EP2883255A2 - Surface treatment for a layer made from a fluorinated material to make it hydrophilic - Google Patents

Surface treatment for a layer made from a fluorinated material to make it hydrophilic

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Publication number
EP2883255A2
EP2883255A2 EP13779362.6A EP13779362A EP2883255A2 EP 2883255 A2 EP2883255 A2 EP 2883255A2 EP 13779362 A EP13779362 A EP 13779362A EP 2883255 A2 EP2883255 A2 EP 2883255A2
Authority
EP
European Patent Office
Prior art keywords
layer
hydroxide
fluorinated
oxo
aluminum
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Withdrawn
Application number
EP13779362.6A
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German (de)
French (fr)
Inventor
Mohammed Benwadih
Olivier Poncelet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Publication date
Application filed by Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Publication of EP2883255A2 publication Critical patent/EP2883255A2/en
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/80—Constructional details
    • H10K10/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/474—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising a multilayered structure
    • H10K10/476—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising a multilayered structure comprising at least one organic layer and at least one inorganic layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

Definitions

  • the invention relates to a treatment method for hydrophilizing a surface of a layer of a fluorinated material, a method of depositing a layer of a metallic or semiconductor material on the surface of a layer made of a fluorinated material, and a device comprising a layer of a fluorinated material, a surface of which has been treated by the treatment method of the invention, and a layer of a metallic material.
  • Many devices include layers of a fluorinated material such as a fluoropolymer (also referred to herein as fluoropolymer) or a material containing at least one fluorine atom.
  • a fluorinated material such as a fluoropolymer (also referred to herein as fluoropolymer) or a material containing at least one fluorine atom.
  • fluoropolymers are used in the manufacture of electronic components such as organic transistors, for electrical insulation, or in the manufacture of mechanical parts subjected to extreme conditions of use, in terms of temperature or aggressiveness of solvents.
  • fluoropoîymomme and in particular the Cytop ®, which is a fluoropolymer, exhibit properties particularly suited to form the dielectric material of the gate of a transistor or a capacitance or the encapsulation layers used in this field.
  • Patent FR 2 919 521 proposes a device comprising a fluoropolymer layer of which at least part of the surface is covered with a polymer comprising at least one fluorinated function and at least one acid or base function and forming a layer of hooked on said fluoropolymer, said hook layer being covered by another layer.
  • the hook layer is an ionic conductive material that disrupts the proper operation of the transistor.
  • the aim of the invention is to provide a process which makes it possible to render the hydrophilic layer of a fluorinated material hydrophilic, in order to allow the deposition of other layers on this layer of fluorinated material,
  • the invention proposes a treatment process for rendering a hydrophilic surface of a layer made of a fluorinated material, characterized in that it comprises a step a) of depositing a layer of a (oxo) hydroxide d an element of the alcalino-terrous metal group or group II or group III of the periodic table of the elements or of a rare earth, or a mixture thereof on said surface.
  • said element is magnesium or aluminum and Mg (OH) 2 magnesium hydroxide or Al (OH) 3 aluminum hydroxide is deposited.
  • the thickness of the (oxo) hydroxide layer is between 10 nm and 1 ⁇ m, more preferably, this thickness is between 10 and 300 nm, inclusive. Even more preferably, it is equal to 50 nm.
  • step a) of depositing on said surface is a step of hydrolysis, on said surface, of a salt of said element.
  • step a) is a step of depositing said (oxo) hydroxide of said element in suspension in a solvent.
  • said suspension is a colloidal sol of said (oxo) hydroxide of said element.
  • the layer of a fluorinated material is a layer of a fluorinated polymer or fluorinated silane.
  • the invention also proposes a method for depositing a layer of a material chosen from a metallic material, an electrically conductive material, a semiconductor material and an insulating material, on the surface of a layer made of a fluorinated material. characterized in that it comprises a step of treating said surface of the layer with a fluorinated material to make it hydrophilic, by the process according to the invention, followed by a step of depositing said layer of a metallic material, or conductor of electricity, or semiconductor, or insulator.
  • the material is a metallic material selected from silver, chromium, gold, titanium, aluminum, platinum, palladium, copper, nickel, molybdenum, an ink conductor, in particular comprising metal nanoparticles.
  • the material is a metallic electrically conductive material
  • it is preferably selected from a conductive polymer, such as PEDOT / PSS: sodium poly (3,4-ethylenedioxythiophene) (PEDOT) / polystyrene sulfonate (PSS), polyaniline, the conductive metal oxides chosen from ⁇ (indium-tin-oxide), ⁇ (conducting alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanopipes, graphene , silver / graphene mixtures, or even copper / graphene mixtures.
  • PEDOT / PSS sodium poly (3,4-ethylenedioxythiophene) (PEDOT) / polystyrene sulfonate (PSS), polyaniline
  • the conductive metal oxides chosen from ⁇ (indium-tin-oxide), ⁇ (conducting alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanopipes, graphene , silver / graphene
  • the invention also proposes a device characterized in that it comprises a layer made of a fluorinated material, one surface of which is coated with an (oxo) hydroxide layer of an element selected from the group of alkaline earth metals or from the group II or III of the periodic table of the elements, or a rare earth, and a layer of a material selected from a metal material, an electrically conductive material, a semiconductor material, and an insulating material, deposited on the surface of the (oxo) hydroxide layer not in contact with the layer of a fluorinated material.
  • an (oxo) hydroxide layer of an element selected from the group of alkaline earth metals or from the group II or III of the periodic table of the elements, or a rare earth
  • a layer of a material selected from a metal material, an electrically conductive material, a semiconductor material, and an insulating material, deposited on the surface of the (oxo) hydroxide layer not in contact with the layer of a fluorinated
  • the (oxo) hydroxide is an (oxo) hydroxide of a member selected from among beryllium, magnesium, calcium, strontium, indium, barium, radium , aluminum, zinc, scandium, yttrium, and mixtures thereof.
  • the (oxo) hydroxide is Mg (OH) 2 magnesium hydroxide or Al (OH) 3 aluminum hydroxide.
  • the thickness of the (oxo) hydroxide layer is between 10 and 300 nm, inclusive. Preferably, it is equal to 50 nm.
  • the layer of a fluorinated material is a layer of a fluorinated polymer or a fluorinated silane.
  • the layer made of a metallic material it is preferably made of a material chosen from among silver, chromium, gold, titanium, aluminum, platinum, palladium, copper, nickel and molybdenum. , a conductive ink, in particular comprising metal nanoparticles.
  • the layer made of an electrically conductive material is preferably made of a material chosen from a conductive polymer such as PEDOT / PSS: sodium poly (3,4-ethylenedioxythiophene) (PEDOT) / poly (styrene sulphonate) ( PSS), polyaniline, conductive metal oxides selected from ⁇ (indium-tin-oxide), AZO (alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanotubes graphene, silver / graphene mixtures, or copper / graphene mixtures.
  • PEDOT / PSS sodium poly (3,4-ethylenedioxythiophene) (PEDOT) / poly (styrene sulphonate) ( PSS), polyaniline, conductive metal oxides selected from ⁇ (indium-tin-oxide), AZO (alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanotubes graphene, silver / graphene mixtures, or copper
  • a preferred device according to the invention is an organic transistor.
  • FIG. 1 schematically represents the structure of an organic transistor before depositing the gate
  • FIG. 2 represents the transistor of FIG. 1 being processed by the method of the invention before depositing the gate
  • FIG. 3 diagrammatically represents the transistor obtained after the treatment carried out as shown in FIG. 2,
  • FIG. 4 represents the transistor of FIG. 3 with the gate deposited
  • FIG. 5 represents the increase in the thickness of the layer obtained during the treatment of the surface of a fluoropolymer by the process of the invention as a function of time
  • FIG. 6 shows a photograph taken with an optical microscope at a magnification x 5 of the surface of a layer of fluorinated polymer, Cytop ® of the prior art on which an electrode was printed with a silver ink to P ,
  • FIG. 7 shows a photograph taken with an optical microscope at a magnification x 5 of the surface of a layer of fluorinated polymer, Cytop ®, treated according to the invention wherein an electrode was printed with an ink to money, and
  • FIG. 8 represents the variation of the gate voltage, Vg, in volts, of a transistor of the prior art and of a transistor according to the invention.
  • the invention proposes to cover the surface of the layer made of a fluorinated material with the aid of an additional layer called "hooked" layer which makes it possible to obtain a hydrophilic surface on which a layer may be deposited, in particular of a metal such as silver, chromium, gold, titanium, aluminum, platinum, palladium, copper, nickel, molybdenum, a conductive ink, in particular comprising metal nanoparticles.
  • a metal such as silver, chromium, gold, titanium, aluminum, platinum, palladium, copper, nickel, molybdenum
  • the electrically conductive material it is preferably chosen from a conducting polymer such as PEDOT / PSS: poly (3,4-ethylenedioxythiophene) (PEDOT) / sodium polystyrene sulphonate (PSS), polyaniline, conductive metal oxides selected from PITO (indium-tin-oxide), AZO (alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanotubes, graphene, silver mixtures graphene or copper / graphene mixtures. An adherent structure is then obtained.
  • a conducting polymer such as PEDOT / PSS: poly (3,4-ethylenedioxythiophene) (PEDOT) / sodium polystyrene sulphonate (PSS), polyaniline, conductive metal oxides selected from PITO (indium-tin-oxide), AZO (alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanotubes, graphene, silver mixtures graphene or
  • the invention proposes to modify the wettability of the surface of the layer in a fluorinated material by creating a layer of hook formed of an alkaline earth metal hydroxide or oxohydroxide, or an element of the group II or group III of the periodic table of the elements, or of a rare earth.
  • this layer will be called "(oxo) hydroxide layer” to mean both a layer of a hydroxide of the element and a layer of an oxohydroxide of the element. .
  • This element may be beryllium, magnesium, calcium, strontium, indium, barium, radium, aluminum, zinc, scandium, yttrium, and mixtures thereof.
  • Magnesium or aluminum will preferably be used as the element, in which case the layer formed will be a brucite, Mg (OH) 2 or gibbsite, Al (OH) 3 layer, respectively.
  • the layers of brucite or gibbsite have the advantage of being electrically insulating and have a fairly high permittivity of the order of 8 and more.
  • brucite and gibbsite grow on fluoropolymer layers and have the ability to adhere to both fluorinated polymers such as Tefion ® or Cytop ® , as a layer of fluorinated silane, than to other materials, for example, fluorine glues.
  • this ink adheres to brucite or gibbsite, which allows to deposit, particularly in the case of transistors where the layer of dielectric material is often a fluorinated polymer, another layer of a metal, for example to form the gate electrode, by techniques such as printing, spin coating, or gluing.
  • the invention finds application more particularly in the field of organic transistors. Indeed, it is now accepted that in order to obtain organic transistors which have little hysteresis and high mobility, it is necessary for the dielectric material of the gate to consist of a polymer having a low value of c (called low K ) (J. Veres et al., "Gaste Insulators in Organic Field-Effect Transistors", Chem Mater 2004, 16, 4543-4555).
  • fluoropolymers are materials of choice. It is therefore necessary to deposit the other layers that constitute the stack of a transistor on this layer.
  • FIG. 1 schematically represents the structure of an organic transistor before the deposition of the gate.
  • such a transistor consists of a substrate, denoted 1 in FIG. 1, generally made of polyethylene naphthalate (PEN) having a thickness generally of 125 ⁇ m.
  • PEN polyethylene naphthalate
  • silica silicon, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyetherimide ( PEI), polyether sulphone (PES), polysulfone (PSF), polyphenylene sulphide (PPS), polyether ether ketone (PEEK), polyacrylate (PA), polyamide imide (PAI), polystyrene, polyethylene polypropylene, a polyamine resin, a carbonate resin or a cellulosic resin.
  • source electrode and drain electrode On this substrate is deposited two electrodes noted 2 in Figure 1, called source electrode and drain electrode.
  • Electrodes are structured, that is to say that their surface is not flat. These electrodes are structured by a laser treatment or by photolithography.
  • Electrodes are generally made of gold, have a thickness of 30 nm and are deposited by evaporation.
  • these electrodes 2 and a portion of the substrate 1 are coated with a layer, denoted 3 in FIG. 1, of a semiconductor material, generally of the TIPS PENTACENE type, which is a small semiconductor molecule deposited by a printing technique such as gravure, or tetracene or anthracene.
  • a semiconductor material generally of the TIPS PENTACENE type, which is a small semiconductor molecule deposited by a printing technique such as gravure, or tetracene or anthracene.
  • a layer denoted 3 in FIG. 1
  • a semiconductor material generally of the TIPS PENTACENE type, which is a small semiconductor molecule deposited by a printing technique such as gravure, or tetracene or anthracene.
  • organic semi-conducting materials considered in the context of the present invention. These may be molecules of low molecular weight (commonly called "small molecules"), and especially molecules with a molecular weight of less than 1000 g / mol, or poly
  • organic semiconductors have the common point to present a conjugate system from ⁇ alternating single and double carbon-carbon bonds.
  • organic semiconductor of low molecular weight there may be mentioned, for example, those of the polyacene, oligothiophene or phthalocyanine type.
  • polymeric organic semiconductors that may be mentioned are those of polyacetylene, polyphenylene, polythiophene or poly (phenylene / vinylene) type.
  • It may especially be an organic semiconductor selected from pentacene, tetracene, anthracene, naphthalene, alpha-6-thiophene, alpha-4-thiophene, perylene and its derivatives, rubrene and its derivatives, coronene and its derivatives, perylene tetracarboxylic diimide and its derivatives, perylene tetracarboxylic dianhydride and its derivatives, polythiophene and its derivatives, polyparaphenylene-vinylene and its derivatives, polyparaphenylene and its derivatives, polyfluorene and its derivatives, a polyfluorene-oligothiophene copolymer and its derivatives, polythiophene-vinylene and its derivatives, a polythiophene heterocyclic aromatic copolymer and its derivatives, an oligonaphthalene and its derivatives, alpha-5-thiophene oligothiophene and its derivatives, phthalo
  • the gate electrode must then be deposited.
  • a layer, denoted 4 in FIG. 1, of fluoropolymer is deposited on the layer 3.
  • the fluoropolymer used is generally a fluoropolymer CYTOP ® with a thickness between 500 and 800 nm, inclusive.
  • this gate electrode denoted 6 in FIG. 4, It is then necessary to deposit the gate electrode, denoted 6 in FIG. 4, on this layer 4 made of fluoropolymer.
  • This gate electrode has a thickness of between 50 nm and 1 ⁇ , inclusive. Due to the evoked difficulties of deposition on the fluoropolymer layer 4, there is a lack of adhesion between the layer 4 and the upper layer 6, namely the gate electrode. These layers are not uniform.
  • the treatment method of the invention for rendering the surface of the layer 4 hydrophilic in a fluorinated material is diagrammatically shown in FIG.
  • a drop, denoted 10 in FIG. 2 of a liquid solution of one element of the group is deposited.
  • This drop 10 covers the entire layer 4.
  • a layer, noted in FIG. 2, of hydroxide or oxohydroxide of the element is then obtained after drying in order to evaporate the solvent from the deposited solution.
  • the element when the element is magnesium or aluminum, due to brucite's affinity, Mg (OH) 2 , and gibbsite, Al (OH) 3 , with the fluorinated surface of layer 4 it a sheet of brucite or gibbsite forms on the entire exposed surface of layer 4.
  • This layer 5 varies as a function of the contact time between the solution of the element of the group of alkaline-earth metals or of group II or III of the periodic table or of the rare earth, on the surface of layer 4 .
  • the layer 5, said hooked, has a thickness generally between 10 nm and 1 ⁇ , inclusive. It is preferably between 10 and 300 nm, inclusive. But in a transistor, it is preferably 50 nm.
  • the solution deposited on the layer 4 may be a solution of the element to be deposited itself, for example a colloidal sol of the hydroxide of the element or of the oxohydroxide of the element.
  • a colloidal sol of magnesium hydroxide Mg (OH) 2 or aluminum hydroxide Al (OH) 3 can be used ,
  • magnesium chloride MgCl 2 or magnesium fluoride MgF 2 or aluminum chloride may be used and dissolved in water. This solution will be deposited on layer 4 and a sodium hydroxide solution will then be poured on the magnesium chloride solution. The formation reaction of the brucite film on layer 4 starts from pH 9.
  • Figure 5 shows the variation in thickness of a layer of brucite Mg (OH) 2 as a function of immersion time of a Cytop ® layer in a solution containing 100 mg of MgCl 2 in 200 mL of water, which was added sodium hydroxide solution, NaOH concentration of 0.5 mol / l, until a pH of 9.
  • the invention also proposes a process for depositing a layer 6 made of a metallic material, or an electrically conductive material such as a conductive polymer such as PEDOT / PSS, (poly (3,4-ethylenedioxythiophene) ) (PEDOT) and sodium polystyrene sulfonate (PSS), or a semiconductor material such as one of those mentioned above, or an insulating material, on the surface of a layer 4 in a fluorinated material, this process comprising a step of treating the surface of the layer 4 to create the hook layer 5, as shown above, by the treatment method of the invention, then the deposition of said layer 6 of a metal or semiconductor material.
  • a conductive polymer such as PEDOT / PSS, (poly (3,4-ethylenedioxythiophene) ) (PEDOT) and sodium polystyrene sulfonate (PSS), or a semiconductor material such as one of those mentioned above, or an insulating material
  • the metallic material is preferably selected from silver, chromium, gold, titanium, aluminum, platinum, palladium, copper, nickel, molybdenum, a conductive ink, in particular comprising metal nanoparticles.
  • the electrically conductive material it is preferably chosen from a conducting polymer such as PEDOT / PSS: poly (3,4-ethylenedioxythiophene) (PEDOT) / sodium polystyrene sulfonate (PSS), polyaniline, the conductive metal oxides chosen from ⁇ (indium-tin-oxide), AZO (alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanotubes, graphene, mixtures silver / graphene, or copper / graphene mixtures.
  • a conducting polymer such as PEDOT / PSS: poly (3,4-ethylenedioxythiophene) (PEDOT) / sodium polystyrene sulfonate (PSS), polyaniline, the conductive metal oxides chosen from ⁇ (indium-tin-oxide), AZO (alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanotubes, graphene, mixtures silver / graphene, or copper
  • the devices obtained by these methods are also an object of the invention.
  • a device comprises a layer 4 made of a fluorinated material, such as a fluorinated polymer or a fluorinated silane, one surface of which is coated with a layer of an elemental hydroxide or oxohydroxide. of the alkaline earth metal group or group II or III of the Periodic Table of the Elements or rare earth, or mixtures thereof.
  • a fluorinated material such as a fluorinated polymer or a fluorinated silane, one surface of which is coated with a layer of an elemental hydroxide or oxohydroxide. of the alkaline earth metal group or group II or III of the Periodic Table of the Elements or rare earth, or mixtures thereof.
  • the device of the invention may further comprise a layer 6 of a metallic or electrically conductive or semiconductor or insulating material deposited on all or part of the surface of the layer 5.
  • a gold layer 2 30 nm thick, was deposited by evaporation or by vapor deposition (PVD). This layer 2 of gold is etched to form the source and drain electrodes. This can be done by photolithography or laser ablation.
  • PEN polyethylene naphthalate
  • PVD vapor deposition
  • a layer 3 of 100% thick TIPS PENTACENE semiconducting material is then deposited by gravure printing.
  • a dielectric material which is here a fluorinated polymer, Cytop ®, with a thickness of 800 nm.
  • This layer 4 was formed by screen printing.
  • This layer 4 is then treated by the treatment method of the invention.
  • a second solution of NaOH is made in water at a concentration of 100 mg / mL.
  • the device obtained is immersed in the MgCl 2 solution.
  • the NaOH solution is slowly added until a pH of 9 is reached.
  • the hydrolysis reaction starts on the fluorine of layer 4 due to the difference in electronegativity between fluorine, which is electronegative, and magnesium, which is electropositive.
  • a brucite germ Mg (OH) 2 is formed on the surface of layer 4.
  • the device is kept in the solution.
  • the water drop contact angle is less than 5 °.
  • the grid electrode 6 still containing silver nanoparticles is then deposited by ink jet on the surface of this layer 5.
  • the device shown in FIG. 6 is then obtained.
  • the electrode 6 has a thickness of 1 ⁇ .
  • Figure 6 is a photograph taken from above of the device. As can be seen, the grid formed does not dew and has sharp contours.
  • the contact angle of the drop of water on the surface obtained was measured.
  • the contact angle was 110 °.
  • the device obtained is shown in FIG. 7 where the layer 4 represents the device seen from above, the fluoropolymer layer being marked 4 and the ink layer of silver nanoparticles being denoted 6.
  • the treatment method of the invention for rendering the surface of a hydrophilic fluorinated material is quite effective. .
  • Examples 1 and 2 were then electrically tested by plotting the characteristic curves of a field effect transistor.
  • the curve has a larger current.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Thin Film Transistor (AREA)
  • Chemically Coating (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The invention concerns a treatment method to make a surface of a layer made from a fluorinated material hydrophilic, a method for depositing a layer made from a metal or semi-conductive layer on the surface of a layer made from a fluorinated material, and a device comprising a layer made from a fluorinated material of which one surface has been treated by the treatment method of the invention, and a layer made from a metal material. The method of the invention comprises a step a) of depositing a layer of an oxo-hydroxide of an element from the alkaline earth metal group or from group II or III of the periodic table or of a rare earth or of a mixture of same, onto said surface. The method of the invention is applicable in the field of electronics, in particular.

Description

TRAITEMENT DE SURFACE D'UNE COUCHE EN UN MATERIAU FLUORE POUR LA RENDRE HYDROPHILE  SURFACE TREATMENT OF A LAYER IN A FLUORINE MATERIAL TO MAKE IT HYDROPHILIC
L'invention concerne un procédé de traitement pour rendre hydrophile une surface d'une couche en un matériau fluoré, un procédé de dépôt d'une couche en un matériau métallique ou semi-conducteur sur la surface d'une couche en un matériau fluoré, ainsi qu'un dispositif comprenant une couche en un matériau fluoré, dont une surface a été traitée par le procédé de traitement de l'invention, et une couche en un matériau métallique.  The invention relates to a treatment method for hydrophilizing a surface of a layer of a fluorinated material, a method of depositing a layer of a metallic or semiconductor material on the surface of a layer made of a fluorinated material, and a device comprising a layer of a fluorinated material, a surface of which has been treated by the treatment method of the invention, and a layer of a metallic material.
De nombreux dispositifs comprennent des couches en un matériau fluoré tel qu'un polymère fluoré (également appelé ici fluoropolymère) ou en un matériau contenant au moins un atome de fluor.  Many devices include layers of a fluorinated material such as a fluoropolymer (also referred to herein as fluoropolymer) or a material containing at least one fluorine atom.
Par exemple, les fluoropoîymères sont utilisés dans la fabrication de composants électroniques tels que les transistors organiques, pour l'isolation électrique, ou dans la fabrication de pièces mécaniques soumises à des conditions extrêmes d'utilisation, en termes de température ou d'agressivité de solvants.  For example, fluoropolymers are used in the manufacture of electronic components such as organic transistors, for electrical insulation, or in the manufacture of mechanical parts subjected to extreme conditions of use, in terms of temperature or aggressiveness of solvents.
Dans le cas particulier de l'électronique organique, les fluoropoîymères, et notamment le Cytop®, qui est un polymère fluoré, présentent des propriétés particulièrement adaptées pour constituer le matériau diélectrique de la grille d'un transistor ou d'une capacité ou encore les couches d'encapsulations utilisées dans ce domaine. In the particular case of organic electronics, fluoropoîymères, and in particular the Cytop ®, which is a fluoropolymer, exhibit properties particularly suited to form the dielectric material of the gate of a transistor or a capacitance or the encapsulation layers used in this field.
Toutefois, l'utilisation de tels matériaux fluorés, en particulier de tels polymères fluorés, qui sont hydrophobes, pose un problème, à la connaissance des inventeurs non résolu à ce jour : lorsque l'on veut déposer d'autres couches en d'autres matériaux sur la couche de matériau fluoré préalablement déposée en couche mince, il est impossible de déposer par voie humide ces couches, que ce soit par la méthode dite "à la tournette" (« spin coating » en anglais) ou par diverses méthodes d'impression.  However, the use of such fluorinated materials, in particular such fluorinated polymers, which are hydrophobic, poses a problem, to the knowledge of the inventors unsolved to date: when it is desired to deposit other layers in others materials on the layer of fluorinated material previously deposited in a thin layer, it is impossible to deposit wet these layers, either by the method called "spin coating" ("spin coating" in English) or by various methods of impression.
Il est également impossible de coller entre elles deux pièces en fluoropoîymères, ou de coller un matériau plastique sur un fluoropolymère.  It is also impossible to stick two pieces of fluoropolymers between them, or to glue a plastic material on a fluoropolymer.
Ceci rend donc très délicate la fabrication de dispositifs complexes comprenant différents éléments indispensables à leur fonctionnement. C'est par exemple le cas pour un transistor complet, dans lequel la mise en place du matériau diélectrique (le matériau fluoré) requiert des étapes ultérieures de fabrication. Le brevet FR 2 919 521 propose un dispositif comprenant une couche en polymère fluoré dont une partie au moins de la surface est recouverte d'un polymère comportant au moins une fonction fluorée et au moins une fonction acide ou base et formant une couche d'accroché sur ledit polymère fluoré, ladite couche d'accroché étant recouverte par une autre couche. This makes it very difficult to manufacture complex devices comprising various elements essential to their operation. This is for example the case for a complete transistor, in which the introduction of the dielectric material (the fluorinated material) requires subsequent manufacturing steps. Patent FR 2 919 521 proposes a device comprising a fluoropolymer layer of which at least part of the surface is covered with a polymer comprising at least one fluorinated function and at least one acid or base function and forming a layer of hooked on said fluoropolymer, said hook layer being covered by another layer.
Cependant, la couche d'accroché est en un matériau conducteur ionique qui perturbe le bon fonctionnement du transistor.  However, the hook layer is an ionic conductive material that disrupts the proper operation of the transistor.
L'invention vise à fournir un procédé qui permette de rendre hydrophile la couche naturellement hydrophobe d'un matériau fluoré, afin de permettre le dépôt d'autres couches sur cette couche en matériau fluoré,  The aim of the invention is to provide a process which makes it possible to render the hydrophilic layer of a fluorinated material hydrophilic, in order to allow the deposition of other layers on this layer of fluorinated material,
A cet effet, l'invention propose un procédé de traitement pour rendre hydrophile une surface d'une couche en un matériau fluoré caractérisé en ce qu'il comprend une étape a) de dépôt d'une couche d'un (oxo)hydroxyde d'un élément du groupe des métaux al calino -terreux ou du groupe II ou du groupe III du tableau périodique des éléments ou d'une terre rare, ou d'un mélange de ceux-ci sur ladite surface.  For this purpose, the invention proposes a treatment process for rendering a hydrophilic surface of a layer made of a fluorinated material, characterized in that it comprises a step a) of depositing a layer of a (oxo) hydroxide d an element of the alcalino-terrous metal group or group II or group III of the periodic table of the elements or of a rare earth, or a mixture thereof on said surface.
De préférence, à l'étape a), on dépose un (oxo)hydroxyde d'un élément choisi parmi le béryllium, le magnésium, le calcium, le strontium, l'indium, le baryum, le radium, l'aluminium, le zinc, le scandium, l'yttrium, et les mélanges de ceux-ci.  Preferably, in step a), a (oxo) hydroxide of an element selected from among beryllium, magnesium, calcium, strontium, indium, barium, radium, aluminum, zinc, scandium, yttrium, and mixtures thereof.
Plus préférablement, à l'étape a), ledit élément est du magnésium ou de l'aluminium et on dépose un hydroxyde de magnésium Mg(OH)2 ou un hydroxyde d'aluminium Al(OH)3. More preferably, in step a), said element is magnesium or aluminum and Mg (OH) 2 magnesium hydroxide or Al (OH) 3 aluminum hydroxide is deposited.
Encore de préférence, l'épaisseur de la couche en (oxo)hydroxyde est comprise entre 10 nm et 1 μιτι, plus préférablement, cette épaisseur est comprise entre 10 et 300 nm, inclus. Encore plus préférablement, elle est égale à 50 nm.  Still preferably, the thickness of the (oxo) hydroxide layer is between 10 nm and 1 μm, more preferably, this thickness is between 10 and 300 nm, inclusive. Even more preferably, it is equal to 50 nm.
Selon un premier mode de mise en oeuvre du procédé de traitement de l'invention, l'étape a) de dépôt sur ladite surface est une étape d'hydrolyse, sur ladite surface, d'un sel dudit élément.  According to a first embodiment of the treatment method of the invention, step a) of depositing on said surface is a step of hydrolysis, on said surface, of a salt of said element.
Lorsque l'élément est le magnésium, de préférence ledit sel est du When the element is magnesium, preferably said salt is
MgCl2 et l'hydrolyse est effectuée à pH 9. Selon un second mode de mise en œuvre du procédé de traitement de l'invention, l'étape a) est une étape de dépôt dudit (oxo)hydroxyde dudit élément en suspension dans un solvant. MgCl 2 and hydrolysis is carried out at pH 9. According to a second embodiment of the treatment method of the invention, step a) is a step of depositing said (oxo) hydroxide of said element in suspension in a solvent.
Dans ce second mode de réalisation, de préférence, ladite suspension est un sol colloïdal dudit (oxo)hydroxyde dudit élément.  In this second embodiment, preferably, said suspension is a colloidal sol of said (oxo) hydroxide of said element.
De préférence, la couche en un matériau fluoré est une couche en un polymère fluoré ou en silane fluoré.  Preferably, the layer of a fluorinated material is a layer of a fluorinated polymer or fluorinated silane.
L'invention propose également un procédé de dépôt d'une couche en un matériau choisi parmi un matériau métallique, un matériau conducteur d'électricité, un matériau semi-conducteur et un matériau isolant, sur la surface d'une couche en un matériau fluoré, caractérisé en ce qu'il comprend une étape de traitement de ladite surface de la couche en un matériau fluoré pour la rendre hydrophile, par le procédé selon l'invention, suivie d'une étape de dépôt de ladite couche en un matériau métallique, ou conducteur d'électricité, ou semi-conducteur, ou isolant.  The invention also proposes a method for depositing a layer of a material chosen from a metallic material, an electrically conductive material, a semiconductor material and an insulating material, on the surface of a layer made of a fluorinated material. characterized in that it comprises a step of treating said surface of the layer with a fluorinated material to make it hydrophilic, by the process according to the invention, followed by a step of depositing said layer of a metallic material, or conductor of electricity, or semiconductor, or insulator.
De préférence, dans ce procédé, le matériau est un matériau métallique choisi parmi l'argent, le chrome, l'or, le titane, l'aluminium, le platine, le palladium, le cuivre, le nickel, le molybdène, une encre conductrice, en particulier comprenant des nanoparticules métalliques.  Preferably, in this process, the material is a metallic material selected from silver, chromium, gold, titanium, aluminum, platinum, palladium, copper, nickel, molybdenum, an ink conductor, in particular comprising metal nanoparticles.
Lorsque le matériau est un matériau conducteur d'électricité métallique, il est de préférence choisi parmi un polymère conducteur, tel que le PEDOT/PSS : poly(3,4-éthylènedioxythiophène) (PEDOT) / polystyrène sulfonate) de sodium (PSS), la polyaniline, les oxydes métalliques conducteurs choisis parmi ΓΙΤΟ (indium-étain-oxyde), ΓΑΖΟ (alliage conducteur d'oxyde d'aluminium et de zinc), le W03 (oxyde de tungstène), les nano tubes de carbone, le graphène, les mélanges argent/graphène, ou encore, les mélanges cuivre/graphène. When the material is a metallic electrically conductive material, it is preferably selected from a conductive polymer, such as PEDOT / PSS: sodium poly (3,4-ethylenedioxythiophene) (PEDOT) / polystyrene sulfonate (PSS), polyaniline, the conductive metal oxides chosen from ΓΙΤΟ (indium-tin-oxide), ΓΑΖΟ (conducting alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanopipes, graphene , silver / graphene mixtures, or even copper / graphene mixtures.
L'invention propose aussi un dispositif caractérisé en ce qu'il comprend une couche en un matériau fluoré dont une surface est revêtue d'une couche en (oxo)hydroxyde d'un élément choisi dans le groupe des métaux alcalino-terreux ou du groupe II ou du groupe III du tableau périodique des éléments, ou d'une terre rare, et une couche en un matériau choisi parmi un matéiiau métallique, un matériau conducteur d'électricité, un matériau semi-conducteur, et un matériau isolant, déposée sur la surface de la couche en (oxo)hydroxyde non en contact avec la couche en un matériau fluoré. The invention also proposes a device characterized in that it comprises a layer made of a fluorinated material, one surface of which is coated with an (oxo) hydroxide layer of an element selected from the group of alkaline earth metals or from the group II or III of the periodic table of the elements, or a rare earth, and a layer of a material selected from a metal material, an electrically conductive material, a semiconductor material, and an insulating material, deposited on the surface of the (oxo) hydroxide layer not in contact with the layer of a fluorinated material.
De préférence, dans le dispositif de l'invention, l'(oxo)hydroxyde est un (oxo)hydroxyde d'un élément choisi parmi le béryllium, le magnésium, le calcium, le strontium, l'indium, le baryum, le radium, l'aluminium, le zinc, le scandium, l'yttrium, et les mélanges de ceux-ci.  Preferably, in the device of the invention, the (oxo) hydroxide is an (oxo) hydroxide of a member selected from among beryllium, magnesium, calcium, strontium, indium, barium, radium , aluminum, zinc, scandium, yttrium, and mixtures thereof.
Plus préférablement, l'(oxo)hydroxyde est un hydroxyde de magnésium Mg(OH)2 ou un hydroxyde d'aluminium Al(OH)3. More preferably, the (oxo) hydroxide is Mg (OH) 2 magnesium hydroxide or Al (OH) 3 aluminum hydroxide.
De préférence, dans le dispositif de l'invention, l'épaisseur de la couche en (oxo)hydroxyde est comprise entre 10 et 300 nm, inclus. De préférence, elle est égale à 50 nm.  Preferably, in the device of the invention, the thickness of the (oxo) hydroxide layer is between 10 and 300 nm, inclusive. Preferably, it is equal to 50 nm.
Toujours de préférence, la couche en un matériau fluoré est une couche en un polymère fluoré ou en un silane fluoré.  Still preferably, the layer of a fluorinated material is a layer of a fluorinated polymer or a fluorinated silane.
Quant à la couche en un matériau métallique, elle est de préférence en un matériau choisi parmi l'argent, le chrome, l'or, le titane, l'aluminium, le platine, le palladium, le cuivre, le nickel, le molybdène, une encre conductrice, en particulier comprenant des nanoparticules métalliques.  As for the layer made of a metallic material, it is preferably made of a material chosen from among silver, chromium, gold, titanium, aluminum, platinum, palladium, copper, nickel and molybdenum. , a conductive ink, in particular comprising metal nanoparticles.
Quant à la couche en un matériau conducteur d'électricité, elle est de préférence en un matériau choisi parmi un polymère conducteur tel que PEDOT/PSS : poly(3,4-éthylènedioxythiophène) (PEDOT) / poly(styrène sulfonate) de sodium (PSS), la polyaniline, les oxydes métalliques conducteurs choisis parmi ΓίΤΟ (indium-étain-oxyde), l'AZO (alliage d'oxyde d'aluminium et de zinc), le W03 (oxyde de tungstène), les nanotubes de carbone, le graphène, les mélanges argent/graphène, ou encore, les mélanges cuivre/graphène. As for the layer made of an electrically conductive material, it is preferably made of a material chosen from a conductive polymer such as PEDOT / PSS: sodium poly (3,4-ethylenedioxythiophene) (PEDOT) / poly (styrene sulphonate) ( PSS), polyaniline, conductive metal oxides selected from ΓίΤΟ (indium-tin-oxide), AZO (alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanotubes graphene, silver / graphene mixtures, or copper / graphene mixtures.
Un dispositif préféré selon l'invention est un transistor organique. A preferred device according to the invention is an organic transistor.
L'invention sera mieux comprise, et d'autres caractéristiques et avantages de celle-ci apparaîtront plus clairement à la lecture de la description explicative qui suit et qui est faite en référence aux figures annexées dans lesquelles : The invention will be better understood, and other features and advantages thereof will appear more clearly on reading the explanatory description which follows and which is given with reference to the appended figures in which:
- la figure 1 représente schématiquement la structure d'un transistor organique avant le dépôt de la grille,  FIG. 1 schematically represents the structure of an organic transistor before depositing the gate,
- la figure 2 représente le transistor de la figure 1 en cours de traitement par le procédé de l'invention avant le dépôt de la grille, - la figure 3 représente schématiquement le transistor obtenu après le traitement réalisé comme montré en figure 2, FIG. 2 represents the transistor of FIG. 1 being processed by the method of the invention before depositing the gate, FIG. 3 diagrammatically represents the transistor obtained after the treatment carried out as shown in FIG. 2,
- la figure 4 représente le transistor de la figure 3 avec la grille déposée,  FIG. 4 represents the transistor of FIG. 3 with the gate deposited,
- la figure 5 représente l'augmentation de l'épaisseur de la couche obtenue lors du traitement de la surface d'un polymère fluoré par le procédé de l'invention, en fonction du temps,  FIG. 5 represents the increase in the thickness of the layer obtained during the treatment of the surface of a fluoropolymer by the process of the invention as a function of time,
- la figure 6 montre une photographie prise au microscope optique à un grossissement x 5 de la surface d'une couche en un polymère fluoré, le Cytop®, de l'art antérieur sur laquelle une électrode a été imprimée avec une encre à P argent, - Figure 6 shows a photograph taken with an optical microscope at a magnification x 5 of the surface of a layer of fluorinated polymer, Cytop ® of the prior art on which an electrode was printed with a silver ink to P ,
- la figure 7 montre une photographie prise au microscope optique à un grossissement x 5 de la surface d'une couche en un polymère fluoré, le Cytop®, traitée selon l'invention, sur laquelle une électrode a été imprimée avec une encre à l'argent, et - Figure 7 shows a photograph taken with an optical microscope at a magnification x 5 of the surface of a layer of fluorinated polymer, Cytop ®, treated according to the invention wherein an electrode was printed with an ink to money, and
- la figure 8 représente la variation de la tension de grille, Vg, en volt, d'un transistor de l'art antérieur et d'un transistor selon l'invention.  FIG. 8 represents the variation of the gate voltage, Vg, in volts, of a transistor of the prior art and of a transistor according to the invention.
Pour permettre le dépôt de couches, en particulier en un matériau métallique ou en un matériau conducteur d'électricité ou en un matériau semiconducteur, ou un matériau isolant, sur la surface d'une couche en un matériau fluoré, l'invention propose de recouvrir la surface de la couche en un matériau fluoré à l'aide d'une couche additionnelle dite couche "d'accroché" qui permet d'obtenir une surface hydrophile sur laquelle peut être déposée une couche, en particulier en un métal tel que l'argent, le chrome, l'or, le titane, l'aluminium, le platine, le palladium, le cuivre, le nickel, le molybdène, une encre conductrice, en particulier comprenant des nanoparticules métalliques.  To allow the deposition of layers, in particular of a metallic material or of an electrically conductive material or of a semiconductor material, or an insulating material, on the surface of a layer made of a fluorinated material, the invention proposes to cover the surface of the layer made of a fluorinated material with the aid of an additional layer called "hooked" layer which makes it possible to obtain a hydrophilic surface on which a layer may be deposited, in particular of a metal such as silver, chromium, gold, titanium, aluminum, platinum, palladium, copper, nickel, molybdenum, a conductive ink, in particular comprising metal nanoparticles.
Quant au matériau conducteur d'électricité, il est de préférence choisi parmi un polymère conducteur tel que PEDOT/PSS : poly(3,4- éthylènedioxythiophène) (PEDOT) / poly(styrène sulfonate) de sodium (PSS), la polyaniline, les oxydes métalliques conducteurs choisis parmi PITO (indium-étain- oxyde), l'AZO (alliage d'oxyde d'aluminium et de zinc), le W03 (oxyde de tungstène), les nanotubes de carbone, le graphène, les mélanges argent/graphène, ou encore, les mélanges cuivre/graphène. On obtient alors une structure adhérente. As for the electrically conductive material, it is preferably chosen from a conducting polymer such as PEDOT / PSS: poly (3,4-ethylenedioxythiophene) (PEDOT) / sodium polystyrene sulphonate (PSS), polyaniline, conductive metal oxides selected from PITO (indium-tin-oxide), AZO (alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanotubes, graphene, silver mixtures graphene or copper / graphene mixtures. An adherent structure is then obtained.
L'invention propose de modifier la mouillabilité de la surface de la couche en un matériau fluoré en créant une couche d'accroché formée d'un hydroxyde ou d'un oxohydroxyde d'un métal alcalino-terreux, ou d'un élément du groupe II ou du groupe III du tableau périodique des éléments, ou d'une terre rare.  The invention proposes to modify the wettability of the surface of the layer in a fluorinated material by creating a layer of hook formed of an alkaline earth metal hydroxide or oxohydroxide, or an element of the group II or group III of the periodic table of the elements, or of a rare earth.
Selon l'élément, on formera soit un hydroxyde pur, soit un oxohydroxyde, c'est-à-dire un oxyde hydraté.  Depending on the element, either a pure hydroxide or an oxohydroxide, i.e., a hydrated oxide, will be formed.
Ainsi, dans ce qui suit, d'une manière générale, on appellera cette couche "couche d'(oxo)hydroxyde" pour signifier aussi bien une couche en un hydroxyde de l'élément qu'une couche en un oxohydroxyde de l'élément.  Thus, in what follows, in general, this layer will be called "(oxo) hydroxide layer" to mean both a layer of a hydroxide of the element and a layer of an oxohydroxide of the element. .
Cet élément peut être le béryllium, le magnésium, le calcium, le strontium, l'indium, le baryum, le radium, l'aluminium, le zinc, le scandium, 1'yttrium, et les mélanges de ceux-ci.  This element may be beryllium, magnesium, calcium, strontium, indium, barium, radium, aluminum, zinc, scandium, yttrium, and mixtures thereof.
On préférera tout particulièrement utiliser, en tant qu'élément, le magnésium ou l'aluminium, auquel cas la couche formée sera une couche de brucite, Mg(OH)2 ou de gibbsite, Al(OH)3, respectivement. Magnesium or aluminum will preferably be used as the element, in which case the layer formed will be a brucite, Mg (OH) 2 or gibbsite, Al (OH) 3 layer, respectively.
En effet, les couches de brucite ou de gibbsite présentent l'intérêt d'être électriquement isolantes et possèdent une permittivité assez élevée de l'ordre de 8 et plus.  Indeed, the layers of brucite or gibbsite have the advantage of being electrically insulating and have a fairly high permittivity of the order of 8 and more.
Mais surtout, la brucite et la gibbsite croissent sur des couches en polymères fluorés et présentent des aptitudes à adhérer tant aux polymères fluorés tels que le Téfion® ou le Cytop®, qu'à une couche en un silane fluoré, qu'à d'autres matériaux, par exemple, des colles fluorées. But above all, brucite and gibbsite grow on fluoropolymer layers and have the ability to adhere to both fluorinated polymers such as Tefion ® or Cytop ® , as a layer of fluorinated silane, than to other materials, for example, fluorine glues.
De plus, lorsque l'on utilise une encre conductrice, c'est-à-dire une encre contenant un métal, cette encre adhère à la brucite ou à la gibbsite, ce qui permet de déposer, en particulier dans le cas des transistors où la couche en matériau diélectrique est souvent en un polymère fluoré, une autre couche en un métal, par exemple pour former l'électrode de grille, par des techniques telles que l'impression, le dépôt à la tournette, ou le collage.  In addition, when using a conductive ink, that is to say an ink containing a metal, this ink adheres to brucite or gibbsite, which allows to deposit, particularly in the case of transistors where the layer of dielectric material is often a fluorinated polymer, another layer of a metal, for example to form the gate electrode, by techniques such as printing, spin coating, or gluing.
Ainsi, l'invention trouve application plus particulièrement dans le domaine des transistors organiques. En effet, il est maintenant admis que pour obtenir des transistors organiques qui présentent peu d'hystérésis et de fortes mobilités, il est nécessaire que le matériau diélectrique de la grille soit constitué d'un polymère présentant une faible valeur de c (dit low K) (J. Veres et al « Gâte Insulators in Organic Field-Effect Transistors », Chem. Mater. 2004, 16, 4543-4555). Thus, the invention finds application more particularly in the field of organic transistors. Indeed, it is now accepted that in order to obtain organic transistors which have little hysteresis and high mobility, it is necessary for the dielectric material of the gate to consist of a polymer having a low value of c (called low K ) (J. Veres et al., "Gaste Insulators in Organic Field-Effect Transistors", Chem Mater 2004, 16, 4543-4555).
Parmi les polymères low K, les fluoropolymères sont des matériaux de choix. Il faut donc déposer les autres couches qui constituent l'empilement d'un transistor sur cette couche.  Of the low K polymers, fluoropolymers are materials of choice. It is therefore necessary to deposit the other layers that constitute the stack of a transistor on this layer.
La figure 1 représente schématiquement la structure d'un transistor organique avant le dépôt de la grille.  FIG. 1 schematically represents the structure of an organic transistor before the deposition of the gate.
Comme on le voit en figure 1, un tel transistor est constitué d'un substrat, noté 1 en figure 1 , généralement en polyéthylène naphthalate (PEN) ayant une épaisseur généralement de 125μπι.  As seen in FIG. 1, such a transistor consists of a substrate, denoted 1 in FIG. 1, generally made of polyethylene naphthalate (PEN) having a thickness generally of 125 μm.
A titre d'exemple de matériaux susceptibles de former un tel substrat, on peut notamment citer la silice, le silicium, le téraphtalate de polyéthylène (PET), le naphtaîate de polyéthyle (PEN), le polyimide (PI), le polyéther imide (PEI), le polyéther sulfone (PES), le polysulfone (PSF), le sulfure de polyphényîène (PPS), le polyéther éther cétone (PEEK), le polyacrylate (PA), le polyamide imide (PAÎ), le polystyrène, le polyéthylène, le polypropylène, une résine polyamine, une résine carbonate ou encore une résine cellulosique.  By way of example of materials capable of forming such a substrate, mention may notably be made of silica, silicon, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyetherimide ( PEI), polyether sulphone (PES), polysulfone (PSF), polyphenylene sulphide (PPS), polyether ether ketone (PEEK), polyacrylate (PA), polyamide imide (PAI), polystyrene, polyethylene polypropylene, a polyamine resin, a carbonate resin or a cellulosic resin.
Sur ce substrat on dépose deux électrodes notées 2 en figure 1, appelées électrode source et électrode drain.  On this substrate is deposited two electrodes noted 2 in Figure 1, called source electrode and drain electrode.
Ces électrodes sont structurées, c'est-à-dire que leur surface n'est pas plane. Ces électrodes sont structurées par un traitement au laser ou par photolithographie.  These electrodes are structured, that is to say that their surface is not flat. These electrodes are structured by a laser treatment or by photolithography.
Ces électrodes sont généralement en or, ont une épaisseur de 30nm et sont déposées par évaporation.  These electrodes are generally made of gold, have a thickness of 30 nm and are deposited by evaporation.
Comme montré en figure 1, ces électrodes 2 et une partie du substrat 1 sont revêtues d'une couche, notée 3 en figure 1 , en un matériau semi- conducteur, généralement du type TIPS PENTACENE, qui est une petite molécule semi-conductrice déposée par une technique d'impression telle que l'héliogravure, ou en tétracène ou en anthracène. A titre d'autres exemples de tels matériaux on peut citer deux types de matériaux semi -conducteurs organiques considérés dans le cadre de la présente invention. Il peut s'agir de molécules de faible masse moléculaire (couramment appelées « petites molécules »), et notamment de molécules de masse moléculaire inférieure à 1000 g/mol, ou de polymères constitués de macromolécules de plus grande masse moléculaire. Ces deux types de semi-conducteurs organiques ont pour point commun de présenter un système conjugué provenant de Γ alternance de simples et de doubles liaisons carbone-carbone. A titre de semi-conducteur organique de faible masse moléculaire, on peut par exemple citer ceux de type polyacène, oligothiophène ou phtalocyanine. A titre de semi-conducteur organique polymère, on peut par exemple citer ceux de type polyacétylène, poîyphénylène, polythiophène ou poly(phénylène/vinylène). Il pourra notamment s'agir d'un semi-conducteur organique choisi parmi le pentacène, le tétracène, l'anthracène, le naphthalène, l'alpha-ô-thiophène, l'alpha-4-thiophène, le pérylène et ses dérivés, le rubrène et ses dérivés, le coronène et ses dérivés, le diimide tétracarboxylique de pérylène et ses dérivés, le dianhydride tétracarboxylique de pérylène et ses dérivés, le polythiophène et ses dérivés, le polyparaphenylène-vinylène et ses dérivés, le polyparaphénylène et ses dérivés, le polyfluorène et ses dérivés, un copolymère de polyfluorène- oligothiophène et ses dérivés, le polythiophène-vinylène et ses dérivés, un copolymère aromatique hétérocyclique de polythiophène et ses dérivés, un oligonaphthalène et ses dérivés, l'alpha-5-thiophène oligothiophène et ses dérivés, la phthalocyanine qui ne contient pas de métal et ses dérivés, le dianhydride pyromellitique et ses dérivés, le diimide pyromellitique et ses dérivés, le dianhydride d'acide tétracarboxylique de pérylène et ses dérivés, le diimide tétracarboxylique de pérylène et ses dérivés, le diimide tétracarboxylique de naphtalène et ses dérivés ou le dianhydride-acide tétracarboxylique de naphtalène et ses dérivés. As shown in FIG. 1, these electrodes 2 and a portion of the substrate 1 are coated with a layer, denoted 3 in FIG. 1, of a semiconductor material, generally of the TIPS PENTACENE type, which is a small semiconductor molecule deposited by a printing technique such as gravure, or tetracene or anthracene. As other examples of such materials one can mention two types of organic semi-conducting materials considered in the context of the present invention. These may be molecules of low molecular weight (commonly called "small molecules"), and especially molecules with a molecular weight of less than 1000 g / mol, or polymers consisting of macromolecules of greater molecular weight. These two types of organic semiconductors have the common point to present a conjugate system from Γ alternating single and double carbon-carbon bonds. As organic semiconductor of low molecular weight, there may be mentioned, for example, those of the polyacene, oligothiophene or phthalocyanine type. Examples of polymeric organic semiconductors that may be mentioned are those of polyacetylene, polyphenylene, polythiophene or poly (phenylene / vinylene) type. It may especially be an organic semiconductor selected from pentacene, tetracene, anthracene, naphthalene, alpha-6-thiophene, alpha-4-thiophene, perylene and its derivatives, rubrene and its derivatives, coronene and its derivatives, perylene tetracarboxylic diimide and its derivatives, perylene tetracarboxylic dianhydride and its derivatives, polythiophene and its derivatives, polyparaphenylene-vinylene and its derivatives, polyparaphenylene and its derivatives, polyfluorene and its derivatives, a polyfluorene-oligothiophene copolymer and its derivatives, polythiophene-vinylene and its derivatives, a polythiophene heterocyclic aromatic copolymer and its derivatives, an oligonaphthalene and its derivatives, alpha-5-thiophene oligothiophene and its derivatives, phthalocyanine which does not contain metal and its derivatives, pyromellitic dianhydride and its derivatives, pyromellitic diimide and its derivatives Examples are: perylene tetracarboxylic acid dianhydride and its derivatives, perylene tetracarboxylic diimide and its derivatives, naphthalene tetracarboxylic diimide and its derivatives or naphthalene tetracarboxylic acid dianhydride and its derivatives.
L'électrode grille doit ensuite être déposée. Pour cela, une couche, notée 4 en figure 1, en polymère fluoré est déposée sur la couche 3.  The gate electrode must then be deposited. For this, a layer, denoted 4 in FIG. 1, of fluoropolymer is deposited on the layer 3.
Le polymère fluoré utilisé est généralement un fluoropolymère CYTOP® d'une épaisseur comprise entre 500 et 800 nm, inclus. The fluoropolymer used is generally a fluoropolymer CYTOP ® with a thickness between 500 and 800 nm, inclusive.
II faut alors déposer l'électrode grille, notée 6 en figure 4, sur cette couche 4 en polymère fluoré. Cette électrode grille a une épaisseur comprise entre 50 nm et 1 μηι, inclus. En raison des difficultés évoquées de dépôt sur la couche 4 en polymère fluoré, il existe un défaut d'adhérence entre la couche 4 et la couche 6 supérieure, à savoir l'électrode grille. Ces couches ne sont donc pas uniformes. It is then necessary to deposit the gate electrode, denoted 6 in FIG. 4, on this layer 4 made of fluoropolymer. This gate electrode has a thickness of between 50 nm and 1 μηι, inclusive. Due to the evoked difficulties of deposition on the fluoropolymer layer 4, there is a lack of adhesion between the layer 4 and the upper layer 6, namely the gate electrode. These layers are not uniform.
Grâce au procédé de l'invention de traitement d'une surface pour rendre hydrophile la surface d'une couche en un matériau fluoré, il est possible de déposer des encres conductrices par sérigraphie ou par impression jet d'encre, ou par héliogravure, ou par flexogravure, ou par toute autre technique de dépôt d'une solution liquide. Il est alors possible d'imprimer la grille d'un transistor.  With the method of the invention for treating a surface to render the surface of a fluorinated material layer hydrophilic, it is possible to deposit conductive inks by screen printing or by inkjet printing, or by gravure printing, or by flexogravure, or by any other technique of depositing a liquid solution. It is then possible to print the gate of a transistor.
Le procédé de traitement de l'invention pour rendre hydrophile la surface de la couche 4 en un matériau fluoré est schématiquement représenté en figure 2.  The treatment method of the invention for rendering the surface of the layer 4 hydrophilic in a fluorinated material is diagrammatically shown in FIG.
Comme on le voit en figure 2, où les couches identiques à celles montrées en figure 1 portent les mêmes numéros qu'en figure 1, on dépose une goutte, notée 10 en figure 2, d'une solution liquide d'un élément du groupe des métaux al calino -terreux, ou du groupe III du tableau périodique des éléments, ou d'une terre rare, sur la surface de la couche fluorée 4.  As can be seen in FIG. 2, where the layers identical to those shown in FIG. 1 bear the same numbers as in FIG. 1, a drop, denoted 10 in FIG. 2, of a liquid solution of one element of the group is deposited. alcalino-terrous metals, or group III of the periodic table of the elements, or of a rare earth, on the surface of the fluorinated layer 4.
Cette goutte 10 recouvre l'ensemble de la couche 4.  This drop 10 covers the entire layer 4.
On obtient alors une couche, notée 5 en figure 2, d'hydroxyde ou d'oxohydroxyde de l'élément, après un séchage pour évaporer le solvant de la solution déposée.  A layer, noted in FIG. 2, of hydroxide or oxohydroxide of the element is then obtained after drying in order to evaporate the solvent from the deposited solution.
En particulier, lorsque l'élément est le magnésium ou l'aluminium, en raison de raffinité de la brucite, Mg(OH)2, et de la gibbsite, Al(OH)3, avec la surface fluorée de la couche 4, il se forme un feuillet de brucite ou de gibbsite sur toute la surface exposée de la couche 4. In particular, when the element is magnesium or aluminum, due to brucite's affinity, Mg (OH) 2 , and gibbsite, Al (OH) 3 , with the fluorinated surface of layer 4 it a sheet of brucite or gibbsite forms on the entire exposed surface of layer 4.
L'épaisseur de cette couche 5 varie en fonction du temps de contact entre la solution de l'élément du groupe des métaux alcalino -terreux ou du groupe II ou III du tableau périodique ou de la terre rare, sur la surface de la couche 4.  The thickness of this layer 5 varies as a function of the contact time between the solution of the element of the group of alkaline-earth metals or of group II or III of the periodic table or of the rare earth, on the surface of layer 4 .
On peut alors déposer une encre conductrice d'électricité pour former l'électrode de grille sur la couche 5 ainsi formée, comme montré en figure 4, où l'électrode de grille est notée 6. La couche 5, dite d'accroché, a une épaisseur généralement comprise entre 10 nm et 1 μτη, inclus. Elle est de préférence comprise entre 10 et 300 nm, inclus. Mais dans un transistor, elle est de préférence de 50 nm. An electrically conductive ink can then be deposited to form the gate electrode on the layer 5 thus formed, as shown in FIG. 4, where the gate electrode is denoted 6. The layer 5, said hooked, has a thickness generally between 10 nm and 1 μτη, inclusive. It is preferably between 10 and 300 nm, inclusive. But in a transistor, it is preferably 50 nm.
La solution déposée sur la couche 4 peut être une solution de l'élément à déposer lui-même, par exemple un sol colloïdal de l'hydroxyde de l'élément ou de l'oxohydroxyde de l'élément. En particulier, dans le cas de la brucite et de la gibbsite, on pourra utiliser respectivement un sol colloïdal d'hydroxyde de magnésium Mg(OH)2 ou d'hydroxyde d'aluminium Al(OH)3, The solution deposited on the layer 4 may be a solution of the element to be deposited itself, for example a colloidal sol of the hydroxide of the element or of the oxohydroxide of the element. In particular, in the case of brucite and gibbsite, a colloidal sol of magnesium hydroxide Mg (OH) 2 or aluminum hydroxide Al (OH) 3 can be used ,
Mais, on pourra également utiliser une solution aqueuse d'un sel de cet élément et procéder à l'hydrolyse in situ, c'est-à-dire directement sur la couche 4, de ce sel pour obtenir l'(oxo)hydroxyde de l'élément voulu.  However, it will also be possible to use an aqueous solution of a salt of this element and carry out hydrolysis in situ, that is to say directly on layer 4, of this salt to obtain the (oxo) hydroxide of the desired element.
Par exemple, on pourra utiliser du chlorure de magnésium MgCl2 ou du fluorure de magnésium MgF2 ou du chlorure d'aluminium que l'on mettra en solution dans de l'eau. Cette solution sera déposée sur la couche 4 et une solution de soude sera alors versée sur la solution de chlorure de magnésium. La réaction de formation du film de brucite sur la couche 4 démarre à partir de pH 9. For example, magnesium chloride MgCl 2 or magnesium fluoride MgF 2 or aluminum chloride may be used and dissolved in water. This solution will be deposited on layer 4 and a sodium hydroxide solution will then be poured on the magnesium chloride solution. The formation reaction of the brucite film on layer 4 starts from pH 9.
Puis l'épaisseur de la couche de brucite croît sur la couche 4.  Then the thickness of the brucite layer increases on the layer 4.
La figure 5 montre la variation d'épaisseur d'une couche de brucite Mg(OH)2 en fonction du temps de trempage d'une couche en Cytop® dans une solution contenant 100 mg de MgCl2 dans 200 mL d'eau, à laquelle on a ajouté une solution de soude, NaOH de concentration 0,5 mol/1, jusqu'à obtenir un pH de 9. Figure 5 shows the variation in thickness of a layer of brucite Mg (OH) 2 as a function of immersion time of a Cytop ® layer in a solution containing 100 mg of MgCl 2 in 200 mL of water, which was added sodium hydroxide solution, NaOH concentration of 0.5 mol / l, until a pH of 9.
Comme on le voit en figure 5, on obtient une couche 5 de brucite d'une épaisseur de 50 nm en 5 minutes.  As can be seen in FIG. 5, a layer of brucite having a thickness of 50 nm is obtained in 5 minutes.
Pour obtenir un transistor, il faut ensuite de déposer l'électrode 6 de grille sur cette couche 5 d'accroché.  To obtain a transistor, it is then necessary to deposit the gate electrode 6 on this layer 5 hooked.
Ainsi, l'invention propose également un procédé de dépôt d'une couche 6 en un matériau métallique, ou en un matériau conducteur d'électricité tel qu'un polymère conducteur tel que le PEDOT/PSS, (poly(3,4- éthylènedioxythiophène) (PEDOT) et le poly(styrène sulfonate) de sodium (PSS)), ou en un matériau semi-conducteur tels que l'un de ceux cités précédemment, ou en un matériau isolant, sur la surface d'une couche 4 en un matériau fluoré, ce procédé comprenant une étape de traitement de la surface de la couche 4, pour y créer la couche d'accroché 5, comme montré ci-dessus, par le procédé de traitement de l'invention, puis le dépôt de ladite couche 6 en un matériau métallique ou semiconducteur. Thus, the invention also proposes a process for depositing a layer 6 made of a metallic material, or an electrically conductive material such as a conductive polymer such as PEDOT / PSS, (poly (3,4-ethylenedioxythiophene) ) (PEDOT) and sodium polystyrene sulfonate (PSS), or a semiconductor material such as one of those mentioned above, or an insulating material, on the surface of a layer 4 in a fluorinated material, this process comprising a step of treating the surface of the layer 4 to create the hook layer 5, as shown above, by the treatment method of the invention, then the deposition of said layer 6 of a metal or semiconductor material.
Le matériau métallique est de préférence choisi parmi l'argent, le chrome, l'or, le titane, raluminium, le platine, le palladium, le cuivre, le nickel, le molybdène, une encre conductrice, en particulier comprenant des nanoparticules métalliques.  The metallic material is preferably selected from silver, chromium, gold, titanium, aluminum, platinum, palladium, copper, nickel, molybdenum, a conductive ink, in particular comprising metal nanoparticles.
Quant au matériau conducteur d'électricité, il est de préférence choisi parmi un polymère conducteur tel que le PEDOT/PSS : poly(3,4- éthylènedioxythiophène) (PEDOT) / poly(styrène sulfonate) de sodium (PSS), la polyaniline, les oxydes métalliques conducteurs choisis parmi ΓΙΤΟ (indium-étain- oxyde), l'AZO (alliage d'oxyde d'aluminium et de zinc), le W03 (oxyde de tungstène), les nanotubes de carbone, le graphène, les mélanges argent/graphène, ou encore, les mélanges cuivre/graphène. As for the electrically conductive material, it is preferably chosen from a conducting polymer such as PEDOT / PSS: poly (3,4-ethylenedioxythiophene) (PEDOT) / sodium polystyrene sulfonate (PSS), polyaniline, the conductive metal oxides chosen from ΓΙΤΟ (indium-tin-oxide), AZO (alloy of aluminum oxide and zinc), WO 3 (tungsten oxide), carbon nanotubes, graphene, mixtures silver / graphene, or copper / graphene mixtures.
Les dispositifs obtenus par ces procédés sont également un objet de l'invention.  The devices obtained by these methods are also an object of the invention.
Ainsi, un dispositif selon l'invention comprend une couche 4 en un matériau fluoré, tel qu'un polymère fluoré ou un silane fluoré, dont une surface est revêtue d'une couche d'un hydroxyde ou d'un oxohydroxyde d'un élément du groupe des métaux alcalino-terreux ou du groupe II ou III du tableau périodique des éléments ou d'une terre rare, ou de mélanges de ceux-ci.  Thus, a device according to the invention comprises a layer 4 made of a fluorinated material, such as a fluorinated polymer or a fluorinated silane, one surface of which is coated with a layer of an elemental hydroxide or oxohydroxide. of the alkaline earth metal group or group II or III of the Periodic Table of the Elements or rare earth, or mixtures thereof.
Le dispositif de l'invention peut de plus comprendre une couche 6 en un matériau métallique ou conducteur d'électricité ou semi- conducteur, ou isolant, déposée sur toute ou partie de la surface de la couche 5.  The device of the invention may further comprise a layer 6 of a metallic or electrically conductive or semiconductor or insulating material deposited on all or part of the surface of the layer 5.
Afin de mieux faire comprendre l'invention, on va maintenant en décrire, à titre d'exemple purement illustratif et non limitatif, un mode de mise en œuvre.  In order to better understand the invention, a mode of implementation will now be described by way of purely illustrative and nonlimiting example.
Exemple 1  Example 1
Sur un substrat 1 en polyéthylène naphtalate (PEN) d'une épaisseur de 125 μτη, on a déposé une couche 2 en or, de 30 nm d'épaisseur, par évaporation ou par dépôt en phase vapeur (PVD). Cette couche 2 d'or est gravée pour former les électrodes source et drain. Cela peut être fait par photolithographie ou par ablation laser. On a substrate 1 made of polyethylene naphthalate (PEN) with a thickness of 125 μτη, a gold layer 2, 30 nm thick, was deposited by evaporation or by vapor deposition (PVD). This layer 2 of gold is etched to form the source and drain electrodes. This can be done by photolithography or laser ablation.
On dépose ensuite une couche 3 d'un matériau s emi -conducteur TIPS PENTACENE d'une épaisseur de 100 nm, par héliogravure.  A layer 3 of 100% thick TIPS PENTACENE semiconducting material is then deposited by gravure printing.
On procède ensuite au dépôt de la couche 4 en un matériau diélectrique, qui est ici un polymère fluoré, le Cytop®, d'une épaisseur de 800 nm. Then is deposited on the layer 4 of a dielectric material, which is here a fluorinated polymer, Cytop ®, with a thickness of 800 nm.
Cette couche 4 a été formée par sérigraphie.  This layer 4 was formed by screen printing.
On procède ensuite au traitement de la surface de cette couche 4 par le procédé de traitement de l'invention.  The surface of this layer 4 is then treated by the treatment method of the invention.
A cet effet, on a utilisé une solution constituée de 100 mg de chlorure de magnésium, MgCl2, que l'on dissout dans de l'eau à une concentration de 100 mg/mL. For this purpose, a solution consisting of 100 mg magnesium chloride, MgCl 2 , was used and dissolved in water at a concentration of 100 mg / mL.
On fabrique une seconde solution de NaOH dans de l'eau à une concentration de 100 mg/mL.  A second solution of NaOH is made in water at a concentration of 100 mg / mL.
On plonge le dispositif obtenu dans la solution de MgCÎ2. The device obtained is immersed in the MgCl 2 solution.
On ajoute doucement la solution de NaOH jusqu'à obtenir un pH de 9.  The NaOH solution is slowly added until a pH of 9 is reached.
Lorsque le pH est inférieur à 9, par exemple égal à 8, la réaction est très lente à démarrer. Lorsque le pH est supérieur à 10, la réaction est très rapide mais les autres couches pourraient être endommagées.  When the pH is less than 9, for example equal to 8, the reaction is very slow to start. When the pH is above 10, the reaction is very fast but the other layers could be damaged.
La réaction d'hydrolyse démarre sur le fluor de la couche 4 en raison de la différence d'électronégativité entre le fluor, qui est électronégatif, et du magnésium, qui est électropositif.  The hydrolysis reaction starts on the fluorine of layer 4 due to the difference in electronegativity between fluorine, which is electronegative, and magnesium, which is electropositive.
Un germe de brucite Mg(OH)2 se forme sur la surface de la couche 4.  A brucite germ Mg (OH) 2 is formed on the surface of layer 4.
On maintient le dispositif dans la solution.  The device is kept in the solution.
On obtient au final un dépôt sous forme de feuillets en brucite qui recouvrent toute la surface de la couche 4. Au bout de 5 minutes, on obtient une couche transparente d'une épaisseur de 50 nm.  Finally, a deposition in the form of brucite sheets which cover the entire surface of the layer 4 is obtained. After 5 minutes, a transparent layer with a thickness of 50 nm is obtained.
La brucite cristallise dans le système rhomboédrique.  Brucite crystallizes in the rhombohedral system.
On lave ensuite à l'eau et on sèche à la souflette ou on procède à un léger recuit à 100°C pendant 5min. On mesure l'angle de contact de goutte d'eau de la surface de la couche 5 ainsi formée. It is then washed with water and blown dry or lightly annealed at 100 ° C. for 5 minutes. The droplet contact angle of the surface of the layer 5 thus formed is measured.
L'angle de contact de goutte d'eau est inférieur à 5°.  The water drop contact angle is less than 5 °.
On procède ensuite au dépôt de l'électrode 6 de grille encore contenant des nanoparticules d'argent, par jet d'encre sur la surface de cette couche 5.  The grid electrode 6 still containing silver nanoparticles is then deposited by ink jet on the surface of this layer 5.
On obtient alors le dispositif montré en figure 6. L'électrode 6 a une épaisseur de 1 μηι.  The device shown in FIG. 6 is then obtained. The electrode 6 has a thickness of 1 μηι.
La Figure 6 est une photographie vue de dessus du dispositif. Comme on le voit, la grille formée ne démouille pas et présente des contours nets.  Figure 6 is a photograph taken from above of the device. As can be seen, the grid formed does not dew and has sharp contours.
Exemple 2 (comparatif)  Example 2 (comparative)
On a fabriqué le même dispositif qu'à l'exemple 1 mais sans traiter la couche 4 avec le procédé de traitement de l'invention.  The same device as in example 1 was manufactured but without treating layer 4 with the treatment method of the invention.
On a mesuré l'angle de contact de goutte d'eau sur la surface obtenue.  The contact angle of the drop of water on the surface obtained was measured.
L'angle de contact était de 110°.  The contact angle was 110 °.
Le dispositif obtenu est montré en figure 7 où la couche 4 représente le dispositif vu de dessus, la couche de polymère fluoré étant notée 4 et la couche d'encre de nanoparticules d'argent étant notée 6.  The device obtained is shown in FIG. 7 where the layer 4 represents the device seen from above, the fluoropolymer layer being marked 4 and the ink layer of silver nanoparticles being denoted 6.
Comme on le voit d'après les figures 6 et 7 et d'après les mesures d'angle de goutte d'eau, le procédé de traitement de l'invention pour rendre la surface d'un matériau fluoré hydrophile est tout à fait efficace.  As seen from Figures 6 and 7 and from the water drop angle measurements, the treatment method of the invention for rendering the surface of a hydrophilic fluorinated material is quite effective. .
On a alors testé électriquement les dispositifs obtenus aux exemples 1 et 2 en traçant les courbes caractéristiques d'un transistor à effet de champ.  The devices obtained in Examples 1 and 2 were then electrically tested by plotting the characteristic curves of a field effect transistor.
Les courbes obtenues sont montrées en figure 8.  The curves obtained are shown in FIG.
Comme on le voit en figure 8, avec la couche de traitement selon l'invention, la courbe présente un plus grand courant.  As seen in FIG. 8, with the treatment layer according to the invention, the curve has a larger current.

Claims

REVENDICATIONS
1. Procédé de traitement pour rendre hydrophile une surface d'une couche (4) en un matériau fluoré caractérisé en ce qu'il comprend une étape a) de dépôt d'une couche (5) d'un (oxo)hydroxyde d'un élément du groupe des métaux alcalino-terreux ou du groupe II ou du groupe III du tableau périodique des éléments ou d'une terre rare ou d'un mélange de ceux-ci, sur ladite surface, 1. A treatment method for rendering a surface of a layer (4) hydrophilic in a fluoro material, characterized in that it comprises a step a) of depositing a layer (5) of a (oxo) hydroxide an element of the group of alkaline earth metals or group II or group III of the periodic table of elements or of a rare earth or a mixture thereof, on said surface,
2. Procédé selon la revendication 1, caractérisé en ce qu'à l'étape a), on dépose un (oxo)hydroxyde d'un élément choisi parmi le béryllium, le magnésium, le calcium, le strontium, l'indium, le baryum, le radium, l'aluminium, le zinc, le scandium, l'yttrium, et les mélanges de ceux-ci.  2. Method according to claim 1, characterized in that in step a), a (oxo) hydroxide of an element selected from among beryllium, magnesium, calcium, strontium, indium, barium, radium, aluminum, zinc, scandium, yttrium, and mixtures thereof.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'à l'étape a), ledit élément est du magnésium ou de l'aluminium et en ce qu'on dépose un hydroxyde de magnésium Mg(OH)2 ou un hydroxyde d'aluminium Al(OH)3. 3. Method according to claim 1 or 2, characterized in that in step a), said element is magnesium or aluminum and in that one deposits a magnesium hydroxide Mg (OH) 2 or a Al (OH) 3 aluminum hydroxide.
4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'épaisseur de la couche (5) est comprise entre 10 nm et 1 μηι, inclus, de préférence entre 10 et 300 nm, inclus, plus préférablement est égale à 50 nm.  4. Method according to any one of the preceding claims, characterized in that the thickness of the layer (5) is between 10 nm and 1 μηι, inclusive, preferably between 10 and 300 nm, inclusive, more preferably is equal to at 50 nm.
5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'étape a) de dépôt sur ladite surface est une étape d'hydrolyse, sur ladite surface, d'un sel dudit élément.  5. Method according to any one of the preceding claims, characterized in that the step a) of depositing on said surface is a step of hydrolysis, on said surface, of a salt of said element.
6. Procédé selon la revendication 5, caractérisé en ce que le sel de l'élément est MgCl2 et en ce que l'hydrolyse est effectuée à pH 9. 6. Method according to claim 5, characterized in that the salt of the element is MgCl 2 and in that the hydrolysis is carried out at pH 9.
7. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'étape a) est une étape de dépôt dudit (oxo)hydroxyde dudit élément en suspension dans un solvant.  7. Method according to any one of claims 1 to 4, characterized in that step a) is a step of depositing said (oxo) hydroxide of said element in suspension in a solvent.
8. Procédé selon la revendication 7, caractérisé en ce que ladite suspension est un sol colloïdal dudit (oxo)hydroxyde dudit élément.  8. Process according to claim 7, characterized in that said suspension is a colloidal sol of said (oxo) hydroxide of said element.
9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la couche (4) en un matériau fluoré est une couche en un polymère fluoré ou en silane fluoré. 9. Method according to any one of the preceding claims, characterized in that the layer (4) of a fluorinated material is a layer of a fluorinated polymer or fluorinated silane.
10. Procédé de dépôt d'une couche (6) en un matériau choisi parmi un matériau métallique ou conducteur d'électricité ou semi- conducteur, ou isolant, sur la surface d'une couche (4) en un matériau fluoré, caractérisé en ce qu'il comprend une étape de traitement de ladite surface de la couche (4) pour la rendre hydrophile par le procédé selon l'une quelconque des revendications précédentes, pour former une couche (5) suivie d'une étape de dépôt de ladite couche (6) en un matériau métallique ou conducteur d'électricité ou s emi -conducteur, ou isolant, sur la couche (5). Method for depositing a layer (6) of a material selected from a metallic or electrically conductive or semiconductor material, or an insulator, on the surface of a layer (4) made of a fluorinated material, characterized in that it comprises a step of treating said surface of the layer (4) to render it hydrophilic by the method according to any one of the preceding claims, to form a layer (5) followed by a step of depositing said layer (6) of a metallic material or conductor of electricity or semiconductor, or insulator, on the layer (5).
11. Procédé selon la revendication 10, caractérisé en ce que le matériau est en un matériau métallique est choisi parmi l'argent, le chrome, l'or, le titane, l'aluminium, le platine, le palladium, le cuivre, le nickel, le molybdène, une encre conductrice, en particulier comprenant des nanoparticules métalliques.  11. Method according to claim 10, characterized in that the material is made of a metallic material is selected from silver, chromium, gold, titanium, aluminum, platinum, palladium, copper, copper nickel, molybdenum, a conductive ink, in particular comprising metal nanoparticles.
12. Procédé selon la revendication 10, caractérisé en ce que le matériau est un matériau conducteur d'électricité choisi parmi le PEDOT/PSS (poly(3,4-éthylènedioxythiophène) (PEDOT) / poly(styrène suifonate) de sodium (PSS)), la polyaniline, ΓΙΤΟ (indium-étain-oxyde), ΓΑΖΟ (alliage conducteur d'oxyde d'aluminium et de zinc), le W03, les nanotubes de carbone, le graphène, les mélanges argent/graphène, et les mélanges cuivre/graphène. 12. The method of claim 10, characterized in that the material is an electrically conductive material selected from PEDOT / PSS (poly (3,4-ethylenedioxythiophene) (PEDOT) / poly (styrene sulfonate) sodium (PSS) ), polyaniline, ΓΙΤΟ (indium-tin-oxide), ΓΑΖΟ (conducting alloy of aluminum oxide and zinc), WO 3 , carbon nanotubes, graphene, silver / graphene mixtures, and mixtures copper / graphene.
13. Dispositif caractérisé en ce qu'il comprend une couche (4) en un matériau fluoré dont une surface est revêtue d'une couche (5) en (oxo)hydroxyde d'un élément choisi dans le groupe des métaux al calino -terreux, ou du groupe II ou du groupe III du tableau périodique des éléments, ou d'une terre rare, et d'une couche (6) en un matériau choisi parmi un matériau métallique ou conducteur d'électricité ou semi-conducteur, ou isolant, déposée sur la surface de la couche (5) non en contact avec la couche (4).  13. Device characterized in that it comprises a layer (4) of a fluorinated material whose surface is coated with a layer (5) of (oxo) hydroxide of a member selected from the group of al-calino-terrous metals , or group II or group III of the periodic table of the elements, or a rare earth, and a layer (6) of a material selected from a metallic material or electrically conductive or semiconductor, or insulating deposited on the surface of the layer (5) not in contact with the layer (4).
14. Dispositif selon la revendication 13, caractérisé en ce que l'(oxo)hydroxyde est un (oxo)hydroxyde choisi parmi le béryllium, le magnésium, le calcium, le strontium, l'indium, le baryum, le radium, l'aluminium, le zinc, le scandium, l'yttrium, et les mélanges de ceux-ci.  14. Device according to claim 13, characterized in that the (oxo) hydroxide is an (oxo) hydroxide selected from beryllium, magnesium, calcium, strontium, indium, barium, radium, aluminum, zinc, scandium, yttrium, and mixtures thereof.
15. Dispositif selon la revendication 13 ou 14, caractérisé en ce que l'(oxo)hydroxyde est un hydroxyde de magnésium Mg(OH)2 ou un hydroxyde d'aluminium Al(OH)3. 15. Device according to claim 13 or 14, characterized in that the (oxo) hydroxide is a magnesium hydroxide Mg (OH) 2 or an aluminum hydroxide Al (OH) 3 .
16. Dispositif selon l'une quelconque des revendications 13 à 15, caractérisé en ce que l'épaisseur de la couche (5) est comprise entre 10 nm et 1 μιη, inclus, de préférence entre 10 et 300 nm, inclus, plus préférablement est égale à 50 nm. 16. Device according to any one of claims 13 to 15, characterized in that the thickness of the layer (5) is between 10 nm and 1 μιη, inclusive, preferably between 10 and 300 nm, inclusive, more preferably is equal to 50 nm.
17. Dispositif selon l'une quelconque des revendications 13 à 16, caractérisé en ce que la couche (4) en un matériau fluoré est une couche en un polymère fluoré ou en un silane fluoré.  17. Device according to any one of claims 13 to 16, characterized in that the layer (4) of a fluorinated material is a layer of a fluorinated polymer or a fluorinated silane.
18. Dispositif selon l'une quelconque des revendications 13 à 17, caractérisé en ce que la couche (6) est en un matériau métallique choisi parmi l'argent, le chrome, l'or, le titane, l'aluminium, le platine, le palladium, le cuivre, le nickel, le molybdène, une encre conductrice, en particulier comprenant des nanoparticules métalliques.  18. Device according to any one of claims 13 to 17, characterized in that the layer (6) is a metal material selected from silver, chromium, gold, titanium, aluminum, platinum , palladium, copper, nickel, molybdenum, a conductive ink, in particular comprising metal nanoparticles.
19. Dispositif selon l'une quelconque des revendications 13 à 17, caractérisé en ce que la couche (6) est en un matériau conducteur d'électricité choisi parmi le PEDOT/PSS (poly(3,4-éthylènedioxythiophène) (PEDOT) / poIy(styrène sulfonate) de sodium (PSS)), la polyaniline, ΓΙΤΟ (indium-étain-oxyde), PAZO (alliage d'oxyde d'aluminium et de zinc), l'oxyde de tungstène, les nanotubes de carbone, le graphène, les mélanges argent/graphène et les mélanges cuivre/graphène.  19. Device according to any one of claims 13 to 17, characterized in that the layer (6) is an electrically conductive material selected from PEDOT / PSS (poly (3,4-ethylenedioxythiophene) (PEDOT) / sodium (styrene sulfonate) (PSS)), polyaniline, ΓΙΤΟ (indium tin oxide), PAZO (aluminum oxide and zinc alloy), tungsten oxide, carbon nanotubes, graphene, silver / graphene mixtures and copper / graphene mixtures.
20. Dispositif selon l'une quelconque des revendications 14 à 19, caractérisé en ce qu'il s'agît d'un transistor organique.  20. Device according to any one of claims 14 to 19, characterized in that it is an organic transistor.
EP13779362.6A 2012-08-13 2013-08-12 Surface treatment for a layer made from a fluorinated material to make it hydrophilic Withdrawn EP2883255A2 (en)

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FR1257781A FR2994395B1 (en) 2012-08-13 2012-08-13 SURFACE TREATMENT OF A LAYER IN A FLUORINE MATERIAL TO MAKE IT HYDROPHILIC
PCT/IB2013/056584 WO2014027299A2 (en) 2012-08-13 2013-08-12 Surface treatment for a layer made from a fluorinated material to make it hydrophilic

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US4007059A (en) * 1975-08-20 1977-02-08 General Motors Corporation Electrochemical cell electrode separator and method of making it and fuel cell containing same
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JP2015525004A (en) 2015-08-27
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