Method for fabricating patterned polymer film structures

Abstract

The present invention relates to a method for producing a patterned film on a substrate, the method comprising forming an oxidant layer on the substrate by applying a solution containing an oxidant to the surface of the substrate by coating, drying the oxidant layer, applying an inhibitor on the oxidant layer according to a pattern to partially inhibit the formation of the oxidant layer, and forming a polymer layer by exposing the surface to monomer vapor at a polymerization temperature of 20-95°C under atmospheric pressure.

Description

[Technical Field]

[0001] The present disclosure relates to methods for making patterned films comprising at least one polymer layer. The present disclosure also relates to films comprising at least one polymer layer. The present disclosure further relates to devices comprising the films, as well as systems for making patterned films comprising at least one polymer layer. [Background technology]

[0002] Oxidation of azulene monomers results in polymerization at the 1- and 3-positions, yielding 1,3-polyazulene. Polyazulene (PAz) is a conductive polymer that exhibits high capacitance and redox behavior. PAz films can be produced by electrochemical, chemical, or photochemical polymerization. Their electronic properties, conductivity, redox behavior, and fast charge / discharge characteristics make them useful for applications related to electronics, antistatic coatings, dye-sensitized or organic solar cells, electrochemical transducers, electrochromic devices, electroluminescent devices, organic light-emitting diodes (OLEDs), and supercapacitors. To be suitable for these applications, PAz films must be highly organized, homogeneous, transparent, and thin. Among current methods, electrochemical polymerization produces inhomogeneous films and requires conductive electrode substrates, limiting fabrication to electrode materials only, while oxidative chemical synthesis yields powdered or granular materials. PAz is insoluble, so further casting or processing may be impossible.

[0003] Conductive poly(3,4-ethylenedioxythiophene) (PEDOT) films and their copolymers are also known and used in a variety of fields. These films can be fabricated using the same methods as PAz films. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 221958 [Patent Document 2] International Publication No. 2019 / 211510 Summary of the Invention [Problem to be solved by the invention]

[0005] Fabricating high-quality PAz and / or PEDOT films with the desired properties may be difficult using current fabrication methods, so new approaches may be needed. Ideally, it would also be possible to fabricate patterned films that can be used as is or as the basis for further products. [Means for solving the problem]

[0006] Described herein is a method for producing a patterned film on a substrate, comprising: forming an oxidizer layer on the substrate by applying a solution containing an oxidizer to the surface of the substrate by coating; drying the oxidant layer; applying an inhibitor onto the oxidizer layer according to a pattern to partially inhibit the formation of the oxidizer layer; and Forming a polymer layer by exposing the surface to monomer vapor at a polymerization temperature between 20 and 95°C under atmospheric pressure The present invention relates to a method comprising:

[0007] The present application also relates to devices comprising films obtained by the methods described herein.

[0008] The present disclosure further provides a system for producing a patterned film on a surface of a substrate, the system comprising: an oxidizer unit configured to apply a solution containing an oxidizer to the surface by coating to form an oxidizer layer on the surface; means for drying the oxidizer layer; means for applying an inhibitor onto the oxidant layer in a pattern; and A chamber configured to expose a surface to monomer vapor at a polymerization temperature of 20 to 95°C under atmospheric pressure to form a polymer layer. The present invention relates to a system including: [Brief explanation of the drawings]

[0009] The accompanying drawings, which are included to provide a further understanding of the embodiments and constitute a part of this specification, illustrate various embodiments. [Figure 1] 1A-1C show a schematic representation of a film formed on a substrate according to an embodiment of the method of the present invention and various steps of the method. [Figure 2] 1 shows a gas phase polymerization cell for carrying out gas phase polymerization, according to an embodiment. [Figure 3] 1 shows a setup for continuous VPP processing of a substrate according to an embodiment. [Figure 4] A visualization of the patterns generated by a rubber stamp. [Figure 5] 1 is a visualization of a printed pattern according to an embodiment. [Figure 6] 10 is a visualization of a printed pattern according to another embodiment. [Figure 7] AFM images from the edge of the printed area and height profiles at specific locations from the image are shown. DETAILED DESCRIPTION OF THE INVENTION

[0010] Described herein is a method for producing a patterned film on a substrate, comprising: forming an oxidizer layer on the substrate by applying a solution containing an oxidizer to the surface of the substrate by coating; drying the oxidant layer; applying an inhibitor onto the oxidizer layer according to a pattern to partially inhibit the formation of the oxidizer layer; and Forming a polymer layer by exposing the surface to monomer vapor at a polymerization temperature between 20 and 95°C under atmospheric pressure The present invention relates to a method comprising:

[0011] The method uses the vapor deposition polymerization method described in WO 2020 / 221958 and WO 2019 / 211510, the contents of which are incorporated herein by reference, and in particular the experimental sections thereof, which, unless otherwise noted herein, are incorporated by reference as describing the formation and polymerization of the oxidant layer.

[0012] In this method, an oxidant layer is first formed on the surface of the substrate by coating. The oxidant layer is then dried or left to dry. If drying is performed, it is preferably carried out as described below. After the oxidant layer has dried, i.e., after the solvent used has evaporated, an inhibitor is applied onto the oxidant layer. The inhibitor is applied in a pattern so as to partially inhibit the formation of the oxidant layer. The inhibitor is applied to parts of the oxidant layer where it is not desired to form a polymer layer in a subsequent step. The function of the oxygen scavenger is described in more detail below. After this selective inhibition, a polymer layer is formed by gas-phase polymerization, as described in WO 2022 / 221958.

[0013] Thus, the steps of the method are performed in order. As will be apparent from this description, the method may also include further steps.

[0014] In the context of this specification, unless otherwise specified, the term "polymerization temperature" may refer to the temperature of the monomer vapor during gas-phase polymerization. The polymerization temperature may also refer to the temperature of the reaction chamber or cell in which the polymerization is carried out. Furthermore, the term "surface" may refer to the surface of a substrate, or a surface obtained in a previous process and to be further processed. The term "deposition surface" may also be used interchangeably with the term "surface." Thus, in the context of this specification, the term "surface" may refer to the substrate surface itself or a surface covered with an oxidant layer. Furthermore, the term "surface" may refer to a surface covered with a polymer layer on top of an oxidant layer. Furthermore, the term "surface" may refer to a surface covered with successive layers of oxidant and / or polymer layers, such as when the first layer on the substrate surface is an oxidant layer, followed by a polymer layer. Thus, the "surface" may change during the (deposition) process in which chemicals are applied to the surface.

[0015] As used herein, the term "film," unless otherwise specified, should be understood to refer to a structure whose lateral dimensions are significantly greater than its thickness. In this sense, a film is considered to be a "thin" structure. As used herein, the expression that a film is "disposed on" a surface of a substrate should be understood to mean that the film is formed on or above the substrate, unless otherwise specified.

[0016] The term "temperature of the surface" actually refers to the temperature of the substrate. The temperature of the substrate, and therefore the temperature of the surface, is preferably controlled independently using temperature sensors, heating / cooling devices, etc. The term "polymerization temperature" refers to the temperature of the monomer vapor.

[0017] The terms "inhibit the action of an oxidizing agent" and "inhibit the formation of an oxidizing agent layer" generally mean that the inhibitor prevents the action of the oxidizing agent. Alternatively, the inhibitor may have a significant effect on the oxidizing agent, such that an oxidizing agent layer forms, but not to a sufficient extent to allow the formation of a polymer layer in the area where the inhibitor is applied.

[0018] The quality of the resulting film is highly dependent on the preparation method, particularly the thickness of the different layers and their uniformity. It has been confirmed that this method can produce high-quality films, including films with good sheet resistance, surface roughness, and film uniformity. These are attributed to the selected coating method and the temperature difference between the substrate surface and the monomer vapor. In fact, the temperature difference between the substrate (substrate surface) and the cell / chamber (monomer vapor temperature) controls the condensation rate of the monomer on the substrate surface and the gradient of the monomer vapor near the surface. The substrate temperature and the deposition / condensation rate of the monomer affect the film properties.

[0019] According to one embodiment, the polymer layer comprises a polymer or copolymer of azulene and / or 3,4-ethylenedioxythiophene. Indeed, according to one embodiment, the monomer vapor comprises azulene, 3,4-ethylenedioxythiophene, and combinations thereof. Thus, the polymer may be a homopolymer or copolymer, as desired.

[0020] According to another embodiment, the monomer vapor comprises, in addition to azulene and / or 3,4-ethylenedioxythiophene, further monomers selected from the group consisting of pyrrole, aniline, thiophene, and phenylene.

[0021] In one embodiment, the surface is exposed to at least azulene monomer vapor and at least one additional monomer vapor during the gas phase polymerization. In a further embodiment, the surface is exposed to at least 3,4-ethylenedioxythiophene monomer vapor and at least one additional monomer vapor during the gas phase polymerization. In yet a further embodiment, the surface is exposed to azulene and 3,4-ethylenedioxythiophene monomer vapor during the gas phase polymerization.

[0022] In another embodiment, in the gas-phase polymerization, the surface is exposed to vapors of at least azulene monomer and / or 3,4-ethylenedioxythiophene (EDOT) and at least one additional monomer selected from the group consisting of pyrrole, aniline, thiophene, and phenylene. In a further embodiment, the at least one additional monomer vapor is selected from 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), isobutylene (methylpropene), propylene, methylpentene, butane-1, isobutylene, and any other linear olefin, cyclic olefin, vinyl ether, allyl ether, vinyl ester, and allyl ester. Various mixtures of these monomers can also be used, resulting in copolymers. Thus, the resulting polymer can be a polyolefin elastomer (POE), such as, for example, polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), polyisobutylene (PIB), ethylene propylene rubber (EPR), ethylene propylene diene (M class) rubber (EPDM rubber), etc.

[0023] The inhibitor reduces and / or inactivates the oxidizer layer in the area where it is applied, thereby preventing polymerization of the monomer in that area. The inhibitor is then used to create a negative of the desired film pattern.

[0024] According to one embodiment, the inhibitor is selected from the group consisting of reducing agents and complexing agents. The inhibitor's function is to inhibit the action of the oxidizing agent, so that when the monomer vapor is applied, polymer does not form in the areas where the oxidizing agent is inhibited. It is believed that this method allows for the creation of finer patterns, i.e., smaller and more precise patterns, than when the oxidizing agent is applied in a patterned manner. This is believed to be due, for example, to the properties of the oxidizing agent solution, such as its flow characteristics. This method allows for the formation of a more uniform and flat oxidizing agent layer, so that even the uninhibited areas remain flat and uniform, resulting in a highly conductive and high-quality film. Furthermore, because the properties of the final patterned film depend on the quality of the oxidizing agent layer, primarily its uniformity and flatness, some application methods are believed to produce more precise final results. Typically, spin coating, spray coating, aerosol deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer deposition (ALD), sol-gel deposition, electroplating, roll-to-roll deposition, and dip coating produce more precise oxidizing agent layers than other methods of applying an oxidizing agent solution. Indeed, these coating methods allow precise control of the amount of oxidant, and therefore the layer thickness. For example, in spin coating, this can be achieved by adjusting the rotation speed and dosage, and in spray coating, it can be achieved by adjusting the dosage. In dip coating, control can be achieved by controlling the speed of dipping. Soaking methods such as immersion do not offer a similar level of control. Spin coating, spray coating, and dip coating may be preferred.

[0025] As discussed in more detail below, the oxidizing agent can be selected from the group consisting of iron(II) salts, iron(III) salts, cerium(IV) salts, and copper(II) salts. Thus, if the inhibitor is a reducing agent, it reduces the metal salt to a lower oxidation state, e.g., Fe(III) to Fe(II), thereby inactivating the oxidizing agent. If the inhibitor is a complexing agent (also called a chelating agent), it complexes, or sort of encapsulates, the oxidizing agent (e.g., Fe(III)), making it unable to subsequently react with the monomer. The oxidizing agent can be, for example, iron(III) p-toluenesulfonate, iron(III) trifluoromethanesulfonate, iron(III) chloride, p-toluenesulfonic acid, iodine, bromine, molybdophosphate, ammonium persulfate, DL-tartaric acid, polyacrylic acid, copper chloride, copper bromide, iron(III) chloride, naphthalenesulfonic acid, camphorsulfonic acid, iron(III) toluenesulfonate, iron(III) perchlorate, Cu(ClO4)2·6H2O, ammonium cerium(IV) nitrate, cerium(IV) sulfate, and mixtures thereof. The inhibitor is selected to have sufficient potency to inhibit the action of the oxidizing agent to a sufficient extent. This is particularly important in the case of reducing agents.

[0026] According to a preferred embodiment, the surface is not cleaned between application of the inhibitor and polymerization by vapor deposition. Indeed, it has been observed that such cleaning is not necessary and good results are obtained without cleaning.

[0027] According to one embodiment, the inhibitor is selected from the group consisting of ascorbic acid; oxalic acid; sodium thiosulfate, trisodium citrate; hydrazine and its derivatives; citric acid; lithium aluminum hydride (LiAlH4); sodium borohydride (NaBH4); dithionite, thiosulfate, and iodide ion; formic acid; reducing sugars (galactose, glucose, glyceraldehyde, fructose, ribose, and xylose); ethylenediaminetetraacetic acid (EDTA); trans-1,2-diaminocyclohexanetetraacetic acid (CDTA); trimethylenediaminetetraacetic acid (TMDTA); N-(2-hydroxyethyl)ethylenediamine, N,N',N'-triacetic acid (HEDTA), N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED); catechol; 3,5-disulfocatechol (TIRON); salicylate; and glycine. Of these, citric acid; oxalic acid; citrate; ethylenediaminetetraacetic acid (EDTA); trans-1,2-diaminocyclohexanetetraacetic acid (CDTA); trimethylenediaminetetraacetic acid (TMDTA); N-(2-hydroxyethyl)ethylenediamine, N,N',N'-triacetic acid (HEDTA), N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED); catechol; 3,5-disulfocatechol (TIRON); salicylic acid; and glycine are primarily complexing agents (although they also have some ability to reduce Fe(III) in particular), while the others are reducing agents.

[0028] According to another embodiment, the inhibitor is applied by printing or stamping. Printing can be performed, for example, by an inkjet printer, whose nozzle size is typically on the micrometer scale. Other possible printing techniques include microcontact printing and gravure printing. Stamping can be performed by a rubber stamp. Furthermore, tape casting, press printing, screen printing, offset printing, flexographic printing, or 3D printing (which can also be used to fabricate the substrate) are also possible. The patterned film can be applied as a single layer or as multiple successive layers, depending on the monomer used and the desired film thickness.

[0029] Furthermore, the method may include repeating the steps of forming an oxidant layer, drying the oxidant layer, applying an inhibitor, and forming a polymer layer by vapor-phase polymerization. These steps can be repeated multiple times as needed. The monomers used can be different for each layer. Thus, an oxidant layer can be reapplied on the patterned film, and another pattern can be created on the new oxidant layer using an inhibitor. This process can result in different regions of different thicknesses in the final film. Because the polymer layer is conductive, such structures can have regions of different conductivity.

[0030] In one embodiment, the total thickness of the film is from 20 nm to 50 μm, or from 50 nm to 10 μm, or from 100 nm to 1 μm, or from 200 nm to 500 nm.

[0031] In one embodiment, the method is carried out as a batch process. That is, one film can be produced at a time, for example, in a reaction chamber or cell, in which different process steps can be carried out. In one embodiment, the method is carried out as a continuous process, for example, a roll-to-roll process or a dipping process. That is, the substrate can be moved from one process step to another without interruption. For example, first coated with an oxidizing agent, then dried, followed by application of an inhibitor, and then exposed to monomer vapor. In a continuous process, multiple films can be produced simultaneously in parallel.

[0032] In one embodiment, the film has a rigid structure. In another embodiment, the film has a flexible structure. In a further embodiment, the film can be rolled up.

[0033] In one embodiment, at least one catalyst and / or at least one catalyst additive is used in the gas phase polymerization. In one embodiment, the at least one catalyst and / or catalyst additive is selected from the following: Ziegler-Natta catalyst, AlCl, TiCl, cerium(IV) ammonium nitrate, cerium(IV) tosylate, Fe(III) tosylate, pyridine, p-toluenesulfonic acid (p-TSA), diethylene glycol (DEG), molybdophosphate, molybdo-2-vanadophosphate, poly(styrenesulfonic acid) (PSS), Fe(III) alkylbenzenesulfonate, iodine, bromine, pyrocatechol violet, benzenesulfonic acid (BSA), p-toluenesulfonic acid (TSA), dodecylbenzenesulfonic acid (DBSA), butylbenzenesulfonic acid (BBSA), glycerol, trialkylaluminum-free modified methylaluminoxane, TEMPO ((2,2, (6,6-tetramethylpiperidin-1-yl)oxyl or (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl); peroxides, chlorides, or iodides of Ti, V, Zr, Cr, W, Co, and aluminum (Mg or Li) alkyl TiCl4, alkyl aluminum compounds in hydrocarbon solvents; titanium supported on magnesium salts; VOCl3, VCl4, or VO(OR)3; aluminum alkyl RAlCl2, in which the transition metal (Zr, Ti, or Hf) is sandwiched between cyclopentadienyl rings; Cr, Mo, Co, or Ni supported on alumina, silica, zirconia, or activated carbon; Cr / SiO2, Zr / Al2O3, and Ti / MgO, supported chromium oxides; bis(arene) chromium oxide supported on silica, alumina, or titania.

[0034] In one embodiment, the gas-phase polymerization is continued until the polymer layer is at least 10-100 nm thick, or 20-90 nm thick, or 30-80 nm thick, or 40-60 nm thick. For certain applications, thicker films, i.e., multiple polymer layers, may be useful, while for other applications, thinner films, i.e., fewer layers, may be useful. The number of layers, i.e., film thickness, affects the content and organization of micro- or nano-level active materials, which in turn affects film properties such as conductivity, capacitance, sheet resistance, bandgap, active surface area, and transparency.

[0035] The substrate acts as a carrier or support structure for the film. The substrate is variable, and the material of the substrate can vary depending on the application for which the film is to be used. In one embodiment, the substrate is rigid. In one embodiment, the substrate is flexible, bendable, and / or rollable.

[0036] In one embodiment, the polymer layer is a 1,3-polyazulene layer. In another embodiment, the film comprises at least one 1,3-polyazulene layer. In a further embodiment, the film comprises at least one polymer layer formed from PAz, or a copolymer in which one of the monomers is azulene, or any combination thereof. In yet a further embodiment, the film is a PEDOT film, or a copolymer of 3,4-ethylenedioxythiophene and another monomer. In one embodiment, the film is a copolymer of 3,4-ethylenedioxythiophene and azulene. In one embodiment, the film comprises one or more polymer layers formed from any of the polymers and copolymers listed above.

[0037] In one embodiment, the polymer layer is formed on at least one side of the substrate, hi another embodiment, the polymer layer is formed on the top and bottom surfaces of the substrate.

[0038] In one embodiment, the gas-phase polymerization is continued for 1 to 20 minutes, or 2 to 16 minutes, or 4 to 8 minutes. The polymerization time can affect the thickness of the polymer layer. Continuing the polymerization for a longer period of time may result in a thicker polymer layer. It is also possible that continued polymerization will no longer result in a thicker layer after a certain period of time. This is likely due to the fact that once the surface covered by the oxidant layer is fully occupied by polymer, the monomer will not be able to reach the oxidant even if the polymerization is continued for a longer period of time. The monomer simply deposits and does not polymerize. Furthermore, the deposited unpolymerized monomer is washed away or rinsed away during film washing, leaving only the polymerized film. Such washing can be performed with any suitable liquid, such as acetonitrile.

[0039] The polymer layer is formed on the surface by atmospheric gas-phase polymerization (VPP). VPP is a polymerization technique in which only the monomer is converted into the gas phase. VPP, which is carried out at atmospheric pressure, also has the advantage of being easy to control. No pressure control, sophisticated equipment, or vacuum ovens are required. The method can also be used to fabricate large-area films.

[0040] In one embodiment, VPP is carried out in a reaction chamber or cell. In another embodiment, the temperature of the reaction chamber or cell is controlled. In one embodiment, the temperature of the reaction chamber or cell is controlled by a thermostatic bath.

[0041] In one embodiment, the surface temperature during gas phase polymerization is 21 to 75°C, or 25 to 75°C, or 30 to 60°C, or 35 to 65°C, 40 to 50°C, or 45 to 55°C.

[0042] In one embodiment, during gas-phase polymerization, the polymerization temperature (i.e., the temperature of the reaction chamber) is 20-90°C, or 35-85°C, or 40-80°C, or 45-75°C, or 50-70°C, or 55-65°C. The use of lower polymerization temperatures has the added benefit of saving costs through the use of less power. It may also be suitable for temperature-sensitive substrates, such as biomolecule-treated substrates or plastics and other delicate substrates.

[0043] In one embodiment, during gas-phase polymerization, the surface temperature differs from the polymerization temperature, i.e., there is a temperature difference of more than 0° C. The temperature difference can be, for example, >0 to 30° C., or 1 to 25° C., or 5 to 20° C., or 10 to 15° C. In one embodiment, during gas-phase polymerization, the surface temperature is >0 to 30° C., or 1 to 25° C., or 5 to 20° C., or 10 to 15° C. lower than the polymerization temperature, or >0 to 20° C., or 1 to 15° C., or 5 to 10° C. higher than the polymerization temperature. In one embodiment, during gas-phase polymerization, the surface temperature is >0-30°C, or 1-30°C, or 1-25°C, or 2-25°C, or 3-25°C, or 4-20°C, or 5-20°C, or 10-15°C lower than the polymerization temperature, or >0-20°C, or 1-15°C, or 2-15°C, or 3-15°C, or 4-10°C, or 5-10°C higher than the polymerization temperature. Gas-phase polymerization can be carried out in a cell or reaction chamber, but can also be carried out without such equipment. However, for easier temperature control and formation of monomer vapor, it is preferable to use a cell or reaction chamber. The reaction chamber can be a large space, for example, for producing large quantities of product.

[0044] Typically, the surface temperature will be lower than the temperature of the monomer, i.e., the polymerization temperature. In practice, a temperature difference of about 1°C has been found to be sufficient to positively influence the rate of condensation of the monomer on the surface. The temperature difference has been found to positively influence the properties of the resulting film. For example, it can affect one or more of the film's electrical conductivity, the type of defects on the film, the film's transparency, the film's surface roughness, the film's heat resistance, and the film's transmittance.

[0045] The surface temperature can affect the sheet resistance of the film. The sheet resistance can increase or decrease. Furthermore, it can affect the stability of the film structure, potentially avoiding stress-induced breakage during cleaning. A decrease in sheet resistance after temperature treatment can indicate a decrease in the doping level of a conductor or semiconductor, or a reorganization or disruption of the polymer chain structure. In one embodiment, the surface temperature is at least 0° C. or higher. In another embodiment, the surface temperature is at least room temperature or higher.

[0046] In one embodiment, the polymerization temperature (i.e., the temperature of the reaction chamber) is 20 to 95°C, and the surface temperature is 25 to 75°C; the polymerization temperature is 25 to 74°C, and the surface temperature is 26 to 75°C; the polymerization temperature is 25 to 90°C, and the surface temperature is 25 to 75°C; or the polymerization temperature is 35 to 85°C, and the surface temperature is 30 to 70°C; or the polymerization temperature is 40 to 80°C, and the surface temperature is 35 to 65°C; or the polymerization temperature is 45 to 75°C, and the surface temperature is 40 to 50°C; or the polymerization temperature is 50 to 60°C, and the surface temperature is 45 to 55°C.

[0047] In one embodiment, the cell or reaction chamber contains a saturating amount of monomer vapor, which may vary depending on the size of the cell or chamber.

[0048] In one embodiment, the oxidizing agent is selected from the group consisting of iron(II), iron(III), cerium(IV), and copper(II) salts. In one embodiment, the oxidizing agent is selected from the group consisting of iron(III)-p-toluenesulfonate (FETOS), FeCl3, CuCl2, CuBr2, and iron(III) trifluoromethanesulfonate (Fe(OTf)3). The oxidizing strength of the oxidizing agent may vary. Film structure and polymer composition may vary depending on which oxidizing agent is used. The oxidizing agents listed above are believed to enable the formation of high-quality films.

[0049] In one embodiment, the concentration of the oxidizing agent-containing solution is 60 to 500 mM, or 70 to 480 mM, or 120 to 320 mM, or 180 to 240 mM. The solvent in the oxidizing agent-containing solution may be selected from the group consisting of organic solvents and mixtures thereof, such as n-butanol, methyl alcohol, 2-butyl alcohol, n-propyl alcohol, isopropanol, ethyl cellosolve, ethyl alcohol, ethyl acetate, acetonitrile, and methyl ethyl ketone. The purpose of the oxidizing agent is to deprotonate the monomer and initiate polymerization. In one embodiment, the solution consists of a solvent and an oxidizing agent. In one embodiment, the oxidizing agent layer is dried before polymerization. By drying the oxidizing agent layer before polymerization, traces of the solvent can be removed before proceeding to the polymerization step. In one embodiment, the polymerization reaction is a gas-solid reaction at the interface between the two.

[0050] The oxidizer solution may also contain a base inhibitor, which reduces the activity of the oxidizer and slows down the rate of polymerization, potentially altering the conductivity of the final polymer. The base inhibitor may be selected from the group consisting of amine-based compounds, saturated or unsaturated heterocyclic compounds containing nitrogen atoms (such as pyridine-, imidazole-, or pyrrole-based compounds), water vapor, glycerol, glycol derivatives, and mixtures thereof.

[0051] In one embodiment, a solution containing an oxidizing agent is spin-coated onto a surface. In one embodiment, the solution containing an oxidizing agent is spin-coated onto a surface at 1000 to 2800 rpm for 20 to 90 seconds. In one embodiment, the solution containing an oxidizing agent is spin-coated onto a surface at 1200 to 2600 rpm, or 1400 to 2400 rpm, or 1600 to 2200 rpm, or 1800 to 2000 rpm for 30 to 80 seconds, or 40 to 70 seconds, or 50 to 60 seconds. In one embodiment, the surface coated with the oxidizing agent is dried before gas-phase polymerization. In one embodiment, the surface coated with the oxidizing agent is dried on a hot plate at a temperature of 70 to 110°C for 10 to 150 seconds, for example, at 90°C for 90 seconds.

[0052] Different oxidizers may behave differently at different temperatures, and even one oxidizer may behave differently at different temperatures, so it may be necessary to perform some simple tests to find the optimum conditions.

[0053] In one embodiment, the method includes cleaning the surface prior to forming the oxidizer layer. In one embodiment, the substrate may be cleaned by sonication with a solvent. In one embodiment, the solvent for sonication may be selected from the group consisting of organic solvents. In one embodiment, the solvent for sonication is selected from the group consisting of acetone, ethanol, water, and mixtures thereof.

[0054] In one embodiment, the cleaned surface can be immersed in a hot solution. In one embodiment, the cleaned surface can be immersed in a hot solution of 5:1:1 by volume of H2O:NH4OH (25%):H2O2 (30%) at a temperature of 50-100°C, e.g., 85°C. Cleaning has the added benefit of removing organic impurities remaining on the surface. In one embodiment, this can be followed by an oxygen plasma treatment. Oxygen plasma treatment refers to a plasma treatment in which oxygen is introduced into the plasma chamber.

[0055] Oxygen plasma treatment has the added function of further cleaning the substrate. Oxygen is the most commonly used gas in plasma cleaning techniques due to its low cost and availability.

[0056] In one embodiment, the method includes a step of annealing the film after gas-phase polymerization at a temperature of 60-100°C. In one embodiment, the temperature of the annealing step is 70-90°C or about 80°C. In one embodiment, annealing of the film lasts for 140-40 seconds, or 50-120 seconds, or 60-90 seconds, e.g., 120 seconds. Annealing can be carried out on a hot plate or in an oven. In one embodiment, the system therefore includes a heating unit configured to anneal the film at a temperature of 60-100°C.

[0057] In one embodiment, after annealing, the film is cooled to room temperature. The film can be annealed to avoid stress fracture of the film during the washing process. In one embodiment, the annealed and cooled film is washed. In one embodiment, washing involves immersion washing the film in MeCN and / or ethanol. Washing has the additional purpose of removing unreacted oxidant, monomer, and other impurities that may reduce conductivity. The solvent used can affect the sheet resistance of the film. For example, traces of water present in the solvent can reduce the sheet resistance. In one embodiment, after washing, the film is dried under a stream of dry nitrogen gas.

[0058] In one embodiment, the substrate is non-conductive. In one embodiment, the substrate comprises or consists of glass, paper, cellulose, fiber, cloth, wood, leather, cotton, ceramic, quartz, rubber, polymer, or any combination thereof. In one embodiment, the glass may be a microscope slide, fluorine-doped tin oxide (FTO) glass, or indium tin oxide (ITO)-coated glass. The polymer film produced according to this method can also be used as a substrate for producing additional products. In one embodiment, the non-conductive substrate comprises or consists of a polymer. The polymer may be polyethylene terephthalate (PET), poly-3,4-ethylenedioxythiophene-polystyrene sulfonate (PEDOT:PSS), polycarbonate (e.g., those sold under the Makrofol™ trademark, such as Makrofol PC or Makrofol DE1-1), polyethylene naphthalate (PEN), polyester, polyamide (PI), polyester sulfone (PES), polystyrene (PS), and amorphous polyester (A-PET or PET-G), and mixtures thereof. In another embodiment, the rubber is selected from the group consisting of ethylene propylene rubber (EPR) and ethylene propylene diene monomer (M-class) rubber (EPDM rubber). Furthermore, the substrate may be a semiconductor material based on Si, Ge, or III-V elements (e.g., In, As, Ga), or cellulose nanotubes (CNTs), silver nanowire materials, graphene, or other similar combinations of materials and substrates.

[0059] In one embodiment, the thickness of the substrate is 5 μm to 2 cm. The thickness of the substrate may vary depending on the intended use of the film or the material of the substrate.

[0060] In this specification, unless otherwise specified, the expression that a substrate is "non-conductive" is understood to mean that the substrate has a sheet resistance of 10 Mohms / square (M / □) or more.

[0061] In one embodiment, the substrate is conductive, such as fluorine-doped tin oxide (FTO) glass, indium tin oxide (ITO) coated glass, gold (Au) coated substrate, silver (Ag) coated substrate, or silicon. Depending on the application, conductive or non-conductive substrates can be useful.

[0062] Film roughness, also known as surface roughness, is a measure of the deviation of the normal vector direction of the actual surface from the ideal shape. If the deviation is large, the surface is rough; if the deviation is small, the surface is smooth.

[0063] In one embodiment, the average roughness (Ra) of the film is less than 200 nm, or less than 150 nm, or less than 100 nm, or less than 80 nm, or less than 50 nm, or less than 25 nm, or less than 15 nm, or less than 10 nm.

[0064] The roughness average of PAz films is obtained from atomic force microscope (AFM) images using WSXM5 software. The roughness average is the average of the absolute values ​​of the differences between the average height of the sample and the height of each single point. This value varies depending on the interval range. It indicates the uniformity or roughness of the PAz film. It can be calculated using the following equation (1):

[0065] [Formula 1] TIFF2025532750000002.tif18168 formula (1) where: ra is the roughness average, is the average height, aij is the height of each sample point, i and j represent the position of a point (entry) on the two-dimensional plane, N is the number of "aij" points considered on the surface.

[0066] The root mean square (rms) roughness of the film is obtained from the AFM images using WSXM5 software, which can be calculated by the following equation (2):

[0067] [Formula 2] TIFF2025532750000003.tif20168 formula (2) This number depends on the range of the interval. Min: The minimum height of the interval in question. Max: The maximum height of the interval in question.

[0068] In one embodiment, the roughness of the film is measured before any annealing and washing steps, which helps to determine how these steps affect the roughness of the film, as this is an important property of the film.

[0069] A smooth film has the added benefit that the conductivity and permeability remain uniform across the surface of the film.

[0070] In one embodiment, the transmittance of the film is 10 to 95%, or 20 to 85%, or 30 to 75%. In one embodiment, the transmittance of the film is measured at 300 to 1100 nm, or 550 to 1100 nm, or 550 nm.

[0071] An Agilent 8453 spectrometer can be used to record UV-Vis spectra. The % transmittance (%T) is calculated from the absorbance (Abs) data using the following equation (3):

[0072] (%T)=(10^(-absolute value))*100 Equation (3) 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 2 In one embodiment, the areal capacitance of the film is 0 to 25 mF / cm 2 , or 0.01 to 15 mF / cm 2 , or 0.05 to 10 mF / cm 2 , or 0.2 to 7 mF / cm 2 , or 1 to 5 mF / cm 2 , or 2 to 4 mF / cm 2 is.

[0073] In one embodiment, the volumetric capacity of the film is 200 to 2000 F / cm 3 , or 250 to 1500F / cm 3 , or 300~1200F / cm 3 , or 500 to 1000F / cm 3 , or 600-800F / cm 3 In one embodiment, the volumetric capacity of the film is 5000 to 18000 F / cm 3 , or 6000~17500F / cm 3 , or 7000~17000F / cm 3 is.

[0074] In one embodiment, areal capacitance (CA) and volumetric capacitance (CV) values ​​are determined by electrochemical characterization by cyclic voltammetry. The charge (Q) is calculated by integrating the cyclic voltammogram in the potential range of −0.25 V to 0.9 V in Origin software and further processed using equations (4) and (5) to obtain the capacitance value.

[0075] Area capacitance CA=Q / (ΔV*A) Equation (4) Volume capacity CV=Q / (ΔV*V) Equation (5) Here, "ΔV" is the potential window, "A" is the area, and "V" is the volume of the working electrode.

[0076] 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 any washing of the film. After washing, the conductivity may be higher or lower than before the washing step. If the polymerization temperature is low, the conductivity before the washing step will be lower. If the polymerization temperature is high, the conductivity after the washing step will be lower.

[0077] In one embodiment, the sheet resistance of the film is 1 to 80 MΩ / □, or 2 to 70 MΩ / □, or 5 to 50 MΩ / □, or 10 to 40 MΩ / □, or 15 to 30 MΩ / □. In one embodiment, the sheet resistance of the film is 0.01 to 2 MΩ / □, or 0.05 to 1.5 MΩ / □, or 0.08 to 1.1 MΩ / □, or 0.2 to 1.1 MΩ / □, or 0.6 to 1 MΩ / □. The sheet resistance can be measured before or after optional washing of the film. After washing, the sheet resistance value may be higher or lower than before the washing step. If the polymerization temperature is low, the sheet resistance value after the washing step will be lower. If the polymerization temperature is high, the sheet resistance value after the washing step will be higher.

[0078] In one embodiment, the sheet resistance is measured before any annealing and washing steps, which helps to determine how these steps affect the resistance of the film.

[0079] A Jandel Model RM3000+ equipped with a cylindrical four-point probe head can be used to obtain sheet resistance (rsheet) values ​​for polymer films. The specific resistance (r) of a film is obtained by multiplying the sheet resistance by the film thickness (d) as shown in Equation (6).

[0080] r=rsheet d Equation (6) The conductivity (s) of the film is obtained according to equation (7).

[0081] s=1 / r formula (7) The methods described herein have the additional advantage of producing highly organized, transparent, and uniform multilayer thin films. Furthermore, the methods described herein have the additional advantage of being low-cost, simple, and rapid due to atmospheric pressure-controlled polymerization, short reaction times, low temperatures, and low monomer loadings.

[0082] The methods described herein have the additional utility of being able to fabricate films layer by layer that are useful for different applications. The methods described herein also have the additional utility of being able to fabricate flexible thin films on plastic materials that can be used in bendable electronics. Furthermore, the methods allow for the fabrication of thin films on the nanometer to micrometer scale.

[0083] The methods described in this application have the additional utility of being suitable for producing films with different properties, such as conductivity and roughness values, and are therefore useful for a variety of applications.

[0084] The present invention further relates to a film obtainable by the method of the present invention, i.e., a film comprising at least one partially patterned polymer layer formed by vapor phase polymerization and disposed on at least one surface of a substrate. According to one embodiment, the total thickness of the film is between 10 nm and 100 μm. All variations and embodiments described above in relation to the method apply mutatis mutandis to the film.

[0085] The present application also relates to a device comprising a film obtained by the method described above. All variants and embodiments described in relation to the method apply mutatis mutandis to the device.

[0086] The device can be, for example, 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, an electrode, a touchscreen, a circuit board, an antenna, a field effect transistor, a photodetector, or a thermoelectric device. Devices of particular interest are electrodes and antennas, and the method allows for the fabrication of conductive patterns directly on the surface of a substrate. Indeed, the method allows for the fabrication of a variety of printed electronics, such as those used in clothing.

[0087] The present application further relates to the use of the above-defined film as an antistatic coating or electrode in electronic devices.

[0088] The present disclosure further provides a system for producing a patterned film on a surface of a substrate, the system comprising: an oxidizer unit configured to apply a solution containing an oxidizer to the surface by coating to form an oxidizer layer on the surface; means for drying the oxidizer layer; means for applying an inhibitor onto the oxidant layer in a pattern; and A chamber configured to expose a surface to monomer vapor at a polymerization temperature between 20 and 95°C under atmospheric pressure to form a polymer layer. The present invention relates to a system comprising:

[0089] The components of the system are in sequential order as described above. Optionally, the temperature of the chamber is configured to differ from the temperature of the surface, the difference being typically between 0 and 30°C. Additionally, all variations and embodiments described above in relation to the method apply mutatis mutandis to the system. If the surface is maintained at a temperature other than the polymerization temperature, the system includes means for maintaining the surface at the desired temperature.

[0090] As mentioned above, the system preferably includes at least one temperature control system for the substrate and chamber, and optionally temperature sensors in the chamber and on the heating block for accurate and precise temperature control of both the chamber, i.e., the monomer vapor, and the surface of the substrate. The system also preferably includes means for maintaining a desired temperature, such as a heating and / or cooling device.

[0091] Detailed Description of the Drawings 1A-1C show schematic diagrams of films formed on a substrate according to an embodiment of the method of the present invention, and various steps of the method. In FIG. 1A, an oxidant layer 2 is formed on the surface of a substrate 4. In FIG. 1B, a pattern of inhibitor 12 is applied to the oxidant layer. FIG. 1C shows the situation after polymerization, where a polymer film 3 has formed on the surface of oxidant layer 2 in areas where activity is not inhibited.

[0092] 2 shows a gas phase polymerization (VPP) cell for conducting gas phase polymerization according to one embodiment. The polymerization or reaction chamber 5 includes a stand 7 for the substrate 4 and a metal block 8. A thermostatic chamber 10 is attached to the polymerization chamber 5 to maintain the temperature of the monomer vapor 9 at the polymerization temperature. A thermostatic chamber 11 is attached to the metal block 8 to maintain the temperature of the substrate 4, and therefore the surface temperature, at a controlled, predetermined temperature. The polymerization chamber 5 includes a lid 6 that is used to close the polymerization chamber 5.

[0093] Figure 3 shows the setup for a continuous VPP process for a substrate according to one embodiment. Using roll-to-roll technology, a solution containing an oxidant 13 is deposited onto a substrate 4, followed by drying the oxidant in an oven or heater 14. An inhibitor is then applied by a printer 15, and the substrate is preheated 16, which can also be performed in an oven or heater. In the next step, the substrate 4 is exposed to monomer vapor in a polymerization chamber 5. The roller speed determines the time the substrate stays in the chamber. The temperature of the substrate or deposition surface is controlled by a heater and / or temperature controller 17. The film is then heated and annealed in a heater 18, followed by rinsing with a cleaning solution 19. Finally, the film is dried (using nitrogen gas) in a dryer 20, resulting in a substrate covered with a patterned film 21.

[0094] Figures 4 to 7 are explained in more detail in the experimental section below.

[0095] (Experimental part) Several different patterned films were prepared.

[0096] Materials and Equipment The materials and equipment used are as follows:

[0097] Acetone manufactured by VWR Chemicals Ethanol manufactured by Altia Oy ammonium hydroxide from Sigma-Aldrich; Hydrogen Peroxide manufactured by VWR Chemicals n-Butanol from Lab Scan Pyridine from Lab Scan Acetonitrile manufactured by Merck 3,4-Ethylenedioxythiophene (EDOT) manufactured by TCI Iron(III)-p-toluenesulfonate from Aldric, molar mass 677.52 g / mol Sodium thiosulfate from Merck, molar mass 248.18 g / mol Ascorbic acid from Merck, molar mass 176.13 g / mol Oxalic acid from Merck, molar mass 126.07 The substrates were glass or polyethylene terephthalate (PET). The glass was manufactured by Menzel-Glaeser or RFFrance and was cut into 76mm x 26mm plates. The PET plates were manufactured by Goodfellow, product number ES30-FM-000225.

[0098] We used a VWR Ultrasonic Cleaner USC-THD, a Jandel conductivity measuring device, Model RM3000+, equipped with a Jandel SE No. 376573 measuring tip and an Rμ100 tip. We also used a Harrick Plasma oxygen plasma cleaner, Plasma Cleaner PDC002. The inkjet printer was manufactured by Dimatix.

[0099] (Cleaning the board) The substrate was cleaned before applying the oxidizing agent. The glass plate was cleaned using acetone, water, and ethanol, each of which was ultrasonically treated for 5 minutes. A cleaning solution consisting of 50 ml of water, 10 ml of ammonium hydroxide, and 10 ml of hydrogen peroxide was then prepared and heated to 80°C. The plate was immersed vertically in the solution for 5 minutes. The substrate was then rinsed with water, then with ethanol, and allowed to dry for at least 1 hour. Just before the start of the experiment, the plate was cleaned with oxygen gas plasma for 5 minutes.

[0100] The PET plate was similarly cleaned by ultrasonic treatment, followed by drying under ambient conditions and oxygen plasma cleaning for 5 minutes, after which it was immediately transferred to the spin coater and oxidizer coated.

[0101] (Oxidizer Solution, Its Preparation and Application) The oxidant was the same in all examples: a solution containing iron(III) p-toluenesulfonate, n-butanol, and pyridine. The oxidant solution was prepared by adding 0.160 mg of iron(III) p-toluenesulfonate to an Eppendorf tube and adding 850 μL of n-butanol. Then, 11.3 μL of pyridine was pipetted into the tube, and the solution was mixed. n-butanol was added until the total volume reached 1 mL. If the iron(III) p-toluenesulfonate did not dissolve, it was dissolved using ultrasound.

[0102] After oxygen plasma cleaning, the substrate was placed on a rotating support and rotation was initiated. Then, 60 μL / 6.5 cm of the oxidizing agent solution prepared above was applied. 2 The solution was pipetted over 20 seconds at 60 μL / in 2 . After 1 minute of rotation, the substrate was transferred to a heating plate (90°C) for 90 seconds.

[0103] (Preparation and application of inhibitor solution) Various inhibitors were tested. For the printed inhibitors, the solid inhibitors were dissolved in a mixture of water (30 vol-%) and propylene glycol (70 vol-%) at a concentration of 0.01 M. For the stamped inhibitors, the inhibitors were dissolved in water.

[0104] The inhibitors were applied using either a rubber stamp or inkjet printing. When using a rubber stamp, the stamp was moistened with a soft tissue paper moistened with the desired solution. Rubber stamps were used on glass substrates, while inkjet printing was used on PET substrates. Rubber stamps were also tested with undried oxidant layers.

[0105] (polymerization) Polymerization was performed in the same manner in all examples. That is, the VPP process was used with EDOT as the sole monomer. Liquid EDOT was applied in a volume of 50 μL to the bottom of a heated VPP chamber (75 °C). It was allowed to evaporate for approximately 15 minutes. After applying the inhibitor pattern, the substrate was placed in the chamber with the treated surface facing down. The substrate was kept in the chamber for 90 seconds, a hot copper plate (65 °C) was placed on the substrate for 60 seconds, and the chamber was closed for another 90 seconds. The finished product was removed from the chamber and placed again on a heat plate (90 °C) with the film facing up for 90 seconds. If there were problems with film formation, the process was repeated several times. The cooled film and substrate were washed twice with acetonitrile and dried with nitrogen gas.

[0106] (rubber stamping) After preparing an oxidant layer on a glass substrate, a rubber stamp was wetted with a 0.01 M aqueous solution of ascorbic acid (1), sodium thiosulfate (2), or oxalic acid (3), and the stamp was pressed onto the fresh oxidant layer.

[0107] Figure 4 shows the resulting images of a PEDOT film on a glass substrate after the VPP process (ascorbic acid on the far left, sodium thiosulfate in the center, and oxalic acid on the far right). It was not possible to completely remove PEDOT from the stamped areas. The resistance of the stamped areas was very high, and additional cleaning steps had some effect in further improving removal. Raman spectra and microscopy images show the reaction of PEDOT residue even in the clear stamped areas.

[0108] (inkjet printing) Printing was performed using a PET substrate, and the inhibitor was printed after the oxidant layer had dried. The rest of the protocol was as described above.

[0109] The printing process involved printing a reducing agent onto the surface of a dried oxidizing agent to create a pattern that would not polymerize. Two solutions were prepared for testing: 0.01M trisodium citrate and 0.01M thiosulfate. Both solutions were a mixture of 70% propylene glycol and 30% water. Using these "inks," the test pattern shown on the left side of Figure 5 was first printed to establish the appropriate printing parameters for best results. While the visual quality of the resulting pattern was very good (see the right side of Figure 5), conductivity measurements indicated that the reduction of the oxidizing agent was not complete, with only a slight decrease in conductivity measured. The thin thickness and high transparency of the VPP film somewhat limit the visibility of the pattern.

[0110] The results of the first attempt were only partially successful, as the printed areas were found to also conduct electricity, although with low conductivity. Further optimization of the reducing agent concentration and the amount of liquid (droplet size) in the printing process is needed to fully inactivate the oxidizing agent layer.

[0111] For the second set of patterned films, a 0.01M solution of ascorbic acid, neutralized to pH 5 with NaOH, was again prepared in a 70% / 30% propylene glycol / water mixture. This time, a complete array of electrodes was printed (left side of Figure 6), and the visual quality of the printed pattern was again excellent (right side of Figure 6). However, the conductivity was virtually identical in printed and non-printed areas. During the initial printing, a raster printing pattern was observed, and using an optical microscope, an array of holes was observed on the surface rather than a uniform coating of reducing agent, necessitating a slight change in parameters from the initial test. After the parameter update, the surface was uniformly coated.

[0112] Atomic force microscope images from the edge of the printed pattern show that the reducing agent reduces the film thickness by approximately 20 nm. Figure 7 shows an AFM image from the edge of the printed area (left). A height profile was determined from the image (right). The lines in the AFM image indicate where the profile was obtained.

[0113] Furthermore, the second printing did not completely deactivate the oxidant layer. Electrical conductivity was observed in the printed areas; however, this could be optimized by increasing the concentration and droplet size of the printed reducing agent. Because the VPP film was at least 20 nm thick (approximately 40 nm), reducing the thickness by 20 nm would not completely remove the film. Furthermore, sheet resistance values ​​indicate the presence of a conductive layer in the printed areas. The sheet resistance was 290 Ω / □ in the unprinted areas and 320 Ω / □ in the printed areas.

[0114] (Conclusion) Although the oxidant reduction was not complete, the small droplets remained consistent throughout the pattern, indicating that continuous "holes" were created throughout the printed electrode pattern. These results suggest that a reducing solution as high as 0.236 M would work, matching the concentration of FETOS in the oxidant solution.

Claims

1. 1. A method for producing a patterned film on a substrate, comprising: forming an oxidizer layer on the substrate by applying a solution containing an oxidizer to the surface of the substrate by coating; drying the oxidant layer; applying an inhibitor onto the oxidizer layer in a pattern to partially inhibit the formation of the oxidizer layer; and forming a polymer layer by exposing said surface to monomer vapors at a polymerization temperature of 20-95°C under atmospheric pressure; A method comprising:

2. The method of claim 1 , wherein the monomer vapor comprises azulene, 3,4-ethylenedioxythiophene, and combinations thereof.

3. 3. The method of claim 1 or 2, wherein the monomer vapor comprises an additional monomer selected from the group consisting of pyrrole, aniline, thiophene, and phenylene.

4. 4. The method of claim 1, wherein the inhibitor is selected from the group consisting of reducing agents and complexing agents.

5. The inhibitors include ascorbic acid, oxalic acid, sodium thiosulfate, trisodium citrate, hydrazine and its derivatives, citric acid, lithium aluminum hydride (LiAlH ４ ), sodium borohydride (NaBH ４ 5. The method of claim 4, wherein the hydroxybenzoate is selected from the group consisting of: dithionate, thiosulfate, and iodide ions, formic acid, reducing sugars, ethylenediaminetetraacetic acid, trans-1,2-diaminocyclohexanetetraacetic acid, trimethylenediaminetetraacetic acid, N-(2-hydroxyethyl)ethylenediamine, N,N',N'-triacetic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED), catechol, 3,5-disulfocatechol, salicylate, and glycine.

6. 6. The method of claim 1, wherein the inhibitor is applied by printing or stamping.

7. 7. The process according to any one of claims 1 to 6, wherein the gas phase polymerization is continued for 1 to 20 minutes.

8. 8. The method of any one of claims 1 to 7, wherein the gas phase polymerization is continued until the polymer layer has a thickness of 10 to 100 nm.

9. 9. The process of any one of claims 1 to 8, wherein the temperature of the surface during the gas phase polymerization is from 25 to 75°C.

10. 10. The process according to any one of claims 1 to 9, wherein the polymerization temperature during the gas phase polymerization is from 25 to 90°C.

11. 11. The process of any one of claims 1 to 10, wherein during the gas phase polymerization the temperature of the surface is 0 to 30°C lower than the polymerization temperature or 0 to 20°C higher than the polymerization temperature.

12. The oxidizing agent is iron(III)-p-toluenesulfonate, FeCl ３ , CuCl ２ , CuBr ２ 12. The method of claim 1, wherein the iron(III) trifluoromethanesulfonate is selected from the group consisting of:

13. 13. The method of claim 1, wherein the solution containing the oxidizing agent is spin-coated onto the surface.

14. The method according to claim 13, wherein the concentration of the solution containing the oxidizing agent is 60 to 500 mM.

15. 15. The method of any one of claims 1 to 14, wherein the method comprises, after the gas phase polymerization, annealing the film at a temperature of from 60 to 100°C.

16. 16. The method of any one of claims 1 to 15, further comprising repeating the steps of forming an oxidizer layer, drying the oxidizer layer, applying an inhibitor, and forming a polymer layer by gas phase polymerization.

17. A device comprising a film obtainable by the method according to any one of claims 1 to 16.

18. 20. The device of claim 17, which is 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, an electrode, a touch screen, a circuit board, an antenna, a field effect transistor, a photodetector, or a thermoelectric device.

19. 1. A system for producing a patterned film on a surface of a substrate, comprising: an oxidizer unit configured to apply a solution containing an oxidizer to the surface by coating to form an oxidizer layer on the surface; means for drying said oxidant layer; means for applying an inhibitor onto said oxidizer layer in a pattern; and a chamber configured to form a polymer layer by exposing said surface to monomer vapor at a polymerization temperature of 20-95°C under atmospheric pressure; Including, the system.

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