Method for manufacturing a polymer film

Abstract

To provide a method for producing a conductive PEDOT film excellent in conductivity, average roughness, and light transmittance for electronic devices, and to provide the conductive PEDOT film and an application thereof.SOLUTION: A method for producing a PEDOT film comprising: applying a solution comprising an oxidant and a base inhibitor onto a surface of a substrate to form an oxidant coating on at least one surface of the substrate; and exposing the surface of the substrate coated with the oxidant to PEDOT monomer vapor at a polymerization temperature to polymerize, and during the polymerization step, the temperature of the oxidant-coated substrate is kept at a controlled substrate temperature, the controlled substrate temperature being 2 to 40°C lower than the polymerization temperature.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a poly(3,4-ethylenedioxythiophene) (PEDOT) film. The present disclosure further relates to a conductive PEDOT film. The present disclosure further relates to an electronic device including the conductive PEDOT film and the use of the conductive PEDOT film as an antistatic coating or an electrode in / of the electronic device. The present disclosure also relates to a method for manufacturing a polymer film formed from a copolymer, an electronic device including the conductive polymer film, and the use of the conductive polymer film as an antistatic coating or an electrode in / of the electronic device.

Background Art

[0002] Conductive PEDOT films and their copolymer films are used in different fields such as antistatic coatings, perovskite solar cells, organic solar cells, dye-sensitized solar cells, electrochemical transducers, electrochromic devices, electroluminescent devices, thermoelectric devices, smart windows, OLEDs, optoelectronics, and supercapacitors. Conductive PEDOT films can be manufactured, for example, by electrochemical polymerization of PEDOT on a conductive substrate, oxidative chemical vapor deposition (oCVD), or vacuum vapor polymerization (VVPP) techniques. When forming a conductive PEDOT film for an electronic device, its conductivity, low sheet resistance, morphology (average roughness), and light transmittance are important.

Summary of the Invention

[0003] A method for manufacturing a poly(3,4-ethylenedioxythiophene) (PEDOT) film on a substrate is disclosed, which includes a substrate and at least one PEDOT layer on at least one surface of the substrate. The method includes applying a solution containing an oxidizing agent and a base inhibitor on at least one surface of the substrate to form an oxidizing agent coating on at least one surface of the substrate, and subjecting the formed oxidizing agent-coated substrate to a polymerization step by exposing the surface of the oxidizing agent-coated substrate to 3,4-ethylenedioxythiophene (EDOT) monomer vapor at a polymerization temperature, thereby forming a PEDOT layer on the surface of the oxidizing agent-coated substrate. During the polymerization step, the temperature of the oxidizing agent-coated substrate is maintained at a controlled substrate temperature, and the controlled substrate temperature is 2 to 40 °C lower than the polymerization temperature.

[0004] A method for manufacturing a polymer film formed from a copolymer in which one of the monomers is (3,4-ethylenedioxythiophene) (EDOT) on a substrate including a substrate and at least one polymer layer on at least one surface of the substrate is disclosed. The method includes applying a solution containing an oxidizing agent and a base inhibitor on at least one surface of the substrate to form an oxidizing agent coating on at least one surface of the substrate, and subjecting the formed oxidizing agent-coated substrate to a polymerization step by exposing the surface of the oxidizing agent-coated substrate to vapor of at least two different monomers, one of the monomers being an EDOT monomer, at a polymerization temperature, thereby forming a polymer layer on the surface of the oxidizing agent-coated substrate. During the polymerization step, the temperature of the oxidizing agent-coated substrate is maintained at a controlled substrate temperature, and the controlled substrate temperature is 2 to 40 °C lower than the polymerization temperature.

[0005] Furthermore, a conductive PEDOT film is disclosed. The conductive PEDOT film can include a non-conductive substrate and a PEDOT layer having anions from one or more oxidants embedded in the PEDOT layer on the non-conductive substrate, and the conductive PEDOT film has a conductivity of more than 2100 S / cm and a sheet resistance of less than 200 Ω / sq.

[0006] Furthermore, as disclosed in the present disclosure, a conductive PEDOT film obtainable by a method for manufacturing a PEDOT film including a non-conductive substrate and at least one PEDOT layer on at least one surface of the non-conductive substrate is disclosed.

[0007] Furthermore, a conductive polymer film formed from a copolymer, wherein one of the monomers of the copolymer is (3,4-ethylenedioxythiophene) (EDOT), is disclosed. The conductive polymer film can include a non-conductive substrate and a polymer layer film formed from a copolymer having anions from one or more oxidants embedded in the polymer layer on the non-conductive substrate, and the thickness of the conductive polymer film is 10 to 500 nm or 10 to 200 nm.

[0008] Furthermore, a conductive polymer film formed from a copolymer, wherein one of the monomers is (3,4-ethylenedioxythiophene) (EDOT), is disclosed. As disclosed in the present disclosure, the conductive polymer film is obtainable by a method for manufacturing a polymer film including a non-conductive substrate and at least one polymer layer on at least one surface of the non-conductive substrate.

[0009] Furthermore, an electronic device is disclosed. The electronic device can include a conductive PEDOT film or a conductive polymer film formed from a copolymer wherein one of the monomers is EDOT as disclosed in the present disclosure.

[0010] Furthermore, the use of a conductive PEDOT film and a conductive polymer film formed from a copolymer in which one of the monomers is EDOT as disclosed in the present disclosure is disclosed.

[0011] The accompanying drawings are included to provide a further understanding of the embodiments, form a part of this specification, and illustrate various embodiments.

Brief Description of the Drawings

[0012]

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Embodiments for Carrying Out the Invention

[0013] This application relates to a method for manufacturing a poly(3,4-ethylenedioxythiophene) (PEDOT) film comprising a substrate and at least one PEDOT layer on at least one surface of the substrate, the method comprising: a) applying a solution comprising an oxidizing agent and a base inhibitor onto at least one surface of the substrate to form an oxidizing agent coating on at least one surface of the substrate; b) subjecting the oxidizing agent-coated substrate formed in step a) to a polymerization step by exposing the surface of the oxidizing agent-coated substrate to 3,4-ethylenedioxythiophene (EDOT) monomer vapor at a polymerization temperature, thereby forming a PEDOT layer on the surface of the oxidizing agent-coated substrate; comprising: During the polymerization step, the temperature of the oxidizing agent-coated substrate is maintained at a controlled substrate temperature, and the controlled substrate temperature is 2 to 40 °C lower than the polymerization temperature.

[0014] This application also relates to a method for manufacturing a polymer film formed from a copolymer in which one of the monomers is (3,4-ethylenedioxythiophene) (EDOT), the polymer film comprising a substrate and at least one polymer layer formed from a copolymer in which one of the monomers is the EDOT monomer on at least one surface of the substrate, the method comprising: a) applying a solution comprising an oxidizing agent and a base inhibitor onto at least one surface of the substrate to form an oxidizing agent coating on at least one surface of the substrate; a) applying a solution comprising an oxidizing agent and a base inhibitor onto at least one surface of the substrate to form an oxidizing agent coating on at least one surface of the substrate; b) The oxidant-coated substrate formed in step a) is subjected to a polymerization step by exposing the surface of the oxidant-coated substrate to the vapor of at least two different monomers, one of the monomers being an EDOT monomer, at a polymerization temperature, to form a polymer layer on the surface of the oxidant-coated substrate. comprising During the polymerization step, the temperature of the oxidant-coated substrate is maintained at a controlled substrate temperature, and the controlled substrate temperature is 2 to 40 °C lower than the polymerization temperature.

[0015] The expression that the PEDOT layer or the polymer layer is "on" the surface of the substrate in the PEDOT film should be understood in this specification, unless otherwise specified, to mean that the PEDOT layer or the polymer layer is respectively polymerized or formed, or formed to lie on the substrate, or at least partially embedded therein. The substrate can act as a carrier or support structure for the PEDOT layer or the polymer layer. The substrate can be changed, and the material of the substrate can be changed according to the application for which the PEDOT film or the polymer layer is respectively used.

[0016] The expression "film" should be understood in this specification, unless otherwise specified, to refer to a structure having a lateral dimension substantially larger than its thickness. In that sense, the film can be considered a "thin" structure.

[0017] The polymerization temperature is the temperature of the monomer vapor during the polymerization step.

[0018] In one embodiment, the substrate is a non-conductive substrate. The expression that the substrate is "non-conductive" should be understood in this specification, unless otherwise specified, to mean that the substrate has a sheet resistance of 10 MΩ / sq or more.

[0019] The non-conductive substrate may be a substrate such as glass, polymer, paper, cellulose, fabric, cloth, wood, leather, cotton, pottery, composite materials such as cellulose-wood composite materials, glass fiber, Teflon (registered trademark), rubber, quartz, paint, carbon materials and / or non-conductive minerals. The non-conductive polymer substrate may be selected from the group consisting of plastic materials selected from the group consisting of polyester, polyethylene terephthalate (PET), polycarbonate (PC), polyamide (PI), polyester sulfone (PES), polystyrene resin (PS), and amorphous polyester (A-PET or PET-G), and mixtures thereof. The non-conductive substrate may be a flexible non-conductive substrate. The flexible substrate can be used for the production of a flexible PEDOT film that can be bent and folded.

[0020] The oxidizing agent is a substance that induces the polymerization of the monomer and can act as a dopant after the polymerization of the conductive polymer. The embedded anions can remain within the PEDOT structure to act as dopant ions. The conductivity of the PEDOT polymer can be due to the delocalization of electrons or holes during oxidation (doping). The oxidizing agent can be selected from the group consisting of iron(III) p-toluenesulfonate, iron(III) trifluoromethanesulfonate, iron(III) chloride, p-toluenesulfonic acid, iodine, bromine, molybdophosphoric acid, ammonium persulfate, DL-tartaric acid, polyacrylic acid, copper chloride, copper bromide, ferric chloride, naphthalenesulfonic acid, camphorsulfonic acid, iron(III) toluenesulfonate, iron(III) perchlorate, Cu(ClO 4 ) 2 ·6H 2 O, cerium(IV) ammonium nitrate, cerium(IV) sulfate, and mixtures thereof.

[0021] The base inhibitor reduces the activity of the oxidizing agent and decreases the polymerization rate. This may change the conductivity of the deposited polymer. The base inhibitor can be selected from the group consisting of amine compounds and nitrogen atom-containing saturated or unsaturated heterocyclic compounds, such as pyridine-based, imidazole-based, or pyrrole-based compounds, water vapor, glycerol, and glycol derivatives, and mixtures thereof.

[0022] The oxidizing agent solution of the present invention contains an oxidizing agent, a base inhibitor, and a solvent. The solvent can be selected from the group consisting of organic solvents such as n-butanol methyl alcohol, 2-butyl alcohol, ethyl cellosolve, ethyl alcohol, cyclohexane, ethyl acetate, toluene, acetonitrile, and methyl ethyl ketone, and mixtures thereof.

[0023] In one embodiment, the concentration of the oxidizing agent solution is 60 - 500 mM, or 70 - 480 mM, or 120 - 320 mM, or 180 - 240 mM.

[0024] In one embodiment, the PEDOT layer is doped.

[0025] In one embodiment, the polymer layer formed from a copolymer in which one of the monomers is EDOT is doped.

[0026] In one embodiment, this method is carried out by gas-phase polymerization.

[0027] Vapor phase polymerization is a polymerization technique in which only the monomer(s) is / are converted to the gas phase. The VPP method can include the step of coating a substrate with a solution of an oxidizing agent and a base inhibitor, followed by drying to remove traces of the solvent. In one embodiment, the vapor phase polymerization is carried out at atmospheric pressure. Vapor phase polymerization carried out at atmospheric pressure is easy to control. Pressure control is not required, nor are sophisticated devices or vacuum furnaces. This method can also be used for the production of large area films. In one embodiment, the vapor phase polymerization is carried out by a roll-to-roll technique for producing large area films.

[0028] The polymerization temperature affects the properties of the resulting PEDOT film or polymer film formed from the copolymer, such as the polymerization rate, by controlling the evaporation rate of the monomer and / or the mobility of the polymer chains. As the temperature decreases, the concentration of vapor molecules increases. The substrate temperature and the polymerization temperature control the polymerization rate. The polymerization temperature and the substrate temperature affect the properties of the formed PEDOT film, such as conductivity, transparency, sheet resistance, and morphology. The controlled substrate temperature is a factor in controlling the polymerization rate that controls the morphology of the polymer film formed from the PEDOT film or copolymer. The controlled substrate temperature provides a uniform and homogeneous nature to the polymer film formed from the PEDOT film or copolymer.

[0029] In one embodiment, a solution containing an oxidizing agent and a base inhibitor is applied to one surface of the substrate, and the oxidant-coated surface of the substrate is exposed to EDOT monomer vapor at the polymerization temperature to form one PEDOT layer on the surface of the oxidant-coated substrate, thus producing a single layer PEDOT film.

[0030] In one embodiment, a solution containing an oxidizing agent and a base inhibitor is applied to one surface of a substrate, and the oxidant-coated surface of the substrate is exposed to the vapor of at least two different monomers, one of the monomers being EDOT, at a polymerization temperature to form a single polymer layer on the surface of the substrate coated with the oxidizing agent, thus producing a single-layer polymer film.

[0031] The method for manufacturing a multilayer PEDOT film or a multilayer polymer film formed from a copolymer can be carried out by gas-phase polymerization for each layer. The PEDOT film can be formed by depositing PEDOT layers with a washing step sandwiched therebetween. The polymer film formed from a copolymer can be formed by depositing polymer layers with a washing step sandwiched therebetween.

[0032] In one embodiment, a method for manufacturing a PEDOT film is c) applying the solution containing the oxidizing agent and the base inhibitor onto at least one surface of the PEDOT layer formed in step b) to form an oxidant coating on the at least one surface of the PEDOT layer; d) subjecting the oxidant-coated PEDOT layer formed in step c) to a polymerization step by exposing the surface of the oxidant-coated PEDOT layer to 3,4-ethylenedioxythiophene (EDOT) monomer vapor at a polymerization temperature to form a subsequent PEDOT layer on the surface of the oxidant-coated PEDOT layer; comprising During the polymerization step, the temperature of the oxidant-coated PEDOT film is maintained at a controlled substrate temperature, and the controlled substrate temperature is 2 to 40 °C lower than the polymerization temperature.

[0033] In one embodiment, A method for manufacturing a polymer film formed from a copolymer in which one of the monomers is EDOT is c) Applying a solution containing an oxidizing agent and a base inhibitor onto at least one surface of the substrate to form an oxidizing agent coating on at least one surface of the substrate; d) Subjecting the oxidizing agent-coated substrate formed in step a) to a polymerization step by exposing the surface of the oxidizing agent-coated substrate to the vapor of at least two different monomers, one of the monomers being an EDOT monomer, to form a polymer layer on the surface of the oxidizing agent-coated substrate; comprising; During the polymerization step, the temperature of the oxidizing agent-coated substrate is maintained at a controlled substrate temperature, and the controlled substrate temperature is 2 to 40 °C lower than the polymerization temperature.

[0034] The vapor of at least two different monomers comprises or consists of the vapor of at least one additional monomer selected from the group consisting of 3,4-ethylenedioxythiophene (EDOT) and azulene, pyrrole, aniline, thiophene, phenylene furan, ethylene, tetrafluoroethylene, vinyl chloride, propylene, methyl methacrylate, methyl acrylate, vinyl acetate, ethylene vinyl acetate, styrene, 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), chloroprene (2-chloro-1,3-butadiene), and isobutylene (methylpropylene glycol), polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), polyolefin elastomer (POE): polyisobutylene (PIB), ethylene propylene rubber (EPR), ethylene propylene glycol diene monomer (M-class) rubber (EPDM rubber), or any type of polymer manufactured as a monomer, cyclic olefin, vinyl ether, allyl ether, vinyl ester, and allyl ester.

[0035] In the VPP method, a catalyst can be used in the polymerization. In one embodiment, in step b) and / or d), at least one catalyst and / or at least one catalyst additive is used. In one embodiment, at least one catalyst and / or catalyst additive is, hereinafter, a Ziegler-Natta catalyst, AlCl 3 , cerium ammonium nitrate, cerium tosylate, Fe(III) tosylate is also used as an oxidant, pyridine, p-toluenesulfonic acid (p-TSA), diethylene glycol (DEG), molybdophosphoric acid, molybdo-2-vanadophosphoric acid, poly(styrenesulfonate) (PSS), Fe(III) alkylbenzenesulfonate, iodine, bromine, pyrocatechol violet, benzenesulfonic acid (BSA), p-toluenesulfonic acid, dodecylbenzenesulfonic acid (DBSA), butylbenzenesulfonic acid (BBSA), glycerol, trialkylaluminum-free modified methylaluminoxane. TEMPO ((2,6,6-tetramethylpiperidin-1-yl)oxyl or (2,6,6-tetramethylpiperidin-1-yl)oxidanil), peroxides, Ti, V, Zr, W, Co and aluminum (Mg or Li) alkyl TiCl 4 compounds, titanium supported on a magnesium salt, aluminum alkyl RAlCl 2 including VOCl 3 , VCl 4 or VO(OR) 3 , a transition metal (Zr, Ti or Hf) sandwiched between cyclopentadienyl rings, Cr, Mo, Co or Ni supported on alumina, silica, zirconia and activated carbon, bis(arene)CrO, Cr / SiO supported on chromium oxide 2 , Zr / Al 2 O 3 and Ti / MgO, and is selected from silica, alumina or titania.

[0036] In one embodiment, the temperature of the oxidant-coated substrate is maintained at a controlled substrate temperature during the polymerization step, and the controlled substrate temperature is 2 to 30 °C lower than the polymerization temperature.

[0037] In one embodiment, the temperature of the oxidant-coated substrate is maintained at a controlled substrate temperature during the polymerization step, and the controlled substrate temperature is 2 to 25 °C, or 2 to 22 °C, or 2 to 20 °C, or 2 to 15 °C, or 3 to 25 °C, or 3 to 22 °C lower than the polymerization temperature.

[0038] In one embodiment, the temperature of the oxidant-coated substrate is maintained at a controlled substrate temperature during the polymerization step, and the controlled substrate temperature is 3 to 20 °C lower than the polymerization temperature.

[0039] In one embodiment, the temperature of the oxidant-coated substrate is maintained at a controlled substrate temperature during the polymerization step, and the controlled substrate temperature is 3 to 15 °C lower than the polymerization temperature.

[0040] In one embodiment, the temperature of the oxidant-coated substrate is maintained at a controlled substrate temperature during the polymerization step, and the controlled substrate temperature is 5 to 20 °C lower than the polymerization temperature.

[0041] In one embodiment, the temperature of the oxidant-coated substrate is maintained at a controlled substrate temperature during the polymerization step, and the controlled substrate temperature is 5 to 15 °C lower than the polymerization temperature.

[0042] In one embodiment, the temperature of the oxidant-coated substrate is maintained at a controlled substrate temperature during the polymerization step, and the controlled substrate temperature is 8 to 12 °C lower than the polymerization temperature.

[0043] In one embodiment, a solution containing an oxidizing agent and a base inhibitor is applied onto the surface of one PEDOT layer formed in step b), i.e., one layer of PEDOT film, and the surface of the PEDOT layer coated with the oxidizing agent is exposed to EDOT monomer vapor at the polymerization temperature to form a second PEDOT layer on the surface of the PEDOT layer coated with the oxidizing agent, thus manufacturing a two-layer PEDOT film.

[0044] In one embodiment, this method includes repeating step c) and step d) at least once to manufacture a multilayer PEDOT film.

[0045] In one embodiment, a solution containing an oxidizing agent and a base inhibitor is applied onto the surface of one polymer layer formed from the copolymer formed in step b), i.e., one layer of polymer film, and the surface of the polymer layer coated with the oxidizing agent is exposed to the vapor of at least two different monomers, one of the monomers being the EDOT monomer, at the polymerization temperature to form a second polymer layer on the surface of the polymer layer coated with the oxidizing agent, thus manufacturing a two-layer polymer film.

[0046] In one embodiment, this method includes repeating step c) and step d) at least once to manufacture a multilayer polymer film.

[0047] During the polymerization step, the substrate temperature and the polymerization temperature are controlled separately. In one embodiment, the polymerization temperature is 55 - 95°C and the controlled substrate temperature is 40 - 70°C. In one embodiment, the polymerization temperature is 60 - 85°C and the controlled substrate temperature is 45 - 70°C. In one embodiment, the polymerization temperature is 65 - 80°C and the controlled substrate temperature is 55 - 70°C, or the polymerization temperature is 67 - 77°C and the controlled substrate temperature is 56 - 66°C, or the polymerization temperature is 72 - 77°C and the controlled substrate temperature is 61 - 66°C. High temperatures are not required in the gas-phase polymerization of the present invention.

[0048] In one embodiment, the process is implemented as a batch process. That is, one film can be prepared at a time, for example, in a cell or reaction chamber, in which various method steps can be implemented. In one embodiment, this method is implemented as a continuous process. That is, the substrate can move from one method step to another without interruption. For example, first, coat with an oxidizing agent and then expose to the vapor of the monomer. In a continuous process, multiple films can be prepared simultaneously.

[0049] In one embodiment, the temperature of the oxidizing agent-coated substrate and / or the oxidizing agent-coated PEDOT film is maintained at a controlled substrate temperature substantially throughout the entire polymerization step.

[0050] In one embodiment, the polymerization step is subdivided into successive treatment periods to adjust the polymerization rate.

[0051] In one embodiment, the polymerization step includes two successive treatment periods, and the temperature of the oxidizing agent-coated substrate and / or the oxidizing agent-coated PEDOT film is maintained at a controlled substrate temperature throughout one of the treatment periods.

[0052] In one embodiment, the polymerization step includes two successive treatment periods, and the temperature of the oxidizing agent-coated substrate and / or the polymer film formed from the oxidizing agent-coated copolymer is maintained at a controlled substrate temperature throughout one of the treatment periods.

[0053] In one embodiment, the polymerization step includes three successive treatment periods, and the temperature of the oxidizing agent-coated substrate and / or the oxidizing agent-coated PEDOT film is maintained at a controlled substrate temperature throughout the middle treatment period.

[0054] In one embodiment, the polymerization step includes three consecutive processing periods, and the temperature of the polymer film formed from the oxidant-coated substrate and / or the oxidant-coated copolymer is maintained at a controlled substrate temperature throughout the intermediate processing period.

[0055] During the processing period when the substrate is not maintained at the controlled substrate temperature, the substrate temperature can change towards the ambient temperature, i.e., the polymerization temperature. If the substrate temperature is higher than the polymerization temperature, the substrate temperature is cooled towards the polymerization temperature, or if the substrate temperature is lower than the polymerization temperature at the start of such a processing period, the substrate temperature is heated towards the polymerization temperature.

[0056] In one embodiment, the method of the present application includes a step of cleaning the substrate before step a). In one embodiment, the substrate is cleaned by ultrasonic treatment using a solvent. The solvent can be selected from the group consisting of organic solvents such as acetone and EtOH, water, and mixtures thereof. The cleaning step may be repeated using the same solvent or different solvents.

[0057] In one embodiment, the cleaned substrate is immersed in a hot solution of H 2 O:NH 4 OH (25%):H 2 O 2 (30%) to remove organic impurities remaining on the surface, and subsequently, oxygen plasma treatment is performed.

[0058] In one embodiment, the oxidant solution is spin-coated onto at least one surface of the substrate in step a). In one embodiment, the oxidant solution is spin-coated onto at least one surface of at least one surface of the PEDOT layer formed in step c). In one embodiment, the oxidant solution is spin-coated onto at least one surface of at least one surface of the polymer layer formed from the copolymer formed in step c). In one embodiment, the oxidant solution is spin-coated onto the substrate at 800 - 3500 rpm. In one embodiment, the oxidant solution is spin-coated onto the substrate over a period of 5 - 30 seconds.

[0059] In one embodiment, the method includes, prior to step b), the steps of washing, drying, and / or heating the oxidant-coated non-conductive substrate from step a). In one embodiment, the method includes, prior to step d), the steps of washing, drying, and / or heating the PEDOT film from step c). In one embodiment, the method includes, prior to step d), the steps of washing, drying, and / or heating the polymer film formed from the copolymer from step c). In one embodiment, the oxidant-coated non-conductive substrate is heated at 80 - 100 °C. In one embodiment, the PEDOT film from step c) is heated at 80 - 100 °C. In one embodiment, the polymer film formed from the copolymer from step c) is heated at 80 - 100 °C.

[0060] In one embodiment, the method includes annealing the PEDOT film at a temperature of 50 - 100°C after polymerization. In one embodiment, the method includes annealing the polymer film formed from the copolymer at a temperature of 50 - 100°C after polymerization. The PEDOT film or the polymer film can be annealed to avoid stress rupture of the film during the washing step. Since unconsumed oxidants and monomer traces may reduce conductivity, the annealed PEDOT film or polymer film can be washed to remove unreacted oxidants, monomers, and any other impurities. In one embodiment, the annealed PEDOT film is completely immersion-rinsed in ethanol and subsequently washed with MeCN. In one embodiment, the annealed PEDOT film is dried. In one embodiment, the annealed PEDOT film is dried under a stream of dry nitrogen gas. In one embodiment, the polymer film formed from the annealed copolymer is completely immersion-rinsed in ethanol and subsequently washed with MeCN. In one embodiment, the polymer film formed from the annealed copolymer is dried. In one embodiment, the polymer film formed from the annealed copolymer is dried under a stream of dry nitrogen gas.

[0061] In one embodiment, the method includes washing the PEDOT polymer film received from step b) before step c). In one embodiment, the PEDOT polymer film is washed by annealing the PEDOT film at a temperature of 50 - 100°C after polymerization. In one embodiment, the annealed PEDOT film is completely immersion-rinsed in ethanol and subsequently washed with MeCN. In one embodiment, the annealed PEDOT film is dried. In one embodiment, the annealed PEDOT film is dried under a stream of dry nitrogen gas.

[0062] In one embodiment, this method includes, before step c), a step of washing the polymer film formed from the copolymer received from step b). In one embodiment, the polymer film formed from the copolymer is washed by annealing the polymer film at a temperature of 50 to 100 °C after polymerization. In one embodiment, the polymer film formed from the annealed copolymer is completely immersed and rinsed in ethanol, and then washed with MeCN. In one embodiment, the polymer film formed from the annealed copolymer is dried. In one embodiment, the polymer film formed from the annealed copolymer is dried under a dry nitrogen gas stream.

[0063] The polymerization time may affect properties such as the sheet resistance and roughness average of the formed PEDOT film or the polymer film formed from the copolymer.

[0064] In one embodiment, the duration of the polymerization step is 1 to 20 minutes. In one embodiment, the duration of the polymerization step is 1 to 10 minutes. In one embodiment, the duration of the polymerization step is 2 to 8 minutes. The polymerization step is fast.

[0065] In one embodiment, the duration of the treatment period of the polymerization step, during which the temperature of the non-conductive substrate coated with the oxidant and / or the PEDOT film coated with the oxidant is maintained at a controlled substrate temperature, is 20 to 80% of the duration of the polymerization step.

[0066] In one embodiment, the duration of the treatment period of the polymerization step, during which the temperature of the non-conductive substrate coated with the oxidant and / or the polymer film formed from the copolymer coated with the oxidant is maintained at a controlled substrate temperature, is 20 to 80% of the duration of the polymerization step.

[0067] In one embodiment, the duration of the treatment period of the polymerization step, during which the temperature of the non-conductive substrate coated with an oxidizing agent and / or the PEDOT film coated with an oxidizing agent is maintained at a controlled substrate temperature, is 30% to 60% of the duration of the polymerization step. In one embodiment, the duration of the treatment period of the polymerization step, during which the temperature of the non-conductive substrate coated with an oxidizing agent and / or the PEDOT film coated with an oxidizing agent is maintained at a controlled substrate temperature, is 35% to 40% of the duration of the polymerization step.

[0068] In one embodiment, the duration of the treatment period of the polymerization step, during which the temperature of the non-conductive substrate coated with an oxidizing agent and / or the polymer film formed from the copolymer coated with an oxidizing agent is maintained at a controlled substrate temperature, is 30% to 60% of the duration of the polymerization step. In one embodiment, the duration of the treatment period of the polymerization step, during which the temperature of the non-conductive substrate coated with an oxidizing agent and / or the polymer film formed from the copolymer coated with an oxidizing agent is maintained at a controlled substrate temperature, is 35% to 40% of the duration of the polymerization step.

[0069] In one embodiment, the non-conductive substrate is glass. In one embodiment, the non-conductive substrate is polyethylene terephthalate (PET).

[0070] In one embodiment, the oxidizing agent is iron(III) p-toluenesulfonate hexahydrate (FETOS).

[0071] In one embodiment, the oxidizing agent is iron(III) trifluoromethanesulfonate Fe(OTF) 3 is.

[0072] In one embodiment, the base inhibitor is pyridine.

[0073] In one embodiment, the oxidizing agent solution contains or consists of FETOS and pyridine in n-butanol. In one embodiment, the oxidizing agent solution contains the oxidizing agent at a ratio of 5 wt% to 50 wt% based on the volume of the oxidizing agent solution.

[0074] This application further relates to a conductive PEDOT film, which comprises a non-conductive substrate and a PEDOT layer having anions from one or more oxidants embedded in the PEDOT layer on the non-conductive substrate, and this conductive PEDOT film has a conductivity of more than 2100 S / cm and a sheet resistance of less than 200 Ω / □.

[0075] This application further relates to a conductive PEDOT film obtainable by the method of this application, the above conductive PEDOT film comprises a non-conductive substrate and a conductive PEDOT layer having anions from one or more oxidants embedded in the PEDOT layer on the non-conductive substrate, and the above conductive PEDOT film has a conductivity of more than 2100 S / cm and a sheet resistance of less than 200 Ω / □.

[0076] In one embodiment, the conductive PEDOT film has a sheet resistance of less than 250 Ω / □. In one embodiment, the conductive PEDOT film has a sheet resistance of less than 240 Ω / □.

[0077] In one embodiment, the conductive PEDOT film has a conductivity of more than 3200 S / cm and a sheet resistance of less than 21 Ω / □. In one embodiment, the conductive PEDOT film has a conductivity of more than 3200 S / cm and a sheet resistance of 12 Ω / □.

[0078] The sheet resistance (r sheet ) of the PEDOT film can be calculated using the Van der Pauw method. The resistivity (r) of the film is obtained by multiplying the sheet resistance by the film thickness (d) according to the following formula (1): r = r sheet d (1)

[0079] The conductivity (s) of the film is obtained according to the following formula (2): s = 1 / r (2)

[0080] CV and EIS techniques can be used to evaluate electrochemical properties. The charge (Q) is calculated by integrating the cyclic voltammogram in the potential range of -0.25 to 0.75 V with Origin software. This is further processed using the following equation to obtain the capacitance value. Areal capacitance: C A =Q / (ΔV*A) (3) Volume capacitance: C V =Q / (ΔV*V) (4) Here, "ΔV" is the potential window, "A" is the area, and "V" is the volume of the working electrode.

[0081] In one embodiment, the conductive PEDOT film includes 1 to 20 PEDOT layers on a non-conductive substrate. In one embodiment, the conductive PEDOT film includes 1 to 15 PEDOT layers on a non-conductive substrate. In one embodiment, the conductive PEDOT film includes 1 to 10 PEDOT layers on a non-conductive substrate.

[0082] In one embodiment, the average roughness of the conductive PEDOT film is less than 3.5 nm.

[0083] The average roughness value of the PEDOT film is obtained from the AFM image using WSXM software. The average roughness (R a ) is the average (absolute value) of the difference between the average height of the sample and the height of each individual point. This number varies depending on the range of the interval. It indicates how uniform or rough the PEDOT film is.

[0084] In one embodiment, the % transmittance of the conductive PEDOT film at 550 nm is greater than 30%T. In one embodiment, the % transmittance of the conductive PEDOT film is greater than 80%T.

[0085] The UV-Vis spectrum can be recorded using an Agilent 8453 spectrophotometer. The % transmittance (%T) is calculated from the absorbance data using the following equation (5). (%T)=(10^(Abs))*100 (5)

[0086] In one embodiment, the non-conductive substrate of the PEDOT film is glass. In one embodiment, the non-conductive substrate of the PEDOT film is polyethylene terephthalate (PET).

[0087] In one embodiment, the PEDOT layer has anions from iron(III) p-toluenesulfonate hexahydrate (FETOS) embedded in the PEDOT layer on the non-conductive substrate.

[0088] The thickness of the conductive PEDOT film can be designed according to the characteristics of the conductive PEDOT film, particularly conductivity, resistance, average roughness or transmittance, or a combination of these characteristics. In one embodiment, the thickness of the PEDOT film is 10 to 500 nm, or 10 to 300 nm, or 20 to 200 nm.

[0089] This application further relates to a conductive polymer film formed from a copolymer in which one of the monomers is (3,4-ethylenedioxythiophene) (EDOT). This conductive polymer film includes a non-conductive substrate and a polymer layer formed from a copolymer in which one of the monomers is EDOT, the polymer layer having anions from one or more oxidants embedded in the polymer layer formed from the copolymer on the non-conductive substrate, and the thickness of the conductive polymer film is 10 to 500 nm or 10 to 200 nm.

[0090] In one embodiment, the transmittance of the film at 550 nm is 10 to 95%, or 20 to 85%, or 30 to 75%.

[0091] In one embodiment, the areal capacitance of the film is 0 to 10 mF / cm 2 , or 0.01 to 9 mF / cm 2 , or 0.05 to 8 mF / cm 2 , or 0.2 to 7 mF / cm 2 , or 1 to 5 mF / cm 2 , or 2 to 4 mF / cm 2It is. In one embodiment, the areal capacitance of the film is 0 to 25 mF / cm², 2 or 0.01 to 15 mF / cm², 2 or 0.05 to 10 mF / cm², 2 or 0.2 to 7 mF / cm², 2 or 1 to 5 mF / cm², 2 or 2 to 4 mF / cm². 2

[0092] In one embodiment, the volumetric capacitance of the film is 200 to 2000 F / cm³, 3 or 250 to 1500 F / cm³, 3 or 300 to 1200 F / cm³, 3 or 500 to 1000 F / cm³, 3 or 600 to 800 F / cm³. 3 In one embodiment, the volumetric capacitance of the film is 5000 to 18000 F / cm³, 3 or 6000 to 17500 F / cm³, 3 or 7000 to 17000 F / cm³. 3

[0093] In one embodiment, the conductivity of the film is 0 to 3 S / cm, or 0.01 to 2 S / cm, or 0.05 to 1.5 S / cm, or 0.1 to 1.0 S / cm, or 0.3 to 0.8 S / cm, or 0.4 to 0.6 S / cm. The conductivity can be measured before or after washing the film. The conductivity value after washing can be higher or lower than that before the washing step. When the polymerization temperature is low, the conductivity is lower before the washing step. When the polymerization temperature is high, the conductivity becomes lower after the washing step.

[0094] Using a Jandel model RM3000+ equipped with a cylindrical four-probe head, the sheet resistance (r) of the PEDOT copolymer film sheet ​​)The value was obtained. In one embodiment, the sheet resistance of the film is 1 to 80 MΩ / sq, or 2 to 70 MΩ / sq, or 5 to 50 MΩ / sq, or 10 to 40 MΩ / sq, or 15 to 30 MΩ / sq. In one embodiment, the sheet resistance of the film is 0.01 to 2 MΩ / sq, or 0.05 to 1.5 MΩ / sq, or 0.08 to 1.1 MΩ / sq, or 0.2 to 1.1 MΩ / sq, or 0.6 to 1 MΩ / sq. The sheet resistance may be measured before or after cleaning the film. The sheet resistance value after cleaning may be higher or lower than that before the cleaning step.

[0095] The present invention further relates to a conductive polymer film formed from a copolymer, wherein one of the monomers of the copolymer is (3,4-ethylenedioxythiophene) (EDOT) obtainable by the method of the present application, a non-conductive substrate, and a polymer layer formed from a copolymer in which one of the monomers is EDOT, the polymer layer having anions from one or more oxidizing agents embedded in the polymer layer formed from the copolymer on the non-conductive substrate, and the thickness of the conductive polymer film is 10 to 500 nm or 10 to 200 nm.

[0096] In one embodiment, a conductive polymer film formed from a copolymer in which one of the monomers is the EDOT according to any one of claims 34 to 35 includes 1 to 20 or 1 to 15 polymer layers on a non-conductive substrate.

[0097] In one embodiment, the conductive polymer film is formed from EDOT and azulene. In one embodiment, the conductive polymer film is formed from EDOT and pyrrole. In one embodiment, the conductive polymer film is formed from EDOT and thiophene. In one embodiment, the conductive polymer film is formed from EDOT and phenylene. The conductive polymer film can also be formed from EDOT and at least one monomer selected from the group consisting of azulene, pyrrole, aniline, thiophene, and phenylene.

[0098] This application further relates to an electronic device comprising the conductive PEDOT film of this application.

[0099] This application further relates to an electronic device comprising a conductive polymer film formed from the copolymer of this application.

[0100] In one embodiment, the electronic device is a display, a flat panel display, an optoelectronic device such as an organic light emitting diode (OLED), an organic solar cell, a dye-sensitized solar cell, a perovskite solar cell, a smart window, a fuel cell, an organic electrochemical transistor, an electrochemical transducer, an electrochromic device, an electroluminescent device, an electroluminescent display, an organic capacitor, a supercapacitor, a sensor, a biosensor, an energy harvesting device, an antistatic material, a photovoltaic device, a storage device or a thermoelectric device. In one embodiment, the electronic device is an optoelectronic device. In one embodiment, the electronic device is a transparent electrode. In one embodiment, the electronic device is a supercapacitor.

[0101] This application further relates to the use of the conductive PEDOT film of this application as an antistatic coating or electrode in / on an electronic device.

[0102] This application further relates to the use of the conductive polymer film formed from the copolymer of this application as an antistatic coating or electrode in / on an electronic device.

[0103] The method of the present application has additional utility in that it is simple, low-cost, and rapid for atmospheric pressure-controlled polymerization. Further, the method of the present application has additional utility in manufacturing conductive polymer films formed from thin multilayer PEDOT films or copolymers on a nanometer scale. Further, this method can be used on a large surface area and is not limited to conductive substrates. The conductive polymer film formed from the PEDOT film or copolymer of the present application has additional utility in that it is very uniform, homogeneous, smooth, and flexible. Further, the conductive polymer film formed from the PEDOT film or copolymer of the present application has additional utility in that it has high conductivity and transmittance.

Examples

[0104] Next, various embodiments are referred to in detail, and an example thereof is shown in the accompanying drawings.

[0105] The following description discloses several detailed embodiments so that those skilled in the art can utilize the embodiments based on the present disclosure. Not all steps or features of the embodiments are discussed in detail, and many of the steps or features will be apparent to those skilled in the art based on this specification.

[0106] For the sake of brevity, in the following exemplary embodiments, when components are repeated, the item numbers are retained.

[0107] Figure 1 shows a vapor phase polymerization cell for carrying out vapor phase polymerization. The polymerization cell 1 has a stand 3 for a substrate 4 and a metal block 5. A thermostatic bath 7 is attached to the polymerization cell 1 to keep the temperature of the monomer vapor 6 at the polymerization temperature. A thermostatic bath 8 is attached to the metal block 5 to keep the temperature of the substrate 4 at a controlled substrate temperature. The polymerization cell 1 includes a lid 2 used to close the polymerization cell 1.

[0108] Figures 6 and 7 show the setup for a continuous VPP process for a flexible substrate (Figure 6) and a rigid substrate (Figure 7) according to one embodiment described in this application. A solution containing oxidant 10 is deposited on substrate 4 by roll-to-roll technology, and then oxidant 11 is dried and preheated in a furnace or using heater 12. In the next step, substrate 4 covered with oxidant is exposed to monomer vapor in polymerization chamber or cell 1. The speed of the roller determines the time the substrate spends in the chamber. The temperature of the substrate or deposition surface is controlled by heater / temperature controller 14. Next, the film is annealed 15, followed by washing the solvent 16. Finally, the film is dried (with nitrogen gas) 17 to obtain a substrate covered with film 18.

[0109] Figure 8 shows a scaled-up VPP cell for performing VPP according to one embodiment described in this application. Polymerization cell 1 includes substrate 4 and heater / temperature controller 14 for the substrate. Heating coil 19 is used to vaporize the monomer in the cell and heat it to the desired polymerization temperature. The cell further includes vapor homogenizer 20 and adjustable lead 2 for closing polymerization cell 1. The homogenizer distributes the vapor homogeneously on the surface of substrate 4. The position such as the height of substrate 4 in the polymerization cell can be adjusted based on the substrate size and cell size. The height can be controlled in the VPP cell by raising and lowering heater / temperature controller 14.

[0110] (Example 1: Preparation of PEDOT Film) Glass slides (substrates) (37.5 mm × 25 mm) were each ultrasonically treated and washed with acetone, water, and EtOH for 5 minutes. The washed substrates were placed in H with a volume ratio of 5:1:1 2 O:NH 4 OH (25%):H 2 O 2It was immersed in a high-temperature solution (80 °C) of (30%) for 5 minutes to remove organic impurities remaining on the surface, and then subjected to oxygen plasma treatment for 5 minutes. 60 μL of the oxidant solution was spin-coated onto the substrate at 1450 rpm for 20 seconds. The substrate coated with the oxidant was dried on a hot plate at 90 °C for 90 seconds. The dried substrate was transferred to Cell 1 containing EDOT monomer 6 preheated at 75 °C such that the coated surface faced the vapor. Polymerization was carried out in three different steps over 4 minutes. For the first 90 seconds, Cell 1 was covered with a glass lid 2. Thereafter, the cover of Cell 1 was removed, and for the next 90 seconds, the substrate temperature was maintained at 65 °C by a heated metal block 5. The metal block 5 was removed, and Cell 1 was covered with a glass lid 2 for 60 seconds. Annealing of the film was carried out after polymerization on a hot plate at 90 °C for 90 seconds. After annealing, the film was cooled to room temperature, rinsed thoroughly in ethanol and then in MeCN to remove unreacted oxidant, monomer and any other impurities. Washing was performed to remove traces of unconsumed oxidant and monomer. If not washed, it may reduce the conductance. After washing, the film was dried under a stream of dry nitrogen gas. This procedure was repeated from the step of spin-coating to prepare 1 to 6 layers of PEDOT (1L to 6L of PEDOT) on the glass substrate 4. The temperatures of Cell 1 and the metal block 5 were controlled by thermostats 7, 5.

[0111] The amount of the oxidant solution can vary between 50 and 120 μL. The amount of the oxidant solution can be changed according to the size of the substrate.

[0112] The sheet resistance and surface morphology of the PEDOT film were monitored by changing the parameters of the VPP method. The remaining parameters of this method were kept constant while monitoring one specific parameter at a time. Polymerization was carried out by monitoring the VPP cell temperature, keeping the temperature in Cell 1, which is the polymerization temperature, at 55 °C, 65 °C, 75 °C, and 85 °C, and using polymerization times of 2 minutes, 4 minutes, 6 minutes, and 8 minutes to prepare the PEDOT film. Although the VPP cell temperature and polymerization time were monitored, the substrate temperature was not controlled. The PEDOT film was prepared at different substrate temperatures from 45 °C to 75 °C. The temperature of the metal block 5 was controlled to change the substrate temperature. Annealing of the PEDOT film was carried out at 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, and 110 °C.

[0113] (Characteristic Evaluation) Raman spectra (785 nm excitation) were recorded using a Qontor inVia Raman microscope manufactured by Renishaw. UV-Vis-NIR measurements were recorded using an Agilent 8453 (up to 1000 nm maximum) and a Cary 5E spectrophotometer (VARIAN) (up to 2400 nm maximum) (background correction was performed using an uncoated microscope glass slide). Using the Van der Pauw method, the sheet resistance (r sheet ) of 1L to 6L of PEDOT was calculated. The resistance value was recorded as the average of three measurements using a four-point probe (a square with side a = 2.2 mm) and a Keithley multimeter (model 2000). The resistivity (r) and conductivity (s) of the film were calculated from Equations (1) and (2).

[0114] AFM measurements were performed at room temperature using a Veeco diCaliber scanning probe microscope operating in tapping mode. All AFM images were recorded using a Bruker TESP-MT probe (resonant frequency 320 kHz, spring constant 42 N / m, length 125 μm, width 30 μm, cantilever specifications: 0.01 - 0.025 Ωcm antimony (n)-doped silicon, thickness 4 μm, tip specifications: height 10 - 15 μm, radius 8 nm). The average roughness (root mean square roughness (R a )) of the PEDOT film was determined using WSXM software.

[0115] CV and EIS techniques were used to determine the electrochemical properties. CV measurements were performed in a conventional three-electrode configuration using 0.1 M TBA-BF 4 / MeCN. The VPP-prepared PEDOT films on glass slides covered with different numbers of PEDOT layers were used as the working electrode. The area of the working electrode was 1.13 cm 2 . An Ag / AgCl wire and a platinum wire were used as the reference electrode and counter electrode, respectively. The Ag / AgCl reference electrode was calibrated before and after the electrochemical measurements using the ferrocene redox couple (E 1 / 2 (Fe / Fe + ) = 0.47 V). Cyclic voltammograms were recorded using a Metrohm Autolab potentiostat PGSTAT101 for 1 L - 6 L of PEDOT in the potential range of -0.25 V to 0.75 V at a scan rate of 100 mV / s. The charge (Q) was calculated by integrating the cyclic voltammogram in the potential range of -0.25 to 0.75 V using Origin software. This was further processed using equations (3) and (4) to obtain the capacitance value.

[0116] (Results) Table 1 shows the effect of polymerization temperature on the sheet resistance and root mean square roughness of the PEDOT film.

[0117]

Table 1

[0118] Table 2 shows the influence of the substrate temperature on the sheet resistance and the average roughness of the PEDOT film.

[0119]

Table 2

[0120] The polymerization temperature is a factor that affects the properties of the resulting PEDOT film, such as the polymerization rate, by controlling the evaporation rate of the monomer (reactant), the mobility of the polymer chains, the conductivity, and the morphology. The average roughness (R a ) of the PEDOT film increased with the increase in the temperature of the VPP cell 1 (Table 1). This increase in the average roughness is due to the high-concentration vapor at high temperature forcing the condensation of the vapor on the surface of the substrate. The prepared PEDOT film was very uniform and homogeneous.

[0121] The average roughness of the PEDOT film decreased as the substrate temperature increased (Table 2). This phenomenon is because the monomer vapor condenses rapidly at low temperature, resulting in a decrease in the film uniformity. As the temperature increases, the condensation rate decreases, leading to more uniform film formation. The same behavior also explains the decrease in the sheet resistance of the PEDOT film as the substrate temperature increases up to 65°C. The sheet resistance increased for the film prepared at 75°C because the deposition of the monomer vapor was less due to the high substrate temperature.

[0122] Table 3 shows the influence of the polymerization time on the sheet resistance and the average roughness of the PEDOT film.

[0123]

Table 3

[0124] PEDOT films were prepared with different polymerization times, namely 2 minutes, 4 minutes, 6 minutes, and 8 minutes. The PEDOT film prepared during 6 minutes had the smallest average roughness value, and the PEDOT film prepared with a polymerization time of 4 minutes had the lowest sheet resistance (Table 3). The sheet resistance decreased after annealing. Films annealed at 60 °C, 70 °C, 80 °C, and 90 °C all showed similar sheet resistances. Since the sheet resistance decreases within the annealing temperature range of 60 °C to 90 °C, the completion of the curing and polymerization processes is guaranteed.

[0125] (Characterization of Multilayer PEDOT Films) Figure 2 shows the Raman spectrum of a 6-layer PEDOT film. Bands at 577, 699, 989, 1095, 1255, 1367, 1415, and 1530 cm -1 are assigned to ethylene oxide ring deformation, symmetric C-S-C deformation, ethylene oxide ring deformation, C-O-C deformation, C α -C α’ inter-ring stretching, C β -C β’ stretching, symmetric C α =C β (-O) stretching, and C α =C β stretching, respectively.

[0126] In Figure 3, 1L shows the AFM image of a single layer of PEDOT, 2L shows the AFM image of two layers of PEDOT, 3L shows the AFM image of three layers of PEDOT, 4L shows the AFM image of four layers of PEDOT, 5L shows the AFM image of five layers of PEDOT, and 6L shows the AFM image of six layers of PEDOT. 1L, 3L, and 6L also show the SEM images of PEDOT. Figure 3 shows the AFM images of PEDOT from 1L to 6L and the SEM images of 1L, 3L, and 6L, indicating that the film has a very uniform and homogeneous sheet-like nature. Materials used in optoelectronics need to have high surface smoothness. It can be observed from the AFM images and the average roughness values (Table 4) that for 1L of PEDOT, it does not exceed 1 nm, and for 6L of PEDOT, it does not exceed 4 nm. This indicates that even with a slight increase in surface roughness, the uniform and homogeneous sheet-like nature was not affected by the increment of additional layers. Thickness measurements were verified by averaging multiple measurements over a large scanning area of the PEDOT film. The conductivity of 1L of PEDOT is 2178 S / cm, and that of 6L of PEDOT is 3208 S / cm at its maximum value (Table 4). The vapor-phase polymerization PEDOT film prepared using FETOS as an oxidant forms large densely packed conductive regions that increase the in-plane conductivity. The sheet resistance decreases from 194.56 Ω / □ for 1L of PEDOT to 20.55 Ω / □ for 6L of PEDOT (Table 4). For 2L of PEDOT, the sheet resistance decreased by 57.7% from that of 1L of PEDOT but showed approximately the same conductivity due to the increase in thickness. For 3L of PEDOT, the sheet resistance decreased by 35.4% from that of 2L of PEDOT, and the conductivity increased slightly. The decrease in sheet resistance when progressing from 3L of PEDOT to 6L of PEDOT is approximately linear, but 3L of PEDOT and 4L of PEDOT show approximately the same conductivity value. The decrease in sheet resistance and the increase in conductance when progressing from 1L of PEDOT to 6L of PEDOT also indicate that charge moves rapidly from layer to layer (Table 4). This is facilitated by the efficient delocalization of polarons and polaron pairs or bipolaron PEDOT chains across different layers. This extended conjugation enables faster charge / electron movement across the film.

[0127] Table 4 shows the number of layers (L), thickness (d), sheet resistance (r sheet ), conductivity (s), areal capacitance (C A ), volume capacitance (C v ), percent transmittance (%T), and roughness average (R a ) of 1 - 6 layer PEDOT films fabricated by VPP.

[0128]

Table 4

[0129] According to the conductive polaron theory, electron transfer occurs through the motion of polarons and bipolaron / polaron pairs along the polymer chain, accompanied by the rearrangement of double and single bonds. As the doping level increases, the conductivity increases.

[0130] As can be seen from Table 4, a single layer of PEDOT is very transparent.

[0131] Figure 4 shows the cyclic voltammograms of 1L - 6L PEDOT (scan rate is 100 mV / s and contains 0.1 M TBABF 4 in MeCN).

[0132] Figure 5 shows the cyclic voltammograms of 1L PEDOT on glass and on ITO - coated glass in a 6 mM ferrocene solution, with a scan rate of 20 mV / s.

[0133] In Figure 4, the rectangular - shaped cyclic voltammogram indicates a reversible and efficient charge - discharge process. Table 4 shows an increase in the capacitance value for each layer of the PEDOT film. The 6 - layer film has 10.67 mF / cm 2 (areal capacitance) and 703.58 F / cm 3(Volume capacity) The capacity value was shown. In FIG. 5, the cyclic voltammogram of a single layer of PEDOT is compared with a bare ITO-coated glass in a 6 mM ferrocene solution. From the difference in peak potential, PEDOT needs to be 60 mV lower than the ITO-coated glass. The calculated charge values are 42.93 mC and 36.48 mC for 1 L of PEDOT and ITO-coated glass, respectively. This can be explained by the larger surface area of PEDOT compared to the ITO-coated glass. Overall, the ferrocene response of 1 L of PEDOT is superior to that of the ITO-coated glass.

[0134] Single-layer and multi-layer PEDOT films are highly transparent, have a large surface area, high conductivity, and very low surface roughness, making them suitable for use as alternatives to optoelectronic devices and ITO coating materials.

[0135] It will be apparent to those skilled in the art that, as technology progresses, the basic concepts can be implemented in various ways. Accordingly, the embodiments are not limited to the examples described above, but may instead be modified within the scope of the claims.

[0136] The above-described embodiments can be used in any combination with each other. Some embodiments can also be combined together to form further embodiments. The methods, conductive PEDOT films, optoelectronic devices, or uses disclosed herein can include at least one of the embodiments described hereinabove. It is understood that the above benefits and advantages may be related to one embodiment or to multiple embodiments. Embodiments are not limited to those that solve any or all of the problems described or have any or all of the benefits and advantages described. Further, references to "one" item are to be understood to refer to one or more of those items. The term "comprising" is used herein to mean including the subsequent features or acts without excluding the presence of one or more additional features or acts.

[0137] (Example 2; Preparation of PEDOT Film) The procedure described above for Example 1 was followed, except that 80 μL of the oxidant solution was spin-coated onto the substrate at 2400 rpm for 20 seconds.

[0138] Table 5 illustrates the changes in roughness and sheet resistance of single-layer PEDOT films prepared by first varying the polymerization temperature (cell temperature) while keeping the substrate temperature (approx. room temperature) and polymerization time (4 minutes) constant, then varying the substrate temperature while keeping the polymerization temperature (75 °C) and polymerization time (4 minutes) constant, and finally varying the polymerization time (2 - 8 minutes) while keeping the polymerization temperature (75 °C) and substrate temperature (approx. room temperature) constant. All films were prepared using 80 μL of the oxidant solution. The oxidant was spin-coated onto the substrate at a spin-coating speed of 2400 rpm. The oxidant layer was dried at 90 °C for 90 seconds. Annealing was performed at 90 °C for 90 seconds. The films were washed with acetonitrile and dried under a nitrogen gas flow.

[0139] [Table 5] *The sheet resistance value was obtained using a Jandel model RM3000+ equipped with a cylindrical four-probe head. The sheet resistance of the 15-layer PEDOT film is 4 - 6 Ω / □.

[0140] (Example 3: Preparation of PEDOT Film) The procedure described above for Example 1 was followed, except that different spin speeds, amounts of oxidant, oxidant release times, and total spin times were used.

[0141] Table 6 describes the changes in sheet resistance and % transmittance of PEDOT films prepared using different spin speeds, amounts of oxidant, oxidant release times, and total spin times.

[0142]

Table 6

[0143] (Example 3: Preparation of Polymer Films Formed from Copolymers) The polymer layer was prepared according to the procedure described above for Examples 1 and 2, except that one of the monomers was EDOT and the additional monomer was azulene. Both monomers were simultaneously exposed to the substrate. The parameters and results in the examples are discussed below in relation to Table 7.

[0144] Table 7 describes the sheet resistance, transmittance, and roughness values of films containing polymer layers formed from copolymers of EDOT and azulene prepared using different oxidizing agents. All films were prepared using 80 μL of the oxidizing agent solution. The oxidizing agent was spin-coated onto the substrate at a spin-coating speed of 2400 rpm. The oxidizing agent layer was dried at 90 °C for 90 seconds. In Entries 1 and 2, the polymerization time per layer was 4 minutes and the polymerization temperature (cell temperature) was 65 °C. Annealing was performed for all films. The films were washed twice with acetonitrile and dried under a nitrogen gas stream. The substrate temperature for Entries 1 and 2 was 55 °C. All sheet resistance values were measured immediately after film preparation.

[0145] Table 7: Sheet Resistance and Roughness Values of 1L COPOL Films Prepared Using Different Oxidizing Agents

Table 7

[0146] The polymer layer formed from PEDOT was also adjusted using the same procedure as above, except that iron(III) trifluoromethanesulfonate iron(OTF) was used as the oxidizing agent and it was prepared at a polymerization temperature of 75 °C. 3 except that it was adjusted using the same procedure as above, except that iron(III) trifluoromethanesulfonate iron(OTF) was used as the oxidizing agent and it was prepared at a polymerization temperature of 75 °C.

[0147] Table 8: Evaluation of the Electrochemical Properties of 1 L of COPOL (240 mM, CuCl2) [Table 8] * 0.1 M TBABF in acetonitrile 4 (tetrabutylammonium tetrafluoroborate) was used as the electrolyte solution. Sweep rate = 50 mV / s.

[0148] It is also possible to fabricate the polymer by an interlayer technique by first preparing one layer of PEDOT and then preparing one layer of PAz, and it is even possible to continue this layer formation. It is also possible to start with each layer with PAz and PEDOT on top, and here too continuous layer formation can be carried out.

Claims

1. A non-conductive substrate; a poly(3,4-ethylenedioxythiophene) (PEDOT) layer having anions from one or more oxidizing agents embedded in the PEDOT layer on the non-conductive substrate; A conductive PEDOT film comprising: The conductive PEDOT film is s = 1 / r ｓｈｅｅｔ d (where d is the thickness of the conductive PEDOT film) The electrical conductivity s calculated by the formula is greater than 2100 S / cm, and the sheet resistance r determined by Jandel's four-point probe measurement is ｓｈｅｅｔ is less than 200 Ω / □, The conductive PEDOT film is a 1-5 layer film, the thickness of the film is 10-125 nm, and the roughness average of the conductive PEDOT film is less than 3.5 nm as determined from AFM images recorded using a Bruker TESP-MT probe (resonant frequency 320 kHz, spring constant 42 N / m, length 125 μm, width 30 μm, cantilever specifications: 0.01-0.025 Ωcm antimony (n) doped silicon, thickness 4 μm, tip specifications: height 10-15 μm, radius 8 nm).

2. 2. The conductive PEDOT film of claim 1, wherein the % transmittance of the conductive PEDOT film at 550 nm is greater than 30% T.

3. 3. The conductive PEDOT film of claim 1 or 2, wherein the non-conductive substrate is glass or polyethylene terephthalate (PET).

4. 4. The conductive PEDOT film of claim 1, wherein the PEDOT layer has anions from iron(III) p-toluenesulfonate hexahydrate (FETOS) embedded in the PEDOT layer on the non-conductive substrate.

5. An electronic device, characterized in that it comprises a conductive PEDOT film as defined in any one of claims 1 to 4.

6. 6. The electronic device of claim 5, wherein the electronic device is a display, a flat panel display, an optoelectronic device, an organic solar cell, a dye-sensitized solar cell, a perovskite solar cell, a smart window, a fuel cell, an organic electrochemical transistor, an electrochemical transducer, an electrochromic device, an electroluminescent device, an electroluminescent display, an organic capacitor, a supercapacitor, a sensor, a biosensor, an energy harvesting device, an antistatic material, a photovoltaic device, a storage device, or a thermoelectric device.

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