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    • 专利摘要:
    The present invention relates to a method for obtaining transparent conductive polymeric layers by preparing a composition of monomers or oligomers of thiophene or its derivatives, or mixtures thereof, at least one oxidant, and a transparent polymer or copolymer in at least one organic solvent, the deposition of said composition on the substrate and the heating of said substrate until the polymerization of the conductive polymer. Likewise, the present invention refers to the transparent conductive polymeric layers obtained by said method and its different uses. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2691311A1
    申请号:ES201730735
    申请日:2017-05-26
    公开日:2018-11-26
    发明作者:Pedro Javier RODRIGUEZ CANTÓ；Rafael Abargues López；Juan Pascual Martinez Pastor；Fernando FERNANDEZ LAZARO；Enrique FONT SANCHIS；Nathalie ZINK LORRE；Angela SASTRE SANTOS
    申请人:INTENANOMAT S L；INTENANOMAT SL；Universidad Miguel Hernandez de Elche；Universitat de Valencia；
    IPC主号:
    专利说明:

    Transparent conductive polymeric layers and method of obtaining them Field of the Invention
    The present invention belongs to the field of conductive polymeric materials and
    5 highly transparent based on thiophene and its derivatives. In particular, the present invention relates to thin layers of said materials, processes for obtaining them, as well as their uses (i) in electronic devices (touch screens, solar cells, photodetectors, inorganic or organic light emitting diodes (LEDs) , OLEDs), etc.); (ii) as antistatic coating on electronic circuits, windows, papers, films
    10 photographic, building materials, etc .; (iii) in polymeric capacitors; (iv) in the form of inks for printed organic electronics; (v) as a gas sensor; or (vi) in miniaturization of devices by electron beam lithography and photolithography. Background
    The formation of transparent conductive polymer layers and the possibility of
    15 structuring them are fundamental aspects in the manufacture of semiconductor devices. Basically, these transparent conductive polymers are based on poly (3,4-ethylenedioxythiophene) (PEDOT) since the electronic configuration of the thiophene substituents (ethylenedioxy group) makes the PEDOT in the oxidized or doped state (and therefore conductive) not practically absorb light in the visible for layers with thicknesses
    20 less than 200 nm.
    There are three types of techniques for the in situ synthesis of PEDOT: electro-polymerization, vapor phase polymerization (Vapor Phase Polymerization VPP) and chemical polymerization.
    The electro-polymerization of 3,4-ethylenedioxythiophene (EDOT) is relatively simple to carry out, since it simply requires placing two electrodes in a solution containing the monomer and electrolyte, and applying a potential to polymerize the monomer on the surface of the electrode (Groenendaal et al. Synthetic Metals (2001), 118 (1-3), 105-109). However, this method inevitably requires the use of conductive substrates, which greatly limits their application. In addition, film uniformity and thickness control can often be a problem over large areas of the electrode due to fields
    30 non-homogeneous electric.
    VPP can give homogeneous thin layers with high conductivity, but it requires multiple processing steps including oxidant deposition, solvent removal


    and careful control over the deposition rates of water and monomer in an atmosphere of controlled humidity and temperature (Chen et al. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 1662).
    Chemical polymerization consists in that a mixture containing monomer (EDOT) and oxidant (usually iron (III) salts, such as iron (III) tosylate) is deposited directly on a substrate and then thermal polymerization is initiated (Pettersson, et al. Thin Solid Films 1998, 313, 356). Although this method allows deposition on both conductive and non-conductive substrates, its main limitation is that great skill is needed to obtain homogeneous thin layers reproducibly. This method has tried to be improved, for example by using phosphomolibic acid as an oxidant. However, this process is still industrially unfeasible today due to its reproducibility problems. In addition, this method poses serious problems in the control of the thickness of the layer, especially for thin thicknesses below 200 nm, which has a strong impact on the transparency of the layer. Another problem is that this type of technique generates layers with poor morphology, with a tendency to be fragile and brittle.
    US5300575 refers to dispersions of polythiophenes in the presence of polyanions, the production of said dispersions and their use for the antistatic treatment of plastic moldings. Specifically, US5300575 describes the formation of transparent conductive thin layers from aqueous dispersions of EDOT, poly (styrene sulfonate) (PSS) and an oxidant.
    CA1337950 describes thiophene-based polymers that allow obtaining transparent conductive polymeric films by oxidative polymerization, for example from solutions comprising EDOT, an oxidizing salt and one or more organic solvents. CA1337950 also describes the use of said polymers to impart antistatic properties on substrates with low or no conductivity or as an electrode material for rechargeable batteries.
    It should be noted that none of the methods described above satisfies the requirements regarding the control of the parameters to obtain desired thicknesses in the range of tens or hundreds of nanometers. This is especially critical since in the manufacture of devices hollow conveyor layers with thin thicknesses around 100 nm thick are needed to have a high transparency. The transmittance of the layer (measured in% of transmitted light and that is a measure of the transparency of the layer) decreases linearly with the thickness.


    Currently there is a need to form highly transparent, homogeneous and uniform conductive thin layers, directly on flexible or rigid substrates, both conductive and non-conductive, in a simple and reproducible way. Description of the invention
    The present invention provides a simple and reproducible method for obtaining thin conductive layers (also called transparent films or films) that allows to obtain layer thicknesses from a few nanometers (nm) to several microns. The present invention allows to overcome the limitations of current methods and consists of a simple and reproducible way of in situ formation of thin conductive layers of thiophene or
    10 its derivatives. In the present method, the synthesis of the conductive polymer occurs within another polymer, as shown in Figure 1. Said polymer is transparent and has excellent properties for forming layers on all types of surfaces. In addition, the present method allows absolute control of the layer thickness of up to tens of nanometers.
    The thin conductive and transparent layers of the present invention have greater transparency than similar layers obtained with PEDOT: PSS, especially in the visible spectrum from 550 nm, but especially in the infrared. This allows the application of these materials in devices that operate in the infrared, such as photodetectors or solar cells based on quantum dots.
    With the compositions of the present invention ultrafine layers up to 20 nm thick can be obtained with total control and conductivities up to 100 S / cm.
    In a first aspect, the present invention relates to a method for obtaining transparent conductive layers comprising the following steps:
    to. Prepare a solution comprising 3,4-ethylenedioxythiophene monomers and / or oligomers
    25 (EDOT), at least one oxidant and a transparent polymer selected from poly (methyl methacrylate) (PMMA), poly (lauryl methacrylate) (PLMA), poly (butyl methacrylate) (PBMA), poly (methacrylate methyl-co-methacrylic acid), poly (methyl methacrylate-ethyl coacrylate), poly (methyl methacrylate-butyl methacrylate), poly (methyl methacrylate-ethylene co-dimethacrylate), poly (�-methylstyrene ), poly (benzyl methacrylate),
    30 poly (tert-butyl methacrylate), poly (cyclohexyl methacrylate), poly (ethyl methacrylate), poly (hexadecyl methacrylate), poly (hexyl methacrylate), poly (isobutyl methacrylate), poly (tetrahydrofurfuryl methacrylate) ), poly (ethyl tetrahydrofurfuryl-co-methacrylate methacrylate), poly (acrylonitrile-methyl co-acrylate), polyacrylonitrile, polycarbonate (PC), poly (styrene)


    co-acrylonitrile), poly (styrene-co-allyl alcohol), poly (styrene-co-chloromethylstyrene), poly (styrene-co-4-chloromethylstyrene-co-4-methoxymethylstyrene), poly (styrene-co-maleic acid) , poly (styrene-co-�-methylstyrene), polyacenaphylene, poly (4-bromo styrene), poly (4-chlorostyrene), poly (4-tert-butyl styrene), poly (4-vinylbiphenyl), poly (vinylcyclohexane), poly (4-vinylphene) ), poly (vinyltoluene-co-�-methylstyrene), polystyrene-co-acrylonitrile (PS-co-AN), poly (styrene-co-allyl alcohol) (PS-co-AA), poly (styrene-co-methacrylate methyl) (PS-co-MMA), polyacrylamide (PAM), poly (4-vinylphenol-co-methacrylate methyl) (P4VP-co-MMA), polyethyleneimine and poly (vinyl cinnamate), in at least one solvent organic.
    b. Deposit the composition prepared in step (a) on a substrate,
    C. Heat the substrate obtained in step (b) until the EDOT monomers or oligomers polymerize.
    The layers obtained with the present method are thin layers. In the present description, "thin layer" means a layer with a thickness between 1 nm and 20 microns, preferably between 5 nm and 10 microns, more preferably between 10 nm and 250 nm. In the present description, "transparent" is understood as having a transmittance of more than 70% in wavelengths between 400 and 1550 nm.
    In the present description, "conductive" is understood as the one that is capable of conducting electricity.
    In step (c) it can be seen when the EDOT monomers or oligomers have polymerized because electrical conductivity is observed. Preferably, step (c) is carried out on a heating plate, oven, or by heating by hot air flow, for example using a dryer.
    In the present description, "organic solvent" means organic solvents essentially free of water. The organic solvent does not therefore include mixtures of alcohols such as methanol, ethanol, isopropanol, etc. with water.
    In a preferred embodiment of the method of the first aspect, the solution of step (a) comprises EDOT oligomers. Preferably, the oligomers are dimers, trimers, tetramers or mixtures thereof. In a preferred embodiment, the step solution
    (a) comprises dimers of EDOT (biEDOT or 2EDOT).
    In a preferred embodiment, the solution of step (a) comprises between 0.5 and 10 mg / ml, more preferably between 0.5 and 8 mg / ml, even more preferably between 0.5 and 5 mg / ml of monomer and / or EDOT oligomer with respect to the total volume of the solution. In a


    preferred embodiment, the solution of step (a) comprises between 0.5 and 5 mg / ml EDOT dimer with respect to the total volume of the solution. In a preferred embodiment, the solution of step (a) comprises about 1.2 mg / ml of EDOT monomer and / or oligomer with respect to the total volume of the solution. In a preferred embodiment, the solution of step (a) comprises about 1.2 mg / ml of EDOT dimer with respect to the total volume of the solution. In another preferred embodiment, the solution of step (a) comprises about 5 mg / ml of EDOT dimer and about 0.5 mg / ml of EDOT trimer with respect to the total volume of the solution. In another preferred embodiment, the solution of step (a) comprises approximately 1.2 mg / ml EDOT dimer and approximately 0.12 mg / ml EDOT trimer relative to the total volume of the solution. In another preferred embodiment, the solution of step (a) comprises approximately 5 mg / ml of EDOT dimer and approximately 0.25 mg / ml of EDOT tetramer with respect to the total volume of the solution. In another preferred embodiment, the solution of step (a) comprises
    About 1.2 mg / ml of EDOT dimer and about 0.06 mg / ml of EDOT tetramer with respect to the total volume of the solution.
    In a preferred embodiment of the method of the first aspect, the solution of step (a) further comprises thiophene monomers and / or oligomers or thiophene derivatives with formula I, II, III or IV: I II III IV
    where R1 and R2 are independently selected from H, methyl, ethyl, phenyl, hydroxyl, thiol, carboxyl, F, Cl, Br, I, Si (R5) 3, OR3, SR3, NHR3, NR3R3, COOR3, CONH2, CONHR3 and CONR3R3, R3-O-R4, amino, R3 (CO) -O-R4, R3 (CO) -NH-R4, R3 (CO) -NR4R4, R3 (CO) -O-NH-R4,
    25 or C1-20 alkyl unsubstituted or substituted by methyl, ethyl, hydroxyl, amino, thiol, carboxyl, amido, trifluoromethyl, trichloromethyl, or tribromomethyl;
    where R3 and R4 are independently selected from C1-20 alkyl, phenyl, biphenyl;


    where R5 is C1-20 alkyl;
    where R6 and R7 are independently selected from H, methyl and C2-20 alkyl; Y
    where n is selected from 1 to 4.
    In a preferred embodiment of the first aspect method, the solution of step (a)
    5 consists of a solution of dimers, trimers, tetramers of EDOT or mixtures thereof, at least one oxidant and a transparent polymer selected from poly (methyl methacrylate) (PMMA), poly (lauryl methacrylate) (PLMA), poly (butyl methacrylate) (PBMA), poly (methyl methacrylate -co-methacrylic acid, poly (methyl methacrylate, ethyl co-acrylate), poly (methyl methacrylate-butyl methacrylate), poly (methacrylate
    10-methyl-ethylene dimethacrylate, poly (�-methylstyrene), poly (benzyl methacrylate), poly (tert-butyl methacrylate), poly (cyclohexyl methacrylate), poly (ethyl methacrylate), poly (methacrylate) of hexadecyl), poly (hexyl methacrylate), poly (isobutyl methacrylate), poly (tetrahydrofurfuryl methacrylate), poly (tetrahydrofurfuryl-ethyl methacrylate methacrylate), poly (acrylonitrile-methyl co-acrylate), polyacrylonitrile , polycarbonate (PC), poly (styrene
    15 co-acrylonitrile), poly (styrene-co-allyl alcohol), poly (styrene-co-chloromethylstyrene), poly (styrene-co-4-chloromethylstyrene-co-4-methoxymethylstyrene), poly (styrene-co-maleic acid ), poly (styrene-co-iles-methylstyrene), polyacenaphylene, poly (4-bromo styrene), poly (4-chlorostyrene), poly (4-tert-butyl styrene), poly (4-vinylbiphenyl), poly (vinylcyclohexane), poly ( 4-vinylphenol), poly (vinyltoluene-co-�-methylstyrene), poly (styrene-co-acylonitrile) (PS-co-AN),
    Poly (styrene-co-allyl alcohol) (PS-co-AA), poly (styrene-co-methacrylate) (PS-co-MMA), polyacrylamide (PAM), poly (4-vinylphenol-co-methacrylate) methyl) (P4VP-co-MMA), polyethyleneimine and polyvinyl cinnamate, in at least one organic solvent.
    In an embodiment of the method of the first aspect, the oxidant is an oxidizing salt. Examples of oxidants that can be used in the method of the present invention are inorganic salts of Cu (II) as Cu (ClO4) 2, gold (III) salts as HAuCl4, iron (III) salts as Fe (CH3C6H4SO3) 3 , silver (I) salts such as AgClO4, cerium (II) and (IV) compounds such as Ce (SO4) 2, chromium (VI) as CrO3, permanganate salts such as KMnO4, molybdenum compounds such as MoO3, osmium salt such as OsO4, platinum (IV) salts such as H2PtCl6, palladium (II) salts such as Na2PdCl4, ruthenium salts such as RuCl3, iridium as 30 H2IrCl6; organic oxidizers such as diazonaphthoquinone (DNQ), 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) and 7,7,8,8-tetracyanoquinodimethane (TCNQ), peroxides such as ammonium peroxodisulfate and potassium peroxodisulfate, and photoacids (compounds that under the effect of light become an acid) such as triphenylsulfonium triflate and triphenylsulfonium nonaflate, or mixtures thereof In one embodiment


    preferred, the oxidant is selected from Cu (ClO4) 2, CuCl2, copper (II) tosylate, Cu (NO3) 2, Cu (SO4) 2, copper (II) acetate, FeCl3, iron (III) tosylate , Fe2 (SO4) 3, Fe (NO3) 3, Ce (SO4) 2, (NH4) 2Ce (NO3) 6 cerium (IV) ammonium nitrate, chromium trioxide, Na2CrO4, K2CrO4, HAuCl4 3 x H2O, KAuCl4, AgClO4, AgMnO4, silver neodecanoate, 5 silver trifluoruroacetate, AgNO3, AgBF4, KMnO4, NaMnO4, Ca (MnO4) 2, NH4MnO4, manganese dioxide, MoCl5, MoO3 (H2O) 3, MoO3, Osmium tetraxide VI) potassium, K2OsO4 2H2O, H2PtCl6, RuCl3, Na2PdCl4, palladium trifluoroacetate (II), H2IrCl6, sodium hypochlorite, Br2, iodine, methyltrioxorenium (MTO), AsF5, azobisisobutyronitrile, combined with AIB4-phenyl-nitroxide hydrogen, vanadyl acetylacetonate (VO (acac) 2), V2O5, 2,310 dichloro-5,6-dicyanobenzoquinone (DDQ), 1,4-benzoquinone, benzaldehyde, 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3, 5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), dietary azodicarboxylate ilo (DEAD), N-bromosuccinimide, N-chlorosuccinimide, ammonium peroxodisulfate, potassium peroxodisulfate (K2S2O8), sodium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, 3-chloroperoxybenzoic acid, di-tert-15-di-tert-oxide butyl (DPQ), magnesium monoperoxyphthalate hexahydrate, benzoyl peroxide, diphenyldononium nitrate, diphenyldonodium p-toluenesulfonate, diphenyl diphenyl triflate, (4-methylthiophenyl) methyl phenyl sulfonium triflate, (4-phenyl diphenyl diphenyl) triphenylsulfonium, triphenylsulfonium nonaflate, potassium dichromate (K2Cr2O7), sodium dichromate (Na2Cr2O7), the following molecules numbered from 1 to 6:
    or mixtures thereof.
    In a preferred embodiment of the first aspect method, the oxidant is selected from Cu (ClO4) 2, copper (II) tosylate, copper (II) acetate, FeCl3, iron (III) tosylate, 3 x H2O HAuCl4 and mixtures thereof. Preferably, the oxidant is Cu (ClO4) 2. In a
    In the preferred embodiment, the solution of step (a) comprises between 0.1 and 25 mg / ml of oxidant with respect to the total volume of the solution.


    In a preferred embodiment of the method of the first aspect, the solution of step (a) comprises an oxidizing ratio: monomer or oligomer of between 0.3 and 3.
    In a preferred embodiment of the first aspect method, the transparent polymer is selected from PMMA, PLMA, PBMA, PS-co-MMA, PC, PS-co-AN, PS-co-AA, PAM, P4VP-co-MMA . Preferably, the transparent polymer is PMMA. In a preferred embodiment, the solution of step (a) comprises between 1.0 and 70 mg / ml of transparent polymer with respect to the total volume of the solution. The transparent polymer is soluble in the organic solvent (s).
    In a preferred embodiment of the method of the first aspect, the organic solvent is selected from among methoxypropyl acetate (MPA), glycol ether, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, diethyl carbonate, propylene carbonate , ethyl acetate, cyclohexanone, cyclopentanone, gammabutyrolactone, hexanol, tetrahydrofuran, methanol, acetonitrile and mixtures thereof. Preferably, the organic solvent is MPA, glycol ether, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate or a mixture thereof. In another preferred embodiment, the solvent is MPA.
    In a preferred embodiment of the first aspect method, step (b) is carried out by spin coating, doctor blade, dip coating, drop casting, Layer-by-Layer, spraying ( spray coating) injection printing, screen printing, flexography, or plotter. Preferably, step (b) is carried out by spin coating or doctor blade.
    In a preferred embodiment of the first aspect method, step (c) is carried out at a temperature between 25 ° C and 220 ° C and for a time between 0.5 and 120 minutes. Preferably, step (c) is carried out at a temperature of between 80 ° C and 140 ° C and for a time of between 1 and 10 minutes.
    In a preferred embodiment of the first aspect method, the substrate is selected from: rigid substrates selected from indium and tin oxide (ITO), fluorine doped tin oxide (FTO), silicon, silicon oxide, glass, quartz , graphene, metals selected from gold, silver, nickel, aluminum; carbon nanotubes, perovskites, gallium nitride, titanium oxide, zinc oxide, nickel oxide; Flexible substrates selected from poly (ethylene terephthalate) (PET), poly (ethylene naphthalate) (PEN), poly (dimethylsiloxane) (PDMS), polycarbonate, poly (methyl methacrylate), polystyrene, polyethylene, cellulose, polychloride vinyl (PVC); and textile fibers selected from


    polyamide, polyester, acrylic, cotton and carbon fiber. Preferably, the substrate is selected from ITO, FTO, glass, perovskites, PET, PEN, cellulose and graphene.
    In a preferred embodiment of the method of the first aspect, the composition of step (a) further comprises at least one stabilizing agent selected from imidazole, acetylacetonate, monoethanolamine, diethanolamine, triethanolamine, ethylene diaminetetraacetic acid (EDTA), ethylene diamine, ethylene glycol and polyethylene glycol. In a preferred embodiment, the solution of step (a) comprises between 0.02 and 5 mg / ml of stabilizers, based on the total volume of the solution.
    In a preferred embodiment of the method of the first aspect, the solution of step (a) further comprises between 0.02 and 5 mg / ml of at least one stabilizing agent selected from trifluoroacetic acid, methanesulfonic acid, dimethyl sulfoxide (DMSO), ethylene glycol, polyethylene glycol, H3PO4, H2SO4, glycerol, sorbitol and ethanol, with respect to the total volume of the solution.
    In a preferred embodiment of the method of the first aspect, said method further comprises step (d) washing the layer obtained in step (c). Preferably, the washing of step (d) is done with water, isopropanol or MPA.
    In a preferred embodiment of the method of the first aspect, said method further comprises step (e) treating the layer obtained in step (c) or in step (d) with at least one strong acid or solvent. In a preferred embodiment, step (e) consists of a washing or immersion of several minutes, between 3 and 5 minutes, preferably, in a strong acid or a solvent. Preferably, a solution of the strong acid in water with a concentration of between 50 and 99% is used. Examples of the strong acids and solvents that can be used in step (e) are iodhydric acid (55%), trifluoroacetic acid (99%), methanesulfonic acid (8 M in water), DMSO (99.9%), ethylene glycol (99.9% ), H3PO4 (85%), H2SO4 (98%), glycerol (> 99%), sorbitol (97%), methanol (99.9%) and ethanol (99.8%).
    In a second aspect, the present invention relates to the thin transparent conductive layer obtained by the process according to any of the preceding claims. Preferably, the thickness of the transparent conductive thin layer is between 10 nm and 10 microns. More preferably, the thickness is between 20 and 250 nm.
    In a third aspect, the present invention relates to a composition comprising EDOT monomers and / or oligomers, at least one oxidant and a transparent polymer selected from PMMA, PLMA, PBMA, poly (methyl methacrylate-co-methacrylic acid ), poly (methyl methacrylate-ethyl co-acrylate), poly (methyl methacrylate-co


    butyl methacrylate), poly (methyl methacrylate-ethylene co-dimethacrylate) ,, poly (metmethylstyrene), poly (benzyl methacrylate), poly (tert-butyl methacrylate), poly (cyclohexyl methacrylate), poly ( ethyl methacrylate), poly (hexadecyl methacrylate), poly (hexyl methacrylate), poly (isobutyl methacrylate), poly (tetrahydrofurfuryl methacrylate), poly (ethyl tetrahydrofurfuryl-co-methacrylate methacrylate), poly (acrylonitrile-) methyl co-acrylate), polyacrylonitrile, PC, poly (styrene-co-acrylonitrile), poly (styrene-co-allyl alcohol), poly (styrene-co-chloromethylstyrene), poly (styrene-co-4-chloromethylstyrene-co -4methoxymethylstyrene), poly (styrene-co-maleic acid), poly (styrene-co-�-methylstyrene), polyacenaphylene, poly (4-bromo-styrene), poly (4-chlorostyrene), poly (4-tert-butyl styrene), poly (4-vinylbiphenyl), poly (vinylcyclohexane), poly (4-vinylphenol), poly (vinyltoluene-co-�-methylstyrene), PSco-AN, PS-co-AA, PS-co-MMA, PAM, P4VP-co- MMA, polyethylene ina and polyvinyl cinnamate, in at least one organic solvent.
    In a preferred embodiment of the third aspect composition, the composition comprises dimers, trimers, EDOT tetramers or mixtures thereof, at least one oxidant selected from Cu (ClO4) 2, copper (II) tosylate, copper acetate (II), FeCl3, iron (III) tosylate, 3 x H2O HAuCl4 and mixtures thereof and a transparent polymer selected from PMMA, PLMA, PBMA, PS-co-MMA, PC, PS-co-AN, PS -co-AA, PAM, P4VP-co-MMA in at least one organic solvent selected from MPA, glycol ether, dipropylene glycol methyl ether, glycol ether ester, dipropylene glycol methyl ether acetate or a mixture thereof. In a preferred embodiment of the composition of the third aspect, the composition comprises dimers of EDOT, Cu (ClO4) 2 and PMMA in MPA. In a preferred embodiment, the composition consists essentially of dimers of EDOT, Cu (ClO4) 2 and PMMA in MPA. More preferably, the composition consists of dimers of EDOT, Cu (ClO4) 2 and PMMA in MPA. In a preferred embodiment of the composition of the third aspect, the composition comprises between 0.5 and 10 mg / ml of EDOT monomers and / or oligomers, between 0.1 and 25 mg / ml of at least one oxidant and between 1, 0 and 70 mg / ml of the transparent polymer in at least one organic solvent, with respect to the total volume of the composition. In another preferred embodiment of the composition of the third aspect, the composition comprises between 0.5 and 5 mg / ml of EDOT dimers, between 0.1 and 25 mg / ml of Cu (ClO4) 2 and between 1.0 and 70 mg / ml of PMMA in MPA, with respect to the total volume of the composition.
    In a preferred embodiment of the composition of the third aspect, the composition further comprises thiophene monomers and / or oligomers or thiophene derivatives with formula I, II, III
    or IV:

    I II III IV
    where R1 and R2 are independently selected from H, methyl, ethyl, phenyl, hydroxyl, thiol, carboxyl, F, Cl, Br, I, Si (R5) 3, OR3, SR3, NHR3, NR3R3, COOR3, CONH2, CONHR3 and 5 CONR3R3, R3-O-R4, amino, R3 (CO) -O-R4, R3 (CO) -NH-R4, R3 (CO) -NR4R4, R3 (CO) -O-NH-R4,
    or C1-20 alkyl unsubstituted or substituted by methyl, ethyl, hydroxyl, amino, thiol, carboxyl, amido, trifluoromethyl, trichloromethyl, or tribromomethyl;
    where R3 and R4 are independently selected from C1-20 alkyl, phenyl, biphenyl;
    where R5 is C1-20 alkyl;
    Where R6 and R7 are independently selected from H, methyl and C2-20 alkyl; Y
    where n is selected from 1 to 4.
    In a preferred embodiment of the composition of the third aspect, the composition further comprises between 0.02 and 5 mg / ml of at least one stabilizing agent selected from imidazole, acetylacetonate, monoethanolamine, diethanolamine, triethanolamine, EDTA,
    15 ethylenediamine, ethylene glycol and polyethylene glycol.
    In a preferred embodiment of the composition of the third aspect, the composition further comprises between 0.02 and 5 mg / ml of at least one stabilizing agent selected from trifluoroacetic acid, methanesulfonic acid, DMSO, ethylene glycol, polyethylene glycol, H3PO4, H2SO4, glycerol , sorbitol and ethanol, with respect to the total volume of the solution.
    In a fourth aspect, the present invention relates to a thin transparent conductive layer comprising PEDOT forming an interpenetrated network with a transparent polymer selected from PMMA, PBMA, PLMA, PS-co-AN, PS-co-AA, PAM , PSco-MMA and P4VP-co-MMA. Preferably, the thickness of the layer is between 10 nm and 500 microns or between 20 and 250 nm.


    In a fifth aspect, the present invention relates to the use of the first aspect method for lithography drawing, for direct printing, for nanoprinting lithography, UV photolithography, electron beam lithography, soft lithography, screen printing, jet printing of ink, plotter, flexography, offset or gravure printing.
    When the method is used for direct printing, the composition is used as ink. In a preferred embodiment of the composition of the third aspect, the composition comprises a solvent or mixture of solvents with a surface tension and viscosity suitable for use as ink. The composition of an ink is determined by the printing method to which it is intended and vice versa. The inks presented in this invention are highly stable and allow their formulation with different organic solvents and different concentrations of their components. This makes them potentially suitable for them to be applied in rigid or flexible electronic circuits and devices. Printed electronics is one of the keys to the production of next-generation electronic devices on a large scale and at low cost. and the compositions of the present invention allow, unlike other compositions of the prior art, to formulate these materials as inks for application with direct printing techniques (inkjet printing, screen printing, gravure printing, etc.).
    In another aspect, the present invention relates to the use of the method of the first aspect or the thin layer of the fourth aspect in the manufacture of touch screens, solar cells, photodetectors, inorganic or organic light emitting diodes (LEDs, OLEDs), capacitors polymeric, gas sensors, or as an antistatic surface coating or in miniaturization of devices by electron beam lithography and photolithography. Preferably, the antistatic coating is used in electronic circuits, windows, papers, photographic films or building materials. Description of the figures
    Figure 1. This figure illustrates the method of the invention and its various steps: (a) the composition comprising the EDOT monomers and oligomers (hollow circles) and the transparent polymer (solid circle network) is prepared; (b) the composition is deposited on the substrate; and (c) is heated to carry out the polymerization and give rise to the PEDOT (network of hollow circles) forming an interpenetrated network (IPN) with the transparent polymer.
    Figure 2. The conductive layers of the present invention are more transparent than those of PEDOT: PSS, especially at wavelengths above 550 nm.


    Figure 3. Conductivity of the thin layers of the invention depending on either the amount of oligomer in% by weight in layer (A) or the oxidant / oligomer molar ratio (B).
    Figure 4. A) Scanning electron microscopy (SEM) image of the surface of a thin layer of the present invention. B) Cross section of a 20 nm thin layer of the present invention, deposited on ITO (indium tin oxide) / glass.
    Figure 5: Atomic force microscopy (AFM) images of surfaces of layers deposited on PMMA glass, 2EDOT-PMMA (according to the invention) and PEDOT: commercial PSS.
    Figure 6: Determination of the working function of a conductive thin layer of the invention based on 2EDOT, Cu (ClO4) 2 and PMMA, by Ray photoemission spectroscopy
    X.
    Figure 7. Drops formed on the different substrates of the composition of the invention and of the commercial material PEDOT: PSS, indicating the contact angles.
    Figure 8. SEM image of different conductive thin layer structures with conductivities around 10 S / cm. The bar indicates 10 micrometers.
    Figure 9. A) Scheme of the printing process of inks based on thin conductive layers by microdispensing (Microplotter). B, C) Images of different patterns generated on SiO2.
    Figure 10. A) Schottky structure that replaces the PEDOT: PSS with a thin conductive layer based on 2EDOT and PMMA. B) 450 nm PbS quantum dot layer manufactured by Dr. Blade on a thin layer / ITO substrate. C) Series of photodiodes manufactured on this layer. Examples
    The following examples illustrate the present invention and demonstrate the advantageous properties of the thin conductive layers of the present invention, as well as of the method of the present invention, with respect to other prior art layers.
    Example 1. Compositions
    Compositions were prepared with EDOT dimers (biEDOT or 2EDOT, commercially purchased from abcr GmbH), Cu (ClO4) 2 in MPA with different transparent polymers. The conductivities of these layers are reflected in the following table:


    Polymer Molecular Weight (KDa)Conductivity (S / cm)
    PMMA 96013.6
    PMMA 350twenty
    PLMA 57028
    PS-co-MMA 100-15058
    P4VP-co-MMA 8-12twenty
    PS-co-AN 16512
    PS-co-AA 834,5
    In all cases the composition comprises 1.2 mg / ml of 2EDOT, 3.1 mg / ml of oxidant and 7.1 mg / ml of polymer. 5 Example 2. Transparent conductive thin layers
    From the compositions of Example 1, thin transparent conductive layers on glass were prepared by spin coating. These layers were heat treated on a heating plate at 160 ° C for 5 min. Ultra-thin layers of 100 nm were obtained, being able to reduce the thickness to 20 nm with total control and conductivities of up to 100
    10 S / cm
    The transparency of the conductive thin layers was analyzed and their transmittance was compared with PEDOT: PSS layers of 100 nm layer thickness and conductivity 0.1 S / cm. As Figure 2 shows, the thin layers of the present invention showed greater transparency in the visible spectrum and much greater infrared transparency (around the
    15 13-18%).
    Transmittance (%) at different wavelengths of a 100 nm thick layer of PEDOT: PSS and of a 100 nm layer obtained by the method of the present invention as an interpenetrated network starting from an EDOT and PMMA dimer:


    400 nm 550 nm700 nm900 nm1300 nm1550 nm
    PEDOT: PSS 98.993.586.978.664.658.1
    biEDOT-IPN 98.394.388.281.077.775.6
    Example 3. Conductivity
    The conductivity of the layers was analyzed for different concentrations of oligomer (from 2 to 40% by weight in layer) and different oxidant / oligomer 5 molar ratios (from 0.4 to 3), the conductivity being normally between 0.001 and 200 S / cm and reaching conductivities of up to 600 S / cm (see figure 3A).
    Example 4. Roughness
    The use of compositions with low amounts of oligomer has numerous advantages, such as that the dispersions are better and the amount of oxidant is smaller. This, in turn, involves obtaining smoother surfaces, with less morphological defects. Figure 4 shows scanning electron microscopy (SEM) images of the surface of a layer based on 2EDOT, Cu (ClO4) 2 and PMMA, deposited by spin coating on indium and tin oxide (ITO) and heated to 160 º C for 5 min. These images show how the surface of the material has no roughness or morphological defects and
    15 also perfectly planarizes the rough surface of the ITO layer.
    When the surface of the thin layer of the present invention based on 2EDOT and PMMA is compared by atomic force microscopy (AFM) with a thin layer of PEDOT: PSS, deposited by spin coating on glass according to the same method, it is verified that layers of the present invention are smoother (RRMS = 0.9 nm) than those obtained
    20 with the PEDOT: commercial PSS (RRMS = 2.1 nm) (Fig. 5).
    Example 5. Working function of thin transparent conductive layers
    For the application of these thin conductive layers as a hollow conveyor layer it is necessary to determine their working function, which coincides with the position of the HOMO energy level, and whose value must be close to the value of the working function of the metal used as an anode. (typically ITO, 4.8 eV). Generally, PEDOT: PSS is used as a hollow conveyor layer in most of these devices thanks to its work function of approx. 5.1 eV. However, the acid character of the interfaces with the ITO and active layer


    due to the superficial migration of the PSS and its aqueous nature induce degradation and low stability of the device.
    These problems are solved with the material of the present invention, which, in addition to the advantages already presented above, has a working function of 5.01 eV, as seen in Figure 6.
    Example 6. Use in both rigid and flexible substrates
    For the deposition of the compositions in solution on flexible and rigid substrates, it is necessary to characterize the rheological properties of said compositions in solution. The compositions of the present invention have great "wettability" of
    10 material on the substrate through a low contact angle and low surface tension. The following table indicates the contact angle of a drop of the composition of the invention and a drop of PEDOT: commercial PSS on different substrates:
    Substratum biEDOT-PMMAPEDOT: PSS
    Glass 14th40th
    ITO 19th72º
    PET / ITO 13th79th
    Penis 10th59th
    PET 14th65º
    Yes 22nd65º
    SiO2 10th35th
    Figure 7 shows images of the drops and the contact angles are indicated.
    15 As can be seen, in all cases the contact angle of the composition of the invention is significantly lower than in the case of PEDOT: PSS because the latter is formulated with water, which has a surface tension greater than solvents. organic as the MPA. The use of organic solvents with respect to water is advantageous for application as coatings, since the rheological properties
    20 result in high adhesion and "wettability" of the composition to the substrate, allowing smaller amounts to be used in each deposition. Thus, the number of steps necessary for deposition is significantly reduced. This in turn implies that it is not necessary


    a strict cleaning of the substrate, nor are necessary equipment for the activation of the surface of the substrate that entail additional costs.
    One of the most important requirements of the compositions for use as thin transparent conductive layers is that they can be deposited on both rigid and flexible substrates. The latter are of great importance since the development of new generation devices depends largely on the possibility of manufacturing them on flexible substrates such as PET or PEN. Due to the excellent layer formation properties and low contact angle of the composition of the invention, it is possible to easily deposit it on PET and PEN substrates, obtaining very homogeneous and transparent layers.
    Example 7. Pattern generation and miniaturization
    The generation of macro, micro, and nano scale patterns from the compositions of the invention is possible thanks to its ability to be structured by electron beam lithographic techniques or even UV lithography or to formulate them as inks for direct printing technologies .
    Example 7.1. Lithography
    The lithographic process has been carried out after depositing a layer of 2EDOT, Cu (ClO4) 2 and PMMA in methoxypropyl acetate by spin coating. The resulting layer has been heated at 40 ° C for 2 minutes in order to remove the solvent. This layer has been exposed to an electron beam, applying a voltage of 40 keV and a dose of 300 C / cm2. The development of the structures has been carried out with a mixture of methyl ethyl ketone and isopropanol 1: 1. Finally the structures have been heat treated at 140 ° C for 10 minutes in order to carry out the polymerization of 2EDOT and consequent formation of the transparent conductive thin layer. Figure 9 shows an SEM image of 500-200 nm structures of the conductive thin layer with conductivities around 10 S / cm.
    Example 7.2. Organic printed electronics
    The printing process has been carried out by means of a microdispenser (SonoPlot GIX Microploter II) that allows the direct deposition of the composition (dissolution). This dispenser is composed of a micropipette coupled to a piece of piezoelectric material and is located on the surface of the substrate thanks to a high precision positioning system. Applying the appropriate voltage, the piezoelectric causes the micropipette to vibrate on the vertical axis, and an ultrasonic field causes the solution to flow through the tip and deposit, without any contact between the micropipette and the


    surface. The dimensions of the structure printed by this system can be controlled by increasing or decreasing the amplitude of the applied voltage and adjusting the composition of the ink in terms of viscosity, surface tension and angle of contact with the substrate.
    Figure 9 shows a scheme of the printing process performed and images of the structures generated by this technique from an ink formulated with 2EDOT, Cu (ClO4) 2, PMMA in methoxypropyl acetate (MPA).
    Example 7.3. Device manufacturing
    The efficiency of the material of the present invention as a hollow conveyor layer has been demonstrated through its integration into the manufacture of a photodetector based on PbS quantum dot layers. Recently, a work based on a schottky structure based on layers of quantum PbS points manufactured by Dr. Blade for photodetection of light at 1550 nm has been published (Maulu et al., RSC Adv., 2016, 6, 80201). This structure was manufactured using PEDOT: commercial PSS as a hollow conveyor layer, obtaining a device efficiency similar to that of other reported works manufactured by spin coating and / or using other architectures and technology. Thus, for the demonstration and validation of the material of the present invention, the same device has been manufactured by replacing the PEDOT: PSS with a thin conductive layer based on 2EDOT and PMMA (Figure 10A). Figures 10B and 10C show a layer of 450 nm PbS quantum dots manufactured by Dr. Blade on a conductive thin layer / ITO substrate and on the other hand a series of photodiodes manufactured on this layer. Each square is the gold (or silver) electrode of each photodiode.
    The efficiency of the device manufactured in terms of external quantum efficiency and responsiveness is similar to that of Maulu et al. (R = 0.26 A / W, EQE> 30% @ 1550 nm), thus demonstrating its applicability.
    Example 8. Comparison
    The following is a general comparison of the properties of the material presented in this invention with respect to the CleviosTM commercial product (PEDOT: PSS).
    Comparison of the properties of the commercial product PEDOT: PSS with the material of the invention. σ = conductivity; T = transparency; WF = job function; FT = layer thickness.
    max (S / cm)
    % T @ 550 nmWF (eV)% T @ 1300 nmSolution StabilityLayer forming propertiesCoveringDriving safetyσ adjustableFT adjustable PEDOT: PSS
    <95
    5.01
    <80
    high
    poor
    slow
    yes
    yes limited
    biEDOT-PMMA
    400<954.8-5.4<90highgoodcheap and fastyesyesyes
    twenty


    权利要求:
    Claims (36)
    [1]
    1. A method for obtaining transparent conductive layers comprising the following steps:
    to. Prepare a solution comprising 3,4-ethylenedioxythiophene monomers and / or oligomers
    5 (EDOT), at least one oxidant and a transparent polymer selected from poly (methyl methacrylate) (PMMA), poly (lauryl methacrylate) (PLMA), poly (butyl methacrylate) (PBMA), poly (methacrylate methyl-co-methacrylic acid), poly (methyl methacrylate-ethyl coacrylate), poly (methyl methacrylate-butyl methacrylate), poly (methyl methacrylate-ethylene co-dimethacrylate), poly (Ș-methylstyrene ), poly (benzyl methacrylate),
    10 poly (tert-butyl methacrylate), poly (cyclohexyl methacrylate), poly (ethyl methacrylate), poly (hexadecyl methacrylate), poly (hexyl methacrylate), poly (isobutyl methacrylate), poly (tetrahydrofurfuryl methacrylate) ), poly (tetrahydrofurfuryl-co-methacrylate ethyl methacrylate), poly (acrylonitrile-co-acrylate), polyacrylonitrile, polycarbonate (PC), poly (styrene-acrylonitrile), poly (styrene-co-allyl alcohol), poly (styrene-co-chloromethylstyrene),
    15 poly (styrene-co-4-chloromethylstyrene-co-4-methoxymethylstyrene), poly (styrene-co-maleic acid), poly (styrene-co-Ș-methylstyrene), polyacenaphylene, poly (4-bromo styrene), poly ( 4-chloro-styrene), poly (4-tert-butyl styrene), poly (4-vinylbiphenyl), poly (vinylcyclohexane), poly (4-vinylyl phenol), poly (vinyl toluene-co-Ș-methylstyrene), poly (styrene-co-acrylonitrile) (PS -co-AN), poly (styrene-co-allyl alcohol) (PS-co-AA), poly (styrene-co-methyl methacrylate) (PS-co
    20 MMA), polyacrylamide (PAM), poly (4-vinylphenol-co-methacrylate methyl) (P4VP-co-MMA), polyethyleneimine and polyvinyl cinnamate, in at least one organic solvent.
    b. Deposit the composition prepared in step (a) on a substrate,
    C. Heat the substrate obtained in step (b) until the EDOT monomers or oligomers polymerize.
    The method for obtaining transparent conductive layers according to the preceding claim, wherein the solution of step (a) comprises EDOT oligomers.
    [3]
    3. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the oligomers are dimers, trimers, tetramers or mixtures thereof.
    The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the solution of step (a) further comprises thiophene monomers and / or oligomers or thiophene derivatives with formula I, II, III or IV :

     I II III IV
    where R1 and R2 are independently selected from H, methyl, ethyl, phenyl, hydroxyl, thiol, carboxyl, F, Cl, Br, I, Si (R5) 3, OR3, SR3, NHR3, NR3R3, COOR3, CONH2, CONHR3 and 5 CONR3R3, R3-O-R4, amino, R3 (CO) -O-R4, R3 (CO) -NH-R4, R3 (CO) -NR4R4, R3 (CO) -O-NH-R4,
    or C1-20 alkyl unsubstituted or substituted by methyl, ethyl, hydroxyl, amino, thiol, carboxyl, amido, trifluoromethyl, trichloromethyl, or tribromomethyl;
    where R3 and R4 are independently selected from C1-20 alkyl, phenyl, biphenyl;
    where R5 is C1-20 alkyl;
    Where R6 and R7 are independently selected from H, methyl and C2-20 alkyl; Y
    where n is selected from 1 to 4.
    [5]
    5. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the solution of step (a) comprises EDOT dimers.
    [6]
    6. The method for obtaining transparent conductive layers according to any of the
    The preceding claims, wherein the solution of step (a) consists of a solution of dimers, trimers, EDOT tetramers or mixtures thereof, at least one oxidant and a transparent polymer selected from poly (methyl methacrylate) (PMMA ), poly (lauryl methacrylate) (PLMA), poly (butyl methacrylate) (PBMA), poly (methyl methacrylate -co-methacrylic acid, poly (methyl methacrylate-ethyl acrylate), poly (methacrylate
    20-methyl-butyl methacrylate), poly (methyl methacrylate-ethylene co-dimethacrylate), poly (�-methylstyrene), poly (benzyl methacrylate), poly (tert-butyl methacrylate), poly (methacrylate cyclohexyl), poly (ethyl methacrylate), poly (hexadecyl methacrylate), poly (hexyl methacrylate), poly (isobutyl methacrylate), poly (tetrahydrofurfuryl methacrylate), poly (ethyl tetrahydrofurfuryl-co-methacrylate methacrylate ),
    25 poly (acrylonitrile-methyl co-acrylate), polyacrylonitrile, polycarbonate (PC), poly (styrene-coacrylonitrile), poly (styrene-co-allyl alcohol), poly (styrene-co-chloromethylstyrene),

    poly (styrene-co-4-chloromethylstyrene -co-4-methoxymethylstyrene), poly (styrene-co-maleic acid), poly (styrene-co-�-methylstyrene), polyacenaphylene, poly (4-bromo-styrene), poly (4-chlorostyrene) ), poly (4-tert-butyl styrene), poly (4-vinylbiphenyl), poly (vinylcyclohexane), poly (4vinylphenol), poly (vinyltoluene-co-�-methylstyrene), poly (styrene-co-acrylonitrile) (PS- co-AN), poly (styrene-co-allyl alcohol) (PS-co-AA), poly (styrene-co-methacrylate) (PS-co-MMA), polyacrylamide (PAM), poly (4-vinylphenol -methyl methacrylate) (P4VP-co-MMA), polyethyleneimine and polyvinyl cinnamate, in at least one organic solvent.
    [7]
    7. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the oxidant is selected from Cu (ClO4) 2, copper (II) tosylate, copper (II) acetate, FeCl3, iron (III) tosylate ), 3 x H2O HAuCl4 and mixtures thereof.
    [8]
    8. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the oxidant is Cu (ClO4) 2.
    [9]
    9. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the transparent polymer is selected from PMMA, PLMA, PBMA, PS-co-MMA, PC, PS-co-AN, PS-co-AA, PAM, P4VP-co-MMA.
    [10]
    10. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the transparent polymer is PMMA.
    [11]
    eleven. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the organic solvent is selected from among methoxypropyl acetate (MPA), glycol ether, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, diethyl carbonate, propylene carbonate, ethyl acetate, cyclohexanone, cyclopentanone, gamma-butyrolactone, hexanol, tetrahydrofuran, methanol, acetonitrile and mixtures thereof.
    [12]
    12. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the organic solvent is MPA, glycol ether, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate or a mixture thereof.
    [13]
    13. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein step (b) is carried out by rotation coating (spin coating), doctor blade, dip coating (drop-coating), dropcasting, Layer -by-Layer, spray coating, injection printing, screen printing, flexography, or plotter.

    [14]
    14. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein step (b) is carried out by means of rotation coating (spin coating) or doctor blade.
    [15]
    fifteen. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein step (c) is carried out at a temperature between 25 ° C and 220 ° C and for a time between 0.5 and 120 minutes.
    [16]
    16. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein step (c) is carried out at a temperature of between 80 ° C and 140 ° C and for a time of between 1 and 10 minutes.
    [17]
    17. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the substrate is selected from: rigid substrates selected from indium and tin oxide (ITO), fluorine doped tin oxide (FTO), silicon, silicon oxide, glass, quartz, graphene, metals selected from gold, silver, nickel, aluminum; carbon nanotubes, perovskites, gallium nitride, titanium oxide, zinc oxide, nickel oxide; Flexible substrates selected from poly (ethylene terephthalate) (PET), poly (ethylene naphthalate) (PEN), poly (dimethylsiloxane) (PDMS), polycarbonate, poly (methyl methacrylate), polystyrene, polyethylene, cellulose, polychloride vinyl (PVC); and textile fibers selected from polyamide, polyester, acrylic, cotton and carbon fiber.
    [18]
    18. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the substrate is selected from ITO, FTO, glass, perovskites, PET, PEN, cellulose and graphene.
    [19]
    19. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the composition of step (a) further comprises at least one stabilizing agent selected from imidazole, acetylacetonate, monoethanolamine, diethanolamine, triethanolamine, ethylenediaminetetraacetic acid (EDTA) , ethylenediamine, ethylene glycol and polyethylene glycol.
    [20]
    twenty. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein the solution of step (a) further comprises between 0.02 and 5 mg / ml of at least one stabilizing agent selected from trifluoroacetic acid, methanesulfonic acid. , dimethyl sulfoxide (DMSO), ethylene glycol, polyethylene glycol, H3PO4, H2SO4, glycerol, sorbitol and ethanol, with respect to the total volume of the solution.

    [21]
    twenty-one. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein said method further comprises step (d) washing the layer obtained in step (c).
    [22]
    22 The method for obtaining transparent conductive thin layers according to the preceding claim, wherein the washing of step (d) is done with water, isopropanol or MPA.
    [23]
    2. 3. The method for obtaining transparent conductive layers according to any of the preceding claims, wherein said method further comprises step (e) treating the layer obtained in step (c) or in step (d) with at least one strong acid or a solvent
    [24]
    24. The highly transparent conductive layer obtained by the process according to any of the preceding claims.
    [25]
    25. The transparent conductive layer according to the preceding claim, wherein the thickness is between 10 nm and 10 microns.
    [26]
    26. The transparent conductive layer according to any of the two preceding claims, wherein the thickness is between 20 and 250 nm.
    [27]
    27. A composition comprising EDOT monomers and / or oligomers, at least one oxidant and a transparent polymer selected from PMMA, PLMA, PBMA, poly (methyl methacrylate-co-methacrylic acid), poly (methyl methacrylate-co-acrylate ethyl), poly (methyl methacrylate-butyl methacrylate), poly (methyl methacrylate-ethylene codimethacrylate), poly (�-methylstyrene), poly (benzyl methacrylate), poly (tert-butyl methacrylate) , poly (cyclohexyl methacrylate), poly (ethyl methacrylate), poly (hexadecyl methacrylate), poly (hexyl methacrylate), poly (isobutyl methacrylate), poly (tetrahydrofurfuryl methacrylate), poly (tetrahydrofurfuryl-co methacrylate -ethyl methacrylate), poly (acrylonitrile-co-acrylate), polyacrylonitrile, PC, poly (styrene-co-acrylonitrile), poly (styrene-co-allyl alcohol), poly (styrene-co-chloromethylstyrene), poly (styrene-co-4-chloromethylstyrene-co-4-methoxymethylstyrene), poly (styrene-co-maleic acid), poly (est irenoco-�-methylstyrene), polyacenaphylene, poly (4-bromostyrene), poly (4-chlorostyrene), poly (4-tert-butyl styrene), poly (4-vinylbiphenyl), poly (vinylcyclohexane), poly (4-vinylphenol), poly (vinyltoluene-co
    �-methylstyrene), PS-co-AN, PS-co-AA, PS-co-MMA, PAM, P4VP-co-MMA, polyethyleneimine and polyvinyl cinnamate in at least one organic solvent.
    [28]
    28. The composition according to the preceding claim, comprising dimers, trimers, EDOT tetramers or mixtures thereof, at least one oxidant selected from Cu (ClO4) 2, copper (II) tosylate, copper (II) acetate , FeCl3, iron (III) tosylate, HAuCl4 3

    x H2O and mixtures thereof and a transparent polymer selected from PMMA, PLMA, PBMA, PS-co-MMA, PC, PS-co-AN, PS-co-AA, PAM, P4VP-co-MMA in at least an organic solvent selected from MPA, glycol ether, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate or a mixture thereof.
    29. The composition according to any of the two preceding claims, comprising dimers of EDOT, Cu (ClO4) 2 and PMMA in MPA.
    [30]
    30. The composition according to any of the three preceding claims, comprising between 0.5 and 10 mg / ml of EDOT monomers and / or oligomers, between 0.1 and 25 mg / ml of at least one oxidant and between 1, 0 and 70 mg / ml of the transparent polymer in at least one
    10 organic solvent, with respect to the total volume of the composition.
    [31]
    31. The composition according to any of the four preceding claims, comprising between 0.5 and 5 mg / ml of EDOT dimers, between 0.1 and 25 mg / ml of Cu (ClO4) 2 and between 1.0 and 70 mg / ml of PMMA in MPA, with respect to the total volume of the composition.
    [32]
    32. The composition according to any of the five preceding claims, which further comprises thiophene monomers and / or oligomers or thiophene derivatives with formula I, II, III
    or IV:
     I II III IV
    where R1 and R2 are independently selected from H, methyl, ethyl, phenyl, hydroxyl, thiol, carboxyl, F, Cl, Br, I, Si (R5) 3, OR3, SR3, NHR3, NR3R3, COOR3, CONH2, CONHR3 and CONR3R3, R3-O-R4, amino, R3 (CO) -O-R4, R3 (CO) -NH-R4, R3 (CO) -NR4R4, R3 (CO) -O-NH-R4,
    or C1-20 alkyl unsubstituted or substituted by methyl, ethyl, hydroxyl, amino, thiol, carboxyl, amido, trifluoromethyl, trichloromethyl, or tribromomethyl;
    where R3 and R4 are independently selected from C1-20 alkyl, phenyl, biphenyl;
    Where R5 is C1-20 alkyl;

    where R6 and R7 are independently selected from H, methyl and C2-20 alkyl; Y
    where n is selected from 1 to 4.
    [33]
    33. The composition according to any of the six preceding claims, further comprising between 0.02 and 5 mg / ml of at least one stabilizing agent selected from
    5 imidazole, acetylacetonate, monoethanolamine, diethanolamine, triethanolamine, EDTA, ethylenediamine, ethylene glycol and polyethylene glycol.
    [34]
    34. The composition according to any of the preceding seven claims, which further comprises between 0.02 and 5 mg / ml of at least one stabilizing agent selected from trifluoroacetic acid, methanesulfonic acid, DMSO, ethylene glycol, polyethylene glycol, H3PO4,
    10 H2SO4, glycerol, sorbitol and ethanol, with respect to the total volume of the solution.
    [35]
    35. A transparent conductive layer comprising PEDOT forming a network interpenetrated with a transparent polymer selected from PMMA, PBMA, PLMA, PS-co-AN, PS-co-AA, PAM, PS-co-MMA and P4VP-co- MMA
    [36]
    36. The transparent conductive layer according to the preceding claim, wherein the thickness of the layer is between 10 nm and 500 microns or between 20 and 250 nm.
    [37]
    37. Use of the method according to any of claims 1 to 23 or of the transparent conductive layer according to any of claims 24 to 26, 35 or 36 in the manufacture of touch screens, solar cells, photodetectors, inorganic or organic light emitting diodes (LEDs, OLEDs), polymeric capacitors, gas sensors, or as a coating
    20 surface antistatic or in miniaturization of devices by electron beam lithography and photolithography.
    [38]
    38. The use according to the preceding claim, wherein the antistatic coating is used in electronic circuits, windows, papers, photographic films or building materials.
    [39]
    39. Use of the method according to any of claims 1 to 23 for drawing by
    25 lithography, for direct printing, for nanoprinting lithography, UV photolithography, electron beam lithography, soft lithography, screen printing, inkjet printing, plotter, flexography, offset or gravure printing.

    Fig. 1

    Fig 2

    Fig. 3 A
    B

    Fig. 4
    Fig. 5

    Fig. 6
    Fig. 7

    Fig. 8
    Fig. 9

    Fig. 10
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    引用文献:
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