• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The present invention relates to a heating device (1) comprising: - a base substrate (11); an electroconductive layer (12), called a heating layer, carried by the substrate (11), formed of at least one percolating network of nano-objects comprising metallic nanowires; and - a thermal diffusion layer (13) based on aluminum nitride, covering all or part of the heating layer (12). It also relates to a method for preparing such a heating device.
    公开号:FR3032084A1
    申请号:FR1550666
    申请日:2015-01-28
    公开日:2016-07-29
    发明作者:Jean-Pierre Simonato；Alexandre Carella；Caroline Celle；Abdou Djouadi；Guillaume Droval；Sylvain Sim
    申请人:Centre National de la Recherche Scientifique CNRS；Commissariat a lEnergie Atomique CEA；Universite de Nantes；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a new multilayer heating device based on nanomaterials coated with aluminum nitride. In particular, such a device may have both good heating properties at low voltage and high transparency, making it advantageously suitable for its implementation as a transparent conductive film for heating and / or demister systems for which a visibility requirement is required. Transparent conductive heating films are of growing interest for a wide range of applications, for example for display devices, automotive demisting or de-icing systems, heated windows, etc.
    [0002] Currently, the techniques for producing transparent heating films are based on the use of transparent conductive oxide films (TCOs) and more particularly tin-doped indium oxide (ITO). However, the use of these materials has a certain number of disadvantages, especially with regard to the high and fluctuating cost of indium and the great mechanical fragility of ITO. Also, the manufacturing techniques of these films are complex, requiring vacuum processing and limited to deposits on flat surfaces. Recent advances in the field of nanotechnology have made it possible to provide nano-arrays of nano-objects, in particular based on metal nanowires, combining good properties of electrical conductivity and high transparency. It has been proposed by Celle et al. [1] to produce flexible transparent thin films based on networks of silver nanowires, prepared by spin coating techniques ("spin coating" in English language) or spray ("spray coating" in English), presenting both low voltage and high temperature heating properties. Similarly, Kim et al. [2] developed hybrid layers of carbon nanotubes and silver nanowires. We can also mention Zhang et al. ([3]) which propose a hybrid film architecture based on silver nanowires (AgNWs) and graphene oxide (rLGO), with good performance in terms of transparency and thermal conductivity.
    [0003] The present invention aims to propose a new multilayer heating device, allowing access to a rapid and uniform heating of a surface, while having properties of high transparency. More specifically, the present invention relates, according to a first aspect, a heating device comprising: - a base substrate; an electroconductive layer, called a heating layer, carried by the substrate, and formed of at least one percolating network of nano-objects comprising metallic nanowires; and - a thermal diffusion layer based on aluminum nitride, covering all or part of the heating layer. To the knowledge of the inventors, it has never been proposed to coat an electroconductive layer based on nanoobjects with aluminum nitride. In fact, aluminum nitride is usually crystallized by Molecular Beam Epitaxy (MBE) techniques or by vapor phase epitaxy (MOCVD for "Metal Organic Chemical Vapor Deposition" in the English language). English). These techniques require high temperatures, above 950 ° C, incompatible with a surface deposition of metal nanowires, the latter being altered at high temperature and likely to lose their structural properties. The heating device according to the invention is advantageous in several ways. Firstly, such a device has good low voltage heating properties and makes it possible to reproduce, in a uniform manner, the heat produced on the surface of the device. Thus, as illustrated in the examples which follow, it is possible to achieve in a very short time, with a heating device according to the invention, a homogeneous temperature over the entire exposed surface of the heating device. Such performance is particularly sought after when it is desired to obtain a rapid effect of starting up the heating system, for example in the context of an application for a demisting system, in particular for vehicles. Furthermore, in a particularly advantageous manner, a heating device according to the invention can combine both heating and optical transparency properties, which makes it suitable for the design of various heating and / or semi demister systems. transparent and transparent, for example for windows, shower panels, glasses, heating elements of optoelectronic devices, etc. More particularly, a heating device according to the invention can have a global transmittance, over the entire spectrum. at least 50%, advantageously at least 70% and more particularly at least 80%. The heating device according to the invention can be advantageously prepared by large-area and low-temperature printing techniques. More specifically, the present invention relates, in another of its aspects, to a method of preparing a heating device, comprising at least the steps of: (i) providing a base substrate, one of which faces is covered at least in part with an electroconductive layer, called a heating layer, formed of at least one percolating network of nano-objects comprising metallic nanowires; and (ii) forming, on all or part of the exposed surface of said heating layer, a thermal diffusion layer based on aluminum nitride by high power DC or pulsed magnetron sputtering at a temperature strictly less than 280 ° C.
    [0004] Other characteristics, advantages and modes of application of the heating device according to the invention and its preparation will become more apparent on reading the detailed description which follows, given by way of illustration and not limitation. In the rest of the text, the expressions "between ... and ...", "ranging from ... 25 to ..." and "varying from ... to ..." are equivalent and mean to mean that the terminals are included unless otherwise stated. Unless otherwise indicated, the expression "comprising / including a" shall be understood as "comprising / including at least one".
    [0005] BASIC SUBSTRATE HEATING DEVICE In the context of the present invention, the term "substrate" refers to a solid base structure on at least one side of which are formed the heating layer and the thermal diffusion layer. The base substrate can be of various kinds. It can be a flexible or rigid substrate. The substrate may be transparent, translucent, opaque or colored.
    [0006] It will be understood that the substrate is suitably selected with respect to the intended application for the heater. In particular, in the case where the heating device must satisfy optical transparency properties, for example for an automobile demisting / de-icing system, a transparent glazing unit, etc., the substrate is chosen from semi-transparent or transparent substrates. . By "semi-transparent" is meant to qualify according to the invention a structure / layer having a transmittance, over the entire visible spectrum, greater than or equal to 50%.
    [0007] The transmittance of a given structure represents the light intensity passing through the structure on the visible spectrum. It can be measured by UV-Vis-IR spectrometry, for example using an integrating sphere on a Varian Carry 5000 type spectrometer. The visible spectrum transmittance corresponds to the transmittance for lengths of 25 nm. waves between 350 and 800 nm. The term "transparent" according to the invention means a structure / layer having a transmittance greater than or equal to 80%. The substrate may thus be a substrate made of glass or transparent polymers such as polycarbonate, polyolefins, polyethersulfone, polysulfone, phenolic resins, epoxy resins, polyester resins, polyimide resins, polyetherester resins, resins polyetheramides, polyvinyl (acetate), cellulose nitrate, cellulose acetate, polystyrene, polyurethanes, polyacrylonitrile, polytetrafluoroethylene, polyacrylates such as polymethyl methacrylate, polyarylate, polyetherimides polyether ketones, polyethers ether ketones, polyvinylidene fluoride, polyesters such as polyethylene terephthalate or polyethylene naphthalate, polyamides, zirconia, or derivatives thereof.
    [0008] Preferably, the base substrate may be glass or polyethylene naphthalate. The substrate may in particular have a thickness of between 500 nm and 1 cm, in particular between 200 μm and 5 mm.
    [0009] HEATING LAYER In the context of the invention, the "heating layer", carried by the base substrate, refers to an electroconductive layer formed of at least one percolating network of nano-objects, the nano-objects including at least metallic nanowires. The metal nanowires may be more particularly chosen from nanowires of silver, gold and / or copper. Preferably, the metal nanowires represent at least 40%, in particular at least 60%, of the total mass of the nano-objects of the heating layer. The heating layer may comprise, in addition to metal nanowires, carbon nanotubes and / or graphene, or derivatives thereof such as, for example, graphene oxides. In a first variant embodiment, the heating layer may be in the form of a single layer formed of a percolating network of nano-objects. According to a particular embodiment, the heating layer may be formed of a percolating network of metal nanowires.
    [0010] In another alternative embodiment, the heating layer may have a multilayer percolating network. More particularly, the percolating network of multilayer nano-objects is formed of at least two sub-layers of nano-objects of distinct compositions, in particular based on different nano-objects, at least one of the sub-layers comprising, even being formed of metal nanowires. According to a particular embodiment, at least one of the sub-layers, in particular the upper layer, is formed of metal nanowires.
    [0011] A heating layer comprising at least two different types of nano-objects is hereinafter referred to as a "hybrid" heating layer. By way of example, a hybrid heating layer may consist of a percolating network formed of a first layer of nano-objects, other than metal nanowires, for example carbon nanotubes, and a second layer of metallic nanowires. Advantageously, the heating layer has a transmittance, over the entire visible spectrum, greater than or equal to 50%, in particular greater than or equal to 70% and more particularly greater than or equal to 80%. According to a particularly preferred embodiment, the density of nano-objects of the percolating network of the heating layer according to the invention is between 100 μg / m2 and 500 mg / m2. Those skilled in the art are able to adjust the density of nano-objects to be used to obtain a percolating and conductive network. Indeed, if the network of nano-objects is not dense enough, no conduction path is possible, and the layer will not be conductive. From a certain density of nano-objects, the network becomes percolating and the charge carriers can be transported over the entire surface of the heating layer.
    [0012] Advantageously, the heating layer of a device according to the invention has a surface resistance of less than or equal to 500 ohm / square. The surface resistance, also called "square resistance", can be defined by the following formula: ## EQU1 ## in which: e represents the thickness of the conductive layer (in cm), a represents the conductivity of the layer (in S / cm) (6 = 1 / p), and p represents the resistivity of the layer (in SLCM).
    [0013] The surface resistance can be measured by techniques known to those skilled in the art, for example by a 4-point resistivity meter, for example of the Loresta EP type. Preferably, the heating layer of the device according to the invention has a surface resistance of less than or equal to 200 ohm / square, preferably less than or equal to 100 ohm / square and more preferably less than or equal to 60 ohm / square. A low electrical resistance makes it possible to improve the heating performance, the thermal power dissipated by the heating film being proportional to V 2 / R (Joule effect), V representing the voltage applied across the heating layer 10 (in direct current DC) and R the resistance of the heating layer from one terminal to the other. As illustrated in the examples which follow, a heating layer according to the invention thus has good low voltage heating properties. More particularly, it makes it possible to reach a temperature of at least 80 ° C. by applying low voltages, for example voltages of less than 12 V.
    [0014] Advantageously, as mentioned above, the heating layer according to the invention also has high transparency properties. More particularly, the heating layer advantageously has, over the entire visible spectrum, a transmittance greater than or equal to 50%.
    [0015] Preferably, the heating layer has a transmittance, over the entire visible spectrum, greater than or equal to 70%, in particular greater than or equal to 80%. As an illustration of the invention, percolating networks combining both properties of high electrical conductivity and high transparency are presented in the examples which follow.
    [0016] Thus, a heating layer according to the invention can advantageously combine properties of high electrical conductivity and optical transparency, allowing its implementation to form a semitransparent or transparent heating device, as detailed in the rest of the text.
    [0017] The thickness of the heating layer of a heating device according to the invention may be between 1 nm and 10 μm, in particular between 5 nm and 800 nm.
    [0018] 3032084 8 Preparation of the heating layer The nano-objects can be prepared beforehand according to synthetic methods known to those skilled in the art. For example, silver nanowires can be synthesized according to the synthetic method described in Nanotechnology, 2013, 24, 215501 [4]. The copper nanowires can be obtained by the method described in the publication Nanoresearch 2014, pp 315-324 [5]. The carbon nanotubes may be mono and / or multi-wall nanotubes, purified or unpurified, functionalized or non-functionalized nanotubes; they can be obtained according to known techniques, for example by laser ablation, CVD or arc discharge. The percolating network may be obtained by deposition on the surface of the base substrate of one or more suspensions of nano-objects in a solvent medium (water, methanol, isopropanol, etc.), followed by evaporation of the solvent (s).
    [0019] More particularly, the metal nano-objects can be dispersed beforehand in an easily evaporable organic solvent (for example methanol, isopropanol) or else dispersed in an aqueous medium in the presence of a surfactant. The suspension of nano-objects can then be deposited on the surface of the substrate according to methods known to those skilled in the art, the most commonly used techniques being spraying by spray (coating-in-English), inkjet, dip coating, film pulling, impregnation, doctoring, flexo printing, etc. According to a particular embodiment, the heating layer is formed by nebulized deposition of one or more suspensions of the nano-objects in a solvent medium, followed by evaporation of the solvent (s). The solvent or solvents of the nano-object suspension are then evaporated to form a percolating network of nano-objects allowing the flow of current. In order to further improve the performance of the electroconductive material, the network of nano-objects, for example nanowires, may be annealed at a temperature of between 100 and 150 ° C. As described above, the percolating network of the heating layer of a device according to the invention may consist of several layers of nano-objects 3032084 9 superimposed. In this case, the deposition steps of the suspension of nano-objects and solvent evaporation are repeated as many times as it is desired to obtain layers of nano-objects.
    [0020] THERMAL DIFFUSION LAYER As indicated above, the heating layer is coated in whole or in part with a layer of aluminum nitride (AlN), called "thermal diffusion layer". Aluminum nitride films have particularly advantageous properties in terms of electrical insulation and thermal conductivity, depending on their crystalline quality. Preferably, the AN layer covers the entire heating layer. According to a particularly preferred embodiment, a thermal diffusion layer according to the invention has a thermal conductivity greater than or equal to 20 W.K-1.m-1, in particular between 80 and 250 W.K-1.m-1.
    [0021] Thermal conductivity gives the ability of a material to dissipate heat. It can be measured by a transient hot-band type technique. Such a thermal diffusion layer makes it possible to restore the heat produced by the underlying heating layer uniformly over the entire exposed surface of the heating device.
    [0022] Advantageously, the superposition according to the invention of a heating layer having a low surface resistance and a thermal diffusion layer with a high thermal conductivity allows access, in a very short time, to a uniform heating of the surface. entire surface of the heating device. Such a device is particularly advantageous for applications for heating systems, for example automobile defogging / defrosting, for which it is desired to obtain a rapid effect of starting up the heating system. Preferably, the thermal diffusion layer has a thickness of between 50 nm and 5 μm, in particular between 80 nm and 800 nm. The AN layer according to the invention advantageously has a high transparency.
    [0023] In particular, the AN layer has a transmittance, over the entire visible spectrum, greater than or equal to 50%, in particular greater than or equal to 70%, and more particularly greater than or equal to 80%.
    [0024] Preparation of the thermal diffusion layer The inventors take advantage of the recent optimizations of magnetron sputtering deposition techniques to access, at low temperature, a thin film of AN of good crystalline quality and having good thermal conductivity.
    [0025] Thus, the thermal diffusion layer of a device according to the invention can be formed, on the surface of the percolating network of nano-objects, by magnetron cathodic sputtering in DC or HiPIMS high-power pulsed mode (for "High Power Impulse"). Magnetron Sputtering "in English). The technique of depositing a thin film on a magnetron cathode sputtering substrate generally involves bombarding a target, which forms the cathode of a magnetron reactor and which is made of the material to be deposited, with ions from an electric discharge (plasma). This ionic bombardment causes the target to be sputtered in the form of a "vapor" of atoms or molecules which are deposited in the form of a thin layer on the substrate placed near the target of the magnetron. The HiPIMS technology advantageously makes it possible to generate very high instantaneous currents while maintaining reduced heating of the target due to the use of pulses of short duration. These advanced magnetron sputtering methods are described, for example, by Belkerk et al. [6] and Duquenne et al. [7]. A thin layer of AN of good crystallinity can be more particularly achieved by magnetron sputtering from an aluminum target and an argon / nitrogen reactive mixture. It can be formed at a temperature strictly below 280 ° C, not affecting the stability of the underlying heating layer. Preferably, it is formed at a temperature of less than or equal to 250 ° C, and more particularly less than or equal to 200 ° C.
    [0026] APPLICATIONS As mentioned above, the multilayer heating device according to the invention may, advantageously, possess both good heating performance and high transparency. According to a particularly preferred embodiment, the invention relates to a semi-transparent or transparent heating device, comprising: a semitransparent or transparent base substrate, in particular as defined above, for example glass or polymer transparent; A heating layer having a transmittance, over the entire visible spectrum, greater than or equal to 50%, in particular greater than or equal to 70% and more particularly greater than or equal to 80%; and a heat diffusion layer based on aluminum nitride covering all or part of the heating layer.
    [0027] Advantageously, a heating device according to the invention may have an overall transmittance over the entire visible spectrum of at least 50%, in particular greater than or equal to 70% and more particularly greater than or equal to 80%. "Global" transmittance means the transmittance of the entire structure formed by the substrate stack, heating layer and thermal diffusion layer according to the invention. A heating device according to the invention can be implemented as a thin transparent heating film for various applications, in particular in heating and / or demister systems.
    [0028] Those skilled in the art are able to adapt the shape and dimensions of the heating device according to the invention to integrate it into the desired heating system. The heating device according to the invention can be used by applying a voltage between two opposite edges of the heating layer. Thus, according to a particular embodiment, two non-transparent conductive strips may be deposited on the base substrate, in contact with two opposite edges of the heating layer, as shown in FIG.
    [0029] These strips, called "contact pickups", can be, for example, made from metal paste or silver lacquer, to allow a better connection with external power supply systems. These resumptions of electrical contacts can be carried out according to usual techniques, for example by chemical vapor deposition CVD (for "Chemical Vapor Deposition" in English) or by physical vapor deposition PVD (for "Physical Vapor Deposition" in English). English language). The power supply of the system incorporating a heating device can be fixed or mobile, for example a battery, a battery or a photovoltaic cell, and fed continuously or discontinuously. According to another of its aspects, the present invention thus relates to a heating and / or defogging system comprising a heating device as described above, in particular a semi-transparent or transparent heating device. In general, the heating and / or defogging system may concern all types of systems known in the state of the art requiring the use of a heating film, in particular with high transparency. The system can be implemented for example for a shower panel, a mirroring element, a visor, a mask, glasses, a radiator, a heating element of an optoelectronic device, a transparent food container, for example a baby bottle. By way of example, a heating device according to the invention, made with a flexible and transparent base substrate, can be used for a transparent heating element (transparent electrode) in an optoelectronic device, for example a display screen. .
    [0030] A heating and semi-transparent device according to the invention can also be implemented for a heated windscreen, the heating device being intended for heating the windshield in order to demist or defrost it. The performance of the heating device according to the invention in terms of heating and high transparency makes it possible to quickly access, in the context of an application for an automobile windshield, a clear vision, after activation of the heating device. Of course, the invention is not limited to the systems described above, and other applications of the heating device according to the invention can be envisaged.
    [0031] The invention will now be described by means of the following examples and figures, given by way of nonlimiting illustration of the invention.
    [0032] FIGURES FIG. 1: Schematic representation, in a vertical sectional plane, of the structure of a heating device (1) according to the invention. Figure 2: Diagrammatic view of the application of a voltage by means of a voltage generator (22), on the resumption of contact of a device (1) according to the invention, as operated in the Examples 1 to 4. It should be noted that, for the sake of clarity, the various elements visible in the figures are represented in free scale, the actual dimensions of the different parts not being respected.
    [0033] EXAMPLES Measurement Methods Total transmittance is measured using an integrating sphere on a Varian Carry 5000 spectrometer.
    [0034] Visible spectrum transmittance is transmittance for wavelengths between 350 and 800 nm. The transmittance is measured every 2 nm. Surface electrical resistance is measured by a 4-point resistivity meter of the Loresta EP type.
    [0035] EXAMPLE 1 Formation of the heating layer (12) In a first step, silver nanowires are synthesized and purified according to the process described in Nanotechnology, 2013, 24, 215501 [4].
    [0036] These nanowires are deposited on Eagle XGTM glass (Corning) (substrate (11)) according to a spraying method ("spray-coating" in English).
    [0037] The material thus deposited, constituting the heating layer (12), has a square resistance of 28 ohm / square. Repetitions of electrical contacts (21) are performed on two opposite edges by using a silver lacquer or a metal film deposit, for example by CVD or PVD. Formation of the thermal diffusion layer (13) Aluminum nitride (A1N) is deposited on this heating layer (12) by DC magnetron sputtering. During this deposition, the electrical contact resumptions are protected for use thereafter in order to apply a potential to the device. The DC magnetron sputtering deposition is carried out from a pure aluminum target and an argon and nitrogen plasma under secondary vacuum (pressure between 2 and 3 mTorr) and at low temperature (T = 200 ° C). The power used is 175 W. The ratio of nitrogen and argon QN2 / (QN2 + QAr) amounts to 25 ° A. Under these conditions, the deposition rate is about 40 nm / min, which allows precise control of the thickness of the deposited AN layer. The deposition is carried out for 5 minutes, which makes it possible to obtain a layer 20 (13) of 200 nm. By applying a voltage of 5 V on the resumption of contact, a temperature of 35 ° C is reached in less than one minute, homogeneously over the entire surface of the heating device (1). This heating device (1) has an overall transmittance, measured using an integration sphere on a Varian Carry 5000 spectrometer, of at least 85% over the entire visible spectrum. By applying a voltage of 7V on the resumption of contact, a temperature of 51 ° C is reached in less than one minute, homogeneously over the entire surface of the heating device.
    [0038] EXAMPLE 2 Formation of the Heating Layer (12) In a first step, carbon nanotubes (CSP3 type of Carbon solution) are dispersed in NMP (N-methylpyrrolidone) and deposited on Eagle XGTM glass (Corning ) according to a method of deposition by nebulization ("spray-coating" in English). The transmittance of the deposited layer, over the entire visible spectrum, is 99.2%. Silver nanowires are synthesized and purified according to the process described in Nanotechnology, 2013, 24, 215501. These nanowires are deposited on the layer of carbon nanotubes. The "hybrid" heating layer (12), composed of two sub-layers of nanomaterials of different nature, thus formed, has a square resistance of 20 ohm / square. Repetitions of electrical contacts (21) are performed on two opposite edges 15 by using a silver lacquer or a metal film deposit, for example by CVD. Formation of the thermal diffusion layer (13) The aluminum nitride (A1N) is deposited on this heating layer as described in Example 1. By applying a voltage of 5 V on the contacts of contact (21), a temperature of 45 ° C is reached in less than one minute, homogeneously over the entire surface of the heating device (1).
    [0039] This device (1) has an overall transmittance of at least 88% over the entire visible spectrum. EXAMPLE 3 A heating device (1) similar to that described in Example 1 is produced, using instead of silver nanowires, copper nanowires manufactured according to the method described in the publication Nanoresearch 2014, pp 315 -324 [5]. 3032084 ohm / square.
    [0040] The heating layer (12) thus produced has a square resistance of 53. The deposition of AN is carried out as described in Example 1.
    [0041] By applying a voltage of 9 V on the resumption of contact, a temperature of 63 ° C is reached in less than one minute, homogeneously over the entire surface of the heating device. This device has an overall transmittance of 82% minimum over the entire visible spectrum.
    [0042] EXAMPLE 4 A heating device (1) similar to that described in Example 1 is produced, employing instead of the glass substrate, a substrate (11) of polyethylene naphthalate 125 μm thick.
    [0043] The heating layer (12) thus produced has a square resistance of 19 ohm / square. The deposition of AN is carried out as described in Example 1. By applying a voltage of 9 V on the resumption of contact, a temperature of 71 ° C. is reached in steady state uniformly over the entire surface of the device. heating. This device has an overall transmittance of 90% minimum over the entire visible spectrum. References [1] Celle et al., "Highly Flexible Transparent Film Heaters Based on Random Networks of Silver Nanowires", Nano Research (2012), 5 (6): 427-433; [2] Kim et al., "Transparent flexible heater based on hybrid carbon nanotubes and silver nanowires", Carbon 63 (2013) 530-536; [3] Zhang et al., "Large-size graphene microsheets as a protective layer for transparent conductive silver nanowire film heaters", Carbon 69 (2014) 437-443; [4] Nanotechnology, 2013, 24, 215501; [5] Nanoresearch 2014, pp 315-324; [6] Belkerk et al., "Structural-dependent thermal conductivity of aluminum nitride produced by reactive direct current magnetron sputtering", Appl. Phys. Lett. 101, 151908 (2012); [7] Duquenne et al., Appl. Phys. Lett. 93, 052905 (2008). 5
    权利要求:
    Claims (21)
    [0001]
    REVENDICATIONS1. Heating device comprising: - a base substrate; an electroconductive layer, called a heating layer, carried by the substrate, formed of at least one percolating network of nano-objects comprising metallic nanowires; and - a thermal diffusion layer based on aluminum nitride, covering all or part of the heating layer.
    [0002]
    2. Device according to claim 1, wherein the heating layer has a transmittance, over the entire visible spectrum, greater than or equal to 50%, in particular greater than or equal to 70% and more particularly greater than or equal to 80%.
    [0003]
    3. Device according to claim 1 or 2, wherein the heating layer has a surface resistance of less than or equal to 500 ohm / square, in particular less than or equal to 200 ohm / square, preferably less than or equal to 100 ohm / square and more preferably less than or equal to 60 ohm / square.
    [0004]
    4. Device according to any one of the preceding claims, wherein the metal nanowires represent at least 40% by weight, in particular at least 60% of the total mass of the nano-objects of said heating layer.
    [0005]
    5. Device according to any one of the preceding claims, wherein the metal nanowires are selected from nanowires of silver, gold and / or copper.
    [0006]
    6. Device according to any one of the preceding claims, wherein the heating layer comprises, in addition to metal nanowires, carbon nanotubes and / or graphene, or derivatives thereof.
    [0007]
    7. Device according to any one of the preceding claims, wherein the percolating network of nano-objects of the heating layer has a density of nano-objects of between 100 μg / m2 and 500 mg / m2.
    [0008]
    8. Device according to any one of the preceding claims, wherein the heating layer is in the form of a single layer formed of a percolating network of nano-objects, in particular a percolating network of metal nanowires. 3032084 19
    [0009]
    9. Device according to any one of claims 1 to 7, wherein the heating layer has a multilayer percolating network formed of at least two sub-layers of nano-objects of different compositions, at least one of the underlays comprising, or even being formed, metal nanowires. 5
    [0010]
    10. Device according to any one of the preceding claims, wherein the heating layer has a thickness between 1 nm and 10 iam, in particular between 5 nm and 800 nm.
    [0011]
    Apparatus according to any one of the preceding claims, wherein the thermal diffusion layer has a thermal conductivity greater than or equal to 20 WK-1 m -1, in particular between 80 and 250 WK -1. 1.
    [0012]
    12. Device according to any one of the preceding claims, wherein the thermal diffusion layer has a thickness between 50 nm and 5 i.tm, in particular between 80 and 800 nm.
    [0013]
    13. The device of any one of the preceding claims, wherein the thermal diffusion layer covers the entire heating layer.
    [0014]
    A device according to any preceding claim, wherein the base substrate is a transparent or semi-transparent substrate, in particular glass or transparent polymers such as polycarbonate, polyolefins, polyethersulfone, polysulfone, phenolic resins, epoxy resins, polyester resins, polyimide resins, polyether ester resins, polyether amide resins, polyvinyl acetate, cellulose nitrate, cellulose acetate, polystyrene, polyurethanes, polyacrylonitrile, polytetrafluoroethylene, polyacrylates such as polymethyl methacrylate, polyarylate, polyetherimides, polyether ketones, polyethers ether ketones, polyvinylidene fluoride, polyesters such as polyethylene terephthalate or polyethylene naphthalate, polyamides, zirconia, or their derivatives; preferably the base substrate is glass or polyethylene naphthalate.
    [0015]
    15. Apparatus according to any one of the preceding claims, semitransparent or transparent in which: the base substrate is semi-transparent or transparent, in particular as defined in claim 14; and 3032084 20 - the heating layer has a transmittance, over the entire visible spectrum, greater than or equal to 50%, in particular greater than or equal to 70% and more particularly greater than or equal to 80%.
    [0016]
    16. Device according to the preceding claim, characterized in that it has an overall transmittance, over the entire visible spectrum, of at least 50%, in particular greater than or equal to 70% and more particularly greater than or equal to 80%.
    [0017]
    17. A method of preparing a heating device, comprising at least the steps of: (i) having a base substrate, one of whose faces is at least partially covered with an electroconductive layer, called a layer heater, formed by hand a percolating network of nano-objects comprising metal nanowires; and (ii) forming, on all or part of the exposed surface of said heating layer, an aluminum nitride thermal diffusion layer by high power direct or pulsed DC magnetron sputtering at a lower temperature. at 280 ° C.
    [0018]
    18. The method according to the preceding claim, wherein the thermal diffusion layer is formed in step (ii) at a temperature of less than or equal to 250 ° C, in particular less than or equal to 200 ° C.
    [0019]
    19. The method of claim 17 or 18, wherein the heating layer 20 carried by the substrate of step (i) is previously formed by nebulized deposition of one or more suspensions of the nano-objects in a solvent medium, followed by evaporation of the solvent (s).
    [0020]
    20. Heating and / or defogging system, comprising a heating device as defined in any one of claims 1 to 16 or as obtained by a method according to any one of claims 17 to 19.
    [0021]
    21. System according to the preceding claim, comprising a transparent or semi-transparent heating device as defined in claims 15 or 16, said system being implemented for a glazing unit, a shower panel, a mirroring element, a visor, a mask, glasses, a radiator, a heating element of an optoelectronic apparatus or a transparent food container.
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    同族专利:
    公开号 | 公开日
    WO2016120302A1|2016-08-04|
    EP3251468A1|2017-12-06|
    FR3032084B1|2017-02-10|
    US20180014359A1|2018-01-11|
    EP3251468B1|2020-11-18|
    引用文献:
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    法律状态:
    2016-01-29| PLFP| Fee payment|Year of fee payment: 2 |
    2016-07-29| PLSC| Publication of the preliminary search report|Effective date: 20160729 |
    2017-01-31| PLFP| Fee payment|Year of fee payment: 3 |
    2018-01-31| PLFP| Fee payment|Year of fee payment: 4 |
    2020-01-30| PLFP| Fee payment|Year of fee payment: 6 |
    2021-01-28| PLFP| Fee payment|Year of fee payment: 7 |
    2022-01-31| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1550666A|FR3032084B1|2015-01-28|2015-01-28|HEATING DEVICE, PARTICULARLY SEMI-TRANSPARENT|FR1550666A| FR3032084B1|2015-01-28|2015-01-28|HEATING DEVICE, PARTICULARLY SEMI-TRANSPARENT|
    PCT/EP2016/051648| WO2016120302A1|2015-01-28|2016-01-27|Heating device, in particular a semi-transparent heating device|
    EP16701766.4A| EP3251468B1|2015-01-28|2016-01-27|Heating device, especially semi-transparent|
    US15/545,151| US20180014359A1|2015-01-28|2016-01-27|Heating device, in particular a semi-transparent heating device|
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