• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a poly (thio- or seleno-) phenolic conductive polymeric material containing at least two distinct counteranion species with at least one of them being an anionic form of a sulfuric acid. The invention also relates to a process for preparing such a material and its use as a conductive film. The invention also relates to a substrate coated at least in part by a film of a material as defined above, a device comprising a material as defined above as a conductive material, and their use in the fields. organic electronics, organic thermoelectricity, organic photovoltaics and organic photodetectors.
    公开号:FR3018817A1
    申请号:FR1452265
    申请日:2014-03-19
    公开日:2015-09-25
    发明作者:Alexandre Carella；Nicolas Massonnet；Jean-Pierre Simonato
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a new material based on poly (thioou selenophenes) and to a process for its preparation. Devices such as organic electronic devices, organic photovoltaic devices, organic light-emitting diodes, organic thermoelectric devices or organic photodetectors consist of electrodes employing conductive materials. A generally preferred material is indium tin oxide (ITO). It is interesting on the one hand for its optical transparency and on the other hand for its high conductivity. Unfortunately, this material remains fragile and its implementation in flexible devices remains difficult. In addition, the supply of indium is very expensive. For these reasons, organic materials represent an advantageous alternative to replace indium-tin oxide in these devices.
    [0002] In particular, poly (3,4-ethylenedioxythiophene) (PEDOT) and its derivatives are considered as polymers having a high technological and commercial potential. Indeed, they are biocompatible and they also have good electrochromic dynamic activity and good long-term air stability. However, these materials have moderate conductivities.
    [0003] Different ways have been explored to try to increase the conductivity of these materials. A first option was proposed by Groenendaal et al., Who developed the synthesis of conductive PEDOTs, by electropolymerization of 3,4-ethylenedioxythiophene (EDOT). These materials are synthesized by liquid electropolymerization of EDOT in a solution of salts in acetonitrile. PEDOT: triflate, PEDOT: triflimidate, PEDOT: perchlorate or PEDOT: hexafluorophosphate have been synthesized (Groenendaal et al., Advanced Material, 2003, 15 (11), 855-879). However, the conductivity of these polymers remains too low. In addition, the method of synthesis of these materials is not compatible with all the substrates on which the conductive material is deposited, which must be conductive to serve as an electrode during the polymerization.
    [0004] Another possibility has been described by Fabretto et al. who synthesized PEDOT: OTs. These are prepared by vapor phase oxidative polymerization of EDOT with iron tristosylate Fe (OTs) 3 in a PEG-PPG-PEG matrix (Fabretto et al., Chemistry of Materials, 2012, 24, 3998-4003). However, the synthesis of these materials is very restrictive and is not compatible with the preparation of large areas with high flow. More recently, Park et al. have developed conductive PEDOT: OTs for thermoelectric applications by solution polymerization. These PEDOTs are also synthesized by liquid phase oxidative polymerization of EDOT by iron tristosylate Fe (OTs) 3 in a PEG-PPG-PEG matrix. Pyridine is used as a polymerization inhibitor (Park et al., Energy & Environmental Science, 2013, 6 (3), 788). Nevertheless, the use of pyridine is restrictive because it is very toxic and is therefore not compatible with the industrial production of this material. Therefore, there remains a need for new highly conductive materials that can be further synthesized in a simple manner and adapted to industrial scale production. Thus, according to one of its aspects, the invention relates to a poly (thio- or seleno-) phenolic conductive polymeric material containing at least two distinct counter-anion species with at least one of them being an anionic form of a sulfuric acid. Preferably, only one of the two species is an anionic form of a sulfuric acid. Unexpectedly, the inventors have found that these polymeric materials have a very high conductivity. Their implementation is thus particularly advantageous in organic electronic devices, organic photovoltaic, organic thermoelectric, in organic light emitting diodes, or in organic photodetectors. In addition, their synthesis is easy and compatible with large-scale production.
    [0005] Thus, according to yet another of its aspects, the present invention relates to a method for preparing a material as defined above comprising at least the steps of: (a) having a polymeric material of poly (thio type) or selenophenyl containing at least one anionic species selected from triflate, triflimidate, tosylate, mesylate, perchlorate and hexafluorophosphate, (b) contacting said material with an aqueous solution of a sulfuric acid under conditions favorable to the immobilizing an anionic form of said acid within the polymeric material, and (c) disposing said material containing a first anionic species selected from triflate, triflimidate, tosylate, perchlorate, hexafluorophosphate and a second species corresponding to an anionic form of said acid sulfide.
    [0006] In particular, the material of step (a) is obtained beforehand by polymerization in a solvent medium of thio- or selenophenic monomer (s), in the presence of an oxidizing solution of triflate, triflimidate, tosylate, mesylate, perchlorate. or iron (III) hexafluorophosphate, and an effective amount of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer (PEG-PPG-PEG), and is purified by aqueous washing prior to its implementation in step (b). According to an advantageous variant, this material of step (a) already appears on a surface support of which it was previously formed by polymerization according to the method detailed above. The process according to the invention advantageously makes it possible to obtain highly conductive materials. According to another of its aspects, the present invention relates to the use of a material according to the invention, or obtained according to the method described above, as a conductive film. According to yet another of its aspects, the present invention aims a substrate 25 coated at least in part with a film of a material according to the invention, or obtained according to the method described above. According to yet another of its aspects, the present invention relates to a device comprising as a conductive material a material according to the invention, or obtained according to the method described above. According to another of its aspects, the present invention relates to the use of a material according to the invention, or obtained according to the method described above, or of a substrate according to the invention, in the fields of the organic electronics, organic thermoelectricity, organic photovoltaics and organic photodetectors. Other advantages and features will appear on reading the description and examples which follow. 1VIATERIAU As previously mentioned, a poly (thio- or seleno) phenolic type conductive polymer material according to the invention contains at least two distinct counter-anion species with at least one of them being an anionic form of a sulphuric acid. According to a preferred embodiment, only one of the two species is an anionic form of a sulfuric acid. In a material according to the invention, the sulfurized acid is in particular chosen from sulfuric acid, a sulphonic acid and a perfluorosulfonic acid.
    [0007] Preferably, the sulfurized acid is sulfuric acid. According to another preferred embodiment, the second counter-anion species is at least one anionic species chosen from triflate, triflimidate, tosylate, mesylate, perchlorate and hexafluorophosphate, and in particular is a triflate. The use of triflate makes it possible to obtain films with very good conductive properties. Thus, more preferably, a material according to the invention contains at least hydrogen sulfate and triflate counteranions. According to a first variant embodiment, the material according to the invention is based on a thiophene polymer derived from the polymerization of monomer (s) chosen from 3,4-dialkylthiophenes, 3,4-cycloalkylthiophenes, 3, 4-dialkoxythiophenes, and 3,4-alkylenedioxythiophenes, in which the alkyl groups, which are identical or different, are of formula C.E12. + 1 with n between 1 and 12. Thus, the thiophenic polymer may for example be: poly (3,4-dialkylthiophene) of formula: - a poly (3,4-cycloalkylthiophene) of formula: - a poly (3,4-dialkoxythiophene) of formula: 2 - a poly (3,4-alkylenedioxythiophene) of In particular, the monomers are chosen from thiophene, 3,4-ethylenedioxythiophene (EDOT), 3-hexylthiophene and 3,4-propylenedioxythiophene (PRODOT).
    [0008] Preferably, the monomer is 3,4-ethylenedioxythiophene (EDOT). Thus, the material according to the invention is preferably based on poly (3,4-ethylenedioxythiophene) (PEDOT). According to a second variant embodiment, the material according to the invention is based on a selenophenic polymer deriving from the polymerization of monomer (s) chosen from 3,4-dialkylselenophenes, 3,4-cycloalkylselenophenes, 3 , 4-dialkoxyselenophenes, and 3,4-alkylenedioxyselenophenes, in which the alkyl groups, which are identical or different, are of formula C.E12.-p1 with n ranging from 1 to 12. The selenophenic polymer may for example be: - a poly (3,4-dialkylselenophene) of the formula: - a poly (3,4-cycloalkylselenophene) of the formula: L- - a poly (3,4-dialkoxyselenophen) of the formula: - a poly (3,4-alkylenedioxyselenophene) of In particular, the monomers are selected from selenophene, 3,4-ethylenedioxyselenophene (EDOS), 3-hexylselenophene, and 3,4-propylenedioxyselenophene (PRODOS).
    [0009] Preferably, a material according to the invention has a conductivity of at least 1000 S / cm, and preferably ranging from about 1500 S / cm to about 2500 S / cm. Advantageously, a material according to the invention may be useful as a conductive film.
    [0010] The present invention also relates to a method for preparing a material comprising at least the steps of: (a) providing a poly (thio- or seleno-) phenolic polymeric material containing at least one anionic species selected from triflate, triflimidate, tosylate, mesylate, perchlorate and hexafluorophosphate, (b) contacting said material with an aqueous solution of a sulfurized acid under conditions conducive to the immobilization of an anionic form of said acid within the polymeric material and (c) disposing said material containing a first anionic species selected from triflate, triflimidate, tosylate, perchlorate, hexafluorophosphate and a second species corresponding to an anionic form of said sulfuric acid. The contacting of the material with an aqueous solution of a sulfuric acid may for example be carried out by immersing the material in a bath of the aqueous sulfuric acid solution. Preferably, in a process according to the invention, the material of step (a) is obtained beforehand by polymerization in a solvent medium of thio- or selenophenic monomer (s), in the presence of an oxidizing solution of triflate, triflimidate , tosylate, mesylate, iron (III) perchlorate or hexafluorophosphate, and an effective amount of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer (PEG-PPGPEG), and is purified by aqueous washing prior to its implementation in step ( b). More preferably, the material of step (a) is previously obtained in the presence of an oxidizing solution of triflate.
    [0011] The block copolymer of the polyethylene glycol-polypropylene glycol-polyethylene glycol (PEG-PPG-PEG) type advantageously makes it possible to inhibit the crystallization of the molecules of the oxidizing solution, to slow down the rate of polymerization, and to increase the conductivity of the polymeric material. Advantageously, the contact time of the material with the aqueous sulfuric acid solution is greater than 10 minutes, and preferably greater than 30 minutes. According to an advantageous embodiment, the temperature when the material is brought into contact with the aqueous sulfuric acid solution is between 120 ° C. and 200 ° C., in particular between 140 ° C. and 180 ° C., and preferably equal to 160 ° C.
    [0012] According to an advantageous variant embodiment, the polymeric material of step (a) is in the form of a film appearing on the surface of a solid substrate. Thus, according to another of its aspects, the present invention also relates to a method for increasing the conductivity of a poly (thioou seleno-) phenic type polymeric material containing at least one anionic species distinct from a sulfuric acid, occurring under the form of a film, appearing on the surface of a solid substrate, comprising the step of bringing said film into contact with an aqueous solution of a sulfurized acid under conditions conducive to the immobilization of an anionic form of said acid within the polymeric material. At the end of this step, the film thus treated is dried. According to a particular embodiment, the anionic species distinct from a sulfuric acid is chosen from triflate, triflimidate, tosylate, mesylate, perchlorate and hexafluorophosphate. Advantageously, the contacting of the film with the aqueous solution can be carried out by immersing the substrate directly in a bath of the aqueous sulfuric acid solution.
    [0013] This substrate may in particular be as defined below. SUBSTRATE The present invention also relates to a substrate coated at least in part with a film of a material according to the invention, or obtained according to the process according to the invention.
    [0014] Preferably, the substrate is a substrate of glass, silicon, woven material or of organic and / or polymeric nature, for example a paper substrate. When it is of a polymeric nature, the substrate may for example be polyethylene terephthalate (PEN), polyethyleneenaphthalate (PET), polyimide or polytetrafluoroethylene (PTFE).
    [0015] The examples which follow are presented as an illustration and not a limitation of the field of the invention. EXAMPLES Example 1 Synthesis of PEDOT with Different Acidic Treatment 2 ml of a 20% by weight solution of polyethylene glycol-polypropylene glycol-polyethylene glycol (PEG-PPG-PEG) (Mn = 5800 g / mol) in ethanol is prepared with stirring in an ultrasonic bath for 4 hours. 240 mg of Fe (OTf) 3 are added to the solution with stirring. The solution is left stirring for another 30 minutes. The solution is then cooled to 5 ° C. and 20 μl of EDOT are added.
    [0016] The solution is immediately placed in an ultrasonic bath at 5 ° C for 1 minute. The solution is spin coated on a Corning Eagle XG glass plate (10 x 10 cm), then annealed for 10 minutes on a hot plate at 70 ° C in the open air. The glass plate is cut into a piece of 2.5 x 1.25 cm and the conductivity of the films obtained is measured at 1200 S / cm (+/- 20 S / cm) by measuring 4 points for an average thickness of 70 nm (+/- 5 nm). These films are soaked in an acid bath at pH = 1 for one hour, then dried on a hot plate at 160 ° C for 30 minutes. The conductivity of the films is measured by the Van der Pauw method (4 points) and compared to the value before acid treatment. The values are collated in the table below. Sample Conductivity (S / cm) Acid treatment Conductivity after treatment (S / cm) 1 1 207 CF3S03H (pH = 1) 1 376 2 1 192 HCl (pH = 1) 341 3 1 230 HNO3 (pH = 1) 671 4 1 CH 3 SO 3 H (pH = 1) 1 690 for 1 h 5 1 220 H 2 SO 4 (pH = 1) 2 541 for 1 h It should be noted that samples 1, 4 and 5 which have undergone treatment with a sulphuric or sulphonic acid have conductivities after very high treatment unlike samples 2 and 3 which were treated with HC1 or HNO3.
    [0017] EXAMPLE 2: PEDOT SHEET: Highly conductive HSO4 2 mL of a 20 wt% solution of PEG-PPG-PEG (Mn = 5800 g / mol) in ethanol is prepared with stirring in a Ultrasonic bath for 4 hours. 240 mg of Fe (OTf) 3 are added to the solution with stirring. The solution is left stirring for another 30 minutes.
    [0018] The solution is then cooled to 5 ° C. and 20 μl of EDOT are added.
    [0019] The solution is immediately placed in an ultrasonic bath at 5 ° C for 1 minute. The solution is spin coated on a Corning Eagle XG glass plate (10 x 10 cm), then annealed for 10 minutes on a hot plate at 70 ° C in the open air. The glass plate is cut into a piece of 2.5 x 1.25 cm and the conductivity of the films obtained is measured at 1200 S / cm (+/- 20 S / cm) by measuring 4 points for an average thickness of 70 nm (+/- 5 nm). These films are dipped in a sulfuric acid bath at pH = 1 for a determined period of time (1 min, 10 min, 30 min, 1 h, 2 h, 5 h or 24 h), then dried on a hot plate at 160 ° C. ° C for 30 minutes. The conductivity of the films is measured by the Van der Pauw method (4 points) and compared to the value before acid treatment. The values are collated in the table below.
    [0020] Sample Conductivity (S / cm) Acid Treatment Conductivity after treatment (S / cm) 6 1 262 H 2 SO 4 (pH = 1) 1450 for 1 min 7 1,189 H 2 SO 4 (pH = 1) 1,806 for 10 min 8 1,189 H 2 SO 4 ( pH = 1) 502 for 30 min H1SO4 (pH = 1) 2480 for 1 hr 1 338 H 2 SO 4 (pH = 1) 2512 for 2 h 11 1,186 H 2 SO 4 (pH = 1) 2,521 for 24 hours h All the samples treated with H2SO4 have very high post-treatment conductivities. The conductivities after acid treatment are even higher when the treatment time is greater than 30 minutes. Example 3: PEDOT SHEET: Highly conductive HSO4 2 mL of a 20% by weight solution of PEG-PPG -PEG (Mn = 5800 g.mol -1) in ethanol is prepared with stirring in an ultrasonic bath for 4 hours. 240 mg of Fe (OTf) 3 are added to the solution with stirring.
    [0021] The solution is left stirring for another 30 minutes. The solution is then cooled to 5 ° C. and 20 μl of EDOT are added. The solution is immediately placed in an ultrasonic bath at 5 ° C for 1 minute. The solution is spin coated on a Corning Eagle XG glass plate (10 x 10 cm), then annealed for 10 minutes on a hot plate at 70 ° C in the open air. The glass plate is cut into a piece of 2.5 x 1.25 cm and the conductivity of the films obtained is measured at 1200 S / cm (+/- 20 S / cm) by measuring 4 points for an average thickness of 70 nm (+/- 5 nm).
    [0022] These films are soaked in a sulfuric acid bath at pH = 1 for 30 minutes and then dried on a hot plate at different temperatures (140 ° C, 160 ° C or 180 ° C) for 30 minutes. The conductivity of the films is measured by the Van der Pauw method (4 points) and compared to the value before acid treatment.
    [0023] The values are collated in the table below. Sample Conductivity (S / cm) Acid treatment Conductivity after treatment (S / cm) 12 1 238 H 2 SO 4 (pH = 1) at 1900 ° C 13 276 H 2 SO 4 (pH = 1) at 2520160 ° C 14 1 286 H 2 SO 4 (pH = 1) at 1723 180 ° C 1 238 H 2 SO 4 (pH = 1) at 1,453,200 ° C All samples treated with H 2 SO 4 had very high post-treatment conductivities. The conductivities after acid treatment are all the higher when the treatment temperature is 160 ° C.
    [0024] EXAMPLE 4 PRODOT SERIES: Highly conductive HSO4 2 ml of a 20% by weight solution of PEG-PPG-PEG (Mn = 5800 g / mol) in ethanol is prepared with stirring in a Ultrasonic bath for 4 hours. 240 mg of Fe (OTf) 3 are added to the solution with stirring.
    [0025] The solution is left stirring for another 30 minutes. The solution is then cooled to 5 ° C. and 25 μl of 3,4-propylenedioxythiophene (PRODOT) are added. The solution is immediately placed in an ultrasonic bath at 5 ° C for 1 minute.
    [0026] The solution is spin coated on a Corning Eagle XG glass plate (2.5 x 2.5 cm), then annealed for 10 minutes on a hot plate at 70 ° C in the open air. The film is dipped in a sulfuric acid bath at pH = 1 for 30 minutes, then dried on a hot plate at 160 ° C for 30 minutes.
    [0027] The conductivity of the film, measured by the Van der Pauw method (4 points) is 1500 S.cm-1 and its thickness of 70 nm (+/- 5 nm). EXAMPLE 5: Highly Conductive PEDOS: H504 Sithesis 2 mL of a 20 wt.% Solution of PEG-PPG-PEG (Mn = 5800 g.mol -1) in ethanol is prepared with stirring in a Ultrasonic bath for 4 hours. 240 mg of Fe (OTf) 3 are added to the solution with stirring. The solution is left stirring for another 30 minutes. The solution is then cooled to 5 ° C. and 25 μl of 3,4-ethylenedioxyselenophene (EDOS) are added.
    [0028] The solution is immediately placed in an ultrasonic bath at 5 ° C for 1 minute. The solution is spin coated on a Corning Eagle XG glass plate (2.5 x 2.5 cm), then annealed for 10 minutes on a hot plate at 70 ° C in the open air.
    [0029] The film is dipped in a sulfuric acid bath at pH = 1 for 30 minutes, then dried on a hot plate at 160 ° C for 30 minutes.
    [0030] The conductivity of the film, measured by the Van der Pauw method (4 points) is 1,650 S.cm-1 and its thickness of 70 nm (+/- 5 nm). EXAMPLE 6: PEDOT SHEET: Highly conductive HSO4 from PEDOT: OTs 2 mL of a 20 wt.% Solution of PEG-PPG-PEG (Mn = 5800 g.mo1-1) in water. ethanol is prepared with stirring in an ultrasonic bath for 4 hours. 240 mg of Fe (OTf) 3 are added to the solution with stirring. The solution is left stirring for another 30 minutes.
    [0031] The solution is then cooled to 5 ° C and 20 μl of 3,4-ethylenedioxythiophene (EDOT) is added. The solution is immediately placed in an ultrasonic bath at 5 ° C for 1 minute. The solution is spin coated on a Corning Eagle XG glass plate (2.5 x 2.5 cm), then annealed for 10 minutes on a hot plate at 70 ° C in the open air. The film is dipped in a sulfuric acid bath at pH = 1 for 30 minutes, then dried on a hot plate at 160 ° C for 30 minutes. The conductivity of the film, measured by the Van der Pauw method (4 tips) is 1750 S.cm-1 and its thickness 70 nm (+/- 5 nm).
    权利要求:
    Claims (20)
    [0001]
    REVENDICATIONS1. Poly (thio- or seleno-) phenolic conductive polymeric material containing at least two distinct counteranion species with at least one of them being an anionic form of a sulfuric acid.
    [0002]
    2. The material of claim 1, wherein only one of the two species is an anionic form of a sulfuric acid.
    [0003]
    3. Material according to any one of the preceding claims, wherein said sulfurized acid is selected from sulfuric acid, a sulfonic acid and a perfluorosulfonic acid.
    [0004]
    4. Material according to any one of the preceding claims, wherein the second species of counter-anion is at least one anionic species selected from triflate, triflimidate, tosylate, mesylate, perchlorate and hexafluorophosphate.
    [0005]
    5. Material according to any one of the preceding claims, containing at least hydrogen sulfate and triflate counteranions.
    [0006]
    6. Material according to any one of the preceding claims, characterized in that it is based on a thiophene polymer derived from the polymerization of monomer (s) chosen from 3,4-dialkylthiophenes, 3,4 -cycloalkylthiophenes, 3,4-dialkoxythiophenes, and 3,4-alkylenedioxythiophenes, in which the alkyl groups, which are identical or different, are of formula Cf, H2 ', 1 with n ranging from 1 to 12.
    [0007]
    7. Material according to any one of claims 1 to 5, wherein the monomers are selected from thiophene, 3,4-ethylenedioxythiophene (EDOT), 3-hexylthiophene and 3,4-propylenedioxythiophene (PRODOT).
    [0008]
    8. Material according to any one of the preceding claims, characterized in that it is based on poly (3,4-ethylenedioxythiophene) (PEDOT).
    [0009]
    9. Material according to any one of claims 1 to 5, characterized in that it is based on a selenophenic polymer deriving from the polymerization of monomer (s) selected from 3,4-dialkylselenophenes, 3 , 4-cycloalkylselenophenes, 3,4-dialkoxyselenophenes, and 3,4-alkylenedioxyselenophenes, in which the alkyl groups, which are identical or different, are of formula C, F12 ', 1 with n ranging from 1 to 12.
    [0010]
    10. The material according to any one of claims 1 to 5, wherein the monomers are selected from selenophene, 3,4-ethylenedioxyselenophene (EDOS), 3-hexylselenophene, and 3,4-propylenedioxyselenophene (PRODOS).
    [0011]
    11. Material according to any one of the preceding claims, characterized in that it has a conductivity of at least 1000 S / cm, and preferably ranging from about 1500 S / cm to about 2500 S / cm. cm.
    [0012]
    A process for preparing a material according to any of the preceding claims comprising at least the steps of: (a) providing a poly (thio- or seleno-) phenolic polymeric material 10. containing at least an anionic species selected from triflate, triflimidate, tosylate, mesylate, perchlorate and hexafluorophosphate, (b) contacting said material with an aqueous solution of a sulfuric acid under conditions conducive to the immobilization of an anionic form of said acid within the polymeric material, and (c) disposing said material containing a first anionic species selected from triflate, triflimidate, tosylate, perchlorate, hexafluorophosphate and a second species corresponding to an anionic form of said sulfuric acid.
    [0013]
    13. The method of claim 12, wherein said material of step (a) is obtained beforehand by polymerization in a solvent medium of thio- or seleno-phenic monomer (s), in the presence of an oxidizing solution of triflate. iron, triflimidate, tosylate, mesylate, perchlorate or hexafluorophosphate (III), and an effective amount of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer (PEG-PPG-PEG), and is purified by aqueous washing before it is applied. in step (b).
    [0014]
    14. A process according to claim 12 or 13, wherein the temperature when the material is brought into contact with the aqueous sulfuric acid solution in step b) is between 120 ° C and 200 ° C, in particular between 140 ° C and 180 ° C, and preferably equal to 160 ° C.
    [0015]
    15. A method for increasing the conductivity of a poly (thio- or seleno-) phenolic polymeric material containing at least one distinct anionic species of a sulfide acid, in the form of a film, appearing on the surface solid substrate, comprising the step of contacting said film with an aqueous solution of a sulfurized acid under conditions conducive to the immobilization of an anionic form of said acid within the polymeric material.
    [0016]
    16. Use of a material according to any one of claims 1 to 11, or obtained according to any one of claims 12 to 14, as a conductive film.
    [0017]
    17. Substrate coated at least in part with a film of a material according to any one of claims 1 to 11, or obtained according to any one of claims 12 to 14.
    [0018]
    18. Substrate according to the preceding claim, characterized in that it is a substrate of glass, silicon, woven material or organic and / or polymeric nature, for example a paper substrate.
    [0019]
    19. Device comprising as conductive material a material according to any one of claims 1 to 11, or obtained according to any one of claims 12 to 14. 15
    [0020]
    20. Use of a material according to any one of claims 1 to 11, or obtained according to any one of claims 12 to 14, or a substrate according to claim 17 or 18, or obtained according to claim 15, in the fields of organic electronics, organic thermoelectricity, organic photovoltaics and organic photodetectors.
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    同族专利:
    公开号 | 公开日
    US20170107372A1|2017-04-20|
    FR3018817B1|2017-10-13|
    WO2015140249A1|2015-09-24|
    EP3119830A1|2017-01-25|
    US10377895B2|2019-08-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5098529A|1989-09-07|1992-03-24|Hoechst Aktiengesellschaft|Electrochemical process for the production of electrically conducting poly with carboxylic acids added|
    EP2161293A1|2008-08-05|2010-03-10|NEC TOKIN Corporation|Conductive polymer suspension and method for producing the same, conductive polymer material, electrolytic capacitor, and solid electrolytic capacitor and method for producing the same|WO2018069369A1|2016-10-13|2018-04-19|Commissariat A L'energie Atomique Et Aux Energies Alternatives|Radome equipped with a heating system made of polythiophene or polyselenophene polymers|CN102176103B|2010-12-27|2013-06-26|航天材料及工艺研究所|Variable-emissivity variable-reflectivity electrochromic intelligent thermal control coating and preparation method thereof|FR3057733A1|2016-10-13|2018-04-20|Commissariat A L'energie Atomique Et Aux Energies Alternatives|USE AS A HEATING ELEMENT OF A CONDUCTIVE AND TRANSPARENT POLYMERIC FILM BASED ON POLYPHENIC POLYMERS|
    FR3066499A1|2017-05-19|2018-11-23|Commissariat A L'energie Atomique Et Aux Energies Alternatives|ELECTRICALLY CONDUCTIVE, TRANSPARENT OR SEMI-TRANSPARENT DEVICE BASED ON POLYPHENIC POLYMERS AND POROUS SILICA NANOPARTICLES|
    FR3107614A1|2020-02-21|2021-08-27|Commissariat A L'energie Atomique Et Aux Energies Alternatives|Process for preparing a particulate composite material for an organic electrode|
    法律状态:
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    2021-03-30| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1452265A|FR3018817B1|2014-03-19|2014-03-19|POLYPHENIC CONDUCTIVE POLYMER|FR1452265A| FR3018817B1|2014-03-19|2014-03-19|POLYPHENIC CONDUCTIVE POLYMER|
    PCT/EP2015/055781| WO2015140249A1|2014-03-19|2015-03-19|Conductive polymer of polyphene type|
    US15/127,185| US10377895B2|2014-03-19|2015-03-19|Conductive polymer of polyphene type|
    EP15711146.9A| EP3119830A1|2014-03-19|2015-03-19|Conductive polymer of polyphene type|
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