Polymer semiconductor material and use thereof

Abstract

To provide a polymer semiconductor that shows superior charge transport characteristics, and an organic thin film transistor (OTFT) in which the polymer semiconductor is employed.SOLUTION: A polymer semiconductor represented by formula (1), wherein n, p, and q each independently denote an integer of 1 or more, D denotes a divalent arylene group represented by formula (2), and A denotes a divalent electron-withdrawing aromatic group represented by formula (3). In formulas (2) and (3), X1 and X2 each independently denote a chalcogen atom, Y1, Y2, Y3, and Y4 each independently denote a C-R1 group, where R1 is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 30 carbon atoms, or denote a nitrogen atom. D1 denotes a 1,2-ethenediyl group, a 1,2-ethynediyl group, or a single bond. A1 denotes a divalent electron-withdrawing aromatic group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymeric semiconducting material and its uses. [Background technology]

[0002] In recent years, research and development into polymer semiconductors, which are the constituent materials of organic electronic devices such as organic thin-film transistors (OTFTs), has been actively conducted in order to commercialize these devices. Toward practical application, materials with better charge transport properties (charge mobility) are required.

[0003] Polymer semiconductors are primarily synthesized by polycondensation (cross-coupling polymerization) using cross-coupling reactions. For example, the reaction of an aromatic compound containing two or more halogen atoms with an aromatic tin monomer or an aromatic boron monomer forms cross-coupling bonds between different aromatic groups, between different unsaturated groups (alkenes or alkynes), or even between aromatic and unsaturated groups, resulting in an alternating copolymer. Various combinations of aromatic groups, i.e., the backbone of polymer semiconductors, have been explored, and the charge transport properties, which are the most important property of semiconductors, have been improved.

[0004] On the other hand, the effect of the arrangement (sequence) of each aromatic group in the copolymer skeleton on its charge transport properties was unclear. It was thought that cross-coupling polymerization would produce a perfectly alternating copolymer of different aromatic groups, but Non-Patent Document 1 discloses an example in which a polymer semiconductor having a structure in which the same type of aromatic group is consecutively arranged (homo-coupling structure) due to a side reaction exhibits good charge transport properties. Furthermore, Non-Patent Document 2 discloses a copolymer similar to the conductive polymer of the present invention, but does not describe at all the arrangement of each aromatic group in the skeleton of the copolymer, the presence or absence of a homocoupling structure, or the charge transport properties. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] ACS Applied Polymer Materials, Vol. 3, pp. 830-836, 2021 [Non-patent document 2] Advanced Materials, Vol. 24, pp. 4618-4622, 2012 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a polymer semiconductor that exhibits excellent charge transport properties, a method for producing the same, and an OTFT using the same. [Means for solving the problem]

[0007] The present inventors conducted a detailed analysis of the main chain structure of copolymers obtained by cross-coupling polymerization and found that the presence of a homocoupling structure improves the charge transport properties of polymer semiconductors, thereby completing the present invention.

[0008] That is, the present invention comprises the following gist. [Abstract 1] A polymer semiconductor represented by formula (1). [ka] In the formula, n, p, and q represent the number of (DA), (DD), and (AA) bonds, respectively, and each independently represents an integer of 1 or more. D is a divalent electron-donating aromatic group represented by the following formula (2): [ka] In formula (2), each X1 independently represents a chalcogen atom, and each Y1 and Y2 independently represent a C-R1 group (R1 represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 30 carbon atoms) or a nitrogen atom. d and e are integers of 0 or 1, and cannot both be 0. D1 represents a 1,2-ethenediyl group, a 1,2-ethynediyl group, or a single bond. * represents a bonding site. A is a divalent electron-withdrawing aromatic group represented by the following formula (3): [ka] In formula (3), each X2 independently represents a chalcogen atom, and each Y3 and Y4 independently represents a C-R2 group (R2 represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 30 carbon atoms) or a nitrogen atom. f is an integer of 0 or 1. A1 represents a divalent electron-withdrawing aromatic group represented by any of the following formulae (A-1) to (A-5). * represents a bonding site. [ka] In formulas (A-1) to (A-5), each R3 independently represents an alkyl group having 1 to 30 carbon atoms. Each Z independently represents a hydrogen atom, a fluorine atom, a cyano group, a nitro group, a trifluoromethyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or an amido group having 1 to 20 carbon atoms. * represents a bonding site. [Abstract 2] A method for producing a polymer semiconductor represented by formula (1) by mixing monomer compounds represented by the following general formulae (mono-1-g), (mono-2-g), (mono-1-M) and (mono-2-M) in a molar ratio of S:T:U:V and reacting them in the presence of a base and a transition metal catalyst. [ka] (In the formula, X1 and X2 each independently represent a chalcogen atom, Y1, Y2, Y3, and Y4 each independently represent a C-R1 group (R1 represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 30 carbon atoms) or a nitrogen atom. d, e, and f each independently represent an integer of 0 or 1, provided that d and e do not both represent 0. g represents a leaving group. M represents a hydrogen atom or a boron-containing group. D1 represents a 1,2-ethenediyl group, a 1,2-ethynediyl group, or a single bond. A1 represents a divalent electron-withdrawing aromatic group represented by any of the following formulae (A-1) to (A-5). [ka] (In formulas (A-1) to (A-5), each R3 independently represents an alkyl group having 1 to 30 carbon atoms. Each Z independently represents a hydrogen atom, a fluorine atom, a cyano group, a nitro group, a trifluoromethyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or an amido group having 1 to 20 carbon atoms.) n, p, and q each independently represent an integer of 1 or more. D is a divalent electron-donating aromatic group represented by the following formula (2): [ka] (In the formula, X1, Y1, Y2, d, e and D1 have the same meanings as above, and * represents a binding site.) A is a divalent electron-withdrawing aromatic group represented by the following formula (3): [ka] (In the formula, X2, Y3, Y4, f, *, and A1 have the same meanings as above.) [Effects of the Invention]

[0009] The polymer semiconductor of the present invention is an organic semiconductor having high carrier mobility, and can efficiently drive an organic thin film transistor element using the polymer semiconductor as an active layer. [Brief explanation of the drawings]

[0010] [Figure 1] 1A and 1B are diagrams showing the cross-sectional structure of an organic thin film transistor element. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to these, and various modifications are possible within the scope of the description. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention. In this specification, unless otherwise specified, "P to Q" representing a numerical range means "not less than P and not more than Q."

[0012] [Compound] A compound according to one embodiment of the present invention (sometimes referred to herein as the "polymer semiconductor of this embodiment") is a polymer semiconductor represented by formula (1).

[0013] [ka] (In the formula, n, p, and q have the same meanings as above.)

[0014] D is a divalent electron-donating aromatic group represented by the following formula (2): [ka] (In the formula, X1, Y1, Y2, d, e, and D1 have the same meanings as above.) Furthermore, A is a divalent electron-withdrawing aromatic group represented by the following formula (3). [ka] (In the formula, X2, Y3, Y4, f, and A1 have the same meanings as above.) As the chalcogen atoms represented by X1 and X2, an oxygen atom, a sulfur atom, or a selenium atom is preferred, an oxygen atom or a sulfur atom is more preferred, and a sulfur atom is even more preferred, in that the solubility of the compound of this embodiment is increased. The alkyl group having 1 to 30 carbon atoms represented by R1 or R2 in the C-R1 group or C-R2 group represented by Y1, Y2, Y3 or Y4 in the electron-donating aromatic group (2) and the electron-withdrawing aromatic group (3) includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptyl group, a hexadec ... Examples include a tadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyloctyl group, a 2-hexyldecyl group, a 2-octyldodecyl group, a 2-decyltetradecyl group, a 3-decylpentadecyl group, a 3-dodecylheptadecyl group, a 3-tetradecylnonacosyl group, a 4-decylhexadecyl group, a 4-dodecyloctadecyl group, and a 4-tetradecylicosyl group. R1 or R2 in the C-R1 group or C-R2 group represented by Y1, Y2, Y3 or Y4 in the electron-donating aromatic group (2) and the electron-withdrawing aromatic group (3) is preferably a hydrogen atom, as this increases carrier mobility. In the electron-donating aromatic group (2) and the electron-withdrawing aromatic group (3), d, e, and f are each independently an integer of 0 or 1, and it is preferred that d and e are not both 0, and that d and e are both 1. D1 in the electron-donating aromatic group (2) represents a 1,2-ethenediyl group, a 1,2-ethynediyl group, or a single bond, and is preferably a 1,2-ethenediyl group in that it provides higher carrier mobility.

[0015] A1 in the electron-withdrawing aromatic group (3) represents a divalent electron-withdrawing aromatic group represented by the following formulae (A-1) to (A-5), and (A-1) is preferred in that it results in higher carrier mobility. [ka] Examples of the alkyl group having 1 to 30 carbon atoms represented by R3 in formulas (A-1) to (A-5) include the same alkyl groups having 1 to 30 carbon atoms as exemplified for R1 or R2, and a 2-decyltetradecyl group is preferred in that it provides higher carrier mobility. Examples of the alkoxy group having 1 to 20 carbon atoms represented by Z in formulas (A-1) to (A-5) include a methoxy group, a cyclohexylmethyloxy group, an ethoxy group, a 2-cyclopentylethyloxy group, a propoxy group, a 2-methylpropyloxy group, a 2,2-dimethylpropyloxy group, a 3-cyclopropylpropyloxy group, a 1-methylethyloxy group, a cyclopropyloxy group, a butoxy group, a 2-methylbutyloxy group, a 3-methylbutyloxy group, a 2-butyloxy group, a 3-methylbutan-2-yloxy group, a tert-butyloxy group, a 2-methyl ...2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutan-2-yloxy group, a tert-butyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a 2-methylbutyloxy group, a cyclobutyloxy, pentyloxy, 2-methylpentyloxy, 3-ethylpentyloxy, 2,4-dimethylpentyloxy, 2-pentyloxy, 2-methylpentan-2-yloxy, 4,4-dimethylpentan-2-yloxy, 3-pentyloxy, 3-ethylpentan-3-yloxy, cyclopentyloxy, 2,5-dimethylcyclopentyloxy, 3-ethylcyclopentyloxy, hexyloxy, 2-methylhexyloxy, 3,3-dimethylhexyl Oxy group, 4-ethylhexyloxy group, 2-hexyloxy group, 2-methylhexan-2-yloxy group, 5,5-dimethylhexan-2-yloxy group, 3-hexyloxy group, 2,4-dimethylhexan-3-yloxy group, cyclohexyloxy group, 4-ethylcyclohexyloxy group, 4-propylcyclohexyloxy group, 4,4-dimethylcyclohexyloxy group, heptyloxy group, 2-heptyloxy group, 3-heptyloxy group, 4-heptyloxy group, bicyclo[2.2.1]heptyloxy group, Examples include octyloxy, 2-octyloxy, 3-octyloxy, 4-octyloxy, cyclooctyloxy, bicyclo[2.2.2]octyloxy, nonyloxy, 5-nonyloxy, decyloxy, 2-decyloxy, 5-decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, and icosyloxy. Examples of the alkoxycarbonyl group having 1 to 20 carbon atoms represented by Z in the formulae (A-1) to (A-5) include a methoxycarbonyl group, a cyclopropylmethyloxycarbonyl group, a cyclopentylmethyloxycarbonyl group, a cyclohexylmethyloxycarbonyl group, a 4-propylcyclohexylmethyloxycarbonyl group, an ethoxycarbonyl group, a 1,1-dimethylethyloxycarbonyl group, a propyloxycarbonyl group, a 1-methylethoxycarbonyl group, a 1-methylpropyloxycarbonyl group, a 2-methylpropyloxycarbonyl group, a cyclopropyloxycarbonyl group, a butyloxycarbonyl group, a 2-ethylbutyloxycarbonyl group, a cyclobutyloxycarbonyl group, a pentyloxycarbonyl group, a 2,4-dimethylpentyloxycarbonyl group, a cyclo Examples of the alkyl group include a pentyloxycarbonyl group, a hexyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a 1-pentylhexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a 3,7-dimethyloctyloxycarbonyl group, a 2-butyloctyloxycarbonyl group, a 1-heptyloctyloxycarbonyl group, nonyloxy, a 1-octylnonyloxycarbonyl group, a decyloxycarbonyl group, a 2-hexyldecyloxycarbonyl group, a dodecyloxycarbonyl group, a 2-octyldodecyloxycarbonyl group, a hexadecyloxycarbonyl group, a 2-methylhexadecyloxycarbonyl group, and a 3,7,11,15-tetramethylhexadecyloxycarbonyl group. Examples of the amide group having 1 to 20 carbon atoms, represented by Z in formulas (A-1) to (A-5), include an amide group, an N,N-dimethylamide group, an N,N-diethylamide group, an N,N-dipropylamide group, an N,N-dibutylamide group, an N,N-dipentylamide group, an N,N-dihexylamide group, an N,N-diheptylamide group, an N,N-dioctylamide group, an N,N-dinonylamide group, and an N,N-di(2-ethylhexyl)amide group. Z in the formulae (A-1) to (A-5) is preferably a hydrogen atom or a fluorine atom in that it provides higher charge mobility.

[0016] In the electron-donating aromatic group (2) and the electron-withdrawing aromatic group (3), n, p, and q each independently represent an integer of 1 or greater, and the content of (DD) bonds defined by p×100 / (n+p+q) is preferably 1% to 25%, more preferably 3% to 25%, and even more preferably 6.5% to 20%, in order to further increase the carrier mobility of the polymer semiconductor of this embodiment.

[0017] Furthermore, the content of (AA) bonds defined by q×100 / (n+p+q) is preferably 1% to 25%, more preferably 3% to 25%, and even more preferably 9% to 20%, in order to further increase the carrier mobility of the polymer semiconductor of this embodiment.

[0018] [Method for producing polymer semiconductor] Next, a method for producing the polymer semiconductor of this embodiment (hereinafter sometimes referred to as the "production method of this embodiment") will be described. The method for producing the polymer semiconductor of this embodiment is as shown in the following production steps (A) and (B).

[0019] <Manufacturing process (A)> Production process (A) shown in the following formula is a method for producing the polymer semiconductor of this embodiment by mixing monomer compounds represented by (mono-1-g), (mono-2-g), (mono-1-M), and (mono-2-M) in a molar ratio of S:T:U:V and reacting them in the presence of a transition metal catalyst.

[0020] [ka]

[0021] (In the formula, X1, X2, Y1, Y2, Y3, Y4, D1, A1, d, e, f, D, and A are as defined above. Each g independently represents a halogen atom. Each M independently represents a boron-containing group.)

[0022] As the halogen atom represented by g, a chlorine atom, a bromine atom, or an iodine atom is preferred, a bromine atom or an iodine atom is more preferred, and a bromine atom is even more preferred, in terms of improving the production efficiency of the polymer semiconductor of this embodiment.

[0023] The boron-containing group represented by M is preferably a group represented by B(OR1)2 (wherein R1 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Two R1s can also form a ring together with the boron atom bonded via an oxygen atom). In terms of improving the production efficiency of the conjugated polymer of this embodiment, R1 in the boron-containing group B(OR1)2 is preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a butyl group, or a phenyl group, and more preferably a hydrogen atom. Furthermore, when R1 forms a ring together with the boron atom bonded via an oxygen atom, the group is preferably any of the groups represented by the following formulas (4-1) to (4-5), more preferably a group represented by formula (4-2), formula (4-4), or formula (4-5), more preferably formula (4-2) or formula (4-4), and particularly preferably formula (4-2).

[0024] [ka] The monomer compounds (mono-1-g), (mono-2-g), (mono-1-M), and (mono-2-M) can be synthesized according to the methods shown in the Reference Synthesis Examples or methods described in non-patent literature (e.g., Macromolecules, Vol. 46, pp. 9211-9219, 2013; Chemistry of Materials, Vol. 28, pp. 8580-8590, 2016; Journal of the American Chemical Society, Vol. 128, pp. 9034-9035, 2006). Commercially available products may also be used.

[0025] The (S+T) / (S+T) value calculated from the sum (S+T) of the molar ratios S and T of the monomer compounds (mono-1-g) and (mono-2-g) and the sum (U+V) of the molar ratios U and V of the monomer compounds (mono-1-M) and (mono-2-M) is preferably in the range of 0.90 to 1.10, more preferably 0.95 to 1.05, and even more preferably 0.98 to 1.02.

[0026] Production step (A) must be carried out in the presence of a transition metal catalyst. Examples of transition metal catalysts that can be used include palladium catalysts, nickel catalysts, and platinum catalysts. These transition metal catalysts include "metals," "supported metals," "metal salts such as metal chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, and oxides," and "complex compounds such as olefin complexes, phosphine complexes, amide complexes, amine complexes, carbene complexes, and acetylacetonato complexes." In terms of good reaction yield, palladium catalysts or nickel catalysts are preferred, and palladium catalysts are even more preferred. Furthermore, these metals, supported metals, metal salts, and complex compounds can also be used in combination with tertiary phosphorus compounds or carbene compounds.

[0027] The palladium catalyst used in the production step (A) is not particularly limited, but examples thereof include palladium metal such as palladium black and palladium sponge, and also examples thereof include palladium metal supported on palladium / alumina, palladium / carbon, palladium / silica, palladium / Y-type zeolite, and the like. Also, divalent palladium salts such as palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, π-allylpalladium chloride dimer, palladium acetylacetonate, dichlorobis(acetonitrile)palladium, dichlorobis(benzonitrile)palladium, dichlorodiamminepalladium, and (π-allyl)(cyclopentadienyl)palladium; zerovalent palladium such as bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, and tris(dibenzylideneacetone)dipalladium chloroform adduct; dichlorobis(triphenylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, and dichloro[1,3-bis(diphenylphosphino)propionate]. pan]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium and dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium dichloride (Pd-PEPPSI-IPe Examples of suitable catalysts include palladium catalysts having a tertiary phosphorus compound or a carbene compound as a ligand, such as [1,3-bis(2,6-di-3-pentylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium dichloride (Pd-PEPPSI-IPr), [1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene](3-chloropyridyl)palladium dichloride (Pd-PEPPSI-SIPr), etc.

[0028] Among these palladium catalysts, palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), and bis(tri-tert-butylphosphine)palladium are preferably used because of their good reaction yield.

[0029] The nickel catalyst used in the production step (A) is not particularly limited, but specific examples thereof include zero-valent nickel such as nickel chloride, bis(1,5-cyclooctadiene)nickel, and cyclododeca-1,5,9-triene nickel; nickel fluoride, nickel chloride, nickel bromide, nickel iodide, hexaamminenickel chloride, bis(cyclopentadienyl)nickel, bis(dimethylglyoxinato)nickel, nickel chloride=dimethoxyethane adduct, dichloro(tetramethylethylenediamine)nickel, bis(acetylacetonato)nickel, bis(hexafluoroacetylacetonato)nickel, nickel oxalate, nickel sulfate, nickel carbonate, and trifluoromethanesulfone. Examples of nickel catalysts include divalent nickel salts such as nickel acid, nickel acetate, nickel formate, and nickel nitrate; nickellocene complexes such as bis(cyclopentadienyl)nickel, bis(ethylcyclopentadienyl)nickel, bis(isopropylcyclopentadienyl)nickel, and bis(pentamethylcyclopentadienyl)nickel; and nickel catalysts having, as a ligand, a tertiary phosphorus compound or a carbene compound such as dichloro(1,1'-bis(diphenylphosphino)ethane)nickel, dichloro(1,1'-bis(diphenylphosphino)propane)nickel, and [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]triphenylphosphinenickel dichloride.

[0030] The palladium catalyst or nickel catalyst having the tertiary phosphorus ligand or carbene compound may be prepared in the reaction system by mixing a palladium salt or nickel salt with the tertiary phosphorus ligand or carbene compound. Examples of tertiary phosphorus compounds that can be used include triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tri-tert-butylphosphonium tetrafluoroborate, tricyclohexylphosphine, tri(o-tolyl)phosphine, tris(2-methoxyphenyl)phosphine, trioctylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, 1,2-bis(diphenylphosphino)ethane, and 1,3-bis(diphenylphosphino)propane. , 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, tert-butyldiphenylphosphine, 2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl, bis(diphenylphosphino)methane, 1,4-bis(diphenylphosphino)butane, tri(2-furyl)phosphine, tris(2,5-xylyl)phosphine, (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and the like can be exemplified. Examples of usable carbene compounds include 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene, 1,3-di-tert-butylimidazol-2-ylidene, and 1,3-dimesitylimidazol-2-ylidene.

[0031] In terms of good reaction yield, it is preferable to use triphenylphosphine, tri(tert-butyl)phosphine, tri-tert-butylphosphonium tetrafluoroborate, tricyclohexylphosphine or tri(o-tolyl)phosphine as the tertiary phosphorus compound.

[0032] The molar ratio of the tertiary phosphorus compound to the transition metal catalyst (tertiary phosphorus compound:transition metal catalyst) is preferably in the range of 1:10 to 10:1, and more preferably in the range of 1:5 to 5:1 in terms of good reaction yield.

[0033] The amount of the transition metal catalyst used is not particularly limited, but in terms of a good reaction yield, it is preferably 0.001 to 50 mol % and more preferably 0.1 to 20 mol % based on the total amount of the monomer compounds (mono-1-g) and (mono-2-g).

[0034] A promoter may be used in the production step (A). The promoter is not particularly limited, but specific examples include monovalent or divalent copper salts such as copper fluoride, copper chloride, copper bromide, copper iodide, and copper oxide.

[0035] The production process (A) can be carried out in a solvent. The solvent that can be used is not particularly limited as long as it does not inhibit the reaction, and includes aliphatic hydrocarbon solvents such as hexane, heptane, decane, and tridecane; ether solvents such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; carbonate solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ester solvents such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone; N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP). urea solvents such as N,N,N',N'-tetramethylurea (TMU) and N,N'-dimethylpropyleneurea (DMPU); sulfoxide solvents such as dimethyl sulfoxide (DMSO); alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol; halogenated solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and o-dichlorobenzene (DCB); fluorinated solvents such as bis(2,2,2-trifluoroethyl)N,N-diisopropylphosphoramidate (PF-37) and tris(2,2,2-trifluoroethyl)phosphate (TFEP); nitromethane; water; and the like, and these may be mixed and used in any ratio.Among these, in terms of good reaction yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, fluorinated solvents, aromatic hydrocarbon solvents, and mixed solvents of these with water are preferred, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, and mixed solvents of these with water are more preferred, and tetralin, toluene, chlorobenzene, o-DCB, CPME, THF, a mixed solvent of toluene and water, or a mixed solvent of tetralin and water is even more preferred.

[0036] There are no particular restrictions on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL / mg relative to the monomer compounds (mono-1-g) and (mono-2-g).

[0037] The production step (A) can also be carried out in the presence of a phase transfer catalyst. Usable phase transfer catalysts include ethyltrimethylammonium iodide, didodecyldimethylammonium chloride, dimethyldioctadecylammonium iodide, dimethyldioctylammonium bromide, didecyldimethylammonium bromide, dimethyldimyristylammonium bromide, dihexadecyldimethylammonium bromide, diallyldimethylammonium chloride, dimethyldioctadecylammonium chloride, didodecyldimethylammonium bromide, 4-dimethylamino-1-neopentylpyridinium chloride, dodecyltrimethylammonium bromide, decyltrimethylammonium bromide, 1,1-dimethyl-4-phenylpiperazinium iodide, decamethonium iodide, decamethonium bromide, decyltrimethylammonium chloride, decyltrimethylammonium chloride, ethylhexadecyldimethylammonium bromide, (3-chloro-2-hydroxypropyl)trimethylammonium chloride, carbachol, choline chloride, chlorocholine chloride, bis(2-hydroxyethyl)dimethylammonium chloride, ammonium chloride, benzyldodecyldimethylammonium bromide, benzyltrimethylammonium bromide, benzyldodecyldimethylammonium chloride dihydrate, benzyltrimethylammonium dichloroiodate, benzyltributylammonium chloride, benzyltributylammonium bromide, bromocholine bromide, benzyltrimethylammonium chloride, benzyltriethylammonium iodide, benzyltriethylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyldimethylphenylammonium chloride, benzalkonium chloride, benzoylthiocholine iodide, benzyldimethylhexadecylammonium chloride hydrate, benzoylcholine iodide, benzoylcholine chloride, benzoylcholine bromide, zephiran chloride hydrate, tetrabutylammonium p-toluenesulfonate, tetrabutylammonium nitrate, tetrahexylammonium hydrogensulfate, tetraethylammonium nitrate, tributylammonium chloride,Trimethylpropylammonium bromide, trimethylnonylammonium bromide, tetrabutylammonium acetate, tetrabutylammonium tetrafluoroborate, trimethyl[2-[(trimethylsilyl)methyl]benzyl]ammonium iodide, triethylammonium tetrafluoroborate, tris(2-hydroxyethyl)methylammonium hydroxide, tetrapropylammonium chloride, tetraethylammonium trifluoromethanesulfonate, tetra-n-octylammonium bromide, tetraheptylammonium bromide, tetrahexylammonium bromide, tetrabutylammonium triflate, tetrabutylammonium tetraphenylborate, tetrapentylammonium chloride, tetrapentylammonium bromide, tetramethylammonium acetate, tetraheptylammonium iodide, methyltri-n-octylammonium chloride, tetramethylammonium hexafluorophosphate, tetrabutylammonium bifluoride, tetrabutylammonium tribromide, tetrabutylammonium hexafluorophosphate phosphate, tetrabutylammonium thiocyanate, tetrabutylammonium triiodide, tetramethylammonium sulfate, tetra-n-octylammonium iodide, tetra(decyl)ammonium bromide, tetramethylammonium acetate, tetrahexylammonium iodide, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, trimethyltetradecylammonium chloride, tetrabutylammonium tetrafluoroborate, tetradecyltrimethylammonium bromide, tetramethylammonium tetrafluoroborate, tetrabutylammonium perchlorate, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride (Aliquat 336), tetrapropylammonium bromide, tetrapropylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium iodide, tetramethylammonium bromide, tetramethylammonium chloride,Ammonium salts such as tetramethylammonium iodide, (ferrocenylmethyl)trimethylammonium bromide, (ferrocenylmethyl)dodecyl, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexyltrimethylammonium bromide, triethylammonium chloride, methyltri-n-octylammonium hydrogen sulfate, trimethyl-n-octylammonium bromide, trimethyl-n-octylammonium chloride, trimethylphenylammonium bromide, trimethylphenylammonium chloride, trimethylphenylammonium tribromide, octadecyltrimethylammonium bromide, and tetrabutylammonium bromide; tetrabutylphosphonium tetraphenylborate, tetrabutylphosphonium hexafluorophosphate, and tetrabutylphosphonium Examples of suitable phosphonium salts include ammonium tetrafluoroborate, tetraethylphosphonium tetrafluoroborate, tetraethylphosphonium hexafluorophosphate, tetra-n-octylphosphonium bromide, tetrabutylphosphonium chloride, tetraethylphosphonium bromide, tetraphenylphosphonium chloride, tetrabutylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium sulfate, tetraphenylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium chloride, tributyl-n-octylphosphonium bromide, hexadecyltributylphosphonium bromide, tributyldodecylphosphonium bromide, (2-carboxyethyl)triphenylphosphonium bromide, and tributyl(cyanomethyl)phosphonium chloride, and these may be mixed in any ratio. Among these, ammonium salts are preferred in terms of good reaction yield, and tetrabutylammonium bromide is more preferred.

[0038] The production step (A) must be carried out in the presence of a base, and examples of bases that can be used include metal alkoxides such as sodium butoxide and potassium butoxide; metal alkyls such as butyllithium; metal amides such as lithium hexamethyldisilazide, lithium diisopropylamide, 2,2,6,6-tetramethylpiperidinyllithium, and 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex; lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and charcoal. Examples of suitable bases include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, and tripotassium phosphate; and organic bases such as triethylamine, diisopropylethylamine, pyridine, lutidine, diazabicycloundecene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), and 1,4-diazabicyclo[2.2.2]octane (DABCO). These bases may be mixed in any ratio. Among these, inorganic bases are preferred because of their good reaction yield, and sodium carbonate, potassium carbonate, or tripotassium phosphate are more preferred.

[0039] The amount of base used is not particularly limited, but in terms of good reaction yield, it is preferably 0.1 to 10 molar equivalents, more preferably 1 to 5 molar equivalents, relative to the total amount of the monomer compounds (mono-1-g) and (mono-2-g).

[0040] The temperature at which production step (A) is carried out is not particularly limited, but it can be carried out at a temperature appropriately selected from 0°C to 240°C. In terms of good reaction yield, it is preferably carried out at a temperature appropriately selected from 20°C to 220°C, and more preferably at a temperature appropriately selected from 40°C to 200°C.

[0041] The production step (A) can also be carried out using a microwave reaction device.

[0042] There are no particular limitations on the reaction atmosphere in which the production step (A) is carried out, but it is preferable to carry out the reaction in an inert gas atmosphere such as argon gas or nitrogen gas, or under reduced pressure.

[0043] The time for carrying out the production step (A) varies depending on the monomer compounds (mono-1-g), (mono-2-g), (mono-1-M), and (mono-2-M) used, as well as the solvent and reaction temperature, but is usually preferably 0.1 to 100 hours, more preferably 1 to 78 hours.

[0044] The polymer semiconductor of this embodiment can be obtained by carrying out a conventional treatment after the completion of the production step (A). If necessary, the polymer semiconductor may be purified by any of the commonly used means used by those skilled in the art for purifying polymer compounds, such as washing, precipitation, filtration, dialysis, column chromatography, preparative HPLC, and Soxhlet extraction.

[0045] The monomer compounds (mono-1-g), (mono-2-g), (mono-1-M), and (mono-2-M) used in the production step (A) may be obtained by any method, and can be produced by referring to methods described in non-patent literature (e.g., Macromolecules, Vol. 46, pp. 9211-9219, 2013; Chemistry of Materials, Vol. 28, pp. 8580-8590, 2016; Journal of the American Chemical Society, Vol. 128, pp. 9034-9035, 2006). Alternatively, commercially available products may be used.

[0046] <Manufacturing process (B)> In the production process (B), the monomer compounds (mono-1-g), (mono-2-g), (mono-1-H), and (mono-2H) are mixed in a ratio of S:T:K:L, and reacted in the presence of a transition metal catalyst, thereby producing the polymer semiconductor of this embodiment. [ka]

[0047] (In the formula, X1, X2, Y1, Y2, Y3, Y4, D1, A1, d, e, f, g, D, A, n, p, and q are as defined above, and H represents a hydrogen atom.)

[0048] The (S+T) / (K+L) value calculated from the sum (S+T) of the molar ratios S and T of the monomer compounds (mono-1-g) and (mono-2-g) and the sum (K+L) of the molar ratios K and L of the monomer compounds (mono-1-H) and (mono-2H) is preferably in the range of 0.90 to 1.10, more preferably 0.95 to 1.05, and even more preferably 0.98 to 1.02.

[0049] Production step (B) must be carried out in the presence of a transition metal catalyst, and examples of transition metal catalysts that can be used include the same transition metal catalysts as those exemplified in production step (A). In terms of good reaction yield, a palladium catalyst or nickel catalyst is preferably used, and a palladium catalyst is more preferably used. Furthermore, these metals, supported metals, metal salts, and complex compounds can also be used in combination with tertiary phosphorus compounds, carbene compounds, etc.

[0050] The palladium catalyst or nickel catalyst is not particularly limited, but examples thereof include the palladium catalysts or nickel catalysts exemplified in the production step (A).

[0051] Of these palladium catalysts and nickel catalysts, palladium catalysts are preferred because of their good reaction yield, and it is particularly preferred to use palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium or tris(dibenzylideneacetone)dipalladium.

[0052] These palladium catalysts may be used alone or in combination with a tertiary phosphorus compound, such as the tertiary phosphorus compounds exemplified in Production Step (A).

[0053] It is preferable to use tris(2-methoxyphenyl)phosphine as the tertiary phosphorus compound in terms of good reaction yield.

[0054] The molar ratio of the tertiary phosphorus compound to the transition metal catalyst (tertiary phosphorus compound:transition metal catalyst) is preferably in the range of 1:10 to 10:1, and more preferably in the range of 1:5 to 5:1 in terms of good reaction yield.

[0055] The amount of the transition metal catalyst used is not particularly limited, but in terms of a good reaction yield, it is preferably 0.001 to 50 mol % relative to the total amount of the monomer compounds (mono-1-g) and (mono-2-g), and more preferably 0.1 to 20 mol %.

[0056] A promoter may be used in the production step (B). The promoter is not particularly limited, but specific examples include monovalent or divalent copper salts such as copper fluoride, copper chloride, copper bromide, copper iodide, and copper oxide.

[0057] Production step (B) can be carried out in a solvent. The solvent that can be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include the solvents exemplified in production step (A). From the viewpoint of a good reaction yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, fluorine-containing solvents, mixed solvents of aromatic hydrocarbon solvents and water, mixed solvents of halogenated solvents and water, mixed solvents of ether solvents and water, mixed solvents of aromatic hydrocarbon solvents and sulfoxide solvents, mixed solvents of halogenated solvents and sulfoxide solvents, mixed solvents of ether solvents and sulfoxide solvents, mixed solvents of aromatic hydrocarbon solvents and fluorine solvents, mixed solvents of halogenated solvents and fluorine solvents, and mixed solvents of ether solvents and fluorine solvents are preferred; aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, mixed solvents of aromatic hydrocarbon solvents and fluorine solvents, mixed solvents of halogenated solvents and fluorine solvents, and mixed solvents of ether solvents and fluorine solvents are more preferred; and CPME, THF, toluene, xylene, or mesitylene is even more preferred.

[0058] There are no particular restrictions on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL / mg relative to the total weight of the monomer compounds (mono-1-g) and (mono-2-g).

[0059] Production step (B) must be carried out in the presence of a base, and examples of bases that can be used include the bases exemplified in production step (A). In terms of good reaction yield, inorganic bases are preferred, carbonates are more preferred, and sodium carbonate, potassium carbonate, or cesium carbonate are even more preferred.

[0060] The amount of base used is not particularly limited, but in terms of good reaction yield, it is preferably 0.1 to 10 molar equivalents, more preferably 1 to 5 molar equivalents, relative to the total amount of the monomer compounds (mono-1-g) and (mono-2-g).

[0061] Production step (B) can be carried out in the presence of an acid. The acid can be inorganic or organic. Examples of organic acids include carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, neodecanoic acid, capric acid, benzoic acid, and 1-adamantanecarboxylic acid; and sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and 10-camphorsulfonic acid (CSA). These acids may be mixed in any ratio. Among these, carboxylic acids are preferred because of their high reaction yield, with acetic acid, pivalic acid, neodecanoic acid, and 1-adamantanecarboxylic acid being more preferred.

[0062] The amount of organic acid used is not particularly limited, but in terms of good reaction yield, it is preferably 0.01 to 10 molar equivalents, and more preferably 0.1 to 5 molar equivalents, relative to the total amount of the compounds represented by general formula (mono-1-g) and general formula (mono-2-g).

[0063] In the production step (B), an additive can be used. Examples of the additive include amines such as N,N,N',N'-tetramethylmethylenediamine (TMMDA), N,N,N',N'-tetramethylethylenediamine (TMEDA), N,N,N',N'-tetramethyltrimethylenediamine (TMPDA), N,N,N',N'-tetramethyltetramethylenediamine, N,N,N',N'-tetramethyl-1,6-diaminohexane (TMHDA), and N,N,N',N'-tetraethylethylenediamine (TEEDA), and these may be mixed in any ratio.

[0064] The amount of the additive used is not particularly limited, but in terms of good reaction yield, it is preferably 0.01 to 1 molar equivalent, and more preferably 0.05 to 0.5 molar equivalent, relative to the total amount of the monomer compounds (mono-1-g) and (mono-2-g).

[0065] Production step (B) can be carried out at a temperature appropriately selected from 0°C to 240°C, and is preferably carried out at a temperature appropriately selected from 70°C to 220°C in terms of good reaction yield, and more preferably at a temperature appropriately selected from 80°C to 200°C.

[0066] The production step (B) can also be carried out using a microwave reaction device.

[0067] The production step (B) is preferably carried out in an inert gas atmosphere such as argon gas or nitrogen gas, or under reduced pressure.

[0068] The reaction time varies depending on the monomer compounds (mono-1-g), (mono-2-g), (mono-1-H), and (mono-2H) used, as well as the solvent and reaction temperature, but is preferably 0.1 to 100 hours, more preferably 1 to 90 hours.

[0069] The conjugated polymer of this embodiment can be obtained by carrying out a conventional treatment after the completion of the production step (B). If necessary, it may be purified by any of the general means used by those skilled in the art for purifying polymer compounds, such as washing, precipitation, filtration, dialysis, column chromatography, preparative HPLC, or Soxhlet extraction.

[0070] The monomer compounds (mono-1-g), (mono-2-g), (mono-1-H), and (mono-2H) used in production step (B) may be obtained by any method, and can be produced by referring to, for example, methods described in non-patent literature (Macromolecules, Vol. 46, pp. 9211-9219, 2013; Chemistry of Materials, Vol. 28, pp. 8580-8590, 2016; Journal Polymer Science, Part A: Polymer Chemistry, Vol. 47, pp. 111-120, 2009, etc.). Alternatively, commercially available products may be used.

[0071] The film-forming composition of this embodiment can be obtained by dissolving or dispersing the polymer semiconductor of this embodiment in a solvent. The polymer semiconductor of this embodiment can be dissolved or dispersed in a solvent by any method well known to those skilled in the art, such as stirring, shaking, or ball milling. Heating may be performed during this process.

[0072] The film-forming composition of this embodiment may contain a binder to improve film-forming properties. Examples of such binders include polymers such as polystyrene, poly-α-methylstyrene, polyvinylnaphthalene, poly(ethylene-co-norbornene), polymethyl methacrylate, polytriarylamine, and poly(9,9-dioctylfluorene-co-dimethyltriphenylamine). There are no particular restrictions on the concentration of the binder, but a concentration of 0.1 to 10.0 weight percent is preferred for good coatability.

[0073] [Organic thin film] Next, an organic thin film containing the polymer semiconductor of this embodiment (hereinafter referred to as "organic thin film of this embodiment") will be described.

[0074] The organic thin film of this embodiment is formed using the film-forming composition of this embodiment. The method for forming a film using the film-forming composition of this embodiment is not particularly limited, and examples thereof include simple coating methods such as spin coating, drop casting, dip coating, and cast coating; and printing methods such as dispenser, inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing. Among these, spin coating, drop casting, and inkjet are preferred in terms of efficient film formation.

[0075] Although there are no particular limitations on the thickness of the organic thin film of this embodiment, it is preferably 1 nm to 1000 nm, more preferably 10 nm to 500 nm, in terms of increasing carrier mobility.

[0076] [Organic semiconductor element] Examples of organic semiconductor elements containing the polymer semiconductor of this embodiment include organic thin film transistor elements, organic thermoelectric conversion elements, organic photoelectric conversion elements, and organic imaging elements. Of these, organic thin film transistor elements and organic photoelectric conversion elements are preferred, and organic thin film transistor elements are more preferred.

[0077] A method for producing an organic thin film transistor element including the polymer semiconductor of this embodiment (hereinafter referred to as "organic thin film transistor element of this embodiment"), particularly an organic thin film transistor element including a polymer semiconductor in the active layer, will be described.

[0078] The organic thin film transistor element of the present invention can be obtained by forming the organic thin film of the present invention as an insulating layer and an active layer on a substrate, and then providing a source electrode, a drain electrode, and a gate electrode thereon.

[0079] Figure 1 shows the structure of an element included in the organic thin film transistor element of this embodiment. Here, 1001 is a bottom gate-top contact type, 1002 is a bottom gate-bottom contact type, 1003 is a top gate-top contact type, and 1004 is a top gate-bottom contact type transistor element. 1 is an active layer (organic semiconductor layer), 2 is a substrate, 3 is a gate electrode, 4 is a gate insulating layer, 5 is a source electrode, and 6 is a drain electrode.

[0080] Examples of substrates include plastic substrates such as polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, and cellulose triacetate; inorganic substrates such as glass, quartz, aluminum oxide, silicon, hydrodoped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; and metal substrates such as gold, copper, chromium, titanium, and aluminum. Among these, glass, silicon, and hydrodoped silicon are preferred, with glass being more preferred, due to their excellent transistor performance.

[0081] Examples of the gate electrode include inorganic electrodes such as aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, chromium, graphene, and carbon nanotubes, and organic electrodes such as doped polymer semiconductors (PEDOT-PSS). Of these, inorganic electrodes are preferred because of their good conductivity, and gold is more preferred.

[0082] Examples of insulating layers include inorganic insulating layers such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, barium titanate, and bismuth titanate; and organic insulating layers such as polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, cellulose triacetate, polycyclopentane, polycyclohexane-ethylene copolymer, polyfluorinated cyclopentane, Cytop™, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer, Parylene N™, Parylene C™, Parylene D™, Parylene HT™, and Parylene C-UVF™. Furthermore, the surfaces of these insulating layers may be modified with, for example, silanes such as octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrichlorosilane, and phenyltrimethoxysilane; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid, and octylphosphonic acid; silylamines such as hexamethyldisilazane; or the like.

[0083] Examples of the source electrode and drain electrode include the same electrodes as those exemplified for the gate electrode. Among these, inorganic electrodes are preferred due to their good conductivity, and gold is more preferred. Furthermore, to improve the carrier injection efficiency, these electrodes can be surface-treated using a surface treatment material. Examples of such surface treatment materials include 1-octanethiol, benzenethiol, and pentafluorobenzenethiol. [Example]

[0084] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[0085] The monomers and their precursors used as raw materials in the examples were , , , , , ,

[0089] , , Structural analysis was performed by H-NMR measurement. The molecular weight and molecular weight distribution of the polymer semiconductors obtained in the examples were estimated by Gel Permeation Chromatography (GPC) measurement. Commercially available products were used as reagents.

[0086] <NMR Measurement Conditions> Measuring device: Bruker ASCEND TM ADVANCE III HD (400 MHz) Measuring solvent: deuterated chloroform (CDCl3), deuterated benzene (C6D6) or deuterated o-dichlorobenzene (o-Cl2C6D4) Internal standard substance: tetramethylsilane (TMS)

[0087] <GPC Measurement Conditions> Measuring device: Tosoh Corporation High Temperature GPC Device HLC-8321GPC / HT Column: TSKgel GMH HR -H(20)HT Measuring solvent: 1,2,4-trichlorobenzene (TCB) Measuring temperature: 180 °C Calibration curve: polystyrene standard <0000�40>

[0088] [Synthesis Reference Example 1] [Chemical Formula]

[0089] A solution of the monomer compound (mono-1a-H) (481 mg, 2.50 mmol) in THF (25 mL) was cooled to 0 °C, and N-bromosuccinimide (934 mg, 5.25 mmol) was added. The mixture was stirred overnight at room temperature. The reaction was quenched by adding saturated aqueous sodium thiosulfate (50 mL). Distilled water (50 mL) was added, and the mixture was separated. The aqueous phase was extracted with diethyl ether (3 × 50 mL). The combined organic phase was washed with saturated brine (50 mL) and dried over sodium sulfate. The solvent was removed using an evaporator, and the resulting residue was purified by column chromatography using silica gel and alumina (eluent: hexane). The resulting yellow-white solid was dissolved in methylene chloride (10 mL), and methanol (10 mL) was slowly added. The mixture was then allowed to stand at -20 °C. The precipitated pale yellow crystals were collected by filtration, washed with cooled methanol, and then dried in vacuo to obtain a monomer compound (mono-1a-Br) (610 mg, yield 70%). 1 H-NMR (CDCl3, 25℃, 400MHz): δ6.94(d,J=3.8Hz,2H),6.80(s,2H),6.77(d,J=3.8Hz,2H).

[0090] [Synthesis reference example 2] [ka]

[0091] A solution of the monomer compound (mono-1a-H) (385 mg, 2.0 mmol) in THF (30 mL) was cooled to -78°C and stirred. A 1.55 M hexane solution of n-butyllithium (2.8 mL, 4.4 mmol) was slowly added dropwise, followed by stirring at room temperature for 2 hours. The reaction solution was cooled to -78°C, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (930 mg, 5.0 mmol) was added. The mixture was stirred overnight at room temperature. A saturated aqueous solution of ammonium chloride (50 mL) was added, and the mixture was separated. The aqueous phase was extracted with diethyl ether (3 x 50 mL). The combined organic phase was washed with saturated brine (50 mL) and then dried over sodium sulfate. The solvent was removed using an evaporator, and the resulting residue was purified using a short column (alumina, methylene chloride). The resulting yellow-white solid was dissolved in methylene chloride (5 mL), and then methanol (10 mL) was slowly added and the mixture was cooled to -20°C. The resulting pale yellow crystals were collected by filtration, washed with cooled methanol, and then dried in vacuo to give the monomer compound (mono-1a-Bpin) (348 mg, yield 40%). 1 H-NMR (CDCl3, 25℃, 400MHz): δ7.51(d,J=3.6Hz,2H),7.14(s,2H),7.11(d,J=3.6Hz,2H),1.35(s,24H).

[0092] [Synthesis reference example 3] [ka]

[0093] A solution of the monomer compound (mono-2a-H) (1.95 g, 2.0 mmol) in chloroform (50 mL) was cooled to 0 °C, and N-bromosuccinimide (747 mg, 4.2 mmol) was added. The mixture was stirred overnight at room temperature. The solvent was removed using an evaporator, and the resulting residue was purified by column chromatography using silica gel (eluent: hexane / chloroform = 1 / 1). The resulting dark purple solid was dissolved in methylene chloride (18 mL), and methanol (7 mL) was slowly added. The mixture was then allowed to stand at -20 °C. The precipitated dark purple crystals were collected by filtration, washed with chilled methanol, and dried under vacuum to obtain the monomer compound (mono-2a-Br) (1.84 g, 81% yield). 1 H-NMR (CDCl3, 25℃, 400MHz): δ8.63(d,J=4.2Hz,2H),7.22(d,J=4.2Hz,2H),3 .92(d,J=7.8Hz,4H),1.88(br,2H),1.37-1.14(m,80H),0.91-0.84(m,12H).

[0094] [Synthesis reference example 4] [ka]

[0095] A solution of the monomer compound (mono-2a-H) (194 mg, 0.20 mmol) in THF (4 mL) was cooled to -25 °C, and a 1.1M THF solution (0.43 mL, 0.48 mmol) of lithium diisopropylamide was added and stirred for 2 hours. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.12 mL, 0.60 mmol) was added and stirred overnight at -25 °C. The reaction was quenched with saturated aqueous ammonium chloride (5 mL). Distilled water (15 mL) was added and the mixture was separated. The aqueous phase was extracted with diethyl ether (3 × 20 mL). The combined organic phase was dried over magnesium sulfate, and the solvent was removed using an evaporator. The resulting blue-purple solid was dissolved in methylene chloride (5 mL), and chilled acetone (20 mL) was slowly added. The mixture was then allowed to stand at -20 °C. The precipitated blue-purple crystals were collected by filtration, washed with chilled acetone, and then dried in vacuo to obtain a monomer compound (mono-2a-Bpin) (134 mg, yield 55%). 1 H-NMR (C6D6, 25℃, 400MHz): δ9.58(d,J=3.9Hz,2H),7.86(d,J=3.9Hz,2H),4.17(d,J=7 .6Hz,4H),2.22-2.11(m,2H),1.69-1.17(br,80H),1.06(s,24H),0.97-0.88(m,12H).

[0096] [Example 1] [ka] Monomer compound (mono-1a-Br) (1.8 mg, 0.005 mmol), monomer compound (mono-2a-Br) (107 mg, 0.095 mmol), monomer compound (mono-1a-Bpin) (42.2 mg, 0.095 mmol), monomer compound (mono-2a-Bpin) (6.1 mg, 0.005 mmol), tris(dibenzylideneacetone)dipalladium chloroform adduct (2.1 mg, 2.0 μmol), tri-tert-butylphosphonium tetrafluoroborate (2.3 mg, 8.0 μmol), and tetrabutylammonium bromide (32.2 mg, 0.10 mmol) were dissolved in THF (0.50 mL) and 2 M aqueous potassium phosphate solution (0.15 mL, 0.30 mmol) was added. The mixture was then immersed in an oil bath heated to 60 °C and stirred for 18 h. The reaction solution was cooled to room temperature, diluted with chloroform (20 mL), washed with distilled water (3 × 10 mL), and poured into well-stirred methanol (400 mL). The resulting solid was filtered through a membrane filter (ADVANTEC, 0.5 μm), washed with methanol, and then vacuum-dried. The resulting solid was purified by Soxhlet extraction. Acetone (100 mL) and o-dichlorobenzene (100 mL) were used as solvents. The resulting o-dichlorobenzene extract was poured into well-stirred methanol (400 mL). The resulting black solid was filtered through a membrane filter (ADVANTEC, 0.5 μm) and vacuum-dried to obtain polymer (poly-1a) (112 mg, 96% yield). GPC: Mn=18900g / mol, PDI=2.1. 1 H-NMR(C2D2Cl4,140℃,400MHz):δ8.87-8.78(m,0.20H),8.76(brd,J=3.6Hz,1.8H),7.45(br,0.20H),7.34(brd,J=3.6Hz,1.8H),7. 26(brd,J=3.5Hz,1.8H),7.11(br,0.20H),7.10-6.95(m,4H),4.05(br,4H),2.03(br,2H),1.48-1.22(m,80H),0.94-0.86(m,12H). 1The assignment of signals observed in the H-NMR spectrum was performed according to the method described in non-patent literature (Macromolecules, Vol. 50, pp. 927-934, 2017; Molecules, Vol. 23, p. 981, 2018). The assignment of signals in the aromatic region is as follows: [ka] (1a-2a) Bond: δ8.76(A 1 ),7.34(A 2 ),7.26(A 3 ),7.06(A 4 and A 5 ). (1a-1a) Bond: δ7.11(B 1 ),7.10-6.95(B 2 and B 3 ). (2a-2a) bond: δ8.87-8.78(C 1 ),7.45(C 2 ). The contents of (1a-1a) and (2a-2a) bonds were calculated using the integral ratio of the signals assigned as above, and the results were as follows. (1a-1a) bond content: 5% (2a-2a) Bond content: 5%

[0097] [Example 2] Polymer (poly-1b) was obtained (112 mg, 96% yield) by the same procedure as in Example 1, except that monomer compound (mono-1a-Br) (3.5 mg, 0.01 mmol), monomer compound (mono-2a-Br) (102 mg, 0.090 mmol), monomer compound (mono-1a-Bpin) (40.0 mg, 0.090 mmol), and monomer compound (mono-2a-Bpin) (12.3 mg, 0.010 mmol) were used. GPC: Mn=10900g / mol, PDI=2.1. (1a-1a) bond content: 10% (2a-2a) Bond content: 10%

[0098] [Example 3] Polymer (poly-1c) was obtained (114 mg, 98% yield) by the same procedure as in Example 1, except that monomer compound (mono-1a-Br) (7.0 mg, 0.02 mmol), monomer compound (mono-2a-Br) (90.5 mg, 0.080 mmol), monomer compound (mono-1a-Bpin) (35.5 mg, 0.080 mmol), and monomer compound (mono-2a-Bpin) (24.5 mg, 0.020 mmol) were used. GPC: Mn=16900g / mol, PDI=2.1. (1a-1a) bond content: 17% (2a-2a) Bond content: 17%

[0099] [Example 4] Polymer (poly-1d) was obtained (111 mg, 95% yield) by the same procedure as in Example 1, except that monomer compound (mono-1a-Br) (10.5 mg, 0.030 mmol), monomer compound (mono-2a-Br) (79.2 mg, 0.070 mmol), monomer compound (mono-1a-Bpin) (31.1 mg, 0.070 mmol), and monomer compound (mono-2a-Bpin) (36.8 mg, 0.030 mmol) were used. GPC: Mn=17100g / mol, PDI=2.2. (1a-1a) bond content: 19% (2a-2a) Bond content: 20%

[0100] [Example 5] Polymer (poly-1e) was obtained (107 mg, 92% yield) by the same procedure as in Example 1, except that monomer compound (mono-1a-Br) (14.0 mg, 0.040 mmol), monomer compound (mono-2a-Br) (67.8 mg, 0.060 mmol), monomer compound (mono-1a-Bpin) (26.7 mg, 0.060 mmol), and monomer compound (mono-2a-Bpin) (49.0 mg, 0.040 mmol) were used. GPC: Mn = 9300 g / mol, PDI = 2.1. (1a-1a) bond content: 21% (2a-2a) Bond content: 23%

[0101] [Example 6] Polymer (poly-1f) was obtained (104 mg, 90% yield) by the same procedure as in Example 1, except that monomer compound (mono-1a-Br) (17.5 mg, 0.050 mmol), monomer compound (mono-2a-Br) (56.6 mg, 0.050 mmol), monomer compound (mono-1a-Bpin) (22.2 mg, 0.050 mmol), and monomer compound (mono-2a-Bpin) (61.2 mg, 0.050 mmol) were used. GPC: Mn=11300g / mol, PDI=2.0. (1a-1a) bond content: 23% (2a-2a) Bond content: 24%

[0102] [Example 7] The same procedure as in Example 1 was carried out, except that the monomer compound (mono-2a-Br) was not used, and instead the monomer compound (mono-1a-Br) (35.0 mg, 0.10 mmol), the monomer compound (mono-1a-Bpin) (2.2 mg, 0.005 mmol), and the monomer compound (mono-2a-Bpin) (116 mg, 0.095 mmol) were used, to obtain polymer (poly-1g) (105 mg, yield 94%). GPC: Mn = 9800 g / mol, PDI = 2.1. (1a-1a) bond content: 7% (2a-2a) Bond content: 3%

[0103] [Example 8] The same procedure as in Example 1 was carried out, except that the monomer compound (mono-2a-Br) was not used, and instead the monomer compound (mono-1a-Br) (35.0 mg, 0.10 mmol), the monomer compound (mono-1a-Bpin) (6.7 mg, 0.015 mmol), and the monomer compound (mono-2a-Bpin) (104 mg, 0.085 mmol) were used, to obtain polymer (poly-1h) (104 mg, 96% yield). GPC: Mn=11300g / mol, PDI=1.9. (1a-1a) bond content: 9% (2a-2a) Bond content: 3%

[0104] [Example 9] The same procedure as in Example 1 was carried out, except that the monomer compound (mono-2a-Br) was not used, and instead the monomer compound (mono-1a-Br) (35.0 mg, 0.10 mmol), the monomer compound (mono-1a-Bpin) (4.4 mg, 0.01 mmol), and the monomer compound (mono-2a-Bpin) (110 mg, 0.090 mmol) were used, to obtain polymer (poly-1i) (98.5 mg, 95% yield). GPC: Mn=14400g / mol, PDI=2.3. (1a-1a) bond content: 16% (2a-2a) Bond content: 4%

[0105] [Example 10] The same procedure as in Example 1 was carried out, except that the monomer compound (mono-2a-Br) was not used, and instead the monomer compound (mono-1a-Br) (35.0 mg, 0.10 mmol), the monomer compound (mono-1a-Bpin) (8.9 mg, 0.02 mmol), and the monomer compound (mono-2a-Bpin) (98.0 mg, 0.080 mmol) were used, to obtain polymer (poly-1j) (73.3 mg, 73% yield). GPC: Mn = 9400 g / mol, PDI = 2.1. (1a-1a) bond content: 20% (2a-2a) Bond content: 2%

[0106] [Example 11] The same procedure as in Example 1 was carried out, except that the monomer compound (mono-1a-Bpin) was not used, and instead the monomer compound (mono-1a-Br) (33.3 mg, 0.095 mmol), the monomer compound (mono-2a-Br) (5.7 mg, 0.005 mmol), and the monomer compound (mono-2a-Bpin) (123 mg, 0.10 mmol) were used, to obtain polymer (poly-1k) (115 mg, 95% yield). GPC: Mn = 8000 g / mol, PDI = 1.9. (1a-1a) bond content: 3% (2a-2a) Bond content: 9%

[0107] [ka]

[0108] [Example 12] A suspension of mono-1a-Br (1.8 mg, 0.005 mmol), mono-2a-Br (107 mg, 0.095 mmol), mono-1a-H (42.2 mg, 0.095 mmol), mono-2a-H (4.8 mg, 0.005 mmol), tris(dibenzylideneacetone)dipalladium chloroform adduct (2.1 mg, 2.0 μmol), tris(2-methoxyphenyl)phosphine (2.8 mg, 8.0 μmol), cesium carbonate (97.7 mg, 0.30 mmol), and pivalic acid (10.1 mg, 0.10 mmol) in toluene (0.50 mL) was stirred at room temperature for 30 min. The mixture was then immersed in an oil bath heated to 120 °C and stirred for 24 h. After cooling to room temperature, the reaction solution was diluted with chloroform (20 mL), washed with distilled water (3 × 10 mL), and poured into well-stirred methanol (400 mL). The resulting solid was filtered through a membrane filter (ADVANTEC, 0.5 μm), washed with methanol, and then vacuum-dried. The resulting solid was purified by Soxhlet extraction. Acetone (100 mL) and o-dichlorobenzene (100 mL) were used as solvents. The resulting o-dichlorobenzene extract was poured into well-stirred methanol (400 mL). The resulting black solid was filtered through a membrane filter (ADVANTEC, 0.5 μm) and vacuum-dried to obtain polymer (poly-1L) (26 mg, yield 23%). (1a-1a) bond content: 11% (2a-2a) Bond content: 12%

[0109] [Example 13] A 0.4 wt % o-dichlorobenzene solution of the polymer (poly-1a) synthesized in Example 1 was heated in a glove box under a nitrogen atmosphere to prepare a composition for forming an organic thin film.

[0110] Next, a glass substrate (channel length 25 μm, channel width 10,000 μm) with a patterned Cr / Au source and drain electrodes formed by photolithography was treated with 1-octanethiol to modify the Au source and drain electrodes. The film-forming composition prepared above was spin-coated onto this substrate in a glove box under a nitrogen atmosphere. This was heated to 200°C and held for 30 minutes to form an organic thin film of polymer (poly-1a). Next, a polymethyl methacrylate film approximately 550 nm thick was spin-coated onto the polymer layer and dried at 80°C for 3 hours. Finally, a shadow mask was placed, and silver was evaporated under vacuum to form a gate electrode.

[0111] In a vacuum, the organic thin-film transistor device was connected to a semiconductor parameter analyzer (KEYSIGHT, Model B2902A), and the gate voltage (Vg) was scanned in 1 V increments from +20 to -80 V at a drain voltage (Vd = -60 V) to evaluate the transfer characteristics. The organic thin-film transistor device exhibited p-type characteristics. The average value of the carrier mobility of holes in six devices fabricated in the same manner was 0.62 cm 2 / Vs.

[0112] The same procedure as in Example 13 was repeated except that the polymer (poly-1b) synthesized in Example 2 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average value of the carrier mobility of holes in six devices fabricated in the same manner was 0.50 cm 2 / Vs.

[0113] The same procedure as in Example 13 was repeated except that the polymer (poly-1c) synthesized in Example 3 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average hole carrier mobility of six devices fabricated in the same manner was 0.48 cm 2 / Vs.

[0114] The same procedure as in Example 13 was repeated except that the polymer (poly-1d) synthesized in Example 3 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average hole carrier mobility of six devices fabricated in the same manner was 0.38 cm 2 / Vs.

[0115] The same procedure as in Example 13 was repeated, except that the polymer (poly-1e) synthesized in Example 4 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average hole carrier mobility of six devices fabricated in the same manner was 0.31 cm 2 / Vs.

[0116] The same procedure as in Example 13 was repeated, except that the polymer (poly-1f) synthesized in Example 5 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average hole carrier mobility of six devices fabricated in the same manner was 0.32 cm. 2 / Vs.

[0117] The same procedure as in Example 13 was repeated except that the polymer (poly-1g) synthesized in Example 6 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average value of the carrier mobility of holes in six devices fabricated in the same manner was 0.30 cm. 2 / Vs.

[0118] The same procedure as in Example 13 was repeated, except that the polymer (poly-1h) synthesized in Example 7 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average hole carrier mobility of six devices fabricated in the same manner was 0.31 cm. 2 / Vs.

[0119] The same procedure as in Example 13 was repeated except that the polymer (poly-1i) synthesized in Example 8 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average value of the carrier mobility of holes in six devices fabricated in the same manner was 0.51 cm. 2 / Vs.

[0120] The same procedure as in Example 13 was repeated except that the polymer (poly-1j) synthesized in Example 9 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average hole carrier mobility of six devices fabricated in the same manner was 0.40 cm 2 / Vs.

[0121] The same procedure as in Example 13 was repeated except that the polymer (poly-1k) synthesized in Example 10 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average hole carrier mobility of six devices fabricated in the same manner was 0.45 cm 2 / Vs.

[0122] [Comparative Example 1] The same procedure as in Example 1 was carried out, except that the monomer compound (mono-1a-Br) and the monomer compound (mono-2a-Bpin) were not used, and instead the monomer compound (mono-1a-Bpin) (44.4 mg, 0.10 mmol) and the monomer compound (mono-2a-Br) (113 mg, 0.10 mmol) were used, to obtain a polymer (poly-1-ref) (107 mg, 92% yield). GPC: Mn = 8200 g / mol, PDI = 2.1. 1 H-NMR (C2D2Cl4, 140℃, 400MHz): δ8.78(br,2H),7.33(br,2H),7.25(br,2H),7.0 5(br,4H),4.05(br,4H),2.03(br,2H),1.48-1.22(m,80H),0.94-0.86(m,12H). (1a-1a) bond content: 1% (2a-2a) Bond content: 2%

[0123] Comparative Example 2 The same procedure as in Example 13 was repeated except that the polymer (poly-1-ref) synthesized in Comparative Example 1 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and the average value of the carrier mobility of holes in six devices fabricated in the same manner was 0.25 cm 2 / Vs.

Claims

1. A polymer semiconductor represented by formula (1). 【Chemical 1】 In the formula, n, p, and q represent the number of (DA), (DD), and (AA) bonds, respectively, and each independently represents an integer of 1 or more. D is a divalent arylene group represented by the following formula (2). 【Chemistry 2】 In formula (2), each X1 independently represents a chalcogen atom, and each Y1 and Y2 independently represent a C-R1 group (R1 represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 30 carbon atoms) or a nitrogen atom. d and e are integers of 0 or 1, and cannot both be 0. D1 represents a 1,2-ethenediyl group, a 1,2-ethynediyl group, or a single bond. * represents a bonding site. A is a divalent electron-withdrawing aromatic group represented by the following formula (3). 【Chemistry 3】 In formula (3), each X2 independently represents a chalcogen atom, and each Y3 and Y4 independently represents a C-R2 group (R2 represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 30 carbon atoms) or a nitrogen atom. f is an integer of 0 or 1. A1 represents a divalent electron-withdrawing aromatic group represented by any of the following formulae (A-1) to (A-5). * represents a bonding site. 【Chemistry 4】 In formulas (A-1) to (A-5), each R3 independently represents an alkyl group having 1 to 30 carbon atoms. Each Z independently represents a hydrogen atom, a fluorine atom, a cyano group, a nitro group, a trifluoromethyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or an amide group having 1 to 20 carbon atoms.

2. 2. The polymer semiconductor according to claim 1, wherein the content of (DD) bonds defined by p×100 / (n+p+q) is 3% or more.

3. 2. The polymer semiconductor according to claim 1, wherein the content of (A-A) bonds defined by q×100 / (n+p+q) is 3% or more.

4. 4. The polymer semiconductor according to claim 1, wherein X2 is a sulfur atom and Y2 is a C—H group.

5. 4. The polymer semiconductor according to claim 1, wherein A1 is a group represented by formula (A-1).

6. 4. The polymer semiconductor according to claim 1, wherein A is a group represented by formula (3-1). 【Chemistry 5】 In the formula, each R4 independently represents an alkyl group having 1 to 30 carbon atoms.

7. The polymer semiconductor according to claim 1 , wherein X1 is a sulfur atom.

8. A method for producing a polymer semiconductor represented by formula (1), comprising mixing monomer compounds represented by the following formulae (mono-1-g), (mono-2-g), (mono-1-M), and (mono-2-M) in a molar ratio of S:T:U:V, and reacting the resulting mixture in the presence of a base and a transition metal catalyst. 【Chemistry 6】 (In the formula, X1 and X2 each independently represent a chalcogen atom, Y1, Y2, Y3, and Y4 each independently represent a C-R1 group (R1 represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 30 carbon atoms) or a nitrogen atom. d, e, and f each independently represent an integer of 0 or 1, provided that d and e do not both represent 0. g represents a leaving group. M represents a hydrogen atom or a boron-containing group. D1 represents a 1,2-ethenediyl group, a 1,2-ethynediyl group, or a single bond. A1 represents a divalent electron-withdrawing aromatic group represented by any of the following formulae (A-1) to (A-5): 【Chemistry 7】 (In formulas (A-1) to (A-5), each R3 independently represents an alkyl group having 1 to 30 carbon atoms. Each Z independently represents a hydrogen atom, a fluorine atom, a cyano group, a nitro group, a trifluoromethyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or an amide group having 1 to 20 carbon atoms.) n, p, and q each independently represent an integer of 1 or more. D is a divalent electron-donating aromatic group represented by the following formula (2). 【Chemistry 8】 (In the formula, X1, Y1, Y2, d, e and D1 have the same meanings as above, and * represents a binding site.) A is a divalent electron-withdrawing aromatic group represented by the following formula (3). 【Chemistry 9】 (In the formula, X2, Y3, Y4, f, *, and A1 have the same meanings as defined above.)

9. The method according to claim 8, wherein g is a bromine atom or an iodine atom.

10. The method of claim 9, wherein M is a boron-containing group.

11. The method according to claim 9, wherein M is a hydrogen atom and the reaction is carried out in the presence of an acid.

12. 10. The production method according to claim 9, wherein the transition metal catalyst is a palladium complex having a tertiary phosphine as a ligand.

13. The method according to claim 11, wherein the tertiary phosphine is tri(2-methoxyphenyl)phosphine.

14. 10. The method according to claim 9, wherein the boron-containing group is a group represented by B(OR1)2 (wherein each R1 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; and two R1s can also form a ring together with the boron atom bonded via the oxygen atom).

15. The method according to claim 14, wherein the palladium catalyst is a palladium complex having a tertiary phosphine as a ligand.

16. The method according to claim 15, wherein the tertiary phosphine is tri-tert-butylphosphine.

17. The method according to claim 11 or 14, wherein the base is an inorganic salt.

18. 17. The process of claim 16, wherein the base is potassium phosphate or cesium carbonate.

19. A film-forming composition comprising the polymer semiconductor according to any one of claims 1 to 3.

20. An organic thin film comprising the polymer semiconductor according to any one of claims 1 to 3.

21. An organic semiconductor device comprising the polymer semiconductor according to any one of claims 1 to 3.

22. An organic thin film transistor device comprising the polymer semiconductor according to any one of claims 1 to 3.

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