Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G41/00—Compounds of tungsten
  • C01G41/02—Oxides; Hydroxides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/20—Light-sensitive devices
  • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
• • 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
  • 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
  • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
• • 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
  • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
• • 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
  • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
  • H10K30/353—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising blocking layers, e.g. exciton blocking layers
• • 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
  • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
  • H10K71/441—Thermal treatment, e.g. annealing in the presence of a solvent vapour in the presence of solvent vapors, e.g. solvent vapour annealing
• • 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
  • Y02E10/542—Dye sensitized solar cells
• • 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
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to a solution of tungstate ions suitable for deposition of a tungsten oxide film, in particular with a view to enabling the collection of photogenerated holes in a hybrid photovoltaic device.
• the present invention relates to a process for preparing such a solution, such a tungsten oxide film and their applications.
• the cell yields and lifetimes are greatly improved by the insertion of collector interfacial layer photogenerated carriers between the electrodes and the active material. While there are commercially available solutions and many research studies for the cathode-hole-blocking layer, there are few solutions to help transfer holes and block electrons at the cathode.
• solutions generally employed include a number of elements that are toxic or incompatible with wet deposition type technologies, such as printing or coating techniques.
• peroxotungstic acid was synthesized by reacting a tungsten powder and hydrogen peroxide.
• the sol is then diluted with a mono-alcoholic solvent (2-propanol or 2-propoxy ethanol).
• a mono-alcoholic solvent (2-propanol or 2-propoxy ethanol).
• the addition of alcohol leads to the formation of a tungsten ether (esterification) which polymerizes to peroxo polytungstic acid.
• the ink is slightly orange.
• the prepared ink exhibits problems of stability, especially with respect to storage over time, and there remains a need to increase the photovoltaic conversion efficiency.
• Stubhan et al. (Advanced Energy Materials, 2012, 2, 1433-1438) describes a process for preparing a colloidal solution comprising the dispersion of tungsten oxide particles in an alcohol.
• the present invention aims to solve one or more, and preferably all, of the technical problems described above.
• the present invention aims to solve the technical problem of providing a solution capable of being deposited on a solid support to form a layer of material whose work output is compatible with the electronic level of the photogenerated holes, the work output or extraction work (ed), for a metal, is the energy that must be supplied to an electron located at the level of Fermi to tear it out of the metal and bring it to the level of the vacuum (at the infinite).
• the work output or extraction work for a metal
• the work output or extraction work is the energy that must be supplied to an electron located at the level of Fermi to tear it out of the metal and bring it to the level of the vacuum (at the infinite).
• the electronic affinity (ex) is the energy that must be supplied to extract an electron towards the vacuum level.
• the present invention also aims to solve the technical problem of providing a stable solution over time.
• the present invention also aims to solve the technical problem of providing a transparent solution, and preferably capable of being implemented with a wet deposition process, and in particular by printing or coating.
• the present invention is intended in particular to solve the technical problem of providing a method of preparing such a simple and easily industrialized.
• the present invention aims to solve the technical problem of providing such a method, limiting the negative impact of chemical pollutants or toxic compounds usually used in the processes of the state of the art.
• the present invention also aims to solve the technical problem of providing in particular a method for preparing a material whose work output is compatible with the electronic level of the photogenerated holes, and preferably compatible with a technique of depositing the material. semiconductor material wet.
• the present invention also aims to solve the technical problem of providing a photovoltaic device.
• the present invention aims to solve the technical problem of providing a photovoltaic cell having a satisfactory yield and / or lifetime that is preferably equivalent to those having a p-type interfacial layer made of a reference material.
• PEDOT: PSS refers to the mixture of two polymers, poly (3,4-ethylenedioxythiophene) (PEDOT) and sodium polystyrene sulfonate (PSS).
• the subject of the invention is a solution of tungstate ions W 6+ (VI) comprising as solvent at least one polyalcohol, which may be partially etherified.
• the solvent comprises or consists of a glycolic compound, which may be partially etherified.
• the solvent comprises or consists of ethylene glycol.
• the solution has a concentration of tungstate ions of 0.001 to 1 mol.L -1 .
• the concentration of tungstate ions ranges from 0.01 to 0.5 mol.L -1 , preferably from 0.01 to 0.2 mol.l -1 , and even more preferably from 0.04 to at 0.1 mol.L -1 .
• the concentration of tungstate ions ranges from 0.05 to 0.1 mol.L -1 .
• the tungstate ion solution comprises one or more polyoxotungstate complexes.
• the neutralization of such complexes with a solution of sodium hydroxide generally takes place according to three equivalences at 0.6, 1, 1 and 2.3 H + / W, the latter being able to be shifted to a higher value depending on the starting acidity in relation to the initial concentration of tungsten and / or the preparation temperature of the solution.
• the stable polyanion in the presence of protons, is generally [W 6 0 19 ] 2 " whose neutralization could involve two polyanionic intermediates such as [W 10 O 32 ] 4" then [ ⁇ 7 0 24 ] 6 " , until neutralization of all the acidities.
• transparent is understood to mean a transparent solution, for example here yellow-orange in color.
• polyalcohol a compound comprising at least two hydroxyl groups also called hydroxyl groups, and in particular diols and triols, and especially vicinal diols.
• the polyalcohol is a glycol
• the glycol is selected from alkylene glycols and mixtures thereof.
• the alkylene glycols include their derivatives.
• the derivatives include derivatives of the type partially etherified.
• the "alkylene" etherified glycol is an alkyl ether of akylene glycol, and for example a propylene ether of akylene glycol. There may be mentioned in particular propylene glycol propyl ether.
• Alkyl denotes in particular an alkyl or alkylene group comprising from 1 to 10 carbon atoms.
• etherified is meant a solvent of which one or more of the hydroxy groups present are used for an etherification reaction, in particular for grafting an alkyl group. These reactions are known to those skilled in the art. Etherified polyalcohols and etherified glycols are commercially available.
• the solvent is chosen from ethylene glycol, propylene glycol, propylene glycol propyl ether, or any of their mixtures.
• the solvent has a boiling point of less than 180 ° C. at atmospheric pressure (101325 Pa).
• the solvent has a viscosity suitable for a printing or coating technique and for example ranging from 2 to 64 cP, and for example from 4 to 54 cP, and for example from 4 to 25 cP, or from 8 to at 19 cP at 25 ° C and atmospheric pressure (101325 Pa).
• the solvent is nontoxic to humans.
• One variant concerns the use of a solution of tungstate ions in ethylene glycol in the presence of other compounds.
• One variant relates to the use of a solution of tungstate ions in propylene glycol in the presence of other compounds.
• One variant relates to the use of a solution of tungstate ions in propylene glycol propyl ether in the presence of other compounds.
• solvent is understood to mean a compound that solvates a chemical species and in particular a compound that solvates compounds comprising tungsten in ionic form.
• the solution of tungstate ions is non-colloidal.
• the solution of tungstate ions is single phase.
• it does not have any scattered or suspended solid that can be measured, for example by a dynamic light scattering (DLS) method whose detection limit for the particles present is approximately 1 nm in diameter.
• DLS dynamic light scattering
• the solution according to the present invention has a viscosity suitable for a process for preparing a wet tungsten oxide layer and in particular according to a printing or coating technique,
• said solution has a dynamic viscosity of between 2 and 64 cP, and for example between 4 and 54 cP, and for example between 4 and 25 cP, or between 8 and 19 cP, at 25 ° C. and atmospheric pressure (101,325 Pa).
• the viscosity is obtained by measurement using a densimeter / viscometer of the Anton Paar company: DENSIMETRE DMA 4100 M coupled to Module LOVIS 2000 ME MICROVISCOMETER.
• the measurement method is based on the displacement time of a gold ball along a capillary diameter 1 .59 mm for viscosities of 0.7 to 15 mPa.s and diameter 1 .8 mm for viscosity of 13 to 300 mPas.s.
• a solution according to the present invention can be stable at ambient temperature, and especially for a sufficiently satisfactory time.
• the solution of the invention comprises at least one oxidizing agent.
• an oxidizing agent may be chosen from: a peroxide, and more particularly hydrogen peroxide.
• the invention also relates to a process for preparing a solution of tungstate ions as defined according to the present invention and obtained by a step of increasing the temperature of a suspension or gel of precursors of tungstate ions in a solvent polyalcoholic, and preferably maintained at a temperature above 120 ° C.
• the precursor is tungstate ions selected from the group consisting of Na 2 W0 4, (NH 4) 2 W04, H 2 W0 4 and any mixtures thereof.
• Solvents having a sufficiently low boiling temperature are also preferred to limit heat energy expenditure upon removal of the solvent to form the tungsten oxide layer.
• a solvent having a viscosity of between 1 and 64 mPa.s at 25 ° C. is used.
• a solvent having a boiling temperature of between 100 and 300 ° C., and preferably less than 250 ° C., and more preferably less than 225 ° C., is chosen.
• ethylene glycol which has a viscosity of 16.06 mPa.s at 25 ° C. and a boiling point of 197.3 ° C.
• ethylene glycol has physicochemical properties suitable for wet deposition, for example by printing or coating.
• the temperature for obtaining the solution of tungstate ions from a suspension or gel of tungstate ion precursors ranges from 100 to 300 ° C., and preferably is lower than 250 ° C. and even more preferably lower. at 200 ° C.
• the temperature for obtaining the solution of tungstate ions from the suspension or gel of precursors is between 100 and 150 ° C., and for example between 1 10 and 140 ° C.
• the duration of temperature maintenance during the preparation of the tungstate ion solution from the suspension or gel of precursors is between five minutes and three days, and for example between one hour and forty-eight hours. and typically about twenty-four hours.
• the pressure during the temperature maintenance stage during the preparation of the tungstate ion solution from the suspension or gel of precursors is atmospheric (approximately 10 1325 Pa), a pressure lower than atmospheric pressure. , or a pressure greater than atmospheric.
• the pressure is autogenous, and for example obtained by increasing the temperature in an autoclave.
• the solution obtained does not have a colloid as measured by dynamic light scattering (DLS).
• DLS dynamic light scattering
• the solution comprises polyoxotungstate complexes.
• polyoxotungstate complexes for example by titrimetric determination, for example by sodium hydroxide.
• the number of moles of neutralized H + ions relative to the number of moles of tungsten W present in solution can confirm the presence of different polyoxotungstate complexes in each pH range.
• the invention very advantageously makes it possible to stabilize at room temperature solutions of tungstate ions, and especially of polytungstate ions in a polyalcoholic medium, and in particular in a glycolic medium, and especially in an ethylene glycol or propylene glycol medium, optionally etherified, with from commercial precursors with viscosities adapted to the method of depositing a semiconductor material wet, in particular by printing or coating.
• an increase in temperature is effected, and preferably with a maintenance at the desired temperature, under an autoclave.
• an increase in temperature is carried out, and preferably with a maintenance at the desired temperature, under reflux.
• the formation of the polyoxotungstate complex (s) is carried out by heating, in particular in an autoclave or under reflux.
• the invention also relates to a tungsten oxide layer WO z comprising one or more polyoxotungstate complexes, where z is a number greater than 2.7 and preferably greater than 2.8, calculated by the results of photoelectron spectrometry induced by X-rays, said tungsten oxide having an atomic proportion of tungsten of oxidation state ranging from 3 to 6% relative to the total tungsten, said proportion being calculated by X-ray induced photoelectron spectrometry results.
• tungsten oxide layer means a layer comprising at least one tungsten oxide, without limiting the presence of other components of this tungsten oxide. layer.
• a tungsten oxide layer may be designated as such in a photovoltaic device.
• the tungsten oxide layer comprises an oxide of the WO z type, where z is a number greater than 2.7 and preferably greater than 2.8, calculated by the results of photoelectron spectrometry induced by X-ray (in English, X-Ray photoelectron spectrometry: XPS).
• the tungsten oxide layer comprises an oxide of the WO z type, where z is a number greater than 2.9, calculated by the results of XPS.
• a film according to the article Guillain et al. The above-mentioned preparation prepared from a sol comprises a type oxide WO 2.7 .
• the tungsten oxide layer comprises less than 10%, and preferably less than 7%, of oxidation degree tungsten oxide (W 5+ ), the percentage being expressed as an atomic percentage.
• the ratio of oxidation state tungsten 6 to oxidation degree tungsten can be calculated from spectra obtained by XPS. These include the ratio of peaks associated with transitions from levels 4f 7/2 at 35.7 and 34.5 eV, (C1 s of pollution positioned at 284.7 eV) for W 6+ and W 5+ , respectively .
• Such a layer is particularly suitable for the manufacture of an organic or hybrid electronic device, and in particular for converting solar energy into electricity, such as for example an organic photovoltaic (OPV) cell or hybrid cell, but also the electrochromic glazing, photodector, organic light emitting diode (OLED) and polymer light emitting diode (PLED).
• OCV organic photovoltaic
• OLED organic light emitting diode
• PLED polymer light emitting diode
• the invention also relates to a process for preparing a layer of tungsten oxide WO z deposited on a solid support, said process comprising the preparation of a solution that can be deposited by the wet method on the solid support, said solution comprising tungstate ions W 6+ (VI) and at least one polyalcohol, optionally partially etherified, as a solvent, depositing the solution on a solid support, removing the solvent from the solution, and obtaining a tungsten oxide film WO z on the solid support.
• a process for preparing a layer of tungsten oxide WO z deposited on a solid support said process comprising the preparation of a solution that can be deposited by the wet method on the solid support, said solution comprising tungstate ions W 6+ (VI) and at least one polyalcohol, optionally partially etherified, as a solvent, depositing the solution on a solid support, removing the solvent from the solution, and obtaining a tungsten oxide film WO z on the solid support
• solid support is meant a support of a solid nature, which may for example be flexible or rigid.
• the method of the invention advantageously makes it possible to obtain a stable and transparent solution that can be implemented by a process for depositing a layer by the wet route, and in particular by means of a printing or coating technique.
• said process comprises dissolving tungstate ions in a polyalcoholic solvent, optionally partially etherified, which may constitute a first solvent, optionally at least partial removal of the first solvent to increase the concentration of tungstate ions, the possible dilution by adding a second solvent called "volatile solvent" having a boiling point lower than the boiling temperature of the first solvent, then depositing the solution comprising the volatile solvent on the solid support, and the elimination of the first solvent, and optionally volatile solvent, to form a tungsten oxide film WO z on the solid support.
• a polyalcoholic solvent optionally partially etherified, which may constitute a first solvent
• volatile solvent having a boiling point lower than the boiling temperature of the first solvent
• the removal of the solvent is carried out at a temperature higher than the boiling point of the solvent.
• the process comprises the solution of tungstate ions in the presence of an oxidizing agent.
• the process comprises a step of removing the solvent under vacuum to form the tungsten oxide film.
• the process comprises an elimination step, optionally the removal of the volatile solvent, carried out at a temperature greater than 80 ° C., for example greater than 100 ° C., and preferably a temperature greater than 130 ° C. .
• the process comprises an elimination step, optionally the elimination of the volatile solvent, carried out at a temperature greater than 160 ° C., for example greater than 180 ° C., and preferably a temperature greater than 200 ° C. .
• the temperature for the solvent removal step is less than
• volatile solvent means a solvent having a boiling point lower than the polyalcoholic solvent of the tungstate ions.
• a solvent having a boiling point of less than 180 ° C. and, for example, less than 150 ° C., and more preferably less than 120 ° C. may be used as solvent.
• oxidizing agents it is possible to use in particular: a peroxide such as, for example, hydrogen peroxide.
• the deposition is carried out by printing or coating, and preferably by spin coating, by ink jet printing, by screen printing, by gravure printing, slot die, sheet-by-sheet or unwrapped process.
• the invention also relates to a semiconductor material comprising or consisting of a layer as defined according to the invention or obtainable by a method as defined according to the invention.
• the output work of this material is compatible with the collection of photogenerated holes.
• the invention also relates to a photovoltaic device comprising a layer of active material for photoconversion and a semiconductor material as defined according to the invention.
• the photovoltaic device is a photovoltaic cell, a PIN or NIP type photovoltaic cell, an organic transistor, or a light emitting diode, an organic light-emitting diode (OLED), a polymer electroluminescent diode (PLDE), an electrochromic glazing, or a photodetector.
• organic or hybrid electroluminescent multilayer architectures such as, for example, HTL / ETL, HTL / AL / ETL, HIL / HTL / AL / ETL, HIL / HTL / AL / ETL / EIL, HIIJHTIJ electron-blocking layer or blocking layer / AL / ETL / EIL, HIL / HTL / AL / hole-blocking layer / ETL / EIL.
• HTL denotes the Hole-Transporting Layer
• HIL is the Hole-Injecting Layer
• AL is the Active Layer, for OLEDs, for example.
• EIL means the organic-injecting layer ("electron-blocking layer")
• electron-blocking layer means an "electron-blocking layer” denotes a layer blocking the holes.
• the device of the invention is an OPV device ("Organic Photovoltaic").
• the invention relates to a photovoltaic cell of inverse structure, also called NIP structure.
• the tungsten oxide layer is deposited on an active polymer layer.
• the stack has for example the following sequence:
• a conducting layer based on a conductive oxide acting as a first electrode an n (or N) semiconductor layer;
• a conductive layer acting as a second electrode or an upper electrode acting as a second electrode or an upper electrode.
• the layer comprising tungsten oxide is disposed on the surface of the active layer of the device which is stacked on the layers disposed on the substrate.
• the conductive layer acting as a second electrode or upper electrode is an anode.
• the invention relates to a method of manufacturing a photovoltaic device comprising, besides depositing a solution of tungstate ions according to the invention to form a tungsten oxide layer, the deposition on a substrate of a colloidal solution (in the typical form of sol-gel material) to form a layer of n-type semiconductor material, such as Ti0 2 .
• a method of manufacturing a photovoltaic device comprising, besides depositing a solution of tungstate ions according to the invention to form a tungsten oxide layer, the deposition on a substrate of a colloidal solution (in the typical form of sol-gel material) to form a layer of n-type semiconductor material, such as Ti0 2 .
• a colloidal solution in the typical form of sol-gel material
• the layer of material n can be annealed between 50 and 200 ° C. Its thickness is for example between 10 and 200 nm.
• the active layer of the photovoltaic device is then generally deposited on the layer of material n.
• a temperature treatment of between 50 and 180 ° C. for 0 to 30 minutes often makes it possible to optimize the morphology of the active layer.
• An anodic interfacial layer is then generally deposited on the active layer.
• This interfacial layer can be produced according to the process of the present invention from a solution of tungstate ions. Heat treatment at a temperature typically between 50 and 180 ° C from 0 to 30 minutes usually allows the optimization of the performance of the device.
• An electrode is then typically deposited by liquid or evaporation under vacuum on the p-type layer. Its thickness is for example between 10 and 200 nm.
• the cathode and the anode are typically made of conductive materials:
• - metals such as silver, titanium, aluminum, calcium, magnesium, etc.
• transparent conductors such as In 2 0 3 doped Sn 4+ or ITO, ZnO doped Al 3+ or AZO, indium doped ZnO or IZO, Sn0 2 doped F or FTO - or inorganic / hybrid materials, for example a material based on carbon nanotubes or NTCs, graphene, silver nanowires
• conductive organic materials such as doped polythiophenes or PEDOT: PSS, optionally loaded with metal particles such as silver nanowires, or conductive carbon compounds such as for example carbon nanotubes and / or graphene;
• TCO transparent oxide conductor
• M transparent conductive oxide
• ITO ITO / Ag / ITO stack
• the active absorbent layer is generally composed of an n-type semiconductor material (such as for example one or more doped fullerenes derived from fullerene (such as for example PCBM (methyl [6,6] -phenyl-C 6 -butanoate). ), perylene, n-type semiconductor polymers, etc.) in admixture with a p-type semiconductor material (P3HT, polythiophene and its derivatives, polythiophene or polycarbazole copolymers, etc.) Hybrid perovskites may also be mentioned.
• organic-inorganic such as those of formulation MAMeX 3 , MA represents an organo-ammonium ion, Me represents Pb or Sn, and X is chosen from: Cl, Br, I or a combination of these halides.
• n-type cathodic interfacial layer such as, for example, ZnO, TiO 2 , etc. can be produced according to a technique known to those skilled in the art.
• the anodic interfacial layer comprises, according to the invention, a tungsten oxide layer according to the present invention.
• the tungsten oxide layer is produced by printing.
• the printing strategies are adapted to obtain homogeneous layers of targeted thickness.
• the solution of tungstate ions according to the present invention makes it possible to obtain a very good homogeneity of the deposited film.
• the tungsten oxide concentration of the solution used is adapted according to the printing strategy.
• the solutions of the invention are stable and compatible with printing techniques.
• the power conversion efficiencies (PCE) of the photovoltaic device of the present invention are typically 2 to 5%. Although it is desired to decrease the drying temperature of the interfacial layer of tungsten oxide, it has been found that the conversion efficiency increases with the drying temperature of the interfacial layer of tungsten oxide. The effect of the drying temperature makes it possible to increase the conversion efficiency to a value greater than 3%.
• the improvement mainly concerns the open circuit voltage and the form factor by comparing with respect to the p-type conductive polymers conventionally used in the state of the art, such as PEDOT: PSS.
• the invention relates to a tungsten oxide layer according to the present invention, used as an electron-blocking layer and / or layer for collecting holes).
• Each organic layer may have a structure identical or different from one device to another when there is an assembly of several photovoltaic devices.
• the thickness of the interfacial zone ranges from 5 to 100 nm and advantageously from 30 to 50 nm.
• a typical architecture is the following glass / ITO / WO z / P3HT: PCBM / ETL (n) / Ag or glass / ITO / WO z / P3HT: PCBM / ETL (n) / Ca / Al, ETL (n) designating a electron transporting layer (ETL).
• the tungsten oxide layer is transparent.
• the layer has for example a thickness less than 100 nm and the eye is transparent in the visible.
• OPD organic photodiodes
• the material has a transmittance of at least 90% in the 400 nm-900 nm window with a thickness of 100 nm or more.
• the tungstate ion solutions are concentrated before deposition on a substrate.
• the stability and the transparency of the solutions are preserved after concentration of the tungstate ion solutions, for example after evaporation of at least half the mass of solvent (s) initially present (s).
• This pre-concentration technique makes it possible to limit the quantity of solvents to be removed once the liquid film deposited on the substrate.
• the solution can be concentrated to the solubility limit of the tungstate ions present.
• the films obtained in the cases where the solutions are preconcentrated are more homogeneous. It is considered that a film is homogeneous due to the absence of cracks on the micrograph at magnification x27 at SEM.
• the method of the invention advantageously makes it possible to adjust the drying temperature of the film deposited on a substrate by diluting the solution of tungstate ions, possibly pre-concentrated, with a solvent with a lower boiling point than the solvent initially used. , in particular for the preparation of the tungstate ion solution, with a view to limiting the drying temperature.
• This variant of the invention has an advantage in particular during the deposition on substrates sensitive to high temperatures, such as plastic substrates or reverse architecture.
• the invention relates to the use of a solution of tungstate ions according to the invention or of a tungsten oxide layer as an interfacial layer to the anode, for example to block the electrons in a cell. organic photovoltaic or hybrid.
• the present invention also has the advantage of providing a manufacturing method implementing a non-toxic solvent solution, without the use of hydrogen peroxide or nanoparticle.
• the method according to the present invention also has the advantage of a reduced number of manufacturing steps.
• the present invention also has the advantage of replacing a p-type layer such as, for example, the PEDOT: PSS polymer, which has a trace of acidity, by a tungsten oxide layer.
• the production cost according to the present invention is reduced compared to the current process in particular using the PEDOT: PSS polymer.
• the handling time for the manufacture of the tungstate ion solution is less than one hour and the heating time typically twenty-four hours, which has a very important technical advantage.
• An important advantage of the method of the present invention is its reliability and reproducibility. This aspect results in a reproducible J / V curve in the case of organic solar cells.
• the method of the invention has an advantage over the known method according to the state of the art of using an organic polymer of the PEDOT: PSS type since the dispersion on the molecular weight of the polymer differs according to the suppliers. and evolves as a function of time, and therefore requires adjustment of shaping processes (viscosity for example).
• this parameter according to the prior methods significantly modifies the physical properties of the device.
• the method according to the present invention overcomes this technical disadvantage.
• the invention also relates to the use of a solution of tungstate ions as defined according to the invention, or capable of being obtained according to the process as defined according to the invention, to form a semiconductor layer comprising a tungsten oxide.
• the invention also relates to a method of manufacturing a photovoltaic device comprising the preparation of a semiconductor layer, as defined according to the invention.
• the invention also relates to a method for producing electrical energy comprising the use of a semiconductor material as defined according to the invention, or a photovoltaic device as defined according to the invention, for producing electricity. electrical energy from solar radiation.
• FIG. 1 represents a titrimetric titration with sodium hydroxide (NaOH) of 20 ml of transparent solution synthesized in ethylene glycol according to Example 1.
• NaOH sodium hydroxide
• FIG. 3 represents the XPS spectra of the 4f process of tungsten, the energy calibration on the C1 s of pollution at 284.7 eV, layers deposited on ITO treated at 150 ° C (right) and 225 ° C (left), during one o'clock.
• Figure 4 shows the XPS spectra of the tungsten 4f electronic processes for cells analyzed post-mortem, dried at 250 ° C for one hour.
• the amounts of oxidation degree tungsten are limited to 6 and 3% respectively, the conversion efficiency is directly correlated to this reduction rate.
• the terms "according to the invention” refer to all aspects and embodiments of the invention, including their preferred examples and embodiments, including any of their combinations, without limitation.
• each example has a general scope.
• Example 1 Preparation of tungstate ion solutions according to the invention Various tungsten-based reagents were tested: Na 2 WO 4 , ( ⁇ 4 ) 2 ⁇ 4 and
• H 2 WO 4 and various glycols such as propylene glycol, ethylene glycol, propylene glycol propyl ether.
• the tungsten concentration tested ranged from 0.05 to 0.20 mol.L 1 .
• the yellow suspension or gel is placed in an autoclave at a temperature of 120 ° C. for 24 hours.
• the final solutions obtained are always yellow but transparent and can be used for at least 6 months. The solution is used as such for the deposition of interfacial layers.
• Example 1 .1 The same protocol as Example 1 .1 is implemented using propylene glycol as a solvent in place of ethylene glycol.
• the polyoxotungstate complexes formed in solution are highlighted as follows:
• a titrimetric assay of 20 ml of the clear solution synthesized according to the examples above is carried out.
• the evolution of the pH curve is monitored as a function of the volume of the added base (sodium hydroxide).
• the curves show the same rate whatever the concentration of the precursor, in the range of 0.05 to 0.1 mol / L.
• Three equivalence points are identified, each of which corresponds to the neutralization of a different acidity.
• the number of moles of neutralized H + ions relative to the number of moles of tungsten present in solution confirms the presence of different polyoxotungstate complexes in each pH range (Table 1 below and FIG. 1).
• Table 1 polyoxotungstate complexes formed in solution (calculated from the equivalence points of the black curve of FIG. 1)
• X represents the number of moles of H + ion per mole of tungsten ion.
• compositions deduced from surface analyzes by XPS are indeed different from those of the state of the art: W0 2.985 and W0 2.97 for 3 and 6% of W 5+ , respectively, for example against W0 27 for the sol-gel film according to Guillain et al.
• Example 2 Use of the Solution for the Manufacture of an Organic Photovoltaic Cell
• a glass / ITO / PEDOT: PSS / P3HT: PCBM / Ca / Al architecture cell is prepared in parallel according to a similar procedure.
• Figure 3 illustrates an XPS spectrum of tungsten oxide layer deposited on
• ITO ITO, dried at 150 ° C (right) and 225 ° C (left), for one hour.
• Figure 4 illustrates an XPS spectrum of two cells analyzed post-mortem after one hour of drying 250 ° C (left 6% W 5+ and right spectrum less than 3% W 5+ ).
• Example 3 Methods for producing the inter-facial layer p in a standard PIN-type OPV architecture
• a solution of tungstate ions according to the invention (in particular Example 1 .1) is deposited on a transparent conductive or semiconductor substrate.
• the deposit methods used can be chosen from spin coating, coating / spreading (Dr Blade, slot die, "strip casting"), printing methods (inkjet, screen printing, gravure printing, etc.). .), etc. It is also possible to use a "patterning" (pattern) of the substrate.
• the tungsten oxide layer is produced by inkjet printing, in particular by spin coating or coating, using a platform of printing incorporating printing modules generating drops of 1 ⁇ L to 100 ⁇ L ( ⁇ L: pico-liter).
• the printing strategies are adapted to obtain homogeneous layers of targeted thickness, as well as the concentration of tungsten oxide.
• the thermal annealing applied is similar to that used for the layers produced by coating.
• the layer according to the invention is used on a semiconductor surface of organic or hybrid solar cells.
• the photovoltaic cells prepared comprise a glass or plastic substrate (PET, PEN), covered with a layer of ITO which is itself covered with a semiconductor oxide n such as TiO 2. This is covered with an active film composed of a P3HT / PCBM mixture.
• the active layer is successively coated with a layer of tungsten oxide prepared according to the present invention to form an interfacial layer and then a silver anode.
• the configuration of the cell is therefore as follows: substrate / ITO / Ti0 2 / polymer + PCBIWWO z / anode.
• Step 1 A TiO 2 layer is prepared from a precursor solution by spin coating (see process according to international application WO2013 / 050222). The duration of the coating is 60s to 1000 tr.min "1 then 30 s at 2000 tr.min" 1. The thickness of the layer obtained is approximately 50 nm, the deposition is carried out in air and then dried on a hot plate at 150 ° C. for 1 hour.
• Step 2 The deposition of the active layer is formed by spin coating of a composition of P3HT / PCBM, the n layer, about 1500 tr.min "1 for 40 sec then 2000 tr.min” 1 for 35 s.
• Step 3 A tungsten oxide layer (about 50 nm) is deposited by spin coating at 2000 tr.min "1 for 25 sec then 3000 tr.min” 1 for 25 sec.
• the cell thus prepared is then annealed in a glove box for 15 minutes at 150 ° C.
• Step 4 A silver electrode (100 nm) is then evaporated under vacuum.
• the cells are then characterized in glove box under controlled atmosphere.
• the current-voltage characteristics (I (V)) are recorded on a Keithley® SMU 2400 device under illumination AM1.5 at a power of 1000 Wm -2 .
• the inventors have sought to improve the deposition process of the tungsten oxide layer to obtain an optimal open circuit voltage and an optimal photovoltaic conversion efficiency. It has been tested different drying temperature.
• the inventors have also used different solution concentrations of polyoxotungstates to optimize the homogeneity of the deposited films for the preparation of photovoltaic cells.
• the solutions of tungstate ions are concentrated before they are deposited on the substrate.
• FIG. 5 shows surface scanning microscopy images of films dried at 50 ° C., 10 minutes, obtained from the parent solution of tungsten oxide precursors in the propylene glycol solvent in an autoclave at 120 ° C. for 24 hours. (left shot) and this pre-concentrated solution (right shot) before filing. The results obtained show that the films are more homogeneous in the case where the solutions are more concentrated.

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