Classifications

• • 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
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
• • 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
  • H10K30/50—Photovoltaic [PV] devices
• • 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
  • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
• • 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
• • 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
  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
  • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
• • 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

• a method of manufacturing an active layer capable of emitting an electric current under irradiation is a method of manufacturing an active layer capable of emitting an electric current under irradiation.
• the present invention relates to the field of organic electronics for photovoltaic energy that is to say the conversion of light energy into electricity. More particularly, this invention relates to a method of manufacturing an active layer capable of emitting an electric current under irradiation associating a ferroelectric material and a semiconductive polymer for transforming light energy into electricity.
• Photovoltaic cells There are currently devices for transforming light energy into electricity, photovoltaic cells. These devices consist of a cathode, an active layer and an anode. Photovoltaic cells can be made with inorganic materials or organic materials. Photovoltaic cells made from inorganic materials are well known, their efficiency is high, more than 25% but their manufacturing cost is high because the implementation of inorganic materials is difficult. Organic materials have the advantage of being inexpensive, easy to implement, and flexible devices can be achieved with these materials. However, low yields are obtained using these materials in particular because of the way of transforming the light energy.
• the active layer of organic solar cells is generally composed of P3HT (poly (3-hexy.ththiophene)) and PCBM (methyl [6, 6] -phenyl-C61-butanoate).
• P3HT poly (3-hexy.ththiophene)
• PCBM methyl [6, 6] -phenyl-C61-butanoate
• the difference in energy level between the P3HT and the PCBM generates an internal electric field which makes it possible to dissociate the excitons created in the P3HT, the separation of the electron-hole pairs is therefore done at the P3HT-PCBM interfaces.
• the yields of the photovoltaic organic cells are low, in particular because of excessive recombination of the excitons, it is therefore necessary to find another way of dissociating the excitons to increase the yield of the photovoltaic organic cells.
• the P (VDF-TrFe) film can also be deposited between the two donor and acceptor materials of the active layer as described by Yang et al in their article entitled “Tuning the energy level of equilibrium between donor and acceptor with ferroelectric dipole efficiency in bilayer organic photovoltaic cells ", Advanced Materials, 2012, 24, 1455-1460.
• the photovoltaic current is not induced solely by ferroelectricity because there is concomitant of a donor / acceptor system.
• WO2010131254 discloses a method of manufacturing photovoltaic cells based on a mixture of ferroelectric and semiconductor materials. However, this process comprises many steps of manufacturing the active layer very difficult to apply to industry and large scale. In addition, no figure in this document can prove the operation of this device and therefore the feasibility thereof.
• compositions of organic semiconductor materials and ferroelectric polymers cited in this demand are unlikely to lead to a notable photovoltaic effect.
• polymers such as PVDF and PTrFE are ferroelectric only after a physical treatment such as stretching which is difficult to imagine in the compositions and associated morphologies described in this application.
• the Applicant has observed that the electric field generated by a material capable of crystallizing in ferroelectric form is sufficient to dissociate the excitons for particular compositions, typically major quantities of material capable of crystallizing in ferroelectric form associated with a method of simplified application. These compositions only involve a material capable of crystallizing under ferroelectric form a semi-conducting polymer in an unexpected morphology cylinder type semi ⁇ conductive polymer and provide excellent efficiency of photovoltaic conversion.
• the invention relates to a method for manufacturing a device comprising the following steps: Preparation of a solution comprising at least one solvent, a material or a mixture of materials capable of crystallizing in ferroelectric form and at least one semi-crystalline polymer conductive, these compounds being miscible in the said solvent for concentrations of less than 10% by mass, preferably less than 5%, the material or materials capable of crystallizing in ferroelectric form on the one hand and the conductive polymer or polymers on the other hand not being miscible with each other, Spinning, Dr.
• Blade or any other technique of this solution on a conductive electrode evaporation of the solvent, such that a phase separation between the material (s) capable of crystallizing in ferroelectric form on the one hand and the semiconductor polymer (s) on the other hand establishes a morphology.
• any material or mixture of materials capable of crystallizing in ferroelectric form can be used in the invention.
• the material or mixture of materials capable of crystallizing in ferroelectric form are organic materials, and preferably polymers. It can also be a material capable of crystallizing in ferroelectric form and of another material not necessarily capable of crystallizing in ferroelectric form when taken alone, but on condition that the mixture of the two materials is capable of crystallizing in the form of ferroelectric.
• polymers or mixtures of polymers containing the monomeric entities of vinylidene difluoride and trifluoroethylene, vinylidene difluoride and trifluoroethylene, vinylidene difluoride and hexafluoropropylene optionally added with a third monomer chosen from the following monomers: trifluoroethylene, tetrafluoroethylene, fluoride vinyl, perfluoroalkylvinylethers such as perfluoromethylvinyl ether, dichloroethylene, vinyl chloride, chloro trifluoroethylene, perfluoro (methyl vinyl ether), bromotrifluoroethylene, tetra fluoro propene, hexafluoropropylene.
• a third monomer chosen from the following monomers: trifluoroethylene, tetrafluoroethylene, fluoride vinyl, perfluoroalkylvinylethers such as perfluoromethylvinyl ether, dichloroethylene, vinyl chloride, chloro tri
• Odd polyamides such as PA7, PA9, PAA, PA13 may also be used as well as their mixtures.
• VDF-TrFe a copolymer of vinylidene with trifluoroethylene P
• the semiconductor material is an organic material, and more particularly a polymer.
• the conductive polymer may be an electron donor or acceptor. It can also be a mixture of semiconductor polymers.
• the semiconductive polymer is preferably chosen from polymers containing fluorene, thiophene, phenylenes, phenylenes, phenylene vinylidene, fullerenes, pyrilenes, carbazole derivatives derived from thiophenes such as benzodithiophene or cyclopentadithiophene, derived from fluorene, pyrrole and furan.
• the conductive polymer is poly- (3-hexylthiophene) P3HT.
• the mobilities of the semiconductor polymer are between 10 -7 cm W 1 and 10 4 cm 2 / V -1 s -1 .
• the invention also relates to a device comprising (a) a conductive electrode, (b) a second conductive electrode, (c) an active layer comprising a material capable of crystallizing in ferroelectric form and a semiconductor material, which separates from and the other two electrodes.
• a device comprising (a) a conductive transparent electrode, (b) a conductive metal electrode, (c) an active layer comprising a material capable of crystallizing in ferroelectric form and a semiconductor material, which separates on both sides the two electrodes
• the device comprising (a) a conductive transparent electrode, (b) a conductive electrode, (c) an active layer comprising a material capable of crystallizing in ferroelectric form and a semiconductor material, which separates on both sides the two electrodes, the material capable of crystallizing in ferroelectric form being polarized by mechanical deformation and / or by applying an electric field greater than the coercive field, and even more preferably by applying an electric field greater than the field coercive, to the electrodes of the device.
• transparent electrode an electrode whose transmittance is greater than 60% and preferably greater than 80%, for a thickness of the 100 nm electrode, the transmittance being measured at 555 nm using a spectrophotometer, for example a spectrophotometer lambda 19 from Perkin Elmer.
• conductive electrode is meant an electrode whose conductivity is between 10 and 10 9 S / cm.
• compositions constituting the active layer are chosen so that the proportion of material or materials capable of crystallizing in ferroelectric form is greater than 20% by mass relative to the total material capable of crystallizing in ferroelectric form and semiconductor polymer, and of preferably greater than 50%, and more preferably between 70 and 95%.
• the solvent necessary for the preparation of a solution comprising at least one solvent, a material or a mixture of materials capable of crystallizing in ferroelectric form and at least one semiconductive polymer, these compounds being miscible in the said solvent for concentrations of less than 10% by weight, it is one or more polar and / or aromatic solvents capable of solubilizing the ferroelectric polymer and the semiconductive polymer.
• the solvents will be chosen from the following: tetrahydrofuran, methyl ethyl ketone, dimethylformamide, N, dimethylacetamide,
• Cyclohexaxone Diaceton Alcohol, Diisobutyl Ketone, Butyrolactone, Isophorone, 1, 2-dimethoxyethane, chloroform, dichlorobenzene, ortho-dichlorobenzene.
• the preparation of the active layer is conducted in such a way that a phase separation of the two materials constituting the active layer results in a morphology where a material is dispersed in the other material on a scale below the ym, or has a co- continuity of the two materials to a scale below the ym.
• the types of morphologies mentioned above may also include the presence of a thin layer of the material or materials capable of crystallizing in ferroelectric form of less than 40 nm in contact with one or both electrodes.
• the preparation of the active layer is carried out in such a way that a phase separation of the two materials constituting the active layer leads to a morphology of the cylinder type of the semiconductor polymer after evaporation of the solvent.
• additives to the ferroelectric material provides an additional advantage because it makes it possible to limit the electric field necessary for the polarization essential for the operation of these devices.
• plasticizers are preferred, among which mention may be made of branched or linear phthalates, such as di-n-octyl, dibutyl, -2-ethylhexyl, di-ethylhexyl, di-isononyl and di-isodecyl phatalates.
• plasticizers can be used alone or in combination.
• additives will be introduced in proportions ranging from 0.01 to 95% and preferably from 0.01 to 40% and more preferably from 0.1 to 10% relative to the sum of the mixture of materials capable of crystallizing in ferroelectric form.
• These devices may have a remanent polarization following the polarization of the material capable of crystallizing in ferroelectric form. These devices are capable of producing an electric current under illumination.
• the conductive and preferably transparent electrode may be of organic or metallic nature. It can be composed of carbon nanotubes. It may be composed of semiconductive polymer such as PEDOT-PSS (poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonate)).
• PEDOT-PSS poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonate)
• the devices resulting from the process of the invention are used in temperature ranges below the Curie temperature of the material or materials capable of crystallizing in ferroelectric form considered.
• these devices have a remanent polarization following the polarization of the material capable of crystallizing in ferroelectric form.
• ITO electrode indium tin oxide
• an active layer comprising 90% by weight of P (VDF-TrFe) and 10% by weight of P3HT deposited by spin-coating on the ITO electrode from a 3% by weight solution of the two polymers in THF. a LiF / Al electrode.
• AFM and TEM images illustrate the morphology obtained ( Figure 1 and Figure 2). It shows the cylindrical distribution of the minority polymer (P3HT) (circles of Figure 1 (a)), and dark spots within the active layer ( Figure 2). illumination a current increase of about summer observed ( Figure 3 and Figure 4).

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• 2013
  • 2013-07-11 FR FR1356832A patent/FR3008548B1/fr not_active Expired - Fee Related
• 2014
  • 2014-07-10 WO PCT/FR2014/051772 patent/WO2015004393A1/fr active Application Filing
  • 2014-07-10 EP EP14747092.6A patent/EP3020078A1/fr not_active Withdrawn
  • 2014-07-10 CN CN201480049600.5A patent/CN105518893A/zh active Pending
  • 2014-07-10 SG SG11201600190XA patent/SG11201600190XA/en unknown
  • 2014-07-10 US US14/904,331 patent/US20160141534A1/en not_active Abandoned
  • 2014-07-10 KR KR1020167003533A patent/KR20160032159A/ko not_active Application Discontinuation
  • 2014-07-10 JP JP2016524878A patent/JP2016525793A/ja active Pending

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