Polymer compounds and methods for producing the same, as well as organic thin-film solar cells and organic transistors using the same.

Abstract

To provide a polymer compound that exhibits excellent photoelectric conversion efficiency, a method for producing a polymer compound, an organic thin film solar cell, and an organic transistor.SOLUTION: A polymer compound includes a repeat unit represented by formula (1). In the formula (1), R1 is a hydrogen atom, a halogen atom or an alkyl group, Ar1 is specific arylene group.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a polymer compound and a method for producing the same. The present invention also relates to a compound for producing the polymer compound and a method for producing the same. Furthermore, the present invention relates to a composition for forming an organic semiconductor film containing the polymer compound, an organic semiconductor film, an organic thin film solar cell, an organic transistor, and methods for producing them.

Background Art

[0002] In recent years, research and development on organic thin film solar cells, organic transistors, etc. using organic semiconductor materials have been actively conducted. A solar cell is a device that exhibits an electrical output in response to light input. Against the backdrop of the depletion problem of fossil fuels and the global warming problem, it has attracted attention as clean energy and has been put into practical use. So far, silicon-based solar cells have been widely put into practical use, but organic thin film solar cells have attracted attention as a new solar cell technology because they can be manufactured by a coating process, can be made flexible, and can be made see-through, and various organic thin film solar cell materials have been developed aiming at higher efficiency. In addition, since organic transistors are excellent in light weight, low manufacturing cost, and flexibility compared to inorganic transistor films, applied research on devices such as displays, RFID (radio frequency identifier), and substance sensors has been actively conducted.

[0003] As an organic thin film solar cell material that functions as an electron donor, an electron-deficient skeleton based on naphthalene is known. Since this skeleton has a wide π-conjugated system, it has been used as a building unit of a semiconductor polymer. For example, Patent Document 1 discloses a polymer compound having a structure in which two thiophene rings are condensed to a naphthobisthiadiazole ring in the polymer main chain (for example, the polymer compound represented by Formula 1).

[0004]

Chemical Formula

[0005] [Patent Document 1] Japanese Patent Publication No. 2021-38288 [Overview of the project] [Problems that the invention aims to solve]

[0006] Although various organic thin-film solar cell materials have been disclosed to date, material development is still in its early stages, and there is a need for organic thin-film solar cell materials with even better power generation characteristics, such as improved open-circuit voltage (Voc) and improved short-circuit current density (Jsc). To address these challenges, it is expected that introducing multiple fused thiophene ring structures into the electron-deficient skeleton NTz (naphthobisthiadiazole ring) will deepen the highest occupied orbital (HOMO) level and provide a rigid polymer backbone, thereby improving these properties.

[0007] The present invention has been made in view of the above matters, and its object is to provide a polymer compound that exhibits good photoelectric conversion efficiency, a method for producing the same, a compound for producing the polymer compound and a method for producing the same, and further, an organic semiconductor film forming composition containing the polymer compound, an organic semiconductor film, an organic thin-film solar cell, an organic transistor, and methods for producing the same. [Means for solving the problem]

[0008] The inventors of this invention have diligently studied the above-mentioned problems and completed the present invention. That is, the gist of the present invention is as follows.

[0009] [1] Equation (1):

[0010] [ka] (In formula (1), R 1is a hydrogen atom, a halogen atom or an alkyl group, and Ar 1 is at least one arylene group selected from the groups represented by the following formulae. A polymer compound containing a repeating unit represented by the formula:

[0011] [Chemical formula] (In the formula, R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 and R 10 are each independently a hydrogen atom, a halogen atom or an alkyl group, and R 7 is a hydrogen atom or a halogen atom, and * represents a bond.)

[0012] [2] Formula (5):

[0013] [Chemical formula] (In formula (5), R 1 is a hydrogen atom, a halogen atom or an alkyl group, and X is a halogen atom.) A compound represented by the formula.

[0014] [3] A step of reacting the compound represented by formula (5) described in [2] with a compound represented by formula (6):

[0015] [Chemical formula] (In formula (6), Me is a methyl group, and Ar 1 is at least one arylene group selected from the groups represented by the following formulae.) to obtain a polymer compound containing the repeating unit represented by the formula (1). The method for producing the polymer compound according to [1], which includes this step.

[0016] ]> [Chemical formula] (In the formula, R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 and R 10 Each of these is independently a hydrogen atom, a halogen atom, or an alkyl group, and R 7 (where * represents a hydrogen atom or halogen atom, and * indicates a bonding bond.)

[0017] [4] Equation (4):

[0018] [ka] (In formula (4), R 1 A method for producing the compound according to [2], comprising the step of reacting a compound represented by ( ) with a demethylating agent to obtain a compound represented by formula (5).

[0019] [5] Equation (3):

[0020] [ka] (In formula (3), R 1 A method for producing the compound according to [4], comprising the step of reacting a compound represented by () with an oxidizing agent to obtain a compound represented by formula (4).

[0021] [6] Equation (2):

[0022] [ka] (In formula (2), R 1A method for producing the compound according to [5], comprising the step of reacting a compound represented by (a) with a methylthioling agent to obtain a compound represented by formula (3).

[0023] [7] I) A first step in which a compound represented by formula (2) is reacted with a methylthioling agent to produce a compound represented by formula (3), II) A second step in which the compound represented by formula (3) obtained in the first step is reacted with an oxidizing agent to produce the compound represented by formula (4), III) A third step in which the compound represented by formula (4) obtained in the second step is reacted with a demethylating agent to produce the compound represented by formula (5), and IV) A method for producing a polymer compound according to [1], comprising a fourth step of reacting a compound represented by formula (5) obtained in the third step with a compound represented by formula (6) to produce a polymer compound containing a repeating unit represented by formula (1).

[0024] [8] A composition for forming an organic semiconductor film, comprising the polymer compound described in [1].

[0025] [9] [1] An organic semiconductor film containing the polymer compound described above.

[0026]

[10] [9] Organic thin-film solar cell comprising an organic semiconductor film.

[0027]

[11] [9] An organic transistor comprising an organic semiconductor film.

[0028] A method for producing an organic semiconductor film, comprising the step of depositing or coating an organic semiconductor film composition described in

[12] [8] onto a substrate to form an organic semiconductor film.

[0029] A method for manufacturing an organic thin-film solar cell, comprising the step of depositing or coating an organic semiconductor film composition described in

[13] [8] onto a substrate to form an organic semiconductor film.

[0030] A method for manufacturing an organic transistor, comprising the step of depositing or coating an organic semiconductor film composition described in

[14] [8] onto a substrate to form an organic semiconductor film. [Effects of the Invention]

[0031] According to the present invention, it is possible to provide a polymer compound exhibiting good photoelectric conversion efficiency or mobility, a method for producing the polymer compound, an organic thin-film solar cell containing the polymer compound, and an organic transistor. [Brief explanation of the drawing]

[0032] [Figure 1] This figure shows the current density-voltage characteristics of the organic thin-film solar cell element 1 of the example. [Figure 2] This figure shows the current density-voltage characteristics of the organic thin-film solar cell element 2 of the example. [Figure 3] This figure shows the Id-Vg characteristics of the organic transistor element 1 of the example. [Figure 4] This figure shows the Id-Vg characteristics of the organic transistor element 2 of the example. [Modes for carrying out the invention]

[0033] (polymer compound) The polymer compound according to this embodiment includes a repeating unit represented by formula (1) above (hereinafter referred to as "polymer compound (1)"). R in formula (1) 1 The number of carbon atoms in the alkyl group contained in is preferably 6 to 30. Also, Ar 1 R inside 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 and R 10 The alkyl group contained in the compound preferably has 6 to 30 carbon atoms. These alkyl groups may be linear or branched, but branched alkyl groups are preferred when considering film formation by coating methods such as wet film formation.1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 The halogen atoms contained are preferably fluorine, chlorine, bromine, or iodine.

[0034] The weight-average molecular weight of polymer compound (1) is preferably in the range of 10,000 to 1,000,000. Furthermore, the number-average molecular weight is preferably in the range of 10,000 to 200,000. The average molecular weight is measured using a polystyrene standard sample and gel permeation chromatography (GPC), etc. For example, the Shimadzu Corporation Prominence® GPC system can be used.

[0035] (intermediate compound) The compound according to this embodiment is represented by formula (5) above (hereinafter referred to as "intermediate compound (5)"). R in formula (5) 1 The alkyl group contained in preferably has 6 to 30 carbon atoms. These alkyl groups may be linear or branched, but branched alkyl groups are preferred. 1 The halogen atoms contained in are preferably fluorine, chlorine, bromine, or iodine. Furthermore, the halogen atoms of X are preferably fluorine, chlorine, bromine, or iodine.

[0036] (Method for producing intermediate compound (5) and polymer compound (1)) The method for producing the intermediate compound (5) is not particularly limited. For example, the intermediate compound (5) can be produced by the following reaction scheme. The method for producing the polymer compound (1) is also not particularly limited. For example, the polymer compound (1) can be produced from the intermediate compound (5) described above. A preferred process will be described according to the following reaction scheme, and a more specific example will be described in the examples below.

[0037] [ka]

[0038] In the above formula, R 1 X is a hydrogen atom, a halogen atom, or an alkyl group, and X is a halogen atom, with examples including fluorine, chlorine, bromine, and iodine. Me is a methyl group. Also, n is an integer representing a repeating unit. Ar 1 is at least one arylene group selected from the groups represented by the following formula, and * indicates a bond.

[0039] [ka] In the formula, R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 and R 10 Each of these is independently a hydrogen atom, a halogen atom, or an alkyl group, and R 7 This is a hydrogen atom or a halogen atom.

[0040] The compound represented by formula (2) (hereinafter referred to as "compound (2)") can be manufactured in accordance with the method described in "NPG Asia Mater. 10, 1016-1028 (2018)".

[0041] <1st process> The compound represented by formula (3) (hereinafter referred to as "compound (3)") is produced from compound (2) (step 1).

[0042] The first step specifically involves reacting compound (2) with a methylthiolating agent to produce compound (3). Examples of methylthiolating agents include sodium methanethiolate. The reaction in the first step can be carried out in the presence of a solvent as needed. Any solvent that is inert to the reaction can be used as the solvent, and one or more can be appropriately selected from, for example, amine bases such as 2,2,6,6-tetramethylpiperidineamine; aprotic polar solvents such as N,N-dimethylformamide (DMF) and acetonitrile; ethers such as tetrahydrofuran (THF); etc. The reaction temperature is usually preferably -78°C to 140°C, and more preferably 0 to 120°C. The reaction time is usually 0.5 to 48 hours. The obtained compound (3) may be purified. Furthermore, it is preferable to purify compound (3) before subjecting it to the second step described below.

[0043] <Second process> Next, compound (3) is used to produce compound (4) represented by formula (4) (hereinafter referred to as "compound (4)") (second step).

[0044] The second step specifically involves reacting compound (3) with an oxidizing agent to obtain compound (4). The oxidizing agent is not particularly limited as long as the reaction proceeds, and examples include metachloroperbenzoic acid (m-CPBA), hydrogen peroxide, sodium periodate, potassium peroxymonosulfate (Oxon), etc. The oxidizing agent can be used in a ratio of preferably 1 to 20 equivalents, more preferably 1 to 10 equivalents, per equivalent of compound (3). Any solvent that is inert to the reaction may be used as the solvent, and one or more can be appropriately selected from, for example, organochlorine solvents such as chloroform; ethers such as tetrahydrofuran (THF); etc. The reaction temperature is usually preferably -78 to 100°C, and more preferably 0 to 100°C. The reaction time is usually 0.5 to 48 hours. Compound (4) is preferably purified before being subjected to the third step described below.

[0045] <3rd process> Next, an intermediate compound (5) is produced from compound (4) (third step).

[0046] The third step specifically involves reacting compound (4) with a demethanolizing agent to obtain an intermediate compound (5). The demethanolizing agent is not particularly limited as long as the reaction proceeds, and examples include trifluoromethanesulfonic acid, phosphorus pentoxide, trifluoroacetic acid, trifluoromethanesulfonic anhydride, and phosphoryl chloride. The reaction may be carried out without a solvent, but dichloromethane or the like can also be used. The reaction temperature is usually preferably 0 to 200°C, and more preferably 0 to 120°C. The reaction time is usually 1 to 48 hours. The obtained intermediate compound (5) may be purified. Furthermore, it is preferable to purify the intermediate compound (5) before subjecting it to the fourth step described below.

[0047] <4th process> Next, polymer compound (1) is produced from intermediate compound (5) and the compound represented by formula (6) (hereinafter referred to as "compound (6)") (step 4). Compound (6) can be synthesized, for example, by referring to "WO2009 / 081372," etc.

[0048] The fourth step is specifically a step of producing polymer compound (1) by reacting intermediate compound (5) with compound (6). Intermediate compound (5) and compound (6) are reacted in a solvent in the presence of a catalyst. Examples of solvents include toluene, chlorobenzene, dimethylformamide (DMF), and tetrahydrofuran (THF). Examples of catalysts include tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh3)2Cl2), and tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3). The reaction temperature can be, for example, 80°C to 200°C. The obtained polymer compound (1) may be purified. In this way, polymer compound (1) of the present invention can be produced.

[0049] (Composition for forming organic semiconductor films) Next, the organic semiconductor film-forming composition of the present invention will be described. This organic semiconductor film-forming composition contains the polymer compound (1) of the present invention and is preferably used for forming the organic semiconductor film of the present invention.

[0050] (The polymer compound of the present invention) The polymer compound (1) of the present invention may be produced by the method described above, and may be used alone or in combination of two or more types. The content of the polymer compound in the organic semiconductor film-forming composition is not particularly limited, but it is preferable that, for example, when expressed as the content in the solid content excluding the solvent described later, it be within the same range as the content of the polymer compound in the organic semiconductor film described later.

[0051] (Binder polymer) The composition for forming organic semiconductor films may contain a binder polymer. When the composition contains a binder polymer, a high-quality organic semiconductor film can be obtained. Such binder polymers are not particularly limited and include, for example, insulating polymers such as polystyrene, poly(α-methylstyrene), polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, or polypropylene, or copolymers thereof. In addition to these, other examples include rubbers such as ethylene-propylene rubber, acrylonitrile-butadiene rubber, hydrogenated nitrile rubber, fluororubber, perfluoroelastomer, tetrafluoroethylene propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene rubber, polychloroprene, polyneoprene, butyl rubber, methylphenyl silicone resin, methylphenyl vinyl silicone resin, methyl vinyl silicone resin, fluorosilicone resin, acrylic rubber, ethylene acrylic rubber, chlorosulfonated polyethylene, chloropolyethylene, epichlorohydrin copolymer, polyisoprene-natural rubber copolymer, polyisoprene rubber, styrene-isoprene block copolymer, polyester urethane copolymer, polyether urethane copolymer, polyether ester thermoplastic elastomer, or polybutadiene rubber, or thermoplastic elastomer polymers. Furthermore, examples include photoconductive polymers such as polyvinylcarbazole or polysilane, conductive polymers such as polythiophene, polypyrrole, polyaniline or poly(p-phenylenevinylene), or semiconductor polymers as described in Chemistry of Materials, 2014, 26, 647, etc.

[0052] When considering charge mobility, the binder polymer preferably has a structure that does not contain polar groups. Here, a polar group refers to a functional group having heteroatoms other than carbon atoms and hydrogen atoms. Among the above, polystyrene or poly(α-methylstyrene) are preferred as binder polymers with a structure that does not contain polar groups. Semiconductor polymers are also preferred.

[0053] The glass transition temperature of the binder polymer is not particularly limited and is set appropriately depending on the application. For example, when imparting strong mechanical strength to an organic semiconductor film, it is preferable to raise the glass transition temperature. On the other hand, when imparting flexibility to an organic semiconductor film, it is preferable to lower the glass transition temperature.

[0054] The binder polymer may be used alone or in combination of two or more types. The content of the binder polymer in the organic semiconductor film-forming composition is not particularly limited, but for example, the content in the solid content is preferably within the same range as the content of the binder polymer in the organic semiconductor film described later. When an organic semiconductor film is formed using an organic semiconductor film-forming composition containing a binder polymer, the durability of the organic semiconductor film is further improved. The weight-average molecular weight of the binder polymer is not particularly limited, but is preferably 10 to 10 million, more preferably 30 to 5 million, and even more preferably 50 to 3 million.

[0055] In the organic semiconductor film-forming composition, the polymer compound (1) of the present invention may be uniformly mixed with the binder polymer, or some or all of the polymer compound (1) of the present invention may be phase-separated. In terms of ease of application or uniform application, it is preferable that the polymer compound (1) of the present invention and the binder polymer are uniformly mixed at least during application.

[0056] (solvent) The organic semiconductor film-forming composition may contain a solvent. Such a solvent is not particularly limited as long as it dissolves or disperses the polymer compound (1) described above, and examples include inorganic solvents and organic solvents. Among these, organic solvents are preferred. The solvent may be used alone or in combination of two or more.

[0057] The organic solvent is not particularly limited, but includes hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1,6-dimethylnaphthalene or tetralin; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, propiophenone or butyrophenone; dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloromethane. Halogenated hydrocarbon solvents such as chloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, chlorotoluene, or 1-fluoronaphthalene; heterocyclic solvents such as pyridine, picoline, quinoline, thiophene, 3-butylthiophene, or thieno[2,3-b]thiophene; 2-chlorothiophene, 3-chlorothiophene, 2,5-dichlorothiophene, 3,4-dichlorothiophene, 2-bromothiophene, 3-bromothiophene, 2,3-dibromothiophene, and 2,4-dibromothiophene. , 2,5-dibromothiophene, 3,4-dibromothiophene or 3,4-dichloro-1,2,5-thiadiazole and other halogenated heterocyclic solvents, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, 2-ethylhexyl acetate, γ-butyrolactone or phenyl acetate, alcohol solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve or ethylene glycol, dibutyl ether, tetrahydrofuran, dioxane, dimeth Xyethane, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 4-ethylanisole, dimethylanisole (any of 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, 3,6-) or ether solvents such as 1,4-benzodioxane, N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone or 1,Examples include amide or imide solvents such as 3-dimethyl-2-imidazolidinone, sulfoxide solvents such as dimethyl sulfoxide, phosphate ester solvents such as trimethyl phosphate, nitrile solvents such as acetonitrile or benzonitrile, and nitro solvents such as nitromethane or nitrobenzene.

[0058] Among these, hydrocarbon solvents, ketone solvents, halogenated hydrocarbon solvents, heterocyclic solvents, halogenated heterocyclic solvents, or ether solvents are preferred, with toluene, xylene, mesitylene, amylbenzene, tetralin, acetophenone, propiophenone, butyrophenone, dichlorobenzene, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 1-fluoronaphthalene, 3-chlorothiophene, or 2,5-dibromothiophene being more preferred, and toluene, xylene, tetralin, acetophenone, propiophenone, butyrophenone, anisole, ethoxybenzene, propoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 1-fluoronaphthalene, 3-chlorothiophene, or 2,5-dibromothiophene being particularly preferred.

[0059] The solvent content in the organic semiconductor film-forming composition is preferably 90 to 99.95% by mass, more preferably 95 to 99.9% by mass, and even more preferably 96 to 99.5% by mass.

[0060] (Other ingredients) The organic semiconductor film-forming composition of the present invention may contain components other than the polymer compound (1) and solvent of the present invention. Examples of such components include various additives. Additives commonly used in organic semiconductor film-forming compositions can be used without particular limitations. Examples include surfactants, antioxidants, crystallization control agents, or crystal orientation control agents. Examples of surfactants and antioxidants include those described in paragraphs 0136 and 0137 of Japanese Patent Application Publication No. 2015-195362, and the descriptions in these paragraphs are preferably incorporated herein. The additive content of the organic semiconductor film-forming composition is not particularly limited. For example, the additive content in the solid content is preferably within the same range as the additive content in the organic semiconductor film described later. When an organic semiconductor film is formed using an organic semiconductor film-forming composition with an additive content within the above range, the film-forming properties are excellent, and the heat resistance of the organic semiconductor film is further improved.

[0061] (Preparation method) The method for preparing the organic semiconductor film-forming composition is not particularly limited, and conventional preparation methods can be employed. For example, the organic semiconductor film-forming composition of the present invention can be prepared by appropriately mixing predetermined amounts of each component using a mixer or stirrer. If necessary, each component may be heated during or after the mixing process. The heating temperature is not particularly limited, but is preferably in the range of 40 to 150°C. When using a solvent, it is preferable to heat the temperature within the above temperature range but below the boiling point of the solvent.

[0062] (Organic semiconductor film) Next, the organic semiconductor film of the present invention will be described. The organic semiconductor film of the present invention contains the polymer compound (1) of the present invention. The thickness of the organic semiconductor film is preferably 1 nm to 1000 nm, more preferably 2 nm to 1000 nm, even more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.

[0063] The process for manufacturing the organic semiconductor film may include a step of oriented the polymer compound (1) of the present invention. In the organic semiconductor film obtained by oriented the polymer compound (1) of the present invention through this step, the main chain portion or side chain portion of the polymer compound (1) of the present invention are aligned in one direction, so the mobility is improved.

[0064] As a method for oriented the polymer compound (1) of the present invention, methods known as liquid crystal orientation techniques can be used. Among liquid crystal orientation techniques, the rubbing method, photo-alignment method, shearing method (shear stress application method), and pull-up coating method are easy to use because they are simple and useful, with the rubbing method and shearing method being more preferred.

[0065] Since the organic semiconductor film of the present invention has electron transport or hole transport properties, it can be used in organic semiconductor devices such as organic transistors and organic photoelectric conversion elements (organic thin-film solar cells, light sensors, etc.) by controlling the transport of electrons or holes injected from electrodes, or charges generated by absorbed light. When using the organic semiconductor film of the present invention in these organic semiconductor devices, it is more preferable to orient the polymer compound (1) of the present invention by orientation treatment in order to improve electron transport or hole transport properties.

[0066] (Method for manufacturing organic semiconductor films) The method for manufacturing the organic semiconductor film of the present invention is not particularly limited as long as it includes a step of coating the organic semiconductor film-forming composition of the present invention onto a substrate. In this step, the organic semiconductor film-forming composition of the present invention described above is used. In the present invention, coating the organic semiconductor film-forming composition onto a substrate includes not only the act of directly coating the organic semiconductor film-forming composition onto the substrate, but also the act of coating the organic semiconductor film-forming composition on top of the substrate via another layer provided on the substrate. The other layer on which the organic semiconductor film-forming composition is coated (a layer that is in contact with the organic semiconductor film and serves as the base for the organic semiconductor film) is necessarily determined by the structure of the organic transistor. For example, in the case of a bottom-gate type, it is the gate insulating film, and in the case of a top-gate type (top-gate-bottom contact type and top-gate-top contact type), it is the source electrode or the drain electrode.

[0067] When forming an organic semiconductor film, the substrate may be heated or cooled. By changing the temperature of the substrate, a good film quality can be obtained, and the packing of the polymer compound (1) of the present invention in the organic semiconductor film can be controlled. The temperature of the substrate is not particularly limited. For example, it is preferably set in the range of 0 to 200°C, more preferably in the range of 15 to 100°C, and particularly preferably in the range of 20 to 95°C.

[0068] The method for forming the organic semiconductor film is not particularly limited and includes a vacuum process or a solution process, both of which are preferred.

[0069] Examples of vacuum processes include physical vapor deposition methods such as vacuum deposition, sputtering, ion plating, or molecular beam epitaxy (MBE), or chemical vapor deposition (CVD) methods such as plasma polymerization. Among these, vacuum deposition is preferred.

[0070] As described above, the polymer compound (1) of the present invention is stable even under atmospheric conditions. Therefore, the solution process can be carried out under atmospheric conditions, and furthermore, the organic semiconductor film-forming composition of the present invention can be applied over a large area. Conventional methods can be used for coating organic semiconductor film-forming compositions in solution processes. Examples include coating methods such as drop casting, casting, dip coating, die coating, roll coating, bar coating, or spin coating; various printing methods such as inkjet, screen printing, gravure printing, flexography, offset printing, or microcontact printing; or methods such as the Langmuir-Blodgett (LB) method. Among these, drop casting, casting, spin coating, inkjet, gravure printing, flexography, offset printing, or microcontact printing are preferred.

[0071] In the solution process, the organic semiconductor film-forming composition coated on the substrate is preferably dried. It is even more preferable to dry it gradually. For drying organic semiconductor film-forming compositions, it is preferable to air dry or heat dry them on a heated substrate, followed by vacuum drying, in order to obtain good film quality. The substrate temperature during air drying or heat drying is preferably 20 to 100°C, and more preferably 20 to 80°C. The air drying or heat drying time is preferably 0.5 to 20 hours, and more preferably 1 to 10 hours. The temperature during vacuum drying is preferably 20 to 100°C, and more preferably 20 to 80°C. The vacuum drying time is preferably 1 to 20 hours, and more preferably 2 to 10 hours. The pressure during vacuum drying is 10 -6 ~10 -2 It is preferable that it be Pa -5 ~10 -3 It is more preferable that it be Pa. The organic semiconductor film-forming composition, dried in this manner, can be molded or otherwise shaped into a predetermined shape or pattern as needed.

[0072] (Organic transistor) Next, we will describe the organic thin-film transistor (also known as an organic TFT), which is a preferred form among the above-mentioned organic semiconductor devices using the polymer compound (1) of the present invention. The organic transistor of the present invention comprises the organic semiconductor film of the present invention described above. As a result, the organic transistor of the present invention exhibits high mobility and effectively suppresses the deterioration of semiconductor characteristics over time even when placed in the atmosphere, enabling stable operation. In the present invention, the ambient temperature or humidity in the atmosphere is not particularly limited as long as it is the temperature or humidity of the operating environment of the organic transistor, for example, the temperature can be room temperature (25±15℃) and the humidity can be 10~90RH%.

[0073] The organic transistor of the present invention is preferably used as a field-effect transistor (FET), and more preferably as an insulated-gate FET in which the gate-channel is insulated. The thickness of the organic transistor of the present invention is not particularly limited, but if a thinner transistor is desired, for example, the overall thickness of the transistor is preferably 0.1 to 0.5 μm.

[0074] The organic transistor of the present invention has the organic semiconductor film (also called an organic semiconductor layer or semiconductor active layer) of the present invention, and may further have a source electrode, a drain electrode, a gate electrode, and a gate insulating film. The organic transistor of the present invention has a gate electrode, an organic semiconductor film, a gate insulating film provided between the gate electrode and the organic semiconductor film, and a source electrode and a drain electrode provided in contact with the organic semiconductor film and connected via the organic semiconductor film, on a substrate. In this organic transistor, the organic semiconductor film and the gate insulating film are provided adjacent to each other. The organic transistor of the present invention is not particularly limited in its structure as long as it comprises the above-mentioned layers. For example, it may have any structure such as a bottom-contact type (bottom-gate-bottom-contact type and top-gate-bottom-contact type) or a top-contact type (bottom-gate-top-contact type and top-gate-top-contact type). The organic transistor of the present invention is more preferably a bottom-gate-bottom-contact type or a bottom-gate-top-contact type (collectively referred to as a bottom-gate type).

[0075] The substrate material is not particularly limited, as long as it does not hinder the characteristics of the organic transistor. Examples of substrates that can be used include glass substrates, silicon substrates, flexible film substrates, and plastic substrates.

[0076] In forming an organic semiconductor layer, it is preferable to use the polymer compound (1) of the present invention, which is soluble in organic solvents, so that it can be coated. This allows for coating by a solution process and is advantageous for manufacturing organic transistors. Since the polymer compound of the present invention has excellent solubility, by employing the above-described method for producing an organic semiconductor film, an organic thin film that will become an organic semiconductor layer can be formed successfully.

[0077] The insulating layer material can be any material with high electrical insulation properties, and known materials can be used. Examples of insulating layer materials include SiOx, SiNx, Ta2O5, polyimide, polyvinyl alcohol, polyvinylphenol, organic glass, and photoresist. From the viewpoint of achieving low voltage, it is desirable that the insulating layer be formed from a material with a high dielectric constant.

[0078] When forming an organic semiconductor layer on an insulating layer, it is possible to improve the interfacial properties between the insulating layer and the organic semiconductor layer by surface modification of the insulating layer's surface with a surface treatment agent such as a silane coupling agent before forming the organic semiconductor layer. Examples of surface treatment agents include silylamine compounds such as long-chain alkylchlorosilanes, long-chain alkylalkoxysilanes, arylalkylchlorosilanes, arylalkylalkoxysilanes, fluorinated alkylchlorosilanes, fluorinated alkylalkoxysilanes, and hexamethyldisilazane. It is also possible to treat the surface of the insulating layer with ozone UV or O2 plasma before treating with a surface treatment agent.

[0079] Examples of materials for the gate electrode, source electrode, and drain electrode include metals such as aluminum, gold, silver, copper, alkali metals, and alkaline earth metals, as well as translucent films and transparent conductive films made of these materials.

[0080] Furthermore, it is preferable to form a protective film on the fabricated organic transistor to protect it. This shields the organic transistor from the atmosphere, thereby suppressing the degradation of the organic transistor's characteristics. In addition, the protective film reduces external influences during the process of forming a display device driven by the organic transistor on the organic transistor.

[0081] Examples of protective film materials include UV-curing resins, thermosetting resins, and inorganic compounds such as silicon oxynitride films (SiONx films). Methods for protecting organic transistors include, for example, forming a protective film made of UV-curing resin, thermosetting resin, or a SiONx film on the surface of the organic transistor (covering the organic transistor with a protective film). To effectively isolate the organic transistor from the atmosphere, it is preferable that the process from the fabrication of the organic transistor to the formation of the protective film be carried out in an atmosphere that does not expose the organic transistor to the atmosphere, such as a dry nitrogen atmosphere or a vacuum.

[0082] Such field-effect organic transistors can be manufactured by known methods, for example, the method described in Japanese Patent Publication No. 5-110069. Similarly, electrostatic induction organic transistors can be manufactured by known methods, for example, the method described in Japanese Patent Publication No. 2004-006476.

[0083] (Applications of organic transistors) The polymer compound (1) of the present invention has an extended π-conjugated system structure, and therefore possesses strong intermolecular interactions and high crystallinity. For these reasons, when used in the active layer of an organic transistor, it exhibits excellent properties such as mobility. The above-mentioned organic transistor is not particularly limited in its applications and can be used, for example, in electronic paper, display devices, sensors, electronic tags, and the like.

[0084] (Organic thin film solar cell material) The polymer compound (1) of the present invention can be used in organic thin-film solar cell materials. The organic thin-film solar cell material can form the photoactive layer of an organic thin-film solar cell by a coating method such as a wet deposition method. The polymer compound (1) acts as a so-called p-type organic semiconductor, exhibiting the function of an electron donor.

[0085] The organic thin-film solar cell material may contain only the polymer compound (1) of the present invention, or it may contain other organic thin-film solar cell materials or other components. Preferably, the organic thin-film solar cell material contains an electron-accepting compound that functions as an electron acceptor. The electron-accepting compound may be any compound that functions as a so-called n-type semiconductor material, and known compounds can be used, for example, fullerene-based materials and non-fullerene-based compounds.

[0086] Mixing a non-fullerene compound with a polymer compound (1) to form a photoactive layer is preferable because it yields excellent photoelectric conversion efficiency. Examples of non-fullerene compounds include the following compounds. Y6(2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanilidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) Y6-5(12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-dicarbaldehyde) Y7(2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanilidene))bis(5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalonitrile) Y12(2,2'-((2Z,2'Z)-((12,13-bis(2-butyloctyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanilidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) BTP-eC9(2,2'-[[12,13-bis(2-butyloctyl)-12,13-dihydro-3,9-dinonyldithieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-e:2',3'-g][2,1,3]benzothiadiazolo-2,10-diyl]bis[methanilidene(5,6-chloro-3-oxo-1H-indene-2,1(3H)-diylidene)]]bis[propanedinitrile]) IT-4F(3,9-bis(2-methylene-((3-1,1-dicyanomethylene)-6,7,-difluoro)-indanone))-5,5,11,11,-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaseno[1,2-b:5,6-b']dithiophene)

[0087] (Organic thin film solar cell) Organic thin-film solar cells use the above-described organic thin-film solar cell material as the photoactive layer. The structure of the organic thin-film solar cell is not particularly limited as long as it has a photoactive layer between a pair of electrodes. Examples of the configuration of an organic thin-film solar cell include the following. Note that the p layer and p material refer to layers and materials containing the above-described organic thin-film solar cell material, and the n layer and n material refer to layers and materials containing the above-described electron-accepting compound. (A) Electrode / mixed layer of p material and n material / electrode (B) Electrode / p layer / mixed layer of p material and n material / n layer / electrode (C) Electrode / p layer / n layer / electrode

[0088] The polymer compound (1) of the present invention has an extended π-conjugated system structure, and therefore possesses strong intermolecular interactions and high crystallinity. For these reasons, when used in the photoactive layer of organic thin-film solar cells, it exhibits excellent properties such as photoelectric conversion efficiency. [Examples]

[0089] The synthesis, physical properties, and characteristics of organic thin-film solar cells and organic transistors of polymer compounds (1) containing dithienothiofen naphthobistiadianazole (TTNT) will be described below based on examples. The present invention is not limited to these examples.

[0090] <Synthesis Example 1> (Synthesis of Compound 2) Compound 1 was synthesized beforehand, based on "NPG Asia Mater. 10, 1016-1028 (2018)". Under an argon atmosphere, compound 1 (360 mg, 0.28 mmol) and sodium methanethiolate (NaSMe) (49.4 mg, 0.71 mmol) were placed in a 100 mL three-necked flask connected to a reflux condenser. A mixed solvent of N,N-dimethylformamide (15 mL) and tetrahydrofuran (15 mL) was added, and the mixture was stirred at 80°C for 1 hour. Water was added to the reaction solution, and it was extracted three times with chloroform (30 mL). The organic layer was washed with saline solution (30 mL) and water (30 mL), respectively, and dried using anhydrous sodium sulfate. Subsequently, the mixture was filtered and concentrated, and compound 2 (350 mg, 0.26 mmol, yield 93%) was obtained as an orange solid by silica gel column chromatography using a hexane:ethyl acetate (20:1) mixed solvent as the developing solvent. The reaction equation is shown below.

[0091] [ka]

[0092] The physical properties of compound 2 are as follows: 1 H NMR (400MHz, CDCl3): δ7.48(s,2H),2.62(d,J=7.3Hz,4H),2.28(s,6H),1.76(m,2H),1.18-1.41(m,80H),0.87(m,12H).

[0093] <Synthesis Example 2> (Synthesis of Compound 3) Under an argon atmosphere, compound 2 (310 mg, 0.23 mmol) and chloroform (30 mL) were placed in a 100 mL three-necked flask connected to a reflux condenser. Metachloroperbenzoic acid (80.3 mg) dissolved in chloroform (5 mL) was added at 0°C, and the mixture was stirred at room temperature for 1 hour. Sodium bicarbonate aqueous solution was added to the reaction solution, and the mixture was extracted three times with chloroform (30 mL). The organic layer was washed with saline solution (30 mL) and water (30 mL), respectively, and dried using anhydrous sodium sulfate. Subsequently, the mixture was filtered and concentrated, and compound 3 (312 mg, 0.23 mmol, yield 98%) was obtained as an orange solid by silica gel column chromatography using a hexane:ethyl acetate (5:1) mixed solvent as the developing solvent. The reaction equation is shown below.

[0094] [ka]

[0095] The physical properties of compound 3 are as follows: 1 1H NMR (400MHz, CDCl3): 1 H NMR (400MHz, CDCl3): δ7.07(d,J=3.4Hz,2H),3.72(q,J=6.2Hz,2H),3.56(d,J=3.6Hz,6H),1.77(m,2H),1.41-1.18(m,80H),0.87(m,12H).

[0096] <Synthesis Example 3> (Synthesis of Compound 4) Under an argon atmosphere, compound 3 (68.0 mg, 0.05 mmol) and trifluoroacetic acid (14 mL) were placed in a 100 mL three-necked flask. The reaction solution was cooled to 0°C, phosphorus oxide (142 mg, 0.50 mmol) was quickly added, and the mixture was stirred overnight at 50°C. The mixture was cooled to 0°C, water was added to the reaction solution, and the mixture was extracted three times with chloroform (30 mL). The organic layer was washed with saline solution (30 mL) and water (30 mL) respectively, and dried using anhydrous sodium sulfate. The mixture was then filtered, concentrated, and placed in a 100 mL three-necked flask connected to the reflux junction under an argon atmosphere. Pyridine (48 mL) was added, and the mixture was stirred overnight at 130°C. Dilute hydrochloric acid was added to the reaction solution, and the mixture was extracted three times with chloroform (30 mL). The organic layer was washed with saline solution (30 mL) and water (30 mL) respectively, and dried using anhydrous sodium sulfate. Subsequently, the mixture was filtered, concentrated, and purified by silica gel column chromatography using hexane as the developing solvent to obtain compound 4 (33.0 mg, 0.03 mmol, yield 51%) as an orange solid. The reaction equation is shown below.

[0097] [ka]

[0098] The physical properties of compound 4 are as follows: 1 1H NMR (400MHz, CDCl3): 1 H NMR (400MHz, CDCl3): δ7.07(d,J=3.4Hz,2H),3.72(q,J=6.2Hz,2H),3.56(d,J=3.6H z,6H),2.62(dd,J=7.2Hz2.4Hz,4H)1.77(m,2H),1.41-1.18(m,80H),0.84(m,12H).

[0099] <Synthesis Example 4> (Synthesis of polymer compound P1) 5,5'-Bis(trimethylstanyl)-2,2'-bisthiophene (compound 5) was synthesized beforehand based on "Adv. Mater., 27, 4655, (2015)". Compound 4 (26 mg, 0.02 mmol), 5,5'-bis(trimethylstanyl)-2,2'-bisthiophene (9.8 mg, 0.02 mmol), and toluene (2 mL) were placed in a reaction vial and bubbling with argon for 30 minutes. Subsequently, tetrakis(triphenylphosphine)palladium (0.46 mg, 0.0004 mmol) was added as a catalyst, the vial was sealed with argon, and the container was sealed tightly. The reaction was carried out at 200°C for 2 hours using a microwave reactor. After cooling to room temperature, the reaction mixture was poured into a 5% by mass hydrochloric acid / methanol solution and stirred for 3 hours. The precipitated solid was filtered and washed with methanol, n-hexane, dichloromethane, and chloroform using a Soxhlet extractor, and then extracted with chlorobenzene. The resulting solution was concentrated and reprecipitated in methanol to obtain high molecular weight compound P1 (22 mg, yield 85%) as a black solid (number average molecular weight 23,000, dispersion degree 2.8). The reaction equation is shown below.

[0100] [ka]

[0101] Examples of the polymer compound (1) of the present invention include the compounds shown in Table 1 below. 1 The bonding sites are indicated by *. These compounds can be produced in accordance with the method for producing polymer compound (1) described above and the examples.

[0102] [Table 1]

[0103] Next, organic thin-film solar cell elements and organic transistor elements were fabricated using the synthesized polymer compound P1, and their photoelectric conversion efficiency, mobility, and other properties were evaluated.

[0104] (Evaluation of solar cell element 1 using polymer compound P1) After thoroughly cleaning a glass substrate patterned with an indium tin oxide (ITO) film, it was treated with UV ozone. Next, a ZnO methanol dispersion was spin-coated at 1200 rpm for 10 seconds, and the edges were wiped to expose the ITO. The substrate with the hole extraction layer was brought into a glove box, and polymer compound P1 and n-type low molecular weight material PC were added. 61 BM([6,6]-Phenyl-C 61 - A chlorobenzene solution containing butyric acid methyl ester (polymer compound P1 / PC 61 Using a weight ratio of BM (1 / 2), the photoactive layer (polymer compound P1 / PC) is coated by spin coating. 61 A molybdenum oxide film (BM = approximately 300 nm) was formed. Next, a molybdenum oxide film with a thickness of 7.5 nm and a silver film with a thickness of 100 nm as an electrode layer were sequentially deposited by resistance heating vacuum deposition to create an organic thin-film solar cell element 1 (polymer compound P1 / PC) with a diameter of 4 mm. 61 I created a BM.

[0105] (Evaluation of solar cell element 2 using polymer compound P1) After thoroughly cleaning a glass substrate patterned with an indium tin oxide (ITO) film, it was treated with UV ozone. Next, a ZnO methanol dispersion was spin-coated at 1200 rpm for 10 seconds, and the edges were wiped to expose the ITO. The substrate with the hole extraction layer was brought into a glove box, and polymer compound P1 and n-type low molecular weight material Y12(2,2'-((2Z,2'Z)-((12,13-bis(2-butyloctyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2 A photoactive layer (polymer compound P1 / Y12 = approximately 100 nm) was formed by spin coating using a chlorobenzene solution containing ',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanilidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) (weight ratio of polymer compound P1 / Y12 = 1 / 2). Next, a molybdenum oxide film with a thickness of 7.5 nm and a silver film with a thickness of 100 nm as an electrode layer were sequentially deposited by resistance heating vacuum deposition to fabricate an organic thin-film solar cell element 2 (polymer compound P1 / Y12) with a diameter of 4 mm. The chemical formula of Y12 is shown below.

[0106] [ka]

[0107] The obtained organic thin-film solar cell element was subjected to a solar simulator (AM1.5G filter, irradiance 100mW / cm²). 2 A constant amount of light was irradiated using (), and the generated current and voltage were measured. Figures 1 and 2 show the current density-voltage characteristics of organic thin-film solar cell element 1 and organic thin-film solar cell element 2.

[0108] From the obtained results, the short-circuit current density Jsc (mAcm) -2 ), short-circuit current density Jsc(mAcm -2The EQE (Equivalent Equivalent Equivalent Equivalent), open-circuit voltage Voc (V), and curve factor FF were determined and summarized in Table 2. For organic thin-film solar cell element 1, Jsc = 8.9 mA / cm². 2 Jsc(EQE) = 9.5mA / cm 2 With Voc = 0.70V and FF = 0.67, the photoelectric conversion efficiency (η) was calculated using the formula η = (Jsc × Voc × FF) / 100 to be 4.1%. Furthermore, for organic thin-film solar cell element 2, Jsc = 17.4mA / cm². 2 Jsc(EQE) = 17.3 mA / cm 2 With Voc = 0.73V and FF = 0.65, the photoelectric conversion efficiency (η) was calculated using the formula η = (Jsc × Voc × FF) / 100 to be 8.3%.

[0109] [Table 2]

[0110] (Evaluation of organic field-effect transistors using polymer compound P1: bottom-gate, bottom-contact type) A highly doped p-type silicon substrate, on which gold electrodes for the source and drain electrodes were patterned onto a 300 nm thick silicon oxide film that would serve as the gate electrode, was thoroughly cleaned. The silicon oxide film surface of the p-type silicon substrate was then treated with octadecyltrichlorosilane. Polymer compound P1 was heated and dissolved in chlorobenzene solvent to prepare a 2 g / L solution. A polymer thin film approximately 50 nm thick was then fabricated on the surface-treated p-type silicon substrate by spin coating. This thin film was heated at 200°C for 30 minutes under a nitrogen atmosphere. In this manner, a bottom-gate, bottom-contact transistor element (organic transistor element 1) with a channel length of 20 μm and a channel width of 10,000 μm was fabricated.

[0111] (Evaluation of organic field-effect transistors using polymer compound P1: top-gate, bottom-contact type) After thoroughly cleaning a glass substrate patterned with gold electrodes to serve as the source and drain electrodes, the gold electrode surfaces were treated with octanthiol. Polymer compound P1 was heated and dissolved in chlorobenzene solvent to prepare a 2 g / L solution, and a polymer thin film approximately 50 nm thick was fabricated on the surface-treated glass substrate by spin coating. This thin film was heated at 200°C for 30 minutes under a nitrogen atmosphere. Subsequently, a 2-butanone solution of polymethyl methacrylate (PMMA) was applied by spin coating to fabricate a PMMA insulating layer approximately 550 nm thick. Finally, silver was vacuum-deposited onto the PMMA insulating layer to form a gate electrode 100 nm thick. In this way, a top-gate, bottom-contact type transistor element (organic transistor element 2) with a channel length of 20 μm and a channel width of 10,000 μm was fabricated.

[0112] Under vacuum, the transistor characteristics of the fabricated bottom-gate, bottom-contact transistor element 1 and top-gate, bottom-contact transistor element 2 were measured by varying the gate voltage Vg from 20 to -80V and the source-drain voltage Vd from 0 to -60V. The transfer characteristics are shown in Figures 3 and 4.

[0113] From the results obtained, the hole mobility μ h (cm 2 V -1 s -1 ), threshold voltage V th (V), On / Off ratio I on / off The results were obtained and summarized in Table 3. Devices using polymer compound P1 showed excellent hole mobility.

[0114] [Table 3] [Industrial applicability]

[0115] The polymer compounds according to the present invention are useful for organic thin-film solar cells having even better photoelectric conversion efficiency, or for organic transistors having even better mobility.

Claims

1. Formula (1): 【Chemistry 1】 (In formula (1), R １ is a hydrogen atom, a halogen atom, or an alkyl group, Ar １ A polymer compound containing repeating units represented by the following formula: is at least one arylene group selected from the groups represented by the following formula. 【Chemistry 2】 (wherein, R ２ , R ３ , R ４ , R ５ , R ６ , R ８ , R ９ , and R １０ are each independently a hydrogen atom, a halogen atom or an alkyl group, R ７ is a hydrogen atom or a halogen atom, and * represents a bond.)

2. Formula (5): 【Transformation 3】 (In formula (5), R １ A compound represented by (where is a hydrogen atom, a halogen atom, or an alkyl group, and X is a halogen atom).

3. A compound represented by formula (5) as described in claim 2, Formula (6): 【Chemistry 4】 (In formula (6), Me is a methyl group, and Ar １ A method for producing a polymer compound according to claim 1, comprising the step of reacting a compound represented by (1) with at least one arylene group selected from the groups represented by the following formula, to obtain a polymer compound containing the repeating unit represented by formula (1). 【Transformation 5】 (In the formula, R ２ , R ３ , R ４ , R ５ , R ６ , R ８ , R ９ and R １０ Each of these is independently a hydrogen atom, a halogen atom, or an alkyl group, and R ７ (where * represents a hydrogen atom or halogen atom, and * indicates a bonding bond.)

4. Formula (4): 【Transformation 6】 (In formula (4), R １ A method for producing the compound according to claim 2, comprising the step of reacting a compound represented by ( ) with a demethylating agent to obtain a compound represented by formula (5).

5. Formula (3): 【Transformation 7】 (In formula (3), R １ The process involves reacting a compound represented by ( ) with an oxidizing agent to obtain a compound represented by formula (4), where is a hydrogen atom, a halogen atom, or an alkyl group, Me is a methyl group, and X is a halogen atom. Formula (4): 【Transformation 8】 The process includes a step of reacting a compound represented by formula (4) (wherein R1 is a hydrogen atom, a halogen atom, or an alkyl group, Me is a methyl group, and X is a halogen atom) with a demethylating agent to obtain a compound represented by formula (5), A method for producing the compound described in claim 2.

6. Formula (2): 【Chemistry 9】 (In formula (2), R １ The steps include: reacting a compound represented by (where is a hydrogen atom, a halogen atom, or an alkyl group, and X is a halogen atom) with a methylthioling agent to obtain a compound represented by formula (3); Formula (3): 【Chemistry 10】 A step of reacting a compound represented by formula (3) (wherein R1 is a hydrogen atom, a halogen atom, or an alkyl group, Me is a methyl group, and X is a halogen atom) with an oxidizing agent to obtain a compound represented by formula (4), Formula (4): 【Chemistry 11】 The process includes a step of reacting a compound represented by formula (4) (wherein R1 is a hydrogen atom, a halogen atom, or an alkyl group, Me is a methyl group, and X is a halogen atom) with a demethylating agent to obtain a compound represented by formula (5), A method for producing the compound described in claim 2.

7. I) The first step involves reacting a compound represented by the following formula (2) with a methylthioling agent to produce a compound represented by the following formula (3), Formula (2): 【Chemistry 12】 (In formula (2), R １ (where X is a hydrogen atom, halogen atom, or alkyl group, and X is a halogen atom.) Formula (3): 【Chemistry 13】 (In formula (3), R １ (where is a hydrogen atom, a halogen atom, or an alkyl group, Me is a methyl group, and X is a halogen atom.) II) A second step in which the compound represented by formula (3) obtained in the first step is reacted with an oxidizing agent to produce a compound represented by the following formula (4): Formula (4): 【Chemistry 14】 (In formula (4), R １ (where is a hydrogen atom, a halogen atom, or an alkyl group, Me is a methyl group, and X is a halogen atom.) III) A third step in which the compound represented by formula (4) obtained in the second step is reacted with a demethylating agent to produce a compound represented by the following formula (5), and Formula (5): 【Chemistry 15】 (In formula (5), R １ (where X is a hydrogen atom, a halogen atom, or an alkyl group, and X is a halogen atom.) IV) A fourth step in which the compound represented by formula (5) obtained in the third step is reacted with the compound represented by the following formula (6) to produce a polymer compound containing a repeating unit represented by formula (1). Formula (6): 【Chemistry 16】 (In formula (6), Me is a methyl group, and Ar １ (This is at least one arylene group selected from the groups represented by the following formula.) 【Chemistry 17】 (In the formula, R ２ , R ３ , R ４ , R ５ , R ６ , R ８ , R ９ and R １０ Each of these is independently a hydrogen atom, a halogen atom, or an alkyl group, and R ７ (where * represents a hydrogen atom or halogen atom, and * indicates a bonding bond.) A method for producing a polymer compound according to claim 1, including the method described in claim 1.

8. A composition for forming an organic semiconductor film, comprising the polymer compound described in claim 1.

9. An organic semiconductor film comprising the polymer compound described in claim 1.

10. An organic thin-film solar cell comprising the organic semiconductor film described in claim 9.

11. An organic transistor comprising the organic semiconductor film described in claim 9.

12. A method for producing an organic semiconductor film, comprising the step of depositing or coating the organic semiconductor film-forming composition described in claim 8 onto a substrate to form an organic semiconductor film.

13. A method for manufacturing an organic thin-film solar cell, comprising the step of depositing or coating the organic semiconductor film-forming composition described in claim 8 onto a substrate to form an organic semiconductor film.

14. A method for manufacturing an organic transistor, comprising the step of depositing or coating the organic semiconductor film-forming composition described in claim 8 onto a substrate to form an organic semiconductor film.

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