Conductive polymer precursor solution, conductive polymer film, preparation method and use

Abstract

Provided in the present application are a conductive polymer precursor solution, a conductive polymer film, a preparation method and the use. The conductive polymer precursor solution comprises a main solvent, an Fe3+ oxidant, a chelating agent and a thiophene monomer, wherein the chelating agent comprises at least one of a diketone compound, a hydroxycarboxylic acid compound and a nitrogen-containing heterocyclic compound. The conductive polymer precursor solution of the present application has good stability, and is friendly in terms of operation and makes it convenient to form a flat and uniform conductive polymer film.

Description

Conductive polymer precursor solution, conductive polymer film, preparation method, and use Technical Field

[0001] The present application relates to the field of optoelectronic devices, and in particular to a conductive polymer precursor solution, a conductive polymer film, a preparation method, and uses. Background Art

[0002] With the development of flexible optoelectronic devices, conductive polymer films have attracted great attention from academia and industry due to their high conductivity and good stability, especially in the fields of thermoelectrics, photovoltaics, lighting, sensing, transparent electrodes, bioelectronics, etc. For example, poly(3,4-ethylenedioxythiophene) (PEDOT) has become a widely studied material due to its excellent conductivity and transport properties.

[0003] The current transparent conductive polymer process used by the scientific community is a two-step vapor phase polymerization (VPP) and chemical vapor deposition (CVD) method. Taking the preparation method of poly (3,4-ethylenedioxythiophene) (PEDOT) conductive polymer film as an example, the oxidant is first deposited into a film, and then exposed to 3,4-ethylenedioxythiophene (EDOT) vapor under vacuum, or it can be evaporated together with EDOT to obtain a thin film, or further introduced Lewis base additives (such as pyridine, imidazole, N-methylpyrrolidone (NMP)), and integrated with various non-reactive polymer additives from polyethylene glycol copolymers to produce sufficient doping and improve conductivity. However, the high cost of organic anion-based oxidants, vacuum vapor deposition equipment, and evaporation units that require precise control limit the production of this method on a commercial scale.

[0004] In order to reduce production costs, people have tried to prepare the above-mentioned reactants into solutions and form conductive polymer films based on the solution method. However, due to the strong reactivity of some reactants (for example, oxidants, etc.), the stability of the reactant solution is not easy to ensure, and the reaction is too fast during the film formation process, resulting in uneven film formation, which hinders the commercial application of the solution method.

[0005] Summary of the Invention

[0006] In view of the above-mentioned problems existing in the prior art, the present application provides a conductive polymer precursor solution, a conductive polymer film, a preparation method, and uses.

[0007] The first aspect of the present application provides a conductive polymer precursor solution, comprising a main solvent, Fe 3+ An oxidant, a chelating agent and a thiophene monomer, wherein the chelating agent comprises at least one of a diketone compound, a hydroxycarboxylic acid compound and a nitrogen-containing heterocyclic compound.

[0008] Optionally, the diketone compound includes a compound of formula (A), and / or the hydroxycarboxylic acid compound includes a compound of formula (B), and / or the nitrogen-containing heterocyclic compound includes a compound of formula (C);

[0009] In formula (A), n is an integer from 0 to 8, R1 and R2 are each independently selected from a hydrogen atom, a C1-C8 alkyl group, preferably, R1 and R2 are each independently selected from a C1-C6 alkyl group; in formula (B), m is an integer from 0 to 8; in formula (C), R3, R4, R5, R6, R7, R8, R9 and R 10 Each is independently selected from a hydrogen atom, a C1-C8 alkyl group or an aromatic group.

[0010] Optionally, the diketone compounds include 2,3-butanedione, 2,4-pentanedione, and 2,5-hexanedione.

[0011] Optionally, the hydroxycarboxylic acid compound includes oxalic acid and succinic acid.

[0012] Optionally, the nitrogen-containing heterocyclic compound includes 2,2'-bipyridine.

[0013] Optionally, based on the volume of the main solvent of the conductive polymer precursor solution, the volume fraction of the chelating agent is less than or equal to 2%.

[0014] Optionally, based on the volume of the main solvent of the conductive polymer precursor solution, the volume fraction of the chelating agent satisfies 0.2% to 2%.

[0015] Optionally, the thiophene monomer includes 3,4-ethylenedioxythiophene.

[0016] Optional, Fe 3+ The oxidant includes at least one of Fe2(SO4)3, Fe(ClO4)3, Fe(OTf)3 and Fe(OTs)3.

[0017] Optionally, the main solvent includes at least one of C1-C6 alcohols, acetonitrile or dimethyl nylonate.

[0018] Optionally, the conductive polymer precursor solution further includes a dispersant.

[0019] Optionally, the dispersing agent comprises a polyethylene glycol copolymer.

[0020] Optionally, the polyethylene glycol copolymer includes a triblock copolymer of polyethylene glycol-polypropylene glycol-polyethylene glycol.

[0021] Optionally, the conductive polymer precursor solution further includes a secondary solvent, and the secondary solvent includes at least one of a compound of formula (D), a compound of formula (E), a compound of formula (F), a compound of formula (G), a compound of formula (H), a compound of formula (I), water, an aqueous solution containing hydrogen ions, a cyclic amide, a chain amide, a cyclic urea, a chain urea, a phosphate ester, or a phosphoramide.

[0022] In formula (D), q is an integer from 1 to 8, R 11 Selected from hydrogen atom, C1-C8 alkyl, preferably, R 11 is selected from C1-C6 alkyl; in formula (E), p is an integer from 0 to 8, R 12 、R 13 Each independently selected from hydrogen atom, C1-C8 alkyl, preferably, R 12 、R 13 Each is independently selected from C1-C6 alkyl; in formula (F), R 14 、R 15 、R 16 、R 17 Each independently selected from hydrogen atom, C1-C8 alkyl, preferably, R 14 、R 15 、R 16 、R 17 Each is independently selected from C1-C6 alkyl; in formula (G), R 18 、R 19 、R 20 Each independently selected from hydrogen atom, C1-C8 alkyl, preferably, R 18 、R 19 、R 20 Each is independently selected from C1-C6 alkyl; in formula (H), R 21 、R 22 、R 23 、R 24 、R 25 、R 26 Each independently selected from hydrogen atom, C1-C8 alkyl, preferably, R 21 、R 22 、R 23 、R 24 、R 25 、R 26 Each is independently selected from C1-C6 alkyl; in formula (I), R 27 、R 28 、R 29 Each independently selected from hydrogen atom, C1-C8 alkyl, preferably, R 27 、R 28 、R 29 Each is independently selected from C1-C6 alkyl.

[0023] Optionally, based on the mass of the main solvent, the mass fraction of the secondary solvent is 1% to 25%.

[0024] Alternatively, the cyclic amide comprises N-methylcaprolactam.

[0025] Alternatively, the chain amide includes N,N-diethylacetamide.

[0026] Alternatively, the cyclic urea comprises N,N-dimethylpropylene urea.

[0027] Alternatively, the chain urea comprises tetramethyl urea.

[0028] Optionally, the phosphate ester includes trimethyl phosphate and tributyl phosphate.

[0029] Alternatively, the phosphoramide comprises hexamethylphosphoric triamide.

[0030] Optionally, the aqueous solution containing hydrogen ions is selected from an organic acid solution and an inorganic acid solution.

[0031] Optionally, the concentration of hydrogen ions in the aqueous solution of hydrogen ions is greater than 0.01 mol / L.

[0032] Optionally, the aqueous solution containing hydrogen ions is selected from hydrochloric acid solution, phosphoric acid solution, sulfuric acid solution, perchloric acid solution and acetic acid solution.

[0033] The second aspect of the present application provides a method for preparing a conductive polymer film, comprising: step (a), providing a substrate and the aforementioned conductive polymer precursor solution; step (b), coating the conductive polymer precursor solution on the surface of the substrate, removing the solvent, and causing the thiophene monomer to undergo polymerization reaction to form a conductive polymer film.

[0034] Optionally, the method for preparing the conductive polymer precursor solution includes: step (1), providing a solvent, wherein the solvent includes a main solvent; step (2), 3+ The oxidant and the chelating agent are added to the solvent provided in step (1) and mixed uniformly to form an intermediate solution; in step (3), the thiophene monomer is added to the intermediate solution formed in step (2) and mixed uniformly to form a conductive polymer precursor solution.

[0035] Optionally, the solvent provided in step (1) further comprises a secondary solvent, and the secondary solvent comprises at least one of a compound of formula (D), a compound of formula (E), a compound of formula (F), a compound of formula (G), a compound of formula (H), a compound of formula (I), water, an aqueous solution containing hydrogen ions, a cyclic amide, a chain amide, a cyclic urea, a chain urea, a phosphate ester, or a phosphoramide.

[0036] In formula (D), q is an integer from 1 to 8, R 11Selected from hydrogen atom, C1-C8 alkyl, preferably, R 11 is selected from C1-C6 alkyl; in formula (E), p is an integer from 0 to 8, R 12 、R 13 Each independently selected from hydrogen atom, C1-C8 alkyl, preferably, R 12 、R 13 Each is independently selected from C1-C6 alkyl; in formula (F), R 14 、R 15 、R 16 、R 17 Each independently selected from hydrogen atom, C1-C8 alkyl, preferably, R 14 、R 15 、R 16 、R 17 Each is independently selected from C1-C6 alkyl; in formula (G), R 18 、R 19 、R 20 Each independently selected from hydrogen atom, C1-C8 alkyl, preferably, R 18 、R 19 、R 20 Each is independently selected from C1-C6 alkyl; in formula (H), R 21 、 R 22 、R 23 、R 24 、R 25 、R 26 Each independently selected from hydrogen atom, C1-C8 alkyl, preferably, R 21 、R 22 、R 23 、R 24 、R 25 、R 26 Each is independently selected from C1-C6 alkyl; in formula (I), R 27 、R 28 、R 29 Each independently selected from hydrogen atom, C1-C8 alkyl, preferably, R 27 、R 28 、R 29 Each is independently selected from C1-C6 alkyl.

[0037] Optionally, based on the mass of the conductive polymer precursor solution, the mass fraction of the secondary solvent is 1% to 25%.

[0038] Alternatively, the cyclic amide comprises N-methylcaprolactam.

[0039] Alternatively, the chain amide includes N,N-diethylacetamide.

[0040] Alternatively, the cyclic urea comprises N,N'-dimethylpropylene urea.

[0041] Alternatively, the chain urea comprises tetramethyl urea.

[0042] Optionally, the phosphate ester includes trimethyl phosphate and tributyl phosphate.

[0043] Alternatively, the phosphoramide comprises hexamethylphosphoric triamide.

[0044] Optionally, the aqueous solution containing hydrogen ions is selected from an organic acid solution and an inorganic acid solution; preferably, the concentration of hydrogen ions in the aqueous solution containing hydrogen ions is greater than 0.01 mol / L; preferably, the aqueous solution containing hydrogen ions is selected from a hydrochloric acid solution, a phosphoric acid solution, a sulfuric acid solution, a perchloric acid solution and an acetic acid solution.

[0045] Optionally, before step (2), a polyethylene glycol copolymer is added to the solvent provided in step (1). Preferably, the polyethylene glycol copolymer comprises a triblock copolymer of polyethylene glycol-polypropylene glycol-polyethylene glycol.

[0046] Optionally, the polymerization reaction temperature is 20°C to 150°C, preferably, the polymerization reaction temperature is 20°C to 80°C; the polymerization reaction time is 0.1min to 20min, preferably, the polymerization reaction time is 2min to 10min.

[0047] Optionally, the method of coating the conductive polymer precursor solution on the surface of the substrate includes spin coating, dip coating, screen printing, slit coating or inkjet printing.

[0048] Optionally, the preparation method of the present application further comprises: step (c), washing and drying the conductive polymer film obtained in step (b).

[0049] A third aspect of the present application provides a conductive polymer film, which is prepared by the aforementioned preparation method, and the square resistance and / or transmittance of the conductive polymer film is adjustable.

[0050] The fourth aspect of the present application also provides the use of the conductive polymer film in a film touch screen, an electronic writing tablet, an electrochromic display, a smart window, a solar cell, a light emitting diode, a laser device, a gas sensor, an antistatic coating or a capacitor electrode.

[0051] The technical solution of this application can achieve the following beneficial effects:

[0052] The chelating agent in the conductive polymer precursor solution of the present application can be combined with Fe 3+ The oxidant forms a ring-structured or chain-structured complex to adjust the stability of the precursor solution, which helps to improve the stability of the precursor solution without affecting the polymerization reaction of thiophene monomers when forming a conductive polymer film; at the same time, it also helps to improve the uniformity of film formation, and thus, is conducive to commercial applications.

[0053] In addition, the conductivity and visible light transmittance of the conductive polymer film directly prepared according to the preparation method of the present application can be adjusted and controlled according to the actual industrial application scenario, and compared with the vapor evaporation method, it has a wider commercial applicability. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] The present application is further explained and illustrated below in conjunction with the accompanying drawings. It should be understood that the following drawings are only for illustrative purposes and are not intended to limit the technical solutions of the present application.

[0055] FIG1 is a surface scanning electron microscope image of a conductive polymer film prepared from a conductive polymer precursor solution to which a chelating agent is added according to the present application;

[0056] FIG2 is a surface scanning electron microscope image of a conductive polymer film prepared from a conductive polymer precursor solution without adding a chelating agent;

[0057] FIG3 shows the transmission spectra of conductive polymer films prepared from conductive polymer precursor solutions to which different types of main solvents were added. DETAILED DESCRIPTION

[0058] To make the purpose, technical solutions, and advantages of this application more clear, the technical solutions of this application will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of this application, rather than all the embodiments. The relevant embodiments described herein are illustrative and are used to provide a basic understanding of this application. The embodiments of this application should not be interpreted as limiting this application.

[0059] For the sake of clarity, only some numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form an unspecified range; and any lower limit may be combined with other lower limits to form an unspecified range, and similarly, any upper limit may be combined with any other upper limit to form an unspecified range. In addition, each individually disclosed point or single value may itself serve as a lower limit or upper limit and be combined with any other point or single value, or with other lower limits or upper limits, to form an unspecified range.

[0060] In the description herein, unless otherwise specified, “above” and “below” include the number itself.

[0061] Unless otherwise specified, the terms used in this application have the commonly understood meanings commonly understood by those skilled in the art. Unless otherwise specified, the numerical values ​​of the various parameters mentioned in this application can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the examples of this application).

[0062] A list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

[0063] The term "C1-C8 alkyl" may be any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, and n-octyl and its isomers.

[0064] The present application will be further described below in conjunction with specific embodiments. It should be understood that these specific embodiments are only used to illustrate the present application and are not used to limit the scope of the present application.

[0065] 1. Conductive polymer precursor solution

[0066] One or more embodiments of the present application provide a conductive polymer precursor solution, including a main solvent, Fe 3+ An oxidant, a chelating agent and a thiophene monomer, wherein the chelating agent includes but is not limited to at least one of a diketone compound, a hydroxycarboxylic acid compound and a nitrogen-containing heterocyclic compound.

[0067] The chelating agent in the conductive polymer precursor solution of the present application can be combined with Fe 3+ The oxidant forms a ring-structured or chain-structured complex or regulates the stability of the precursor solution, which helps to improve the stability of the precursor solution without affecting the polymerization reaction of the thiophene monomer when forming the conductive polymer film; at the same time, it also helps to improve the uniformity of film formation, and thus, is conducive to commercial applications.

[0068] In some embodiments, the diketone compound includes a compound of formula (A). In formula (A), n is an integer from 0 to 8, and exemplary, n is any one of 0, 1, 2, 3, 4, 5, 6, 7, or 8; R1 and R2 are each independently selected from a hydrogen atom, a C1-C8 alkyl group, and exemplary, R1 and R2 are each independently selected from a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group and its isomers, an n-hexyl group and its isomers, an n-heptyl group and its isomers, and an n-octyl group and its isomers. In some embodiments, R1 and R2 are each independently selected from a C1-C6 alkyl group.

[0069] In some embodiments, the hydroxycarboxylic acid compound comprises a compound of formula (B). In formula (B), m is an integer from 0 to 8; illustratively, m is any one of 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0070] In some embodiments, the nitrogen-containing heterocyclic compound includes a compound of formula (C). In formula (C), R3, R4, R5, R6, R7, R8, R9 and R 10 Each is independently selected from a hydrogen atom, a C1-C8 alkyl group or an aromatic group; for example, R3, R4, R5, R6, R7, R8, R9 and R 10 Each is independently selected from a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group and its isomers, a n-hexyl group and its isomers, a n-heptyl group and its isomers, a n-octyl group and its isomers, and a benzene ring.

[0071] In some embodiments, diketone compounds include but are not limited to 2,3-butanedione, 2,4-pentanedione, and 2,5-hexanedione.

[0072] In some embodiments, the hydroxycarboxylic acid compound includes, but is not limited to, oxalic acid and succinic acid.

[0073] In some embodiments, nitrogen-containing heterocyclic compounds include, but are not limited to, 2,2'-bipyridine.

[0074] In some embodiments, the volume fraction of the chelating agent is less than or equal to 2% based on the volume of the main solvent of the conductive polymer precursor solution. For example, the volume fraction of the chelating agent is 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2%, or a range consisting of any two of the foregoing values, based on the volume of the main solvent of the conductive polymer precursor solution.

[0075] In some embodiments, the volume fraction of the chelating agent is 0.2% to 2% based on the volume of the main solvent of the conductive polymer precursor solution. For example, the mass fraction of the chelating agent is 0.25%, 0.3%, 0.7%, 0.9%, 1.1%, 1.3%, 1.7%, 1.9%, or a range consisting of any two of the foregoing values, based on the mass of the conductive polymer precursor solution.

[0076] In some embodiments, thiophene monomers include but are not limited to 3,4-ethylenedioxythiophene, which has the structural formula

[0077] In some embodiments, Fe 3+The oxidant includes but is not limited to at least one of Fe2(SO4)3, Fe(ClO4)3, Fe(OTf)3 and Fe(OTs)3. 3+ In the oxidative polymerization reaction, the oxidant has a very strong reaction activity in the polar solvent. In this application, a chelating agent is added to the conductive polymer precursor solution to make Fe 3+ The chelate forms a chelate with the chelating agent, thereby improving the stability of the conductive polymer precursor solution. In a specific example of the present application, the chelating agent is 2,4-pentanedione, which reacts with Fe 3+ A chelation reaction occurs, as follows:

[0078] In some embodiments, the main solvent includes but is not limited to at least one of C1-C6 alcohols, acetonitrile, or dimethyl nylonate.

[0079] In some embodiments, the conductive polymer precursor solution further includes a secondary solvent. The secondary solvent has a mass fraction of 1% to 25% based on the mass of the conductive polymer precursor solution. Exemplarily, the secondary solvent has a mass fraction of 1%, 2%, 5%, 10%, 12%, 15%, 18%, 20%, 25%, or a range consisting of any two of the foregoing values ​​based on the mass of the conductive polymer precursor solution.

[0080] In the present application, the secondary solvent used regulates the precursor solution by providing a suitable solvent environment, thereby resulting in a slow reaction rate and facilitating the formation of a thicker film (20 nm to 500 nm) and a uniform polymerization reaction, thereby forming a better film. Those skilled in the art can select the mass concentration of the secondary solvent according to actual needs.

[0081] In some embodiments, the secondary solvent comprises a compound of formula (D). In formula (D), q is an integer from 1 to 8, and exemplarily, q is any one of 1, 2, 3, 4, 5, 6, 7, and 8; R 11 is selected from hydrogen atom, C1-C8 alkyl, exemplary, R 11 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers. In some embodiments, R 11 Selected from C1-C6 alkyl.

[0082] In some embodiments, the secondary solvent comprises a compound of formula (E). In formula (E), p is an integer from 0 to 8, and exemplary, p is any one of 0, 1, 2, 3, 4, 5, 6, 7, and 8; R 12 、R 13Each independently selected from a hydrogen atom, a C1-C8 alkyl group, exemplary, R 12 、R 13 Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers. In some embodiments, R 12 、R 13 Each is independently selected from C1-C6 alkyl.

[0083] In some embodiments, the secondary solvent comprises a compound of formula (F). 14 、R 15 、R 16 、R 17 Each independently selected from a hydrogen atom, a C1-C8 alkyl group, exemplary, R 14 、R 15 、R 16 、R 17 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers; in some embodiments, R 14 、R 15 、R 16 、R 17 Each is independently selected from C1-C6 alkyl.

[0084] In some embodiments, the secondary solvent comprises a compound of formula (G). 18 、R 19 、R 20 Each independently selected from a hydrogen atom, a C1-C8 alkyl group, exemplary, R 18 、R 19 、R 20 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers; in some embodiments, R 18 、R 19 、R 20 Each is independently selected from C1-C6 alkyl.

[0085] In some embodiments, the secondary solvent comprises a compound of formula (H). 21 、R 22 、R 23 、R 24 、R 25 、R 26Each independently selected from a hydrogen atom, a C1-C8 alkyl group, exemplary, R 21 、R 22 、R 23 、R 24 、R 25 、R 26 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers; in some embodiments, R 21 、R 22 、R 23 、R 24 、R 25 、R 26 Each is independently selected from C1-C6 alkyl.

[0086] In some embodiments, the secondary solvent comprises a compound of formula (I). 27 、R 28 、R 29 Each independently selected from a hydrogen atom, a C1-C8 alkyl group, exemplary, R 27 、R 28 、R 29 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers; in some embodiments, R 27 、R 28 、R 29 Each is independently selected from C1-C6 alkyl.

[0087] In certain embodiments, secondary solvent includes at least one of water, aqueous solution containing hydrogen ions, cyclic amides, chain amides, cyclic urea, chain urea, phosphate or phosphoramide. In certain embodiments, secondary solvent is aqueous solution containing hydrogen ions, wherein the concentration of hydrogen ions is greater than 0.01mol / L. It will be readily understood by those skilled in the art that when the concentration of hydrogen ion solution needs to be selected, those skilled in the art can select suitable concentration according to actual application requirements, and the application does not limit this.

[0088] In some embodiments, the aqueous solution containing hydrogen ions includes, but is not limited to, at least one of a hydrochloric acid solution, a phosphoric acid solution, a sulfuric acid solution, a perchloric acid solution, and an acetic acid solution.

[0089] In some embodiments, cyclic amides include, but are not limited to, N-methylcaprolactam.

[0090] In some embodiments, the chain hydrocarbon amide includes, but is not limited to, N,N-diethylacetamide.

[0091] In some embodiments, cyclic ureas include, but are not limited to, N,N-dimethylpropylene urea.

[0092] In some embodiments, chain ureas include, but are not limited to, tetramethyl urea.

[0093] In some embodiments, the phosphate ester includes, but is not limited to, trimethyl phosphate and tributyl phosphate.

[0094] In some embodiments, phosphoramides include but are not limited to hexamethylphosphoric triamide.

[0095] In some embodiments, the conductive polymer precursor solution further includes a dispersant.

[0096] In some embodiments, dispersants include, but are not limited to, polyethylene glycol copolymers.

[0097] In some embodiments, polyethylene glycol copolymers include, but are not limited to, triblock copolymers of polyethylene glycol-polypropylene glycol-polyethylene glycol.

[0098] 2. Preparation method of conductive polymer film

[0099] One or more embodiments of the present application further provide a method for preparing a conductive polymer film, comprising:

[0100] Step (a), providing a substrate and the aforementioned conductive polymer precursor solution;

[0101] Step (b) is to apply a conductive polymer precursor solution to the surface of the substrate, remove the solvent, and allow the thiophene monomers to undergo polymerization to form a conductive polymer film.

[0102] The preparation method of the present application adopts a one-step solution method to prepare a conductive polymer film. There is no need to perform post-processing steps such as acid treatment, high-temperature treatment, or a combination thereof on the conductive polymer film obtained in step (b). It is low-temperature and low-cost, and can produce PEDOT-based conductive polymer films under ordinary conditions. In addition, the process technology can be easily expanded in different solvents. The operation is safe and simple, which is conducive to commercial applications. The film properties obtained by the preparation method of the present application have good uniformity and variable thickness. The conductive polymer film obtained by this method has a transmittance of not less than 70% in the visible spectrum range, preferably 70-90%, and a sheet resistance of 50-500 Ohm / sq, preferably not more than 200 Ohm / sq. Due to the ability to produce high-quality and easily scalable PEDOT-based conductive polymer films, it becomes an economical alternative to conductive polymer films based on silver and tin oxide.

[0103] Furthermore, the conductivity and visible light transmittance of the conductive polymer film directly produced according to the preparation method of the present application can be adjusted and controlled according to actual industrial application scenarios, which has a wider commercial applicability than the vapor phase evaporation method. It is understood that the conductive polymer precursor solution of the embodiments of the present application can be a solution prepared in advance and stored for a period of time, or a solution prepared freshly before preparing the conductive polymer film.

[0104] Since the conductive polymer precursor solution of the present application has good stability, it is easier to operate.

[0105] In some embodiments, the method for preparing a conductive polymer precursor solution includes:

[0106] Step (1), providing a solvent, wherein the solvent includes the main solvent of the aforementioned embodiment;

[0107] Step (2) is to convert the Fe 3+ The oxidizing agent and the chelating agent of the aforementioned embodiment are added to the solvent provided in step (1), and mixed uniformly to form an intermediate solution;

[0108] Step (3), adding the thiophene monomer of the above embodiment to the intermediate solution formed in step (2), and mixing them evenly to form a conductive polymer precursor solution.

[0109] In some embodiments, the solvent provided in step (1) further comprises the secondary solvent of the aforementioned embodiment.

[0110] In some embodiments, before step (2), the polyethylene glycol copolymer of the aforementioned embodiment is added to the solvent provided in step (1).

[0111] In some embodiments, the polyethylene glycol copolymer comprises a triblock copolymer of polyethylene glycol-polypropylene glycol-polyethylene glycol.

[0112] In some embodiments, the temperature of the polymerization reaction is 20°C to 150°C. Exemplarily, the temperature of the polymerization reaction is 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C or a range consisting of any two of the above values. For example, the temperature of the polymerization reaction is 20°C to 80°C; the time of the polymerization reaction is 0.1 min to 20 min. Exemplarily, the time of the polymerization reaction is 0.1 min, 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 8 min, 10 min, 12 min, 14 min, 16 min, 18 min, 20 min or a range consisting of any two of the above values. For example, the time of the polymerization reaction is 2 min to 10 min.

[0113] In some embodiments, the method of coating the conductive polymer precursor solution on the surface of the substrate includes spin coating, dip coating, screen printing, slot coating, or inkjet printing.

[0114] In some embodiments, the method of coating the conductive polymer precursor solution on the surface of the substrate is conventional spin coating.

[0115] In some embodiments, the preparation method further comprises: step (c), washing and drying the conductive polymer film obtained in step (b).

[0116] In a specific example of the present application, the method for preparing the conductive polymer film of the present application comprises the following steps: mixing a main solvent, a secondary solvent, a chelating agent and a polyethylene glycol copolymer to form a first material solution; adding Fe 3+ An oxidant and a thiophene monomer are prepared to obtain a precursor solution; the precursor solution is coated on a substrate by any method such as spin coating, dip coating, slot die coating or inkjet printing, and heated (for example, 50° C. to 80° C.) for 0.1 min to 20 min, or treated in a vacuum or dry gas environment for 0.1 min to 20 min to remove residual solvent and polymerize the thiophene monomer to form a conductive polymer film; thereafter, the conductive polymer film is washed with a solvent (for example, a main solvent) to remove unnecessary components (for example, Fe 3+ oxidant, polyethylene glycol copolymer and chelating agent), the washing method includes but is not limited to immersing the conductive polymer film in a solvent bath; finally, the washed conductive polymer film is dried, for example, at 50° C. to 80° C. for 2 min to 5 min.

[0117] 3. Conductive polymer film

[0118] One or more embodiments of the present application further provide a conductive polymer film, which is prepared by the preparation method of the aforementioned embodiment, and the square resistance and / or transmittance of the conductive polymer film is adjustable.

[0119] In some embodiments, the conductive polymer film has a sheet resistance of 50 ohm / sq to 500 ohm / sq, and / or a light transmittance in the visible spectrum range of greater than or equal to 70%.

[0120] In some embodiments, the conductive polymer film has a sheet resistance of 50 ohm / sq to 300 ohm / sq.

[0121] In some embodiments, the sheet resistance of the conductive polymer film is 50 ohm / sq to 200 ohm / sq.

[0122] 4. Application of Conductive Polymer Film

[0123] The conductive polymer film of the aforementioned embodiment can be applied to film touch screens, electronic writing tablets, electrochromic displays, smart windows, solar cells, light-emitting diodes, laser devices, gas sensors, antistatic coatings, or capacitor electrodes.

[0124] The technical solution of the present application will be further described below with reference to specific embodiments and comparative examples.

[0125] Examples and Comparative Examples

[0126] The equipment used in the embodiments and comparative examples and the parameter calculation method are as follows:

[0127] Equipment and Method: Coating: Prepared using a spin coater in a clean room. The average transmittance of the glass in the visible light range (380nm to 780nm) is 91.5%.

[0128] Thickness: Use a Dektec profilometer to measure the thickness by taking three measurements at the center of the scrape and then taking the average.

[0129] Sheet resistance: Measured at the center of the film using a four-probe device.

[0130] Transmittance: The light transmittance was measured using a Shimadzu 2400 direct detector without an integrating sphere, and the detector had a slit width of 5 nm.

[0131] The names and structures of representative chelating agents used in this application are shown in Table 1, and representative secondary solvents are shown in Table 2.

[0132] Table 1

[0133] Table 2

[0134] Example 1

[0135] Solid oxidant Fe(ClO4)3 and chelating agent 2,4-pentanedione were added to ethanol solvent to form solution A. The concentration of Fe(ClO4)3 in solution A was 100 mg / mL and the concentration of 2,4-pentanedione in solution A was 20 μL / mL. Then, 10 μL of EDOT was added to 1 mL of solution A to form solution B. After solution B was allowed to stand for 5 minutes, it was immediately filled with solution B on a 20×20 mm 2 The film was spin-coated onto glass at a speed of 1000 rpm for 30 seconds. After forming the film, it was annealed on an 80°C hot plate for 3 minutes. Afterwards, it was immersed in an ethanol bath at room temperature for 5 minutes (three times). The film was then dried on an 80°C hot plate for 3 minutes to produce a conductive polymer film.

[0136] Examples 2-3

[0137] The only difference between Examples 2 and 3 and Example 1 is that after solution B is prepared, it is allowed to stand for 10 minutes and 15 minutes respectively before spin coating to form a film.

[0138] Examples 4 to 6

[0139] The only difference between Examples 4 to 6 and Example 1 is that the volume fraction of the chelating agent is different, which are 0.2%, 0.5% and 1% respectively.

[0140] Example 7

[0141] The only difference between Example 7 and Example 1 is that a triblock copolymer of polyethylene glycol-polypropylene glycol-polyethylene glycol (P123) with a Mw of 5800 is used. Specifically, P123 is first added to an ethanol solvent and thoroughly mixed, wherein the ethanol content is 80wt% and the P123 content is 20wt%. Solid oxidant Fe(ClO4)3 and chelating agent 2,4-pentanedione are added to form solution A. The concentration of Fe(ClO4)3 in solution A is 80mg / mL, and the concentration of 2,4-pentanedione in solution A is 20μL / mL. Then, 10μL EDOT is added to 1mL of solution B to form solution B. Within half an hour, solution B is used to form a 20×20mm 2 The film was spin-coated onto glass at a speed of 1000 rpm for 30 seconds. The film was then annealed on an 80°C hot plate for 3 minutes. The film was then washed three times in an ethanol bath at room temperature for 5 minutes. The film was then dried at 80°C for 3 minutes to produce a conductive polymer film.

[0142] Examples 8 to 11

[0143] The only difference between Examples 8 to 11 and Example 7 is that isopropyl alcohol, n-butanol, acetonitrile, and dimethyl nylonate were used as main solvents, respectively, and the chelating agent content was adjusted to 10 μL / mL. See Table 3 for details.

[0144] Table 3 Using different main solvents

[0145] Example 12

[0146] The main solvent ethanol and the secondary solvent CLM were mixed in proportion to form a solvent system, and a P123 with a Mw of 5800 was added to the above solvent system and mixed thoroughly, wherein the content of ethanol was 74wt%, the content of secondary solvent CLM was 6wt%, and the content of P123 was 20wt%. Then, solid oxidant Fe(ClO4)3 and chelating agent 2,4-pentanedione were added to solution A to form solution A. The concentration of Fe(ClO4)3 in solution A was 80mg / mL, and the concentration of 2,4-pentanedione in solution A was 10μL / mL. Then, 10μL EDOT was added to 1mL of solution A to form solution B. Within half an hour, solution B was used to precipitate the precipitate in a 20×20mm 2 The film was spin-coated onto glass at a speed of 1000 rpm for 30 seconds. The film was then annealed on an 80°C hot plate for 3 minutes. The film was then washed three times in an ethanol bath at room temperature for 5 minutes. The film was then dried at 80°C for 3 minutes to produce a conductive polymer film.

[0147] Examples 13 to 18

[0148] The only difference between Examples 13 to 18 and Example 12 is that N,N'-diethylacetamide, N,N'-dimethylpropylene urea, tetramethyl urea, hexamethylphosphoric triamide, trimethyl phosphate, and tributyl phosphate are added as secondary solvents, respectively. See Table 4 for details.

[0149] Table 4 Film-forming properties using secondary solvents

[0150] Examples 19 to 21

[0151] The only difference between Examples 19 to 21 and Example 12 is that different chelating agents are added, respectively. See Table 5 for details.

[0152] Table 5 Film-forming properties of different chelating agents

[0153] Comparative Example 1

[0154] The only difference between Comparative Example 1 and Example 1 is that no chelating agent is used.

[0155] Comparative Examples 2-3

[0156] The only difference between Comparative Examples 2 and 3 and Comparative Example 1 is that Solution B was allowed to stand for 10 minutes and 15 minutes before being spin-coated to form a film.

[0157] Comparative Example 4

[0158] The only difference between Comparative Example 4 and Example 7 is that no chelating agent is used and the rotation speed is adjusted to 1500 rpm.

[0159] Referring to Figure 2 , in the conductive polymer solutions of Comparative Examples 1-3 (Solution B), where no chelating agent was used, the surface morphology of the conductive polymer film was poor, and the surface morphology became rougher as the conductive polymer solution was allowed to stand for a longer time. This is because the oxidant in the conductive polymer solution is highly active and reacts very quickly after preparation, resulting in poor homogeneity of the conductive polymer solution itself and, consequently, poor morphology of the resulting conductive polymer film.

[0160] Referring to Figure 1, it can be seen that adding a chelating agent to the conductive polymer precursor solution can significantly improve the surface smoothness of the conductive polymer film. And as the time of standing still after the conductive polymer precursor solution is prepared increases, the formed conductive polymer film still has a smooth and uniform surface morphology. It can be seen that after adding a chelating agent to the conductive agent polymer solution, the stability of the conductive polymer solution can be significantly improved, and thus, it can ensure that the operator has enough time to perform the film forming operation. In addition, the applicant has further verified that leaving the conductive polymer solution to stand for a longer period of time, for example, several hours or several days, still does not affect the preparation of the conductive polymer film.

[0161] In Examples 4-6, the amount of the chelating agent in the conductive polymer precursor solution was changed. As the amount of the chelating agent increased, the morphology of the conductive polymer film did not deteriorate significantly (not shown).

[0162] The applicant also found that due to the poor morphology of Comparative Examples 1-3, its sheet resistance was even as high as over 10,000 Ohm / sq, and although Examples 1-6 improved the surface morphology of the conductive polymer film by introducing a chelating agent into the conductive polymer solution, its sheet resistance still did not decrease significantly. In order to improve the conductivity of the conductive polymer film, the applicant further added a dispersant P123 to the conductive polymer precursor solution of Example 7 and Comparative Example 4. The other preparation methods of Example 7 were the same as those of Example 1, and the other preparation methods of Comparative Example 4 were the same as those of Example 1. The sheet resistance of the conductive polymer film obtained in Example 7 was reduced to 312 Ohm / sq. Although the sheet resistance of the conductive polymer film obtained in Comparative Example 4 was lower than 312 Ohm / sq, its surface morphology was still poor, which was not conducive to practical applications. The surface morphology of the conductive polymer film of Example 7 was more excellent, and therefore, it was more suitable for practical applications.

[0163] As shown in Table 3, to further optimize the conductive polymer solution and the conductive polymer film formed therefrom, the applicant also selected different main solvents to prepare the conductive polymer precursor solution in Examples 8 to 11. Combined with Figure 3 , the resulting conductive polymer film achieved an average transmittance of approximately 70% and a sheet resistance of approximately 200 Ohm / sq. It should be noted that Curve 1 in Figure 3 corresponds to the transmittance spectrum of glass, while Curves 2 to 5 correspond to the transmittance spectra of the conductive polymer films produced in Examples 8 to 11.

[0164] Referring to Table 4, in Examples 12 to 18, the applicant further added different types of secondary solvents to the conductive polymer precursor solution based on Example 8, resulting in a further reduction in the sheet resistance of the conductive polymer film and a significant increase in the average light transmittance. This may be because the addition of the secondary solvent further enhances the surface and internal uniformity of the formed conductive polymer film, thereby improving both the conductivity and light transmittance of the conductive polymer film.

[0165] Referring to Table 5, in Examples 19 to 21, the applicant used different chelating agents to prepare the conductive polymer precursor solution based on Example 12. The square resistance of the conductive polymers obtained was below 200 Ohm / sq, and could even be reduced to 62 Ohm / sq; and the average transmittance was above 75%, proving that the solution of the present application is universal and conducive to industrial application.

[0166] Although some exemplary embodiments of the present application have been illustrated and described, the present application is not limited to the disclosed embodiments. On the contrary, those skilled in the art will recognize that some modifications and changes may be made to the described embodiments without departing from the spirit and scope of the present application as described in the appended claims.

Claims

1. A conductive polymer precursor solution, It is characterized in that Including main solvent, Fe 3+ An oxidant, a chelating agent and a thiophene monomer, wherein the chelating agent comprises at least one of a diketone compound, a hydroxycarboxylic acid compound and a nitrogen-containing heterocyclic compound.

2. The conductive polymer precursor solution according to claim 1, It is characterized in that The diketone compound includes a compound of formula (A), and / or the hydroxycarboxylic acid compound includes a compound of formula (B), and / or the nitrogen-containing heterocyclic compound includes a compound of formula (C); In formula (A), n is an integer from 0 to 8, R 1 and R 2 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 1 and R 2 Each independently selected from C 1 -C 6 alkyl; In formula (B), m is an integer from 0 to 8; In formula (C), R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl or aromatic group; Preferably, the diketone compounds include 2,3-butanedione, 2,4-pentanedione, and 2,5-hexanedione; Preferably, the hydroxycarboxylic acid compound includes oxalic acid and succinic acid; Preferably, the nitrogen-containing heterocyclic compound includes 2,2'-bipyridine.

3. The conductive polymer precursor solution according to claim 1, It is characterized in that Based on the volume of the main solvent of the conductive polymer precursor solution, the volume fraction of the chelating agent is less than or equal to 2%; Preferably, based on the volume of the main solvent of the conductive polymer precursor solution, the volume fraction of the chelating agent is 0.2% to 2%.

4. The conductive polymer precursor solution according to any one of claims 1 to 3, It is characterized in that The thiophene monomer includes 3,4-ethylenedioxythiophene.

5. The conductive polymer precursor solution according to any one of claims 1 to 3, It is characterized in that The Fe 3+ Oxidants include Fe 2 (SO 4 ) 3 、Fe(ClO 4 ) 3 、Fe(OTf) 3 and Fe(OTs) 3 At least one of .

6. The conductive polymer precursor solution according to any one of claims 1 to 3, It is characterized in that The main solvent includes C 1 -C 6 At least one of alcohols, acetonitrile or dimethyl nylonate.

7. The conductive polymer precursor solution according to any one of claims 1 to 3, It is characterized in that Also included are dispersants; Preferably, the dispersant comprises a polyethylene glycol copolymer; Preferably, the polyethylene glycol copolymer comprises a triblock copolymer of polyethylene glycol-polypropylene glycol-polyethylene glycol.

8. The conductive polymer precursor solution according to any one of claims 1 to 3, It is characterized in that The method further comprises a secondary solvent, wherein the secondary solvent comprises at least one of a compound of formula (D), a compound of formula (E), a compound of formula (F), a compound of formula (G), a compound of formula (H), a compound of formula (I), water, an aqueous solution containing hydrogen ions, a cyclic amide, a chain amide, a cyclic urea, a chain urea, a phosphate ester or a phosphoramide, In formula (D), q is an integer from 1 to 8, R 11 Selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 11 Selected from C 1 -C 6 alkyl; In formula (E), p is an integer from 0 to 8, R 12 , R 13 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 12 , R 13 Each independently selected from C 1 -C 6 alkyl; In formula (F), R 14 , R 15 , R 16 , R 17 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 14 , R 15 , R 16 , R 17 Each independently selected from C 1 -C 6 alkyl; In formula (G), R 18 , R 19 , R 20 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 18 , R 19 , R 20 Each independently selected from C 1 -C 6 alkyl; In formula (H), R 21 , R 22 , R 23 , R 24 , R 25 , R 26 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 21 , R 22 , R 23 , R 24 , R 25 , R 26 Each independently selected from C 1 -C 6 alkyl; In formula (I), R 27 , R 28 , R 29 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 27 , R 28 , R 29 Each independently selected from C 1 -C 6 alkyl; Preferably, the cyclic amide comprises N-methyl caprolactam; Preferably, the chain amide includes N,N-diethylacetamide; Preferably, the cyclic urea comprises N,N-dimethylpropylene urea; Preferably, the chain urea comprises tetramethyl urea; Preferably, the phosphate ester includes trimethyl phosphate and tributyl phosphate; Preferably, the phosphoramide comprises hexamethylphosphoric triamide; Preferably, the aqueous solution containing hydrogen ions is selected from an organic acid solution and an inorganic acid solution; preferably, the concentration of hydrogen ions in the aqueous solution containing hydrogen ions is greater than 0.01 mol / L; preferably, the aqueous solution containing hydrogen ions is selected from a hydrochloric acid solution, a phosphoric acid solution, a sulfuric acid solution, a perchloric acid solution and an acetic acid solution.

9. A method for preparing a conductive polymer film, It is characterized in that include: Step (a), providing a substrate and a conductive polymer precursor solution according to any one of claims 1 to 8; Step (b) is to apply the conductive polymer precursor solution to the surface of the substrate, remove the solvent, and allow the thiophene monomer to undergo polymerization to form a conductive polymer film.

10. The method for preparing a conductive polymer film according to claim 9, It is characterized in that The method for preparing the conductive polymer precursor solution comprises: Step (1), providing a solvent, wherein the solvent includes the main solvent; Step (2), the Fe 3+ The oxidant and the chelating agent are added to the solvent provided in step (1), and mixed uniformly to form an intermediate solution; Step (3), adding the thiophene monomer to the intermediate solution formed in step (2), and mixing them evenly to form a conductive polymer precursor solution.

11. The method for preparing a conductive polymer film according to claim 10, It is characterized in that The solvent provided in step (1) further includes a secondary solvent, wherein the secondary solvent includes at least one of a compound of formula (D), a compound of formula (E), a compound of formula (F), a compound of formula (G), a compound of formula (H), a compound of formula (I), water, an aqueous solution containing hydrogen ions, a cyclic amide, a chain amide, a cyclic urea, a chain urea, a phosphate ester or a phosphoramide, In formula (D), q is an integer from 1 to 8, R 11 Selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 11 Selected from C 1 -C 6 alkyl; In formula (E), p is an integer from 0 to 8, R 12 , R 13 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 12 , R 13 Each independently selected from C 1 -C 6 alkyl; In formula (F), R 14 , R 15 , R 16 , R 17 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 14 , R 15 , R 16 , R 17 Each independently selected from C 1 -C 6 alkyl; In formula (G), R 18 , R 19 , R 20 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 18 , R 19 , R 20 Each independently selected from C 1 -C 6 alkyl; In formula (H), R 21 , R 22 , R 23 , R 24 , R 25 , R 26 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 21 , R 22 , R 23 , R 24 , R 25 , R 26 Each independently selected from C 1 -C 6 alkyl; In formula (I), R 27 , R 28 , R 29 are independently selected from hydrogen atoms, C 1 -C 8 Alkyl, preferably, R 27 , R 28 , R 29 Each independently selected from C 1 -C 6 alkyl; Preferably, the cyclic amide comprises N-methyl caprolactam; Preferably, the chain amide includes N,N-diethylacetamide; Preferably, the cyclic urea comprises N,N'-dimethylpropylene urea; Preferably, the chain urea comprises tetramethyl urea; Preferably, the phosphate ester includes trimethyl phosphate and tributyl phosphate; Preferably, the phosphoramide comprises hexamethylphosphoric triamide; Preferably, the aqueous solution containing hydrogen ions is selected from an organic acid solution and an inorganic acid solution; preferably, the concentration of hydrogen ions in the aqueous solution containing hydrogen ions is greater than 0.01 mol / L; preferably, the aqueous solution containing hydrogen ions is selected from a hydrochloric acid solution, a phosphoric acid solution, a sulfuric acid solution, a perchloric acid solution and an acetic acid solution.

12. The method for preparing a conductive polymer film according to claim 10, It is characterized in that Prior to step (2), a polyethylene glycol copolymer is added to the solvent provided in step (1). Preferably, the polyethylene glycol copolymer comprises a triblock copolymer of polyethylene glycol-polypropylene glycol-polyethylene glycol.

13. The method for preparing a conductive polymer film according to claim 9, It is characterized in that The polymerization reaction temperature is 20°C to 150°C, preferably, the polymerization reaction temperature is 20°C to 80°C; the polymerization reaction time is 0.1min to 20min, preferably, the polymerization reaction time is 2min to 10min.

14. The method for preparing a conductive polymer film according to claim 9, It is characterized in that The method of coating the conductive polymer precursor solution on the surface of the substrate includes: spin coating, dip coating, screen printing, slit coating or inkjet printing.

15. The method for preparing a conductive polymer film according to claim 9, It is characterized in that The preparation method further comprises: Step (c), washing and drying the conductive polymer film obtained in step (b).

16. A conductive polymer film, It is characterized in that The conductive polymer film is prepared by the preparation method of any one of claims 9 to 15, and the square resistance and / or transmittance of the conductive polymer film is adjustable.

17. Use of the conductive polymer film according to claim 16 in a film touch screen, an electronic writing tablet, an electrochromic display, a smart window, a solar cell, a light emitting diode, a laser device, a gas sensor, an antistatic coating or a capacitive electrode.

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