EP3020078A1 - Method for producing an active layer capable of emitting an electric current under irradiation - Google Patents
Method for producing an active layer capable of emitting an electric current under irradiationInfo
- Publication number
- EP3020078A1 EP3020078A1 EP14747092.6A EP14747092A EP3020078A1 EP 3020078 A1 EP3020078 A1 EP 3020078A1 EP 14747092 A EP14747092 A EP 14747092A EP 3020078 A1 EP3020078 A1 EP 3020078A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ferroelectric
- crystallizing
- polymer
- active layer
- solvent
- 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- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 239000004065 semiconductor Substances 0.000 claims abstract description 22
- 239000002861 polymer material Substances 0.000 claims abstract 4
- 239000000463 material Substances 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- 230000010287 polarization Effects 0.000 claims description 15
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 11
- 230000005684 electric field Effects 0.000 claims description 10
- -1 Cyclohexaxone Chemical compound 0.000 claims description 7
- 229920001940 conductive polymer Polymers 0.000 claims description 7
- 239000011368 organic material Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000005191 phase separation Methods 0.000 claims description 5
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910003472 fullerene Inorganic materials 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 230000003381 solubilizing effect Effects 0.000 claims description 2
- 150000003577 thiophenes Chemical class 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 230000005611 electricity Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract 1
- 230000005621 ferroelectricity Effects 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000001131 transforming effect Effects 0.000 description 3
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 description 1
- XLOFNXVVMRAGLZ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2-trifluoroethene Chemical group FC(F)=C.FC=C(F)F XLOFNXVVMRAGLZ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- AYCANDRGVPTASA-UHFFFAOYSA-N 1-bromo-1,2,2-trifluoroethene Chemical group FC(F)=C(F)Br AYCANDRGVPTASA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 101000701286 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Alkanesulfonate monooxygenase Proteins 0.000 description 1
- 101000983349 Solanum commersonii Osmotin-like protein OSML13 Proteins 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000037230 mobility Effects 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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).
Abstract
Method for producing an active layer capable of emitting an electric current under irradiation The present invention concerns the field of organic electronics for photovoltaic energy, that is to say the conversion of light energy into electricity. The invention relates in particular to a method for producing an active layer capable of emitting an electric current under light irradiation, said layer combining a ferroelectric polymer material and a semiconductor polymer allowing the transformation of light energy into electricity.
Description
Procédé de fabrication d'une couche active susceptible d'émettre un courant électrique sous irradiation. A method of manufacturing an active layer capable of emitting an electric current under irradiation.
La présente invention concerne le domaine de l'électronique organique pour l'énergie photovoltaïque c'est-à dire la conversion de l'énergie lumineuse en électricité. Plus particulièrement, cette invention se rapporte à un procédé de fabrication d'une couche active susceptible d'émettre un courant électrique sous irradiation associant un matériau ferroélectrique et un polymère semi conducteur permettant de transformer l'énergie lumineuse en électricité. 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.
Il existe actuellement des dispositifs permettant de transformer l'énergie lumineuse en électricité, les cellules photovoltaïques . Ces dispositifs sont constitués d'une cathode, d'une couche active et d'une anode. Les cellules photovoltaïques peuvent être réalisées avec des matériaux inorganiques ou des matériaux organiques. Les cellules photovoltaïques réalisées à partir de matériaux inorganiques sont bien connues, leur rendement est élevé, plus de 25 % mais leur coût de fabrication est grand car la mise en œuvre des matériaux inorganiques est difficile. Les matériaux organiques présentent l'avantage d'être peu coûteux, de pouvoir être facilement mis en œuvre et des dispositifs flexibles peuvent être obtenus grâce à ces matériaux. Cependant, de faibles rendements sont obtenus à l'aide de ces matériaux notamment à cause de la manière de transformer l'énergie lumineuse. La couche active des cellules solaires organiques est généralement composée de P3HT (poly (3-hexy.lth.iophène) ) et de PCBM ( [ 6, 6] -phényl-C61- butanoate de méthyle ) . Cette couche active organique absorbe les photons et des excitons c'est-à-dire des paires électron-trou sont générées dans le P3HT. Il est nécessaire de séparer ces charges avec un champ électrique plus élevé
que l'attraction coulombienne entre ces deux charges afin d'obtenir un courant photovoltaïque . C'est donc la dissociation de ces excitons et le transport des charges libres qui va générer le courant photovoltaïque. La différence de niveau énergétique entre le P3HT et le PCBM génère un champ électrique interne qui permet de dissocier les excitons créés dans le P3HT, la séparation des paires électrons-trous se fait donc aux interfaces P3HT-PCBM. Cependant les rendements des cellules organiques photovoltaïques sont faibles notamment à cause de recombinaisons trop importantes des excitons, il est donc nécessaire de trouver une autre manière de dissocier les excitons pour augmenter le rendement des cellules organiques photovoltaïques. 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). This organic active layer absorbs photons and excitons, ie electron-hole pairs, are generated in P3HT. It is necessary to separate these charges with a higher electric field than the Coulomb attraction between these two charges in order to obtain a photovoltaic current. It is thus the dissociation of these excitons and the transport of the free charges which will generate the photovoltaic current. 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. However, 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.
De récentes études dans le domaine des cellules photovoltaïques inorganiques se sont intéressées au phénomène photovoltaïque généré par des matériaux ferroélectriques . Les matériaux ferroélectriques ont la capacité de se polariser lorsque l'on applique un champ électrique supérieur au champ coercitif, propriété intrinsèque du matériau. Deux états de polarisation peuvent ainsi être atteints, lorsque le matériau n'est plus soumis à un champ électrique extérieur, il conserve sa polarisation, c'est une polarisation rémanente. Fridkin et al, dans leur article intitulé « Anomalous photovoltaic effect in ferroelectrics », Soviet Physics Uspekhi, 1978, 21(12) p981, décrivent la capacité du matériau ferroélectrique Li b03 à générer un photocourant et un courant photovoltaïque sous illumination. Il est donc possible d'utiliser la ferroélectricité de certains matériaux inorganiques afin de dissocier des excitons. Choi et al, dans leur article intitulé « Switchable ferroelectric diode and photovoltaic in BiFe03 », Science,
2009, 324, p63, décrivent l'utilisation du matériau multiferroïque inorganique BiFe03. L'état de polarisation du BiFe03 permet la séparation des paires électrons-trous créés au sein même du matériau. Le courant est plus élevé sous illumination, le BiFe03 génère donc un courant photovoltaïque grâce à la ferroélectricité . Yang et al, dans leur article intitulé « Above-band gap voltages from ferroelectric photovoltaic devices », Nature nanotechnology, 2010, 5, pl43 utilisent également le BiFe03 et décrivent le mécanisme responsable de l'effet photovoltaïque dans ce matériau. Recent studies in the field of inorganic photovoltaic cells have focused on the photovoltaic phenomenon generated by ferroelectric materials. Ferroelectric materials have the ability to polarize when applying a higher electric field to the coercive field, intrinsic property of the material. Two states of polarization can thus be achieved, when the material is no longer subjected to an external electric field, it retains its polarization, it is a remanent polarization. Fridkin et al, in their article entitled "Anomalous photovoltaic effect in ferroelectrics", Soviet Physics Uspekhi, 1978, 21 (12) p981, describe the ability of the ferroelectric material Li b03 to generate a photocurrent and a photovoltaic current under illumination. It is therefore possible to use the ferroelectricity of certain inorganic materials to dissociate excitons. Choi et al, in their article "Switchable ferroelectric diode and photovoltaic in BiFe03", Science, 2009, 324, p63, describe the use of the inorganic multiferroic material BiFe03. The polarization state of BiFe03 allows the separation of electron-hole pairs created within the material itself. The current is higher under illumination, so BiFe03 generates a photovoltaic current thanks to ferroelectricity. Yang et al, in their article titled "Above-band gap voltages from ferroelectric photovoltaic devices", Nature nanotechnology, 2010, 5, pl43 also use BiFe03 and describe the mechanism responsible for the photovoltaic effect in this material.
Les récentes études menées sur les matériaux ferroélectriques organiques ne montrent pas de telles propriétés . Recent studies of organic ferroelectric materials do not show such properties.
En revanche, Yuan et al, dans leur article intitulé « Efficiency enhancement in organic solar cells with ferroelectric polymers », Nature Materials, 2011, 10, 296, décrivent l'utilisation d'une faible épaisseur de polymère ferroélectrique P(VDF-TrFe) (poly ( fluorure de vinylidène co trifluoroethylène ) ) insérée entre la couche active et les électrodes. Il a été démontré que le courant photovoltaïque augmente lors de la polarisation du polymère ferroélectrique, la polarisation de ce polymère ferroélectrique permet donc d'augmenter l'efficacité de la dissociation des excitons. Le film de P(VDF-TrFe) peut également être déposé entre les deux matériaux donneurs et accepteurs de la couche active comme le décrivent Yang et al dans leur article intitulé « Tuning the energy level offset between donor and acceptor with ferroelectric dipole layers for increased efficiency in bilayer organic photovoltaic cells », Advanced Materials, 2012, 24, 1455- 1460. Les recherches actuelles sur l'utilisation de la ferroélectricité pour le photovoltaïque, concernent la
capacité du polymère ferroélectrique PVDF-TrFe à augmenter le champ électrique interne de manière à rendre plus efficace la dissociation des excitons. Cependant, le courant photovoltaïque n'est pas induit uniquement par la ferroélectricité car il y a concomitance d'un système donneur/accepteur . On the other hand, Yuan et al, in their article entitled "Efficiency enhancement in organic solar cells with ferroelectric polymers", Nature Materials, 2011, 10, 296, describe the use of a small thickness of ferroelectric polymer P (VDF-TrFe) (poly (vinylidene fluoride trifluoroethylene)) inserted between the active layer and the electrodes. It has been demonstrated that the photovoltaic current increases during the polarization of the ferroelectric polymer, the polarization of this ferroelectric polymer thus makes it possible to increase the efficiency of the dissociation of the excitons. 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. Current research on the use of ferroelectricity for photovoltaic ability of the PVDF-TrFe ferroelectric polymer to increase the internal electric field so as to make exciton dissociation more efficient. However, the photovoltaic current is not induced solely by ferroelectricity because there is concomitant of a donor / acceptor system.
Nalwa et al, dans leur article intitulé « Enhanced charge séparation in organic photovoltaic films doped with ferro electric dipole », Energy Environ., 2012, 5, 7042-7049 décrivent un système ou dans un exemple, le polymère ferroélectrique est mélangé au P3H . Cependant, le procédé d'application par évaporation-solvant et non par « spin casting » ou dite « à la tournette » qui plus est à partir d'un mélange de solvant ne laisse pas imaginer une distribution fine du polymère ferroélectrique au sein de la matrice P3HT mais plutôt un macro-séparation de phase. La polarisation du polymère ferroélectrique n'a que peu de chance de se maintenir car le polymère ferroélectrique n'est en contact qu'avec les polymères semi-conducteurs. La densité de charges dans les polymères semi-conducteurs est trop faible et ne permet donc pas de compenser la polarisation du matériau ferroélectrique . Nalwa et al, in their article "Enhanced charge separation in organic photovoltaic films doped with ferro electric dipole", Energy Environ., 2012, 5, 7042-7049 describe a system or in one example, the ferroelectric polymer is mixed with P3H. However, the method of application by evaporation-solvent and not by "spin casting" or "spin" which moreover from a mixture of solvent does not allow to imagine a fine distribution of the ferroelectric polymer within the P3HT matrix but rather a macro-phase separation. The polarization of the ferroelectric polymer is unlikely to be maintained because the ferroelectric polymer is in contact only with the semiconductor polymers. The charge density in the semiconductor polymers is too low and therefore does not compensate for the polarization of the ferroelectric material.
WO2010131254, révèle un procédé de fabrication de cellules photovoltaïques basées sur un mélange de matériaux ferroélectriques et semi-conducteurs. Cependant ce procédé comprend de nombreuses étapes de fabrication de la couche active très difficilement applicables à l'industrie et à grande échelle. De plus, aucune figure de ce document ne permet de prouver le fonctionnement de ce dispositif et donc la faisabilité de celui-ci. 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.
Par ailleurs, les compositions de matériaux semi conducteur organiques et de polymères ferroélectriques cités dans
cette demande ont peu de chance de conduire à un effet photovoltaique notables. En particulier les polymères tels que le PVDF et le PTrFE ne sont ferro électrique qu'après un traitement physique tel qu'un étirage difficilement imaginable dans les compositions et morphologies associées décrites dans cette demande. Furthermore, the compositions of organic semiconductor materials and ferroelectric polymers cited in this demand are unlikely to lead to a notable photovoltaic effect. In particular, 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.
De façon inattendue, la demanderesse à observée que le champ électrique généré par un matériau capable de cristalliser sous forme ferroélectrique est suffisant pour dissocier les excitons pour des compositions particulières, typiquement des quantités majoritaires de matériau capable de cristalliser sous forme ferroélectrique associé à un procédé d'application simplifié. Ces compositions associent seulement un matériau capable de cristalliser sous forme ferroélectrique à un polymère semi conducteur au sein d'une morphologie inattendue de type cylindre du polymère semi¬ conducteur et permettent une excellente efficacité de conversion photovoltaique. Unexpectedly, 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.
Résumé de l'invention : Summary of the invention
L'invention concerne un procédé de fabrication d'un dispositif comprenant les étapes suivantes : -Préparation d'une solution comprenant un au moins un solvant, un matériau ou un mélange de matériaux capables de cristalliser sous forme ferroélectrique et au moins un polymère semi-conducteur, ces composés étant miscibles dans le dit solvant pour des concentrations inférieures à 10 % massique, de préférence inférieures à 5%, le ou les matériaux capables de cristalliser sous forme ferroélectrique d'une part et le ou les polymères conducteurs d'autre part n'étant pas miscibles entres eux,
-Dépôt à la tournette, au Docteur Blade ou toute autre technique de cette solution sur une électrode conductrice, -Evaporation du solvant, de telle sorte qu'une séparation de phase entre le ou les matériaux capables de cristalliser sous forme ferroélectrique d'une part et le ou les polymères semi-conducteurs d'autre part établisse une morphologie . 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.
Description détaillée: Detailed description:
Tout matériau ou mélange de matériaux capable de cristalliser sous forme ferroélectrique peut être utilisé dans l'invention. De préférence le matériau ou mélange de matériaux capables de cristalliser sous forme ferroélectrique sont des matériaux organiques, et de préférence des polymères. Il peut aussi s'agir d'un matériau capable de cristalliser sous forme ferroélectrique et d'un autre matériau non nécessairement capable de cristalliser sous forme ferroélectrique lorsque pris seul, mais à la condition que le mélange des deux matériaux soit capable de cristalliser sous forme ferroélectrique . Any material or mixture of materials capable of crystallizing in ferroelectric form can be used in the invention. Preferably 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.
On choisira de préférence les polymères ou mélanges de polymères contenant les entités monomériques difluorure de vinylidene et trifluoroéthylène, difluorure de vinylidene et trifluoroéthylène, difluorure de vinylidene et hexafluoropropylene additionnés éventuellement d'un troisième monomère choisi parmi les monomères suivants : trifluoroéthylène, tetrafluoroéthylène, fluorure de vinyle, les perfluoroalkylvinylethers tel que le perfluorométhylvinyléther, dichloréthylène, chlorure de vinyle, , chloro trifluoroéthylène, perfluoro (methyl
vinyl ether) , bromotrifluoroethylene , tetra fluoro propène, hexafluoropropylene . Preferably 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.
Les polyamides impairs, tels que les PA7, PA9, PAU, PA13 pourront aussi être utilisés ainsi que leurs mélanges. Odd polyamides, such as PA7, PA9, PAA, PA13 may also be used as well as their mixtures.
Plus particulièrement il s'agit de copolymère de vinylidène avec du trifluoroéthylène P(VDF-TrFe). More particularly, it is a copolymer of vinylidene with trifluoroethylene P (VDF-TrFe).
Tout matériau semi-conducteur peut être utilisé dans l'invention. De préférence, le matériau semi-conducteur est un matériau organique, et plus particulièrement un polymère. Le polymère conducteur peut être un donneur ou un accepteur d'électrons. Cela peut aussi être un mélange de polymères semi-conducteurs. Any semiconductor material can be used in the invention. Preferably, 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.
Le polymère semi-conducteur est choisi de préférence parmi les polymères contenant des entités fluorènes, thiophènes, phenylènes, phenylènes, phenylène vinylidène, fullerènes, pyrilènes, carbazole, dérivées du thiophènes tels que benzodithiophène ou cyclopentadithiophène, dérivées du fluorène, pyrrole et du furane . 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.
De façon encore préférée, le polymère conducteur est le poly- (3-hexylthiophène) P3HT. More preferably, the conductive polymer is poly- (3-hexylthiophene) P3HT.
Les mobilités du polymère semi-conducteur sont comprises entre 10"7 cm W1 et 104 cm2 /V_1s_1. The mobilities of the semiconductor polymer are between 10 -7 cm W 1 and 10 4 cm 2 / V -1 s -1 .
L' invention concerne également un dispositif comprenant (a) une électrode conductrice, (b) une deuxième électrode conductrice, (c) une couche active comprenant un matériau capable de cristalliser sous forme ferroélectrique et un matériau semi-conducteur, qui sépare de part et d'autre les deux électrodes. De préférence l'invention concerne un dispositif comprenant (a) une électrode transparente conductrice, (b) une électrode métallique conductrice, (c)
une couche active comprenant un matériau capable de cristalliser sous forme ferroélectrique et un matériau semi-conducteur, qui sépare de part et d'autre les deux électrodes 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. Preferably the invention relates to 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
Selon une forme de l'invention, dans le dispositif comprenant (a) une électrode transparente conductrice, (b) une électrode conductrice, (c) une couche active comprenant un matériau capable de cristalliser sous forme ferroélectrique et un matériau semi-conducteur, qui sépare de part et d'autre les deux électrodes, le matériau capable de cristalliser sous forme ferroélectrique étant polarisé par déformation mécanique et /ou en appliquant un champ électrique supérieur au champ coercitif, et de façon encore préférée en appliquant un champ électrique supérieur au champ coercitif, aux électrodes du dispositif. According to one form of the invention, in 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.
Par électrode transparente, on entend une électrode dont la transmittance est supérieure à 60 % et de façon préférée supérieure à 80 %, pour une épaisseur de l'électrode de lOOnm, la transmittance étant mesurée à 555nm à l'aide d'un spectrophotomètre, par exemple un spectrophotomètre lambda 19 de la société Perkin Elmer. By transparent electrode is meant 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.
Par électrode conductrice, on entend une électrode dont la conductivité est comprise entre 10 et 109 S/cm. By conductive electrode is meant an electrode whose conductivity is between 10 and 10 9 S / cm.
Les compositions préférées constituants la couche active sont choisies de telle sorte que la proportion du ou des matériaux capables de cristalliser sous forme ferroélectrique soit supérieure à 20 % massique par rapport au total matériau capable de cristalliser sous forme ferroélectrique et polymère semi-conducteur, et de préférence supérieure à 50%, et de façon encore préférée comprise entre 70 et 95%.
S' agissant du solvant nécessaire à la préparation d'une solution comprenant un au moins un solvant, un matériau ou un mélange de matériaux capables de cristalliser sous forme ferroélectrique et au moins un polymère semi-conducteur, ces composés étant miscibles dans le dit solvant pour des concentrations inférieures à 10 % massique, il s'agit d'un ou plusieurs solvants polaires et/ou aromatiques capables de solubiliser le polymère ferro électrique et le polymère semi conducteur . Les solvants seront choisis parmis les suivants: Tétrahydrofurane, Méthyl Ethyl Cétone, Diméthylformamide, N, -Diméthylacétamide,The preferred 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%. With regard to 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,
Diéethylsulfoxyde, Acétone, Méthylisobutylcétone,Diethyl sulfoxide, acetone, methyl isobutyl ketone,
Cyclohexaxone, Diaceton Alcool, Diisobutyl Cétone, Butyrolactone, Isophorone, 1 , 2-dimethoxyethane, chloroforme, dichlorobenzène, ortho-dichlorobenzène . Cyclohexaxone, Diaceton Alcohol, Diisobutyl Ketone, Butyrolactone, Isophorone, 1, 2-dimethoxyethane, chloroform, dichlorobenzene, ortho-dichlorobenzene.
La préparation de la couche active est conduite de telle sorte qu'une séparation de phase des deux matériaux constituants la couche active conduise à une morphologie ou un matériau est dispersé dans l'autre matériau à une échelle inférieure au ym, ou présente une co-continuité des deux matériaux à une échelle inférieure au ym. Selon une variante de l'invention, les types de morphologies précitées peuvent également inclure la présence d'une fine couche du ou des matériaux capables de cristalliser sous forme ferroélectrique inférieure à 40nm en contact avec une ou les deux électrodes. 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. According to a variant of the invention, 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.
Selon une forme encore préférée de l'invention, la préparation de la couche active est conduite de telle sorte qu'une séparation de phase des deux matériaux constituants la couche active conduise à une morphologie du type cylindre du polymère semi-conducteur après évaporation du solvant, avec contact électrique de la phase polymère semi-
conducteur et de la phase matériau capable de cristalliser sous forme ferroélectrique sur l'électrode conductrice et un angle de l'axe des cylindres compris entre 20 et 90° par rapport au plan de l'électrode conductrice, et de préférence entre 70 et 90 °, de façon encore préférée 90°, la couche ainsi déposée constituant ladite couche active après évaporation du solvant. According to an even more preferred form of the invention, 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. , with electrical contact of the semiconducting polymer phase conductor and the material phase capable of crystallizing in ferroelectric form on the conductive electrode and an angle of the axis of the rolls between 20 and 90 ° with respect to the plane of the conductive electrode, and preferably between 70 and 90 ° , more preferably 90 °, the layer thus deposited constituting said active layer after evaporation of the solvent.
La demanderesse à également découvert que l'addition d'additifs au matériau ferroélectrique procure un avantage supplémentaire car elle permet de limiter le champ électrique nécessaire à la polarisation indispensable au fonctionnement de ces dispositifs. Parmi les additifs on préférera les plastifiants, parmi lesquels on peut citer les phtalates branchés ou linéaires tels que les phatalate de di-n-octyle, dibutyle, -2-éthylhexyle, di-ethyl-hexyle, di-isononyle, di-isodécyle, benzylbutyle, diéthyle, di- cyclohexyle, diméthyle, di-undecyl linéaire, di tridecyl linéaire, les paraffines chlorées, les trimellitates , branchés ou linéaires , en particulier le trimellitate de di-ethyl hexyle, les esters aliphatiques ou les esters polymériques , les époxydes, les adipates, les citrates, les benzoates, ces plastifiants pouvant être utilisés seuls ou de façon combinée. The Applicant has also discovered that the addition of 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. Among the additives, 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. benzylbutyl, diethyl, di-cyclohexyl, dimethyl, linear di-undecyl, di tridecyl linear, chlorinated paraffins, trimellitates, branched or linear, in particular di-ethyl hexyl trimellitate, aliphatic esters or polymeric esters, epoxides adipates, citrates, benzoates, these plasticizers can be used alone or in combination.
Ces additifs seront introduits dans des proportions allant de 0.01 à 95 % et de préférence de 0.01 à 40% et façon encore préférée de 0.1 à 10 % par rapport à la somme du mélange de matériaux capables de cristalliser sous forme ferroélectrique . These 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.
Ces dispositifs peuvent posséder une polarisation rémanente suite à la polarisation du matériau capable de cristalliser sous forme ferroélectrique .
Ces dispositifs sont capables de produire un courant électrique sous illumination. 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.
L'électrode conductrice et de préférence transparente peut être de nature organique ou métallique. Elle peut être composée de nanotubes de carbone. Elle peut être composée de polymère semi-conducteur tel que le PEDOT-PSS (poly(3,4- éthylènedioxythiophène) -poly (styrène sulfonate) ) . 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)).
Elle peut également être hybride c'est-à-dire fabriquée à partie d'un mélange de matériau organique et métallique. It can also be hybrid that is to say made from a mixture of organic and metallic material.
Les dispositifs issus du procédé de l'invention sont utilisés dans des plages de température inférieures à la température de Curie du ou des matériaux capables de cristalliser sous forme ferroélectrique considérés. 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.
De préférence, ces dispositifs possèdent une polarisation rémanente suite à la polarisation du matériau capable de cristalliser sous forme ferroélectrique . Preferably, these devices have a remanent polarization following the polarization of the material capable of crystallizing in ferroelectric form.
Ces dispositifs sont avantageusement utilisés pour produire du courant électrique sous illumination. These devices are advantageously used to produce electric current under illumination.
Exemple : Example:
Le dispositif suivant a été utilisé : The following device was used:
-un substrat de verre sur lequel est déposée une électrode en ITO (Oxyde d' indium-étain) d'épaisseur 100 nm. a glass substrate on which is deposited an ITO electrode (indium tin oxide) with a thickness of 100 nm.
-une couche active comprenant 90 % massique de P(VDF-TrFe) et 10 % massique de P3HT déposé par spin-coating sur l'électrode d' ITO à partir d'une solution à 3% massique des deux polymères dans le THF.
-une électrode en LiF/Al. 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.
Des images AFM et TEM illustrent la morphologie obtenue (Figure 1 et Figure 2) . On y voit bien la distribution cylindrique du polymère minoritaire (P3HT) (cercles de la figure 1 (a) ) , et taches sombres au sein de la couche active (figure 2 ) . illumination une augmentation de courant d'environ été observée (Figure 3 et Figure 4) .
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).
Claims
Revendications Claims
1 Procédé de fabrication d'un dispositif comprenant les étapes suivantes : 1 Process for manufacturing a device comprising the following steps:
-Préparation d'une solution comprenant un au moins un solvant, un matériau ou un mélange de matériaux capables de cristalliser sous forme ferroélectrique et au moins un polymère semi-conducteur, ces composés étant miscibles dans le dit solvant pour des concentrations inférieures à 10% massique, le ou les matériaux capables de cristalliser sous forme ferroélectrique d'une part et le ou les polymères conducteurs d'autre part n'étant pas miscibles entres eux, -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 semiconductor polymer, these compounds being miscible in said solvent for concentrations less than 10% mass, the material(s) capable of crystallizing in ferroelectric form on the one hand and the conductive polymer(s) on the other hand not being miscible with each other,
-Dépôt à la tournette, au Docteur Blade ou toute autre technique de cette solution sur une électrode conductrice, -Deposition using a spinner, Doctor Blade or any other technique of this solution on a conductive electrode,
-Evaporation du solvant, de telle sorte qu'une séparation de phase entre le ou les matériaux capables de cristalliser sous forme ferroélectrique d'une part et le ou les polymères semi-conducteurs d'autre part établisse une morphologie . -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.
2 Procédé selon la revendication 1 dans lequel on dépose une deuxième électrode conductrice, transparente ou non, sur la couche active préalablement formée. 2 Method according to claim 1 in which a second conductive electrode, transparent or not, is deposited on the active layer previously formed.
3 Procédé selon la revendication 2 dans lequel les compositions constituants la couche active sont choisies de telle sorte que la proportion du ou des matériaux capables de cristalliser sous forme ferroélectrique soit supérieure
à 20 % massique par rapport au total matériau capable de cristalliser sous forme ferroélectrique et polymère semi¬ conducteur . 3 Method according to claim 2 in which the compositions constituting the active layer are chosen such that the proportion of the material(s) capable of crystallizing in ferroelectric form is greater at 20% by mass relative to the total material capable of crystallizing in ferroelectric and semiconducting polymer form.
4 Procédé selon la revendication 3 dans lequel la préparation de la couche active est conduite de telle sorte qu'une morphologie du type cylindre du polymère semi¬ conducteur soit établie après évaporation du solvant, avec contact électrique de la phase polymère semi-conducteur et de la phase matériau capable de cristalliser sous forme ferroélectrique sur les deux électrodes et un angle de l'axe des cylindres compris entre 20 et 90° par rapport au plan des électrodes. 4 Method according to claim 3 in which the preparation of the active layer is carried out such that a cylinder type morphology of the semiconductor polymer is established after evaporation of the solvent, with electrical contact of the semiconductor polymer phase and of the material phase capable of crystallizing in ferroelectric form on the two electrodes and an angle of the axis of the cylinders of between 20 and 90° relative to the plane of the electrodes.
5 Procédé selon la revendication 4 dans lequel un des matériaux constituant les matériaux capables de cristalliser sous forme ferroélectrique est un plastifiant. 5 Method according to claim 4 in which one of the materials constituting the materials capable of crystallizing in ferroelectric form is a plasticizer.
6. Procédé selon la revendication 5, caractérisé en ce que un des matériaux capables de cristalliser sous forme ferroélectrique est un matériau organique, préférablement un matériau polymère. 6. Method according to claim 5, characterized in that one of the materials capable of crystallizing in ferroelectric form is an organic material, preferably a polymer material.
7. Procédé selon la revendication 6, caractérisé en ce que le matériau polymère capable de cristalliser sous forme ferroélectrique consiste en un polymère ou mélange de polymères contenant du fluor, de préférence un copolymère contenant du fluorure de vinylidène. 7. Method according to claim 6, characterized in that the polymer material capable of crystallizing in ferroelectric form consists of a polymer or mixture of polymers containing fluorine, preferably a copolymer containing vinylidene fluoride.
8. Procédé selon la revendication 7, caractérisé en ce que le matériau polymère capable de cristalliser sous forme ferroélectrique ferroélectrique est un copolymère de fluorure de vinylidène et de trifluoroethylène P(VDF-TrFe) .
8. Method according to claim 7, characterized in that the polymer material capable of crystallizing in ferroelectric ferroelectric form is a copolymer of vinylidene fluoride and trifluoroethylene P (VDF-TrFe).
9. Procédé selon la revendication 8, caractérisé en ce que le polymère semi-conducteur est un matériau organique provenant de la famille des fluorènes, thiophènes, phenylènes, phenylènes vinylidène, fullerènes, pyrilènes. 9. Method according to claim 8, characterized in that the semiconductor polymer is an organic material coming from the family of fluorenes, thiophenes, phenylenes, phenylenes vinylidene, fullerenes, pyrilenes.
10. Procédé selon la revendication 9, caractérisé en ce que le polymère semi-conducteur donneur d'électrons est du poly- (3-hexylthiophène) P3HT. 10. Method according to claim 9, characterized in that the electron-donating semiconductor polymer is poly-(3-hexylthiophene) P3HT.
11. Procédé de fabrication selon la revendication 10 qui comprend un ou plusieurs solvants polaires et/ou aromatiques capables de solubiliser le polymère ferroélectrique et le polymère semi-conducteur . 11. Manufacturing process according to claim 10 which comprises one or more polar and/or aromatic solvents capable of solubilizing the ferroelectric polymer and the semiconductor polymer.
12. Procédé de fabrication selon la revendication 11 caractérisé en ce que le ou les solvants peut ou peuvent être choisis parmis les solvants suivants: Tétrahydrofurane, Méthyl Ethyl Cétone, Diméthylformamide, N, -Diméthylacétamide, Diéethylsulfoxyde, Acétone,12. Manufacturing process according to claim 11 characterized in that the solvent(s) may or may be chosen from the following solvents: Tetrahydrofuran, Methyl Ethyl Ketone, Dimethylformamide, N, -Dimethylacetamide, Diethylsulfoxide, Acetone,
Méthylisobutylcétone, Cyclohexaxone, Diaceton Alcool, Diisobutyl Cétone, Butyrolactone, Isophorone, 1,2- dimethoxyethane, chloroforme, dichlorobenzène, ortho- dichlorobenzène 15. Dispositif photovoltaïque obtenu le procédé d'une des revendications 1 à 14. Methyl isobutyl ketone, Cyclohexaxone, Diaceton Alcohol, Diisobutyl Ketone, Butyrolactone, Isophorone, 1,2- dimethoxyethane, chloroform, dichlorobenzene, ortho-dichlorobenzene 15. Photovoltaic device obtained by the process of one of claims 1 to 14.
13. Dispositif photovoltaïque obtenu le procédé d'une des revendications 1 à 12. 13. Photovoltaic device obtained by the method of one of claims 1 to 12.
14. Dispositif, selon la revendication 13, où le ou les matériaux capables de cristalliser sous forme ferroélectrique est polarisé par déformation mécanique
ou/et en appliquant un champ électrique, supérieur au champ coercitif, aux électrodes du dispositif. 14. Device according to claim 13, where the material(s) capable of crystallizing in ferroelectric form is polarized by mechanical deformation and/or by applying an electric field, greater than the coercive field, to the electrodes of the device.
15. Dispositif selon la revendication 14, qui possède une polarisation rémanente suite à la polarisation du matériau capable de cristalliser sous forme ferroélectrique . 15. Device according to claim 14, which has a remanent polarization following the polarization of the material capable of crystallizing in ferroelectric form.
16. Utilisation d'un dispositif selon une des revendications 13 à 15 capable de produire du courant électrique sous illumination.
16. Use of a device according to one of claims 13 to 15 capable of producing electric current under illumination.
Applications Claiming Priority (2)
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FR1356832A FR3008548B1 (en) | 2013-07-11 | 2013-07-11 | PROCESS FOR PRODUCING AN ACTIVE LAYER CAPABLE OF EMITTING AN ELECTRIC CURRENT UNDER IRRADIATION |
PCT/FR2014/051772 WO2015004393A1 (en) | 2013-07-11 | 2014-07-10 | Method for producing an active layer capable of emitting an electric current under irradiation |
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US (1) | US20160141534A1 (en) |
EP (1) | EP3020078A1 (en) |
JP (1) | JP2016525793A (en) |
KR (1) | KR20160032159A (en) |
CN (1) | CN105518893A (en) |
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CN104868048B (en) * | 2015-05-13 | 2018-02-02 | 重庆科技学院 | A kind of photo-induced telescopic composite membrane and its CD-ROM driver of making |
KR20190059922A (en) * | 2016-10-05 | 2019-05-31 | 메르크 파텐트 게엠베하 | Organic semiconducting compound |
EP3523835B1 (en) | 2016-10-05 | 2022-11-16 | Raynergy Tek Inc. | Organic photodetector |
EP3367455B1 (en) * | 2017-02-24 | 2023-12-13 | Centre National de la Recherche Scientifique (CNRS) | Method for producing a multicolour optoelectronic device comprising multiple photoactive materials |
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US20110269966A1 (en) * | 2010-04-30 | 2011-11-03 | Deepak Shukla | Semiconducting articles |
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2014
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SG11201600190XA (en) | 2016-02-26 |
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FR3008548A1 (en) | 2015-01-16 |
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