also comes from its integration of two objects 80a, 80b.
(79) The object 80a is a logic chip which is surrounded by particles 4. This chip 80a has bonding pads 84 directed upwards and downwards, the latter being intended to be in contact with the conductive areas 38b covering the pads 84 of the photodiodes 80c. The object 80b is a micro-battery lying on beads, in particular with its lower pads 84 lying on conductive beads of this upper assembly 50. In this respect, these electrically conductive beads 4 are intended to contact the areas 38b covering the conductive beads of the intermediate assembly 50.
(80) The substrate 38 of this upper assembly 50 also has differentiated areas. The clearest, referenced 38a, are made of an electrically insulating material, and the darkest, referenced 38b and covering the pads 84 of both objects 80a, 80b, are electrically conductive.
(81) Thus, once superimposed and adhering to each other, these three layer-shaped assemblies 50 make it possible to obtain an opto-electronic device 62 in which the solar energy are collected by the photovoltaic cell 80d transfers energy to the micro-battery 80b. In parallel, the transparent beads filter the solar spectrum before it is detected by the photodiode 80c, the detected signal being then processed by the chip 80a.
(82) Of course, diverse modifications can be brought by those skilled in the art to the invention which has just been described, solely by way of non-limiting examples. In particular, the invention does not only apply to the production of an assembly with the compact film of running particles, but can be adapted to create an assembly with this film held static on the carrier liquid, until it is extracted together with the substrate.