WO2013014591A1 - Procede de fonctionnalisation de nanofils metalliques et de fabrication d'electrodes - Google Patents
Procede de fonctionnalisation de nanofils metalliques et de fabrication d'electrodes Download PDFInfo
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- WO2013014591A1 WO2013014591A1 PCT/IB2012/053719 IB2012053719W WO2013014591A1 WO 2013014591 A1 WO2013014591 A1 WO 2013014591A1 IB 2012053719 W IB2012053719 W IB 2012053719W WO 2013014591 A1 WO2013014591 A1 WO 2013014591A1
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- WIPO (PCT)
- Prior art keywords
- nanowires
- substrate
- functionalized
- electrodes
- formula
- Prior art date
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Definitions
- the invention relates to a method for functionalizing metallic nanowires and to a method for manufacturing electrodes comprising such functionalized metal nanowires. It also relates to a device comprising these functionalized metal nanowires or at least one electrode comprising such functionalized metal nanowires.
- Materials with an optimal combination of high electrical conductivity and optical transparency are extremely important components in the development of many high value-added areas such as photovoltaic cells, OLEDs and PLEDs, photodetectors and any electronic device involving use of photons.
- TCO transparent conductive oxides
- ITO Indium Tin Oxide
- doped tin oxides Today most of the materials of this type are transparent conductive oxides (TCO) and in particular ITO (Indium Tin Oxide) or doped tin oxides. These products are derived from ancient patents such as Corning's from the 1940s. But the requirements for future optoelectronic devices are changing and it is now essential to obtain films that can be obtained in milder conditions for compatibility issues. , especially with organic materials, but also by large surface printing techniques to reduce production costs, while improving certain properties such as lightness or mechanical flexibility.
- NTC nano carbon tubes
- the electrode is brought into contact with another material having a different output work. Indeed this can result in a Schottky type resistance which is undesirable in some devices.
- it is necessary to align the energy levels of the electrode and the material at its interface.
- organic or hybrid materials used in organic electronics, or organic or hybrid materials with electronic photo properties for example photovoltaic photo or photodetectors
- a disadvantage related to the use of these electrodes is that the output work of the electrode is not necessarily adapted to the active materials to which these electrodes will be associated for the manufacture of a functional device.
- the aim of the invention is to improve the ohmic contacts between the active layers of a device and the electrodes of this device by modifying the basic conducting nanometric elements that constitute the electrodes, by forming a network. percolating metallic nanowires by means of a chemical functionalization based on organic molecules.
- the electrodes consist of solid and thick silver films whose manufacturing process is not transposable to the production of flexible and / or printable devices according to large surface printing techniques.
- This solution seemed therefore a priori difficult to transpose to electrodes consisting of a percolating network of silver nanowires, and more generally metallic because either the functionalization of the nanowires is carried out before their dispersion in a solvent, dispersion necessary to be able to deposit them on a substrate, and in this case, the self-assembled monolayer would form a screen between each nanowire so that the network deposited on the substrate would percolate more, or the nanowires are functionalized after their dispersion when they are in film form and again this does not seem a priori feasible because it is well known that the nanowires after dispersion are covered with residue of the polymer used for their dispersion, which would prevent the grafting of the molecules intended to form the self-assembled layer, or the nanowires.
- EP 1 741 717 A1 describes nanobarrels of gold, having an aspect ratio of 18 functionalized with a long-chain molecule (11 carbon atoms) and electronically neutral whose role is to facilitate the solubilization of an active drug ingredient.
- the molecule grafted on nanobarrels does not allow to modify the electrostatic environment near the nanobarreau and therefore does not allow to modify the work of output of an electrode made from these nanobarreaux.
- the invention provides a method for functionalizing metal nanowires comprising a step of forming a monomolecular layer self-assembled on at least a portion, preferably at least 10%, of their outer surface, characterized in that:
- the nanowires are in a metal chosen from silver (Ag), gold (Au), copper (Cu), platinum (Pt), palladium (Pd), nickel (Ni), cobalt ( Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), and iron (Fe), preferably selected from Ag, Au and Cu, more preferably selected from Ag and Au, and than
- R'-Zn-R 2 Formula (I)
- R 1 represents a hydrogen atom, an acyl group, a hydrocarbon group, linear, branched or cyclic, saturated or unsaturated, comprising from 1 to 100 atoms, and optionally comprising 1 or more heteroatoms and / or one or more chemical functions; comprising at least one heteroatom, preferably R ! represents a hydrogen atom, an acyl group, or a methyl, ethyl, propyl or butyl group,
- an electron-withdrawing group preferably a linear, branched or cyclic hydrocarbon group, saturated or unsaturated, aromatic or nonaromatic, substituted in whole or in part with nitro, trifluoromethyl, cyano, amide, ester, carboxylic acid, halide or 2-dicyanomethylene groups; -3-cyano-2,5-dihydrofuran and / or comprising at least one fluorine atom,
- an electron-donor group preferably a hydrocarbon group, linear or branched, cyclic and / or aromatic, totally or partially substituted with alkoxy, amine, thioether, and
- R 2 is an electron-withdrawing group and the compound of formula (I) is chosen from para-trifluoromethylthiophenol, , 5-bis-trifluoromethylthiophenol, pentafluorothiophenol, pentafluoroselenophenol, perfluorododecanethiol, perfluorooctadecanethiol, para-nitrothiophenol, para-cyanothiophenol, 3,5-bis-nitrothiophenol and 3,5-bis-cyanothiophenol.
- R 2 is an electron donor group and the compound of formula (I) is chosen from para-methoxythiophenol, the 3 , 5-bis-methoxythiophenol, paramethoxyselenophenol, para-thiomethylthiophenol, dimethyldi sulfide, and di-paramethoxyphenyldisulfide, diethylsulfide, butanethiol.
- the nanowires preferably have an aspect ratio (length / diameter ratio) greater than or equal to 20, preferably between 20 and 50,000, more preferably between 100 and 10,000.
- a solvent preferably selected from water, methanol, ethanol, hexane, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran and N-methylpyrrolidone, and mixtures of two or more thereof.
- step b) functionalization of the metal nanowires by the process according to the invention, and c) deposition of the functionalized nanowires obtained in step b) or unfunctionalized nanowires of step a) on a substrate.
- step c) is carried out before step b) in which case the non-functionalized nanowires are first deposited on the substrate at step c) and are then functionalized in step b).
- step b) is performed before step c), in which case the nanowires deposited in step c) are already functionalized.
- the substrate is a rigid substrate.
- the substrate is a flexible substrate.
- the substrate may be of a material selected from glass, woven or nonwoven fabric, plastic or foam.
- plastics that can be used to form the substrate are polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide, polyamide 6 or polyamide 6,6, polyethylene (PE), polypropylene (PP).
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PP polypropylene
- the textiles used to form the substrate are woven or non-woven fabrics of polyamide fibers, polyester, cotton, linen.
- Foams usable as substrates are polyurethane or rubber foams.
- the electrode manufacturing method of the invention may furthermore comprise, prior to step c) of deposition of the metal nanowires on the substrate, a step d) of treatment of the substrate surface, preferably by application of a paint layer, an anticorrosive material, a hydrophilic material, a water repellent material and / or a flame retardant material.
- step c) of deposition of the nanowires is a vapor deposition step, by ink jet printing, at the spin-coater, by fxxography, gravure or raclette.
- the electrode manufacturing method of the invention may furthermore comprise a step e) of evaporating the solvent of the dispersion obtained in step a), after the steps a), b) and c).
- the electrode manufacturing method of the invention may furthermore comprise a step f) of heat treatment of the network of functionalized metal nanowires deposited on the substrate, at a temperature of between 50 ° C and 300 ° C, limits included.
- the electrode manufacturing method of the invention may furthermore comprise a step g) of coating the substrate coated with the functionalized metal nanowires, forming the electrodes, with encapsulation, preferably with a fluoropolymer or a silicone polymer, or a mixture thereof.
- the invention also proposes a device characterized in that it comprises metal nanowires obtained by the functionalization method according to the invention.
- the invention also proposes a device characterized in that it comprises at least one electrode obtained by the electrode manufacturing method according to the invention.
- the invention finally proposes the use of functionalized nanowires obtained by the functionalization method according to the invention for the manufacture of electrodes.
- the invention relates to the use of metal nanowires functionalized with organic molecules for the manufacture of electrodes, in particular transparent, possibly flexible.
- metal nanowires functionalized with molecules means objects comprising a central part composed of metallic nanowires whose radius is less than 100 nm and the length of between 1 and 500 ⁇ , and whose surface is coated at least partially with
- the metals used are preferably Ag, Au, Cu, Pt, Pd, Ni, Co, Rh, Ir, Ru, Fe, and more preferably Ag, Au, Cu.
- nanowires are for example obtained in solution.
- the nanowires are synthesized from reduced metal precursors in solution.
- the method for functionalizing the metal nanowires of the invention comprises a step of forming on the surfaces of the nanowires, of a monomolecular self-assembled layer, from one or more precursors of the following formula I:
- Z represents a sulfur or selenium atom
- R 1 represents a hydrogen atom, or a linear, branched or cyclic hydrocarbon group, saturated or unsaturated, optionally perfluorinated or partially fluorinated, comprising from 1 to 100 carbon atoms and optionally comprising one or more heteroatoms;
- R represents either an electron-withdrawing group, preferably a hydrocarbon group, linear, branched or cyclic, saturated or unsaturated, aromatic or nonaromatic, substituted in whole or in part by nitro, trifluoromethyl, cyano, amide, ester, carboxylic acid, halide groups; or 2-dicyanomethylene-3-cyano-2,5-dihydrofuran, or comprising a fluorine atom, or an electron-donor group, preferably a hydrocarbon group, linear or branched, cyclic and / or aromatic, totally or partially substituted with groups alkoxy, amine, thioether.
- R and R may be the same or different.
- R 1 is chosen from a hydrogen atom, an acyl group, a methyl, ethyl, propyl or butyl group.
- This functionalization can totally or partially cover the surface of the nanowires. When it covers only partially the surface of the nanowires, the functionalization covers at least 10% of this surface.
- Suitable solvents are alcohols, water, ketones, in particular acetone, amines, ethers, alkylaromatic or haloaromatic solvents, N-methylpyrrolidone, dimethylformamide.
- Preferred solvents are water, methanol, ethanol, hexane, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, N-methylpyrrolidone or mixtures of two or more thereof.
- the grafting of the molecules of formula (I) can also be done by ligand exchange, that is to say that the molecules of formula (I) can replace any organic species initially present around the nanowires (before the addition of the compound of
- the preferred molecules of formula (I) used in the metal nanowires functionalization method of the invention are, when the group R 2 is an electron-withdrawing group, chosen from para-trifluoromethylthiophenol, 3,5-bis-trifluoromethylthiophenol, pentafluorothiophenol, pentafluoroselenophenol, perfluorododecanethiol, perflurooctadecanethiol, para-nitrothiophenol, para-cyanothiophenol, 3,5-bis-nitrothiophenol and 3,5-bis-cyanothiophenol.
- group R 2 is an electron-withdrawing group, chosen from para-trifluoromethylthiophenol, 3,5-bis-trifluoromethylthiophenol, pentafluorothiophenol, pentafluoroselenophenol, perfluorododecanethiol, perflurooctadecanethiol, para-nitrothiophenol, para-cyanothiophenol, 3,5-bis-nitrothi
- the preferred molecules with which the metal nanowires of the invention are functionalized when the group R is an electron-donor group, are para-methoxythiophenol, 3,5-bis-methoxythiophenol, paramfhoxyselenophenol, para-tetrathylphenol, dimethyldisulphide and di-paramethoxyphenyl disulphide.
- the invention also relates to a method for manufacturing electrodes, in particular transparent, possibly flexible, made from functionalized metallized nanowires according to the invention.
- This process comprises the following steps:
- a solvent preferably selected from water, methanol, hexane, toluene, acetone, and mixtures of two or more thereof.
- the metal nanowires are already functionalized by the molecules of formula (I) before they are deposited on the surface of the substrate of the electrode.
- the electrode is then composed of a percolating network of metal nanowires functionalized with molecules of formula (I).
- a preferred method for depositing the functionalized nanowires on the surface of the substrate is to vaporize a dispersion containing the functionalized metal nanowires by the method of the invention, that is to say to generate microdrops containing the functionalized metal nanowires and to project under pressure or electrical stress on the desired substrate.
- the non-functionalized metal nanowires are deposited first on the surface of the substrate forming the electrode.
- the electrode is composed of a percolating network of non-functionalized metal nanowires.
- the functionalization of the nanowires is then carried out.
- This functionalization is carried out as previously described: the electrode and its substrate are brought into contact with the molecules of formula (I).
- the contacting can be carried out by dipping in a solution containing one or more molecules of formula (I), preferably by spraying the solution onto the electrodes.
- the functionalized or nonfunctionalized metal nanowires can be deposited on the surface of the substrate by vaporization, ink jet printing, deposit at the spin-coater, or by other flexographic techniques, rotogravure, squeegee deposit.
- the substrate of the electrodes on which the functionalized or non-functionalized metal nanowires are deposited can be extremely varied: it can be, for example, plastic, glass, woven or non-woven textile, foam, etc.
- This substrate may be optionally treated before deposition of the nanowires, for example by deposition of a surface layer based on paint, an anticorrosion product, a flame retardant, hydrophilic or hydrophobic coating.
- the solvent of the dispersion containing the nanowires that are deposited is preferably water, methanol, hexane, toluene, acetone, or a mixture of two or more thereof.
- This solvent is evaporated if necessary, by heating the substrate, after the deposition of functionalized nanowires in the first embodiment of the invention, or in the second embodiment of the invention optionally under vacuum.
- the functionalization of the nanowires after their deposition on the surface of the substrate can be carried out by dipping the substrate covered with nanowires in a solution containing one or more molecules of formula (I) by spraying. of the solution on the electrodes by vaporization, ink jet printing.
- Another technique consists in placing electrodes in a space containing molecules of formula (I), for example at their saturating vapor pressure.
- the electrodes can be used as such or covered with an encapsulating material such as a polymer, for example a fluorinated polymer and / or a silicone-type polymer.
- an encapsulating material such as a polymer, for example a fluorinated polymer and / or a silicone-type polymer.
- the electrodes obtained by the use of molecules of formula (I) in which the R group is an electron-withdrawing group leads to the increase of the output work of these electrodes.
- the output work of the electrodes obtained is greater than 5 eV whereas the output work of electrodes formed from silver nanowires without functionalization is approximately 4,7 eV.
- molecules of formula (I) in which R is an electron donor group leads to the reduction of the output work of the electrodes obtained by the process of the invention, that is to say at values less than those of electrodes formed of nonfunctionalized silver nanowires.
- the values of the output work of the electrodes produced by the method of the invention with silver nanowires functionalized with molecules of formula I, the group R 2 of which is electron donor is 4.5 eV while the work of exit of electrodes made from nonfunctionalized silver nanowires is about 4.7 eV.
- the nanowires have an aspect ratio, that is to say a length / diameter ratio greater than or equal to 20. More preferably, this aspect ratio is between 20 and 50,000. .
- this aspect ratio is between 100 and 10 000.
- the use of nanowires having a high aspect ratio provides a more effective percolating system. and more transparent with fewer conductive nanowires.
- the "mesh" thus obtained with nanowires with a high aspect ratio is a bit wide, but using fewer nanowires (ideally having smaller diameters), light is better passed through (improved transparency) and the number is increased. inter-wire connections.
- Silver nanowires are manufactured according to the following method:
- PVP polyvinylpyrrolidone
- EG ethylene glycol
- EG ethylene glycol
- the mixture is stirred at 600 rpm at 120 ° C until complete dissolution of the PVP + NaCl (about 4-5 minutes).
- this mixture is added dropwise to a solution of 40 ml of EG in which are dissolved 0.68 g of AgNO 3 (silver nitrate).
- the oil bath was heated to 160 ° C and allowed to stir at 700 rpm for 80 minutes. Three washes are made with methanol by centrifuging at 2000 rpm for 20 min, then the nanowires are precipitated with acetone and finally redispersed in water.
- Electrodes are made by depositing the nanowires previously manufactured on substrates consisting of a square plate of 4cmx4cm glass, by spraying using an Aztek A4709 airbrush.
- the plates obtained are soaked for 10 min in a 50 mM solution of thiophenol in toluene and then rinsed with acetone and dried under argon.
- the plates obtained have a square resistance of between 15 and 40 ohm / sq. For a transmittance between 78 and 82% (at 550 nm).
- Example 2 The procedure was as in Example 1 but during the manufacture of silver nanowires, they are precipitated with acetone and redispersed in methanol and not water.
- the plates obtained have a square resistance of between 15 and 40 ohm / sq for a transmittance between 78 and 82% (at 550 nm).
- Example 2 The procedure was as in Example 1 but the nanowires were deposited on square plates 4 cm ⁇ 4 cm polyethylene terephthalate (PET) by spin coating.
- PET polyethylene terephthalate
- the plates obtained have a square resistance of between 15 and 40 ohm / sq for a transmittance of between 78 and 82%.
- Silver nanowires were made as in Example 1.
- Electrodes were obtained by depositing these nanowires on 4 cm ⁇ 4 cm square glass plates by spraying the dispersion using an Aztek A4709 airbrush.
- the silver nanowires of the electrodes obtained are not, as in the case of Example 1, functionalized.
- the plates obtained have a square resistance of between 15 and 40 ohrn / sq for a transmittance of between 78 and 82%.
- Silver nanowires were made by the same method as in Example 2.
- nanowires were deposited on 4 cm ⁇ 4 cm square glass plates by vaporizing the nanowires dispersion obtained previously using Aztek A4709 airbrush.
- the plates obtained have a square resistance of between 15 and 40 ohm / sq for a transmittance of between 78 and 82%.
- the plates obtained have a square strength of between 15 and 40 ohm / sq.
- Kelvin probe force microscopy (KPFM) measurements were performed on each of the plates obtained in Examples 1 to 3 and Comparative Examples 1 to 3.
- Gold nanowires are manufactured according to the following process:
- Electrodes are made by depositing these nanowires on a square plate of 4cmx4cm glass.
- the plates are then placed on a hot plate at 80 ° C.
- a solution of 20 mM 4-methoxythiophenol in toluene is sprayed using Aztek A4709 airbrush for 10 seconds.
- the plates are left to air dry for 30min.
- the plates obtained have a square resistance of between 30 and 50 ohm / sq for a transmittance of between 75 and 78% (at 550 nm).
- Example 4 The procedure is as in Example 4 except that the gold nanowires are deposited on polyethylene terephthalate plates.
- the plates obtained have a square resistance of between 30 and 50 ohm / sq for a transmittance of between 75 and 78% (at 550 nm).
- Golden nanowires were manufactured by the same method as in Example 4. Electrodes were then produced by vaporizing the dispersion of these gold nanowires on glass plates having the same dimensions as in FIG. Example 4 and spraying the dispersion using an Aztek A4709 airbrush.
- the gold nanowires were not then functionalized.
- the glass plates on which the gold nanowires have been deposited are simply placed on a hot plate at 80 ° C. Pure toluene is sprayed onto these plates using Aztek A4709 airbrush for 10 seconds.
- the plates are then allowed to air dry for 30 minutes.
- the plates obtained have a square resistance of between 30 and 50 ohm / sq for a transmittance of between 15 and 78% (at 550 nm).
- Example 5 The procedure was as in Example 5 except that the gold nanowires were not functionalized.
- the plates obtained after depositing the gold nanowires were placed on a hot plate at 80 ° C and sprayed with pure toluene using Aztek A4709 airbrush for 10 seconds. Then, they were allowed to air dry for 30 minutes.
- the plates obtained have a square resistance of between 30 and 50 ohm / sq for a transmittance of between 75 and 78% (at 550 nm).
- Silver nanowires are manufactured according to the following method:
- pentafluorothiphenol is added at a concentration of 10 ⁇ M. The solution is left standing for 12 hours at room temperature.
- Electrodes are made by depositing the nanowires previously manufactured on substrates consisting of a square plate of 4cmx4cm glass, by evaporation using an Aztek A4709 airbrush.
- the plates obtained have a square resistance ranging between 18 and 40 ohm / sq for a transmittance between 77 and 82% (at 550 nm) and exhibit an output work of 5.4 eV (compared to 4.7 eV for non-functionalized nanowires ( Comparative Example 1)).
- Example 7
- Copper nanowires were prepared according to the method described by Zheng in Chemistry Letters Vol. Electrodes are made by depositing these nanowires on substrates consisting of a 4 cm ⁇ 4 cm square glass plate, by spraying using an Aztek A4709 airbrush.
- the plates obtained are soaked for 10 min in dry toluene and then rinsed with acetone and dried under argon.
- the plates obtained have a square resistance of between 20 and 200 ohm / sq for a transmittance between 52 and 77% (at 550 nm).
- Copper nanowires were prepared according to the method described by Zheng in Chemistry Letters Vol. Electrodes are made by depositing these nanowires on substrates consisting of a 4 cm ⁇ 4 cm square glass plate, by spraying using an Aztek A4709 airbrush.
- the plates obtained are soaked for 10 min in a 50 mM solution of perfluorothiophenol in toluene and then rinsed with acetone and dried under argon.
- the plates obtained have a square resistance of between 20 and 200 ohm / sec for a transmittance between 52 and 77% (at 550 nm).
- the invention is placed in a strong industrial and scientific context since the demand for electrodes, in particular transparent, is experiencing significant growth.
- the electrodes of the invention, and the nanowires, obtained by the methods of the invention can be used in many applications such as touch screens, flexible screens, flexible photovoltaic cells, flexible photonic detectors, large flexible electronics surface, etc.
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EP12758622.0A EP2734310A1 (fr) | 2011-07-22 | 2012-07-20 | Procede de fonctionnalisation de nanofils metalliques et de fabrication d'electrodes |
US14/233,964 US20150083466A1 (en) | 2011-07-22 | 2012-07-20 | Method For The Functionalisation Of Metal Nanowires And The Production Of Electrodes |
KR1020147004226A KR20140090971A (ko) | 2011-07-22 | 2012-07-20 | 금속 나노 와이어의 기능화 방법 및 전극의 제조 |
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DE102013226998B4 (de) * | 2013-12-20 | 2015-08-06 | Technische Universität Dresden | Verfahren zur Herstellung einer Nanodrahtelektrode für optoelektronische Bauelemente sowie deren Verwendung |
CN104988475A (zh) * | 2015-06-03 | 2015-10-21 | 南京理工大学 | 一种铜镍合金纳米线柔性电极及其制备方法 |
KR101756559B1 (ko) * | 2015-12-30 | 2017-07-11 | 영남대학교 산학협력단 | 나노 입자, 이를 포함하는 분산계, 나노 입자의 제조 장치 및 제조 방법 |
FR3060203B1 (fr) | 2016-12-08 | 2019-05-24 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Photodetecteur a couche de collecte de porteurs de charge comprenant des nanofils fonctionnalises |
FR3070973B1 (fr) * | 2017-09-11 | 2022-02-04 | Commissariat Energie Atomique | Procede de preparation d'un aerogel metallique electriquement et thermiquement conducteur |
KR102196345B1 (ko) | 2019-02-28 | 2020-12-29 | 부경대학교 산학협력단 | 신축성 전극 및 이의 제조 방법 |
CN113385685B (zh) * | 2021-05-18 | 2023-01-31 | 南京师范大学 | 一种氰基修饰的Pt基超细纳米线的制备方法及其所得材料和应用 |
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Also Published As
Publication number | Publication date |
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KR20140090971A (ko) | 2014-07-18 |
FR2978066B1 (fr) | 2016-01-15 |
US20150083466A1 (en) | 2015-03-26 |
JP2014529353A (ja) | 2014-11-06 |
FR2978066A1 (fr) | 2013-01-25 |
EP2734310A1 (fr) | 2014-05-28 |
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