EP3074471A1 - Ink for forming p layers in organic electronic devices - Google Patents

Ink for forming p layers in organic electronic devices

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Publication number
EP3074471A1
EP3074471A1 EP14812650.1A EP14812650A EP3074471A1 EP 3074471 A1 EP3074471 A1 EP 3074471A1 EP 14812650 A EP14812650 A EP 14812650A EP 3074471 A1 EP3074471 A1 EP 3074471A1
Authority
EP
European Patent Office
Prior art keywords
ionomer
nanoparticles
type
layer
metal oxide
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Withdrawn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
EP14812650.1A
Other languages
German (de)
French (fr)
Inventor
Matthieu Manceau
Solenn Berson
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
Priority date (The priority date 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 date listed.)
Filing date
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 EP3074471A1 publication Critical patent/EP3074471A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02601—Nanoparticles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to the field of organic electronic devices such as organic photovoltaic cells, organic light-emitting diodes (OLEDs) and organic photodetectors (OPDs).
  • organic electronic devices such as organic photovoltaic cells, organic light-emitting diodes (OLEDs) and organic photodetectors (OPDs).
  • These devices consist of a first and a second electrode, respectively disposed above and below a stack of several layers including in particular a so-called “active” layer adjacent to a so-called “P-type” layer and a "N-type” layer.
  • the object of the invention is to provide an improved P-type layer, and in this respect advantageous for accessing organic electronic devices, whose thermal and air stability is improved and which has high performances.
  • Organic electronic devices and in particular organic photovoltaic cells, are generally classified according to the structure of their architecture: standard or inverse.
  • the layers are deposited in the following order:
  • conductive layer as a second electrode (cathode).
  • the stack is inverted and the layers are arranged in the following sequence:
  • first electrode cathode
  • an N-type semiconductor layer called an "electron transport layer"
  • the P-type semiconductor layers are formed essentially from a mixture of two polymers, the poly (3,4-ethylenedioxythiophene) (PEDOT) and sodium poly (styrene sulfonate) (PSS) called PEDOT: PSS. As such, these layers have the property of being hydrophilic.
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • PSS sodium poly (styrene sulfonate)
  • This material has many advantages in terms of conductivity, transparency, stability including photochemical and oxidation.
  • the electrically active layers consist of a mixture containing at least two semiconductor materials: an N-type material, an electron acceptor, and a P-type material, which is a donor. electrons (hole transporter). These active layers are therefore generally hydrophobic.
  • PEDOT PSS is obtained from a complex formulation of two polymers and several solvents and additives, is not conducive to adjustments. It is indeed difficult to intervene at the level of the formulation without fear of destabilizing it.
  • P-type semiconducting metal oxides such as, for example, V 2 O 5 , O, M0O 3 and WO 3 , in the form of nanoparticles, may constitute an alternative to the use of PEDOT: PSS.
  • These metal oxides are also generally very transparent, and may have good wettability and strong adhesion to the active layer. In addition, their reduced conductivity can be perfectly compensated by reducing the thickness of the final layer.
  • the present invention precisely aims to meet this need.
  • the object of the invention is to propose an improved solution for producing a P layer and more generally for producing organic electronic devices and consequently improved modules in terms of stability, performance and service life.
  • Another object of the invention is to propose a method for preparing an organic electronic device, in which the implementation of the P-type layer is facilitated in particular with respect to that of the P-type PEDOT: PSS layers.
  • the main subject of the present invention is an ink, capable of forming a P-type layer in an organic electronic device, characterized in that it comprises at least nanoparticles of metal oxide (s) semiconducting P-type selected from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof and an ionomer said ionomer being a perfluorosulfonated copolymer, the mass ratio between the ionomer and the nanoparticles of metal oxide (s) P-type semiconductors ranging from 0.005 to 0.115.
  • the weight ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles is between 0.01 and 0.055.
  • the nanoparticles of P-type semiconducting metal oxide (s) are formed wholly or partly of WO 3.
  • the present invention relates to a P type layer of an organic electronic device, characterized in that it comprises at least nanoparticles of metal oxide (s) semiconducting type P selected from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof and an ionomer which is a perfluorosulphonated copolymer, the mass ratio between the ionomer and the nanoparticles of the metal oxide (s) semiconductors of type P being between 0.005 and 0, 115.
  • metal oxide (s) semiconducting type P selected from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof and an ionomer which is a perfluorosulphonated copolymer, the mass ratio between the ionomer and the nanoparticles of the metal oxide (s) semiconductors of type P being between 0.005 and 0, 115.
  • the present invention is an organic electronic device comprising a P-type layer as defined above.
  • the present invention relates to the use of nanoparticles of WO 3 to form a P-type layer in an organic electronic device, characterized in that said nanoparticles are formulated with at least one ionomer, preferably said ionomer being a perfluorosulfonated copolymer, in said P-type layer in an ionomer / nanoparticle mass ratio of WO 3 between 0.005 and 0.115.
  • ionomer preferably ionomer being a perfluorosulfonated copolymer
  • the other expected properties namely uniformity and homogeneity of the layer P on the active layer, and performance in OPV cells, are furthermore unaltered by such a combination.
  • the organic electronic device may be an organic photovoltaic cell, an organic light-emitting diode (OLED) or an organic photodetector (OPD), in standard or inverse structure (NIP).
  • OLED organic light-emitting diode
  • OPD organic photodetector
  • the ink according to the invention comprises at least nanoparticles of P-type semiconductor metal oxide (s) and an ionomer.
  • the mass ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles is between 0.005 and 0.115.
  • the mass ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles is between 0.01 and 0.055.
  • the nanoparticles of P-type semiconductive metal oxide (s) are advantageously chosen from the following metal oxides: V 2 O 5 , O, M0O 3 , WO 3 and mixtures thereof.
  • the P-type semiconductor metal oxide nanoparticles are formed wholly or in part of WO 3 .
  • the nanoparticles of metal oxide (s) semiconducting type P can be in the form of hydrates.
  • the amount of P-type semiconducting metal oxide nanoparticles ranges from 90% to 99.5%, preferably from 95% to 99% by weight, relative to the total weight of the P-type semiconducting metal oxide (s).
  • the term "ionomer” means a synthetic polymer, homopolymer or copolymer, comprising ionic or ionizable groups such as carboxylate, sulphonate or phosphonate functions. It can also be called “ionic polymer”.
  • the ionomer used according to the invention is not an electrically conductive polymer.
  • the ionomer used according to the invention is advantageously a perfluorosulfonated copolymer, and in particular a sulfonated tetrafluoroethylene copolymer.
  • the ionomer is a tetrafluoroethylene backbone copolymer comprising perfluorovinyl ether groups and whose terminal ends are functionalized with sulphonate groups or sulphonic acid functional groups.
  • the ionomer used in the invention is Nafion ® marketed by Dupont.
  • the amount of ionomer (s) ranges from 0.5% to 10%, preferably from 1% to 5% by weight, relative to the total weight of the nanoparticles of semi-metallic oxide (s). P-type conductors and ionomer (s).
  • an ink according to the invention may comprise from 0.5% to 20% by weight of dry matter relative to the total weight of the ink.
  • dry material is understood to mean the constituents of the ink with the exception of the solvent, that is to say essentially the nanoparticles of P-type semiconducting metal oxide (s) and the ionomer.
  • An ink according to the invention may further comprise an alcoholic solvent, in particular a lower alcohol, preferably a C 2 -C 4 lower monoalcohol and in particular ethanol, n-propanol, isopropanol, n-propanol and the like. butanol, 2-butanol or methylpropanol.
  • an ink according to the invention may comprise from 80% to 99.5% by weight of alcoholic solvent relative to the total weight of the ink.
  • the ink is usually formulated without surfactant.
  • these post-treatments can be performed such treatments capable of homogenizing the mixture or to sediment the secondary particles. More specifically, these treatments may consist of agitation or centrifugation.
  • the ink according to the invention consists of an organic solvent, at least nanoparticles of P-type semiconducting metal oxide (s) chosen from V 2 O 5 , NiO , M0O 3 , WO 3 and mixtures thereof and at least one ionomer which is a perfluorosulphonated copolymer, the mass ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles chosen from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof ranging from 0.005 to 0.115.
  • P-type semiconducting metal oxide s
  • the ink thus formed is useful for constituting the P layer of an organic electronic device.
  • the present invention relates to a P-type layer of an organic electronic device, characterized in that it comprises at least nanoparticles of metal oxide (s) semiconductor semiconductors. type P and an ionomer, the mass ratio between the ionomer and the nanoparticles of metal oxide (s) semiconductor P type is between 0.005 and 0.115, and preferably between 0.01 and 0.055.
  • the layer according to the invention consists of at least P-type semiconductor metal oxide nanoparticles selected from V 2 O 5 , NiO, M0O 3 , WO 3 and their mixtures and at least one ionomer which is a perfluorosulfonated copolymer, the mass ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles selected from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof ranging from 0.005 to 0.115.
  • the layer P may be formed by depositing the ink layer on the surface of the substrate under consideration by any wet process such as solution coating, dipping, inkjet printing, spin coating, dip coating, roller coating, spray coating.
  • the deposit will be implemented by spin-coating, by strip casting, for example by scraping ("doctor bleading" in English), soaking, by spin coating, slot dye, spray jet. ink, by gravure or by screen printing.
  • the thickness of the layer can be controlled during the deposition. Indeed, the constituents of the expected layer P being dissolved in a liquid, the fluid layer can be spread on the support in a thin film.
  • a drying step is advantageously carried out.
  • the solvent (s) of the ink can be easily evaporated during this drying step.
  • This step is in particular carried out at a temperature ranging from 80 ° C. to 140 ° C. for a period ranging from 1 minute to 30 minutes.
  • the thickness of the layer P according to the invention varies from 0.01 microns to approximately 50 microns.
  • the thickness of the layer P is less than 20 microns, preferably less than 5 microns, and preferably less than 1 micron.
  • the thickness of the layer P is between 0.05 microns and 0.1 microns.
  • the invention also relates to a method of forming a P-type layer in an organic electronic device comprising the following steps:
  • the support is respectively an anode electrode or an active layer.
  • the deposition of the ink on the support can be carried out by any suitable wet process.
  • the ink deposit is then dried or allowed to dry.
  • the present invention also relates to an organic electronic device, characterized in that it comprises a P-type layer as defined above.
  • An organic electronic device has a standard structure or a reverse structure.
  • it may be an organic photovoltaic cell, an organic light-emitting diode (OLED) or an organic photodetector (OPD).
  • OLED organic light-emitting diode
  • OPD organic photodetector
  • the invention also relates to a method of forming an organic electronic device, characterized in that it comprises a step of depositing an ink layer as defined above under conditions conducive to the formation of a layer of the type P.
  • the present invention relates to a method of forming an organic electronic device in reverse structure comprising the following steps:
  • - Have a stack composed of the following layers in this order: substrate, cathode, N-type layer, active layer;
  • an ink layer according to the invention depositing on said active layer, an ink layer according to the invention under conditions conducive to the formation of a P-type layer.
  • an anode and preferably a silver electrode.
  • the present invention relates to a method of forming an organic electronic device in standard structure comprising the following steps:
  • an ink layer according to the invention depositing on said anode, an ink layer according to the invention under conditions conducive to the formation of a P-type layer.
  • Example 1 Formulation of an ink
  • An ink is prepared from a commercial dispersion of WO 3 nanoparticles (2.5% by weight, without surfactant, 2-propanol base, particle size 10-20 nm, crystalline structure: triclinic) distributed by the Nanograde Company. Lie and a commercial formulation of Nafion ® (solution of Nafion ® 117 at ⁇ 5% dry matter, marketed by Sigma-Aldrich).
  • the ink thus formed comprises 96.5 wt% isopropanol, 1% by weight of n-propanol, 2.45% by weight of W0 3 and 0.1% by mass Nafion ®.
  • Example 2 Use of the Ink According to Example 1 to Form a P-Coat
  • the organic electronic device under consideration is a NIP device (reverse) structure as follows:
  • N layer is a zinc oxide (ZnO) layer and its active layer is a polymeric [6,6] -phenyl-C6i-methyl butyrate (PCBM) layer.
  • ZnO zinc oxide
  • PCBM polymeric [6,6] -phenyl-C6i-methyl butyrate
  • Example 1 dedicated to forming the layer P, at the surface of the active layer of the stack, is applied by spin coating, spin coating and dried at a temperature of 120 ° C for 2 minutes.
  • the thus formed p-layer contains 4% by weight of Nafion ® and 96% by weight of WO 3.
  • the silver electrode is then formed on its surface.
  • the active surface of the devices is 0.28 cm 2 .
  • a NIP device (reverse) of the same structure, but control, is formed with a layer P comprising only WO 3 .
  • ink used to form this layer P comprises 97.5% by weight of isopropanol, and 2.5% by weight of WO 3 .
  • the corresponding layer P then contains 100% by weight of W0 3 .
  • the performance of the PIN type devices (inverse) of Example 2 are measured at 25 ° C under an inert atmosphere in illumination standard conditions (1000 W / m 2, AM 1.5G).
  • Jsc short circuit current density
  • Table 1 shows the performance of the device with a P layer according to the invention.
  • Table 2 reports the performance of the control device.
  • Performance 2 performance of the device considered after exposure to air for 2 hours, in the absence of light
  • Performance 3 performance of the device under consideration after heat treatment for 2 minutes at 150 ° C. in a glove box.
  • the beneficial effect of Nafion ® appears clearly after exposure to air for 2 hours, in the absence of light, since the efficiency of the cells does not decrease.
  • the initial performance of the devices are evaluated based on the mass ratio Nafion ® / W0 3 in the dry layer.
  • test parameters are identical to those of example 3.

Abstract

The invention relates to an ink that can form a P-type layer in an organic electronic device, characterised in that it comprises at least nanoparticles of P-type semiconductor metal oxide(s) selected from among V2O5, NiO, MoO3, WO3 and mixtures thereof and an ionomer, said ionomer being a perfluorosulfonate copolymer, the mass ratio between the ionomer and the nanoparticles of P-type semiconductor metal oxide(s) selected from among V2O5, NiO, MoO3, WO3 and mixtures thereof being between 0.005 and 0.115. The invention also relates to a P layer of an organic electronic device, an electronic device and the formation method thereof.

Description

Encre pour former des couches P dans des dispositifs électroniques organiques  Ink for forming P-layers in organic electronic devices
La présente invention concerne le domaine des dispositifs électroniques organiques tels que les cellules photovoltaïques organiques, les diodes électroluminescentes organiques (OLED) et les photo-détecteurs organiques (OPD).  The present invention relates to the field of organic electronic devices such as organic photovoltaic cells, organic light-emitting diodes (OLEDs) and organic photodetectors (OPDs).
Ces dispositifs sont constitués d'une première et d'une deuxième électrodes, respectivement disposées au-dessus et en-dessous d'un empilement de plusieurs couches comprenant notamment une couche dite « active » jouxtant une couche dite « de type P » et une couche « de type N ».  These devices consist of a first and a second electrode, respectively disposed above and below a stack of several layers including in particular a so-called "active" layer adjacent to a so-called "P-type" layer and a "N-type" layer.
L'invention vise à proposer une couche de type P améliorée, et à ce titre avantageuse pour accéder à des dispositifs électroniques organiques, dont la stabilité notamment thermique et à l'air est améliorée et qui présente des performances élevées.  The object of the invention is to provide an improved P-type layer, and in this respect advantageous for accessing organic electronic devices, whose thermal and air stability is improved and which has high performances.
Les dispositifs électroniques organiques, et en particulier des cellules photovoltaïques organiques, sont généralement classés selon la structure de leur architecture : standard ou inverse. Organic electronic devices, and in particular organic photovoltaic cells, are generally classified according to the structure of their architecture: standard or inverse.
Dans une structure standard, les couches sont déposées selon l'ordre suivant : In a standard structure, the layers are deposited in the following order:
- un substrat ; a substrate;
- couche conductrice en tant que première électrode (anode) ;  conductive layer as the first electrode (anode);
- couche semi-conductrice de type P dite « couche de transport de trous » ;  - P-type semiconductor layer called "hole transport layer";
- couche électriquement active ;  - electrically active layer;
- couche semi-conductrice de type N dite « couche de transport d'électrons » ; et - N-type semiconductor layer called "electron transport layer"; and
- couche conductrice en tant que seconde électrode (cathode). conductive layer as a second electrode (cathode).
Dans une structure inverse, l'empilement est inversé et les couches sont disposées selon la séquence suivante :  In a reverse structure, the stack is inverted and the layers are arranged in the following sequence:
- un substrat ;  a substrate;
- couche conductrice en tant que première électrode (cathode) ;  conductive layer as first electrode (cathode);
- une couche semi-conductrice de type N dite « couche de transport d'électrons » ;  an N-type semiconductor layer called an "electron transport layer";
- une couche électriquement active ;  an electrically active layer;
- une couche semi-conductrice de type P dite « couche de transport de trous » ;  a P type semiconductor layer called a "hole transport layer";
- seconde électrode (anode) ou électrode supérieure.  - second electrode (anode) or upper electrode.
Généralement, les couches semi-conductrices de type P, considérées dans ces structures, sont formées pour l'essentiel à partir d'un mélange de deux polymères, le poly(3,4-éthylènedioxythiophène) (PEDOT) et le poly(styrène sulfonate) de sodium (PSS) dit PEDOT:PSS. A ce titre, ces couches présentent la propriété d'être hydrophiles. Generally, the P-type semiconductor layers, considered in these structures, are formed essentially from a mixture of two polymers, the poly (3,4-ethylenedioxythiophene) (PEDOT) and sodium poly (styrene sulfonate) (PSS) called PEDOT: PSS. As such, these layers have the property of being hydrophilic.
Ce matériau présente de nombreux avantages en termes de conductivité, transparence, stabilité notamment photochimique et à l'oxydation.  This material has many advantages in terms of conductivity, transparency, stability including photochemical and oxidation.
Par ailleurs, les couches électriquement actives, classiquement considérées dans ces structures, sont constituées d'un mélange contenant au moins deux matériaux semi-conducteurs : un matériau de type N, accepteur d'électrons, et un matériau de type P, donneur d'électrons (transporteur de trous). Ces couches actives sont donc généralement hydrophobes.  Moreover, the electrically active layers, conventionally considered in these structures, consist of a mixture containing at least two semiconductor materials: an N-type material, an electron acceptor, and a P-type material, which is a donor. electrons (hole transporter). These active layers are therefore generally hydrophobic.
II y a donc naturellement une incompatibilité entre ces deux types de couches, So there is naturally an incompatibility between these two types of layers,
Ce défaut d'affinité a par ailleurs pour conséquence de rendre difficile la réalisation de leur empilement. This lack of affinity also has the consequence of making it difficult to perform their stacking.
De plus, le fait que ce matériau PEDOT:PSS est obtenu à partir d'une formulation complexe de deux polymères et plusieurs solvants et additifs, est peu propice à des ajustements. Il est en effet délicat d'intervenir au niveau de la formulation sans craindre de la déstabiliser.  In addition, the fact that this material PEDOT: PSS is obtained from a complex formulation of two polymers and several solvents and additives, is not conducive to adjustments. It is indeed difficult to intervene at the level of the formulation without fear of destabilizing it.
Les oxydes métalliques semi-conducteurs de type P, tels que par exemple V2O5, O, M0O3 et WO3, sous forme de nanoparticules, peuvent constituer une alternative à l'utilisation du PEDOT:PSS. Ces oxydes métalliques sont également généralement très transparents, et peuvent présenter une bonne mouillabilité ainsi qu'une forte adhérence sur la couche active. En outre, leur conductivité réduite peut être parfaitement compensée en réduisant l'épaisseur de la couche finale. P-type semiconducting metal oxides, such as, for example, V 2 O 5 , O, M0O 3 and WO 3 , in the form of nanoparticles, may constitute an alternative to the use of PEDOT: PSS. These metal oxides are also generally very transparent, and may have good wettability and strong adhesion to the active layer. In addition, their reduced conductivity can be perfectly compensated by reducing the thickness of the final layer.
Ainsi, l'utilisation du W03 permet d'atteindre des performances initiales très élevées. Malheureusement, il présente deux inconvénients majeurs : une dégradation très rapide à l'air y compris en absence de lumière, et une stabilité thermique médiocre. Dans les deux cas, ceci entraîne une chute brutale des performances du dispositif qui met en œuvre des particules de W03 à titre de composants de la couche P. Thus, the use of WO 3 makes it possible to achieve very high initial performances. Unfortunately, it has two major disadvantages: very rapid degradation to air even in the absence of light, and poor thermal stability. In both cases, this results in a sudden drop in device performance that implements particles W0 3 as components of layer P.
En conséquence, il demeure un besoin de disposer d'une solution permettant l'obtention d'une couche de type P particulièrement stable, notamment à l'air, à la chaleur et à l'humidité.  Consequently, there remains a need for a solution that makes it possible to obtain a particularly stable P-type layer, especially in air, heat and moisture.
La présente invention a précisément pour objectif de répondre à ce besoin. L'invention a pour objectif de proposer une solution améliorée pour réaliser une couche P et plus généralement pour réaliser des dispositifs électroniques organiques et par conséquent des modules améliorés en termes de stabilité, performances et durée de vie. The present invention precisely aims to meet this need. The object of the invention is to propose an improved solution for producing a P layer and more generally for producing organic electronic devices and consequently improved modules in terms of stability, performance and service life.
L'invention a également pour objectif de proposer un procédé de préparation d'un dispositif électronique organique, dans lequel la mise œuvre de la couche de type P est facilitée notamment par rapport à celle des couches de type P en PEDOT:PSS.  Another object of the invention is to propose a method for preparing an organic electronic device, in which the implementation of the P-type layer is facilitated in particular with respect to that of the P-type PEDOT: PSS layers.
Ainsi, la présente invention a pour objet principal une encre, apte à former une couche de type P dans un dispositif électronique organique, caractérisée en ce qu'elle comprend au moins des nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P choisies parmi V2O5, NiO, M0O3, WO3 et leurs mélanges et un ionomère ledit ionomère étant un copolymère perfluorosulfonaté, le rapport massique entre l'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P étant compris entre 0,005 et 0, 115. Thus, the main subject of the present invention is an ink, capable of forming a P-type layer in an organic electronic device, characterized in that it comprises at least nanoparticles of metal oxide (s) semiconducting P-type selected from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof and an ionomer said ionomer being a perfluorosulfonated copolymer, the mass ratio between the ionomer and the nanoparticles of metal oxide (s) P-type semiconductors ranging from 0.005 to 0.115.
De manière préférée, le rapport massique entre l'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P est compris entre 0,01 et 0,055.  Preferably, the weight ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles is between 0.01 and 0.055.
Avantageusement, les nanoparticules d'oxyde(s) métallique(s) semi- conductrices de type P sont formées en tout ou partie de WO3. Advantageously, the nanoparticles of P-type semiconducting metal oxide (s) are formed wholly or partly of WO 3.
Selon un autre de ses aspects, la présente invention concerne une couche de type P d'un dispositif électronique organique, caractérisée en ce qu'elle comprend au moins des nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P choisies parmi V2O5, NiO, M0O3, WO3 et leurs mélanges et un ionomère qui est un copolymère perfluorosulfonaté, le rapport massique entre l'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P étant compris entre 0,005 et 0, 115. According to another of its aspects, the present invention relates to a P type layer of an organic electronic device, characterized in that it comprises at least nanoparticles of metal oxide (s) semiconducting type P selected from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof and an ionomer which is a perfluorosulphonated copolymer, the mass ratio between the ionomer and the nanoparticles of the metal oxide (s) semiconductors of type P being between 0.005 and 0, 115.
Selon encore un autre de ses aspects, la présente invention vise un dispositif électronique organique comprenant une couche de type P telle que définie ci-dessus.  According to yet another of its aspects, the present invention is an organic electronic device comprising a P-type layer as defined above.
Selon encore un autre de ses aspects, la présente invention concerne l'utilisation de nanoparticules de WO3 pour former une couche de type P dans un dispositif électronique organique, caractérisée en ce que lesdites nanoparticules sont formulées avec au moins un ionomère, de préférence ledit ionomère étant un copolymère perfluorosulfonaté, dans ladite couche de type P dans un rapport massique ionomère/nanoparticules de WO3 compris entre 0,005 et 0, 115. Contre toute attente, les inventeurs ont ainsi constaté que la mise en œuvre, lors de la fabrication de dispositif électronique organique, de nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P telles que le W03 sous une forme combinée à un ionomère s'avère particulièrement avantageuse. Une telle combinaison permet en effet d'accéder à une couche de type P manifestant des propriétés en termes de stabilité thermique et à l'air, significativement améliorées comparativement à une couche de type P formée à partir de mêmes nanoparticules de WO3 mais sous une forme non combinée à un ionomère. Ces avantages sont plus particulièrement illustrés dans les exemples décrits ci- après. According to yet another of its aspects, the present invention relates to the use of nanoparticles of WO 3 to form a P-type layer in an organic electronic device, characterized in that said nanoparticles are formulated with at least one ionomer, preferably said ionomer being a perfluorosulfonated copolymer, in said P-type layer in an ionomer / nanoparticle mass ratio of WO 3 between 0.005 and 0.115. Against all expectations, the inventors have found that the implementation, during the manufacture of organic electronic device, nanoparticles of metal oxide (s) type P semiconductors such as WO 3 in a form combined with an ionomer is particularly advantageous. Such a combination indeed makes it possible to access a P-type layer exhibiting properties in terms of thermal and air stability, significantly improved compared to a P-type layer formed from the same nanoparticles of WO 3 but under a form not combined with an ionomer. These advantages are more particularly illustrated in the examples described below.
Qui plus est, les autres propriétés attendues, à savoir uniformité et homogénéité de la couche P sur la couche active, et performances en cellules OPV, s'avèrent en outre non altérées par une telle combinaison.  Moreover, the other expected properties, namely uniformity and homogeneity of the layer P on the active layer, and performance in OPV cells, are furthermore unaltered by such a combination.
Le dispositif électronique organique selon l'invention peut être une cellule photovoltaïque organique, une diode électroluminescente organique (OLED) ou un photo- détecteur organique (OPD), en structure standard ou inverse (NIP).  The organic electronic device according to the invention may be an organic photovoltaic cell, an organic light-emitting diode (OLED) or an organic photodetector (OPD), in standard or inverse structure (NIP).
D'autres avantages et caractéristiques apparaîtront à la lecture de la description et des exemples qui suivent.  Other advantages and features will appear on reading the description and examples which follow.
Description détaillée detailed description
Comme déjà mentionné, l'encre selon l'invention comprend au moins des nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P et un ionomère.  As already mentioned, the ink according to the invention comprises at least nanoparticles of P-type semiconductor metal oxide (s) and an ionomer.
Le rapport massique entre l 'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P est compris entre 0,005 et 0, 115.  The mass ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles is between 0.005 and 0.115.
De manière préférée, le rapport massique entre Γ ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P est compris entre 0,01 et 0,055.  Preferably, the mass ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles is between 0.01 and 0.055.
Les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P sont avantageusement choisies parmi les oxydes de métaux suivants : V2O5, O, M0O3, WO3 et leurs mélanges. The nanoparticles of P-type semiconductive metal oxide (s) are advantageously chosen from the following metal oxides: V 2 O 5 , O, M0O 3 , WO 3 and mixtures thereof.
De préférence, les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P sont formées en tout ou partie de WO3. Preferably, the P-type semiconductor metal oxide nanoparticles are formed wholly or in part of WO 3 .
Elles ont une taille avantageusement comprise entre 2 nm et 200 nm. Par « taille », on entend de préférence la dimension la plus grande des particules. Selon un mode de réalisation particulier, les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P peuvent être sous forme d'hydrates. They have a size advantageously between 2 nm and 200 nm. By "size" is preferably meant the largest dimension of the particles. According to a particular embodiment, the nanoparticles of metal oxide (s) semiconducting type P can be in the form of hydrates.
De préférence, la quantité de nanoparticules d'oxyde(s) métallique(s) semi- conductrices de type P varie de 90 % à 99,5 %, de préférence de 95 % à 99 % en poids, par rapport au poids total des nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P et d'ionomère(s).  Preferably, the amount of P-type semiconducting metal oxide nanoparticles ranges from 90% to 99.5%, preferably from 95% to 99% by weight, relative to the total weight of the P-type semiconducting metal oxide (s). nanoparticles of P-type semiconducting metal oxide (s) and ionomer (s).
Au sens de la présente invention, on entend par « ionomère », un polymère synthétique, homopolymère ou copolymère, comprenant des groupements ioniques ou ionisables à l'image des fonctions carboxylates, sulfonates ou phosphonates. Il peut également être appelé « polymère ionique ».  For the purposes of the present invention, the term "ionomer" means a synthetic polymer, homopolymer or copolymer, comprising ionic or ionizable groups such as carboxylate, sulphonate or phosphonate functions. It can also be called "ionic polymer".
L'ionomère utilisé selon l'invention n'est pas un polymère conducteur électrique.  The ionomer used according to the invention is not an electrically conductive polymer.
L'ionomère utilisé selon l'invention est avantageusement un copolymère perfluorosulfonaté, et en particulier un copolymère tétrafluoroéthylène sulfonaté.  The ionomer used according to the invention is advantageously a perfluorosulfonated copolymer, and in particular a sulfonated tetrafluoroethylene copolymer.
De manière encore préférée, l'ionomère est un copolymère à squelette tétrafluoroéthylène comprenant des groupes éthers perfluorovinyliques et dont les extrémités terminales sont fonctionnalisées par des groupes sulfonates ou des fonctions acides sulfoniques.  More preferably, the ionomer is a tetrafluoroethylene backbone copolymer comprising perfluorovinyl ether groups and whose terminal ends are functionalized with sulphonate groups or sulphonic acid functional groups.
Avantageusement, l'ionomère utilisé selon l'invention est le Nafion® commercialisé par la société Dupont. Advantageously, the ionomer used in the invention is Nafion ® marketed by Dupont.
De préférence, la quantité d'ionomère(s) varie de 0,5 % à 10 %, de préférence de 1 % à 5 % en poids, par rapport au poids total des nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P et d'ionomère(s).  Preferably, the amount of ionomer (s) ranges from 0.5% to 10%, preferably from 1% to 5% by weight, relative to the total weight of the nanoparticles of semi-metallic oxide (s). P-type conductors and ionomer (s).
En particulier, une encre selon l'invention peut comprendre de 0,5 % à 20 % en poids de matière sèche par rapport au poids total de l'encre.  In particular, an ink according to the invention may comprise from 0.5% to 20% by weight of dry matter relative to the total weight of the ink.
Par « matière sèche » on entend les constituants de l'encre à l'exception du solvant c'est-à-dire essentiellement les nanoparticules d'oxyde(s) métallique(s) semi- conductrices de type P et l'ionomère.  The term "dry material" is understood to mean the constituents of the ink with the exception of the solvent, that is to say essentially the nanoparticles of P-type semiconducting metal oxide (s) and the ionomer.
Une encre selon l'invention peut comprendre en outre un solvant alcoolique, en particulier un alcool inférieur, de manière préférée un mono-alcool inférieur en C2-C4 et en particulier l'éthanol, le n-propanol, l'isopropanol, le n-butanol, le 2-butanol ou le méthylpropanol. En particulier, une encre selon l'invention peut comprendre de 80 % à 99,5 % en poids de solvant alcoolique par rapport au poids total de l'encre. An ink according to the invention may further comprise an alcoholic solvent, in particular a lower alcohol, preferably a C 2 -C 4 lower monoalcohol and in particular ethanol, n-propanol, isopropanol, n-propanol and the like. butanol, 2-butanol or methylpropanol. In particular, an ink according to the invention may comprise from 80% to 99.5% by weight of alcoholic solvent relative to the total weight of the ink.
L'encre est généralement formulée sans tensio-actif.  The ink is usually formulated without surfactant.
Lors de la formulation de l'encre, après mélange des nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P et de l'ionomère, plusieurs post-traitements peuvent être effectués tels des traitements aptes à homogénéiser le mélange ou à sédimenter les particules secondaires. Plus précisément, ces traitements peuvent consister en une agitation ou une centrifugation.  During the formulation of the ink, after mixing the nanoparticles of metal oxide (s) P-type semiconductors and the ionomer, several post-treatments can be performed such treatments capable of homogenizing the mixture or to sediment the secondary particles. More specifically, these treatments may consist of agitation or centrifugation.
Selon une réalisation particulière, l'encre selon l'invention est constituée d'un solvant organique, d'au moins des nanoparticules d'oxyde(s) métallique(s) semi- conductrices de type P choisies parmi V2O5, NiO, M0O3, W03 et leurs mélanges et d'au moins un ionomère qui est un copolymère perfluorosulfonaté, le rapport massique entre l'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P choisies parmi V2O5, NiO, M0O3, WO3 et leurs mélanges étant compris entre 0,005 et 0, 115. According to a particular embodiment, the ink according to the invention consists of an organic solvent, at least nanoparticles of P-type semiconducting metal oxide (s) chosen from V 2 O 5 , NiO , M0O 3 , WO 3 and mixtures thereof and at least one ionomer which is a perfluorosulphonated copolymer, the mass ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles chosen from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof ranging from 0.005 to 0.115.
Comme précisé ci-dessus, l'encre ainsi formée est utile pour constituer la couche P d'un dispositif électronique organique.  As stated above, the ink thus formed is useful for constituting the P layer of an organic electronic device.
Ainsi, selon un autre de ses aspects, la présente invention concerne une couche de type P d'un dispositif électronique organique, caractérisée en ce qu'elle comprend au moins des nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P et un ionomère, le rapport massique entre l'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P étant compris entre 0,005 et 0, 115, et de préférence compris entre 0,01 et 0,055.  Thus, according to another of its aspects, the present invention relates to a P-type layer of an organic electronic device, characterized in that it comprises at least nanoparticles of metal oxide (s) semiconductor semiconductors. type P and an ionomer, the mass ratio between the ionomer and the nanoparticles of metal oxide (s) semiconductor P type is between 0.005 and 0.115, and preferably between 0.01 and 0.055.
Selon une réalisation particulière, la couche selon l'invention est constituée d'au moins des nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P choisies parmi V2O5, NiO, M0O3, WO3 et leurs mélanges et d'au moins un ionomère qui est un copolymère perfluorosulfonaté, le rapport massique entre l'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P choisies parmi V2O5, NiO, M0O3, WO3 et leurs mélanges étant compris entre 0,005 et 0,115. According to a particular embodiment, the layer according to the invention consists of at least P-type semiconductor metal oxide nanoparticles selected from V 2 O 5 , NiO, M0O 3 , WO 3 and their mixtures and at least one ionomer which is a perfluorosulfonated copolymer, the mass ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles selected from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof ranging from 0.005 to 0.115.
De manière générale, la couche P peut être formée par dépôt de la couche d'encre en surface du substrat considéré par tout procédé par voie humide tels que revêtement en solution, trempage, impression jet d'encre, enduction centrifuge, revêtement au trempé, revêtement au rouleau, revêtement par pulvérisation. Le dépôt sera mis en œuvre par enduction centrifuge (« spin-coating »), par coulage en bande, par exemple au racloir (« doctor bleading » en langue anglaise), trempage, par spin coating, par slot dye, par jet d'encre, par héliogravure ou encore par sérigraphie. In general, the layer P may be formed by depositing the ink layer on the surface of the substrate under consideration by any wet process such as solution coating, dipping, inkjet printing, spin coating, dip coating, roller coating, spray coating. The deposit will be implemented by spin-coating, by strip casting, for example by scraping ("doctor bleading" in English), soaking, by spin coating, slot dye, spray jet. ink, by gravure or by screen printing.
L'épaisseur de la couche peut être contrôlée lors du dépôt. En effet, les constituants de la couche P attendue, étant dissous dans un liquide, la couche fluide peut être étalée sur le support selon un film fin.  The thickness of the layer can be controlled during the deposition. Indeed, the constituents of the expected layer P being dissolved in a liquid, the fluid layer can be spread on the support in a thin film.
Après le dépôt, une étape de séchage est avantageusement effectuée. Le ou les solvants de l'encre peuvent être aisément évaporés lors de cette étape de séchage.  After the deposition, a drying step is advantageously carried out. The solvent (s) of the ink can be easily evaporated during this drying step.
Cette étape est notamment effectuée à une température allant de 80°C à 140°C pendant une période allant de 1 minute à 30 minutes.  This step is in particular carried out at a temperature ranging from 80 ° C. to 140 ° C. for a period ranging from 1 minute to 30 minutes.
Il est bien entendu possible de procéder à la formation de la couche P via la superposition de plusieurs couches d'encre selon l'invention.  It is of course possible to proceed with the formation of the layer P via the superposition of several layers of ink according to the invention.
En général, l'épaisseur de la couche P selon l'invention, encore figurée par l'écart existant entre les couches qui encadrent ladite couche P, varie de 0,01 microns à environ 50 microns.  In general, the thickness of the layer P according to the invention, further represented by the gap existing between the layers which surround said layer P, varies from 0.01 microns to approximately 50 microns.
De préférence, l'épaisseur de la couche P est inférieure à 20 microns, de manière préférée inférieure à 5 microns, et avantageusement inférieure à 1 micron.  Preferably, the thickness of the layer P is less than 20 microns, preferably less than 5 microns, and preferably less than 1 micron.
De manière encore plus préférée, l'épaisseur de la couche P est comprise entre 0,05 microns et 0, 1 microns.  Even more preferably, the thickness of the layer P is between 0.05 microns and 0.1 microns.
L'invention concerne également un procédé de formation d'une couche de type P dans un dispositif électronique organique comprenant les étapes suivantes :  The invention also relates to a method of forming a P-type layer in an organic electronic device comprising the following steps:
- disposer d'un support ;  - have a support;
- disposer d'une encre selon l'invention ;  - Have an ink according to the invention;
- procéder au dépôt d'une couche d'encre en surface dudit support ; et, le cas échéant, au séchage de cette couche pour former la couche P.  depositing an ink layer on the surface of said support; and, where appropriate, drying of this layer to form the P layer.
Selon l'architecture de la cellule que l'on souhaite obtenir : structure standard ou inverse, le support est respectivement une électrode de type anode ou une couche active.  Depending on the architecture of the cell that is desired: standard or inverse structure, the support is respectively an anode electrode or an active layer.
Le dépôt de l'encre sur le support peut être effectué par tout procédé par voie humide approprié. Le dépôt d'encre est ensuite séché ou laissé sécher. The deposition of the ink on the support can be carried out by any suitable wet process. The ink deposit is then dried or allowed to dry.
La présente invention vise également un dispositif électronique organique, caractérisé en ce qu'il comprend une couche de type P telle que définie précédemment. The present invention also relates to an organic electronic device, characterized in that it comprises a P-type layer as defined above.
Un dispositif électronique organique selon l'invention possède une structure standard ou une structure inverse.  An organic electronic device according to the invention has a standard structure or a reverse structure.
Comme mentionné précédemment, il peut s'agir d'une cellule photovoltaïque organique, d'une diode électroluminescente organique (OLED) ou d'un photo-détecteur organique (OPD).  As mentioned previously, it may be an organic photovoltaic cell, an organic light-emitting diode (OLED) or an organic photodetector (OPD).
L'invention vise également un procédé de formation d'un dispositif électronique organique, caractérisé en qu'il comprend une étape de dépôt d'une couche d'encre telle que définie précédemment dans des conditions propices à la formation d'une couche de type P.  The invention also relates to a method of forming an organic electronic device, characterized in that it comprises a step of depositing an ink layer as defined above under conditions conducive to the formation of a layer of the type P.
Selon une première variante, la présente invention concerne un procédé de formation d'un dispositif électronique organique en structure inverse comprenant les étapes suivantes :  According to a first variant, the present invention relates to a method of forming an organic electronic device in reverse structure comprising the following steps:
- disposer d'un empilement composé des couches suivantes dans cet ordre : substrat, cathode, couche de type N, couche active ;  - Have a stack composed of the following layers in this order: substrate, cathode, N-type layer, active layer;
- déposer sur ladite couche active, une couche d'encre selon l'invention dans des conditions propices à la formation d'une couche de type P.  depositing on said active layer, an ink layer according to the invention under conditions conducive to the formation of a P-type layer.
Il est ensuite superposé à cette couche de type P, une anode, et de préférence une électrode d'argent.  It is then superimposed on this P-type layer, an anode, and preferably a silver electrode.
Selon une deuxième variante, la présente invention concerne un procédé de formation d'un dispositif électronique organique en structure standard comprenant les étapes suivantes :  According to a second variant, the present invention relates to a method of forming an organic electronic device in standard structure comprising the following steps:
- disposer d'un substrat revêtu d'une électrode (anode),  - Have a substrate coated with an electrode (anode),
- déposer sur ladite anode, une couche d'encre selon l'invention dans des conditions propices à la formation d'une couche de type P.  depositing on said anode, an ink layer according to the invention under conditions conducive to the formation of a P-type layer.
D'une manière générale, il est ensuite superposé successivement à cette couche de type P, les couches suivantes : une couche active, une couche de type N, une cathode. EXEMPLES In general, it is then superimposed successively on this P-type layer, the following layers: an active layer, an N-type layer, a cathode. EXAMPLES
Exemple 1 : Formulation d'une encre Example 1: Formulation of an ink
Une encre est préparée à partir d'une dispersion commerciale de nanoparticules de W03 (2,5 % en poids, sans tensioactif, base 2-propanol, taille des particules 10-20 nm, structure cristalline : triclinique) distribuée par la Société Nanograde Lie et d'une formulation commerciale de Nafion® (Solution de Nafion® 117 à ~ 5% en matière sèche, commercialisé par Sigma-aldrich). An ink is prepared from a commercial dispersion of WO 3 nanoparticles (2.5% by weight, without surfactant, 2-propanol base, particle size 10-20 nm, crystalline structure: triclinic) distributed by the Nanograde Company. Lie and a commercial formulation of Nafion ® (solution of Nafion ® 117 at ~ 5% dry matter, marketed by Sigma-Aldrich).
L'encre ainsi formée comprend 96,5 % en masse d'isopropanol, 1 % en masse de n-propanol, 2,45 % en masse de W03 et 0,1 % en masse de Nafion®. The ink thus formed comprises 96.5 wt% isopropanol, 1% by weight of n-propanol, 2.45% by weight of W0 3 and 0.1% by mass Nafion ®.
Exemple 2 : Utilisation de l'encre selon l'exemple 1 pour former une couche P Example 2 Use of the Ink According to Example 1 to Form a P-Coat
Le dispositif électronique organique considéré est un dispositif de type NIP (inverse) de structure comme suit :  The organic electronic device under consideration is a NIP device (reverse) structure as follows:
Sa couche N est une couche d'oxyde de zinc (ZnO) et sa couche active est une couche polymère/[6,6]-phényl-C6i-butyrate de méthyle (PCBM).  Its N layer is a zinc oxide (ZnO) layer and its active layer is a polymeric [6,6] -phenyl-C6i-methyl butyrate (PCBM) layer.
L'encre de l'exemple 1 dédiée à former la couche P, en surface de la couche active de l'empilement, est appliquée par enduction centrifuge, dépôt à la tournette (« spin- coating ») et séchée, à une température de 120°C pendant 2 minutes. La couche P ainsi formée contient 4 % en masse de Nafion® et 96 % en masse de WO3. The ink of Example 1 dedicated to forming the layer P, at the surface of the active layer of the stack, is applied by spin coating, spin coating and dried at a temperature of 120 ° C for 2 minutes. The thus formed p-layer contains 4% by weight of Nafion ® and 96% by weight of WO 3.
L'électrode d'argent est ensuite formée à sa surface.  The silver electrode is then formed on its surface.
La surface active des dispositifs est de 0,28 cm2. The active surface of the devices is 0.28 cm 2 .
De la même manière, un dispositif de type NIP (inverse) de même structure, mais témoin, est formé avec une couche P comprenant uniquement du WO3. L'encre utilisée pour former cette couche P comprend 97,5 % en masse d'isopropanol, et 2,5 % en masse de W03. La couche P correspondante contient alors 100 % en masse de W03. In the same way, a NIP device (reverse) of the same structure, but control, is formed with a layer P comprising only WO 3 . ink used to form this layer P comprises 97.5% by weight of isopropanol, and 2.5% by weight of WO 3 . The corresponding layer P then contains 100% by weight of W0 3 .
Exemple 3 : Performances et stabilité des dispositifs Example 3: Performance and stability of devices
Les performances des dispositifs de type NIP (inverse) de l'exemple 2, sont mesurées à 25°C sous atmosphère inerte dans des conditions standards d'éclairement (1 000 W/m2, AM 1,5G). The performance of the PIN type devices (inverse) of Example 2, are measured at 25 ° C under an inert atmosphere in illumination standard conditions (1000 W / m 2, AM 1.5G).
Les paramètres testés sont les suivants :  The parameters tested are as follows:
Voc : tension en circuit ouvert ;  Voc: open circuit voltage;
Jsc : densité de courant en court-circuit ;  Jsc: short circuit current density;
FF : « Fill factor » en langue anglaise : facteur de remplissage ;  FF: "Fill factor" in English language: filling factor;
PCE : « Power Conversion Efficiency » en langue anglaise : rendement de conversion de puissance.  PCE: "Power Conversion Efficiency" in English: power conversion efficiency.
Ces paramètres sont testés selon les protocoles décrits dans Perrier et al, Solar Energy Materials and Solar Cells, Juin 2012, Vol. 101, Pages 210-216.  These parameters are tested according to the protocols described in Perrier et al, Solar Energy Materials and Solar Cells, June 2012, Vol. 101, Pages 210-216.
Le tableau 1 ci-dessous rend compte des performances du dispositif doté d'une couche P selon l'invention. Le tableau 2 rend compte des performances du dispositif témoin.  Table 1 below shows the performance of the device with a P layer according to the invention. Table 2 reports the performance of the control device.
- Performance 1 : performance initiale du dispositif considéré ;  - Performance 1: initial performance of the device under consideration;
- Performance 2 : performance du dispositif considéré après une exposition à l'air de 2 heures, en absence de lumière ; et  - Performance 2: performance of the device considered after exposure to air for 2 hours, in the absence of light; and
- Performance 3 : performance du dispositif considéré après un traitement thermique pendant 2 minutes à 150°C en boîte à gants.  Performance 3: performance of the device under consideration after heat treatment for 2 minutes at 150 ° C. in a glove box.
Tableau 1 (Dispositif selon l'invention) Table 1 (Device according to the invention)
Tableau 2 (Dispositif témoin) Table 2 (Control device)
Pour un dispositif doté d'une couche P selon l'invention, l'effet bénéfique du Nafion® apparaît clairement après une exposition à l'air de 2 heures, en absence de lumière, puisque le rendement des cellules ne diminue pas. For a device having a P layer according to the invention, the beneficial effect of Nafion ® appears clearly after exposure to air for 2 hours, in the absence of light, since the efficiency of the cells does not decrease.
De même, on note qu'après un traitement thermique pendant 2 minutes à 150°C en boîte à gants, une augmentation du rendement démontrant que les performances initiales sont optimisées. L'effet bénéfique du Nafion® est donc vérifié. Similarly, it is noted that after a heat treatment for 2 minutes at 150 ° C. in a glove box, an increase in the yield demonstrating that the initial performances are optimized. The beneficial effect of Nafion ® is therefore verified.
A l'inverse, pour ce qui est du dispositif témoin, on distingue clairement que le rendement des cellules diminue significativement, en absence de lumière, après une exposition à l'air de 2 heures. Conversely, with regard to the control device, it is clearly seen that the efficiency of the cells decreases significantly, in the absence of light, after exposure to air for 2 hours.
En outre, après un traitement thermique pendant 2 minutes à 150°C en boîte à gants, leurs performances sont quasiment nulles.  In addition, after a heat treatment for 2 minutes at 150 ° C in a glove box, their performance is virtually zero.
Exemple 4 : Gamme de concentration en Nafion® en association avec WOj Example 4: Concentration range Nafion ® in combination with WO j
D'autre part, les performances initiales des dispositifs sont évaluées en fonction du rapport massique Nafion®/W03 au sein de la couche sèche. On the other hand, the initial performance of the devices are evaluated based on the mass ratio Nafion ® / W0 3 in the dry layer.
Les paramètres tests sont identiques à ceux de l'exemple 3.  The test parameters are identical to those of example 3.
Les résultats sont détaillés dans le tableau 3 ci-après. Tableau 3 The results are detailed in Table 3 below. Table 3
Lorsque le rapport massique Nafion /W03 est compris entre 0,01 et 0, 111, les performances des dispositifs sont très bonnes. When the weight ratio Nafion / W0 3 is between 0.01 and 0.11, the performances of the devices are very good.
Au contraire, lorsque le rapport massique Nafion® AV03 au sein de la couche sèche est égale à 0,25 ou 1, les performances des dispositifs sont mauvaises. On the contrary, when the weight ratio Nafion ® AV0 3 in the dry layer is equal to 0.25 or 1, the performance of the devices are poor.

Claims

REVENDICATIONS
1. Encre, apte à former une couche de type P dans un dispositif électronique organique, caractérisée en ce qu'elle comprend au moins des nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P choisies parmi V2O5, O, M0O3, W03 et leurs mélanges et un ionomère, ledit ionomère étant un copolymère perfluorosulfonaté, le rapport massique entre l'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi- conductrices de type P choisies parmi V2O5, O, M0O3, W03 et leurs mélanges étant compris entre 0,005 et 0, 115. 1. Ink, capable of forming a P-type layer in an organic electronic device, characterized in that it comprises at least P-type semiconductor metal oxide nanoparticles selected from V 2 O 5 , O, M0O 3 , WO 3 and mixtures thereof and an ionomer, said ionomer being a perfluorosulphonated copolymer, the mass ratio between the ionomer and the selected P-type semiconducting metal oxide nanoparticles (s) among V 2 O 5 , O, M0O 3 , WO 3 and mixtures thereof ranging from 0.005 to 0.115.
2. Encre selon la revendication 1, dans laquelle le rapport massique entre l'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P est compris entre 0,01 et 0,055.  2. Ink according to claim 1, wherein the mass ratio between the ionomer and the nanoparticles of metal oxide (s) semiconductor P type is between 0.01 and 0.055.
3. Encre selon l'une quelconque des revendications précédentes, dans laquelle les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P sont formées en tout ou partie de WO3. An ink according to any one of the preceding claims, wherein the P-type semiconductor metal oxide nanoparticles are formed wholly or in part of WO 3.
4. Encre selon l'une quelconque des revendications précédentes, dans laquelle l'ionomère est un copolymère tétrafluoroéthylène sulfonaté, et plus particulièrement un copolymère à squelette tetrafluoroéthylène comprenant des groupes éthers perfluorovinyliques et dont les extrémités terminales sont fonctionnalisées par des groupes sulfonates ou des fonctions acides sulfoniques.  An ink according to any one of the preceding claims, wherein the ionomer is a sulfonated tetrafluoroethylene copolymer, and more particularly a tetrafluoroethylene backbone copolymer comprising perfluorovinyl ether groups and whose terminal ends are functionalized with sulfonate groups or functional groups. sulfonic acids.
5. Encre selon l'une quelconque des revendications précédentes, comprenant en outre un solvant alcoolique, en particulier un alcool inférieur, de manière préférée un mono-alcool inférieur en C2-C4, et en particulier l'éthanol, le n-propanol, l'isopropanol, le n-butanol, le 2- butanol ou le méthylpropanol. Ink according to any one of the preceding claims, further comprising an alcoholic solvent, in particular a lower alcohol, preferably a lower C 2 -C 4 monoalcohol, and in particular ethanol, n-propanol. isopropanol, n-butanol, 2-butanol or methylpropanol.
6. Encre selon l'une quelconque des revendications précédentes caractérisée en ce qu'elle est constituée d'un solvant organique, d'au moins des nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P choisies parmi V2O5, MO, M0O3, WO3 et leurs mélanges et d'au moins un ionomère qui est un copolymère perfluorosulfonaté, le rapport massique entre l'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P choisies parmi V2O5, MO, M0O3, WO3 et leurs mélanges étant compris entre 0,005 et 0,115. 6. Ink according to any one of the preceding claims characterized in that it consists of an organic solvent, at least nanoparticles of metal oxide (s) semiconducting type P selected from V 2 O 5 , MO, M0O 3 , WO 3 and mixtures thereof and at least one ionomer which is a perfluorosulphonated copolymer, the mass ratio between the ionomer and the nanoparticles of metal oxide (s) semiconductors P-type selected from V 2 O 5 , MO, M0O 3 , WO 3 and mixtures thereof ranging from 0.005 to 0.115.
7. Couche de type P d'un dispositif électronique organique, caractérisée en ce qu'elle comprend au moins des nanoparticules d'oxyde(s) métallique(s) semi- conductrices de type P choisies parmi V2O5, O, M0O3, W03 et leurs mélanges et un ionomère, ledit ionomère étant un copolymère perfluorosulfonaté, 7. P-type layer of an organic electronic device, characterized in that it comprises at least nanoparticles of metal oxide (s) semiconducting type P selected from V 2 O 5 , O, M0O 3 , WO 3 and mixtures thereof and an ionomer, said ionomer being a perfluorosulfonated copolymer,
le rapport massique entre Γ ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P choisies parmi V2O5, NiO, M0O3, W03 et leurs mélanges étant compris entre 0,005 et 0,115, et de préférence compris entre 0,01 et 0,055. the mass ratio between the ionomer and the P-type semiconductor metal oxide nanoparticles selected from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof ranging from 0.005 to 0.115, and preferably between 0.01 and 0.055.
8. Couche selon la revendication 7, dans laquelle les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P sont formées en tout ou partie de W03 8. Layer according to claim 7, wherein the nanoparticles of metal oxide (s) semiconducting type P are formed in whole or in part of W0 3
9. Couche selon l'une quelconque des revendications 7 ou 8, dans laquelle l'ionomère est un copolymère tétrafluoroéthylène sulfonaté, et plus particulièrement un copolymère à squelette tétrafluoroéthylène comprenant des groupes éthers perfluorovinyliques et dont les extrémités terminales sont fonctionnalisées par des groupes sulfonates ou des fonctions acides sulfoniques.  9. Layer according to any one of claims 7 or 8, wherein the ionomer is a sulfonated tetrafluoroethylene copolymer, and more particularly a tetrafluoroethylene backbone copolymer comprising perfluorovinyl ether groups and whose terminal ends are functionalized with sulfonate groups or sulphonic acid functions.
10. Couche selon l'une quelconque des revendications 7 à 9 caractérisée en ce qu'elle est constituée d'au moins des nanoparticules d'oxyde(s) métallique(s) semi- conductrices de type P choisies parmi V2O5, NiO, M0O3, WO3 et leurs mélanges et d'au moins un ionomère qui est un copolymère perfluorosulfonaté, le rapport massique entre l'ionomère et les nanoparticules d'oxyde(s) métallique(s) semi-conductrices de type P choisies parmi V2O5, NiO, M0O3, WO3 et leurs mélanges étant compris entre 0,005 et 0, 115. 10. Layer according to any one of claims 7 to 9, characterized in that it consists of at least nanoparticles of metal oxide (s) semiconductive type P selected from V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof and at least one ionomer which is a perfluorosulphonated copolymer, the mass ratio between the ionomer and the selected P-type semiconductor metal oxide nanoparticles among V 2 O 5 , NiO, M0O 3 , WO 3 and mixtures thereof ranging from 0.005 to 0.115.
11. Dispositif électronique organique, caractérisé en ce qu'il comprend une couche de type P telle que définie selon l'une quelconque des revendications 7 à 10.  11. Organic electronic device, characterized in that it comprises a P-type layer as defined according to any one of claims 7 to 10.
12. Dispositif électronique organique selon la revendication 11, caractérisé en ce qu'il possède une structure standard ou une structure inverse.  12. Organic electronic device according to claim 11, characterized in that it has a standard structure or a reverse structure.
13. Dispositif électronique organique selon l'une quelconque des revendications 11 ou 12, caractérisé en ce qu'il s'agit d'une cellule photovoltaïque organique, d'une diode électroluminescente organique (OLED) ou d'un photo-détecteur organique (OPD).  13. An organic electronic device according to any one of claims 11 or 12, characterized in that it is an organic photovoltaic cell, an organic light-emitting diode (OLED) or an organic photodetector ( OPD).
14. Procédé de formation d'un dispositif électronique organique, caractérisé en qu'il comprend une étape de dépôt d'une couche d'encre telle que définie selon l'une quelconque des revendications 1 à 6 dans des conditions propices à la formation d'une couche de type P. 14. A method of forming an organic electronic device, characterized in that it comprises a step of depositing an ink layer as defined in one of the following: any of claims 1 to 6 under conditions conducive to the formation of a P-type layer.
15. Utilisation de nanoparticules de W03 pour former une couche de type P dans un dispositif électronique organique, caractérisée en ce que lesdites nanoparticules sont formulées avec au moins un ionomère dans ladite couche de type P, ledit ionomère étant un copolymère perfluorosulfonaté, dans un rapport massique ionomère/nanoparticules de W03 compris entre 0,005 et 0,115. 15. Use of nanoparticles of WO 3 to form a P-type layer in an organic electronic device, characterized in that said nanoparticles are formulated with at least one ionomer in said P-type layer, said ionomer being a perfluorosulfonated copolymer, in a mass ratio ionomer / nanoparticles of WO 3 between 0.005 and 0.115.
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Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11961875B2 (en) 2017-12-20 2024-04-16 Lumileds Llc Monolithic segmented LED array architecture with islanded epitaxial growth
ES2722475B2 (en) * 2018-02-09 2020-03-25 Torrecid Sa SET OF INKS TO OBTAIN HYBRID ELECTROLUMINISCENT DEVICES
US11271033B2 (en) 2018-09-27 2022-03-08 Lumileds Llc Micro light emitting devices
FR3089969B1 (en) * 2018-12-13 2023-02-24 Genesink Synthesis method of tungsten oxide nanoparticles
CN109749507B (en) * 2019-01-23 2021-11-19 纳晶科技股份有限公司 Functional layer ink, preparation method of functional layer of photoelectric device and photoelectric device
CN110350091A (en) * 2019-07-02 2019-10-18 上海大学 Organic photodetector and preparation method thereof
US11777059B2 (en) 2019-11-20 2023-10-03 Lumileds Llc Pixelated light-emitting diode for self-aligned photoresist patterning
US11848402B2 (en) 2020-03-11 2023-12-19 Lumileds Llc Light emitting diode devices with multilayer composite film including current spreading layer
US11569415B2 (en) 2020-03-11 2023-01-31 Lumileds Llc Light emitting diode devices with defined hard mask opening
US11942507B2 (en) 2020-03-11 2024-03-26 Lumileds Llc Light emitting diode devices
US11735695B2 (en) 2020-03-11 2023-08-22 Lumileds Llc Light emitting diode devices with current spreading layer
US11901491B2 (en) 2020-10-29 2024-02-13 Lumileds Llc Light emitting diode devices
US11626538B2 (en) 2020-10-29 2023-04-11 Lumileds Llc Light emitting diode device with tunable emission
US11955583B2 (en) 2020-12-01 2024-04-09 Lumileds Llc Flip chip micro light emitting diodes
US11705534B2 (en) 2020-12-01 2023-07-18 Lumileds Llc Methods of making flip chip micro light emitting diodes
US11600656B2 (en) 2020-12-14 2023-03-07 Lumileds Llc Light emitting diode device
US11935987B2 (en) 2021-11-03 2024-03-19 Lumileds Llc Light emitting diode arrays with a light-emitting pixel area

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3937113B2 (en) * 1998-06-05 2007-06-27 日産化学工業株式会社 Organic-inorganic composite conductive sol and method for producing the same
JP2003331869A (en) * 2002-05-14 2003-11-21 Hitachi Ltd Proton conductive material
JP4395292B2 (en) * 2002-08-30 2010-01-06 三菱重工業株式会社 Fuel cell electrode catalyst, fuel cell and fuel cell system
US7390438B2 (en) * 2003-04-22 2008-06-24 E.I. Du Pont De Nemours And Company Water dispersible substituted polydioxythiophenes made with fluorinated polymeric sulfonic acid colloids
WO2007094019A1 (en) * 2006-02-17 2007-08-23 Nm Tech Ltd. Nanomaterials And Microdevices Technology A method for preparing nanocrystalline transparent films of tungsten oxide
JP2007336790A (en) * 2006-06-19 2007-12-27 Kuraray Co Ltd Polymer electrochemical element
CN101688052A (en) * 2007-07-27 2010-03-31 E.I.内穆尔杜邦公司 The aqueous dispersion that comprises the conductive polymers of inorganic nanoparticles
JP5205013B2 (en) * 2007-08-31 2013-06-05 株式会社東芝 Anode for fuel cell and fuel cell using the same
JP2010118214A (en) * 2008-11-12 2010-05-27 Toyota Motor Corp Fuel cell
GB2475247B (en) * 2009-11-10 2012-06-13 Cambridge Display Tech Ltd Organic optoelectronic device and method
JP2013127865A (en) * 2011-12-16 2013-06-27 Toyota Motor Corp Electrode catalyst for fuel cell, method for manufacturing ionomer used for electrode catalyst, method for manufacturing membrane electrode assembly, membrane electrode assembly and fuel cell
JP5870722B2 (en) * 2012-02-02 2016-03-01 コニカミノルタ株式会社 Organic photoelectric conversion element and solar cell
EP2631008A1 (en) * 2012-02-22 2013-08-28 nanograde AG Solution-processable tungsten oxide buffer layers and electronics comprising same
WO2013137274A1 (en) * 2012-03-12 2013-09-19 三菱化学株式会社 Method for manufacturing organic thin-film solar-cell module, and organic thin-film solar-cell module
EP2879230A4 (en) * 2012-07-27 2015-10-28 Daicel Corp Photoelectric conversion layer composition and photoelectric conversion element

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2015079378A1 *

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