Conductor Material

Abstract

The present invention provides a conductor material which has high electrical conductivity.　A conductor material according to the present disclosure has a configuration wherein a conjugated polymer compound that has an electron-donating group containing a heteroatom in a side chain is doped with a dopant that contains an anion that is selected from among a nitrogen anion, a boron anion, a phosphorus anion and an antimony anion, and a counter cation. It is preferable that the anion is one represented by formula (1). In formula (1), R1 and R2 may be the same or different and each represents an electron-withdrawing group; and R1 and R2 may combine with each other to form a ring together with an adjacent nitrogen atom.

Description

[Technical field]

[0001] The present disclosure relates to a novel conductive material, a method for producing the conductive material, and an electronic device including the conductive material. This application claims priority to Japanese Patent Application No. 2020-081349, filed in Japan on May 1, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] Conjugated polymer compounds are used as materials for various electronic devices, taking advantage of their light weight and excellent moldability. Furthermore, high electrical conductivity can be imparted to conjugated polymer compounds by doping them with a dopant.

[0003] Dopants include donors (i.e., N-type dopants) that inject electrons as carriers, and acceptors (i.e., P-type dopants) that remove electrons to form holes.

[0004] A representative acceptor is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ). For example, Non-Patent Document 1 describes an example in which F4-TCNQ is doped into PBTTT-C16 (poly[2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene]) as a conjugated polymer compound to prepare a conductive material. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] R. Fujimoto et al. Org. Electron. 47(2017), 139-146 Summary of the Invention [Problem to be solved by the invention]

[0006] However, it was found that the PBTTT-C16 described in Non-Patent Document 1 is not easily oxidized, and even if it is once oxidized, it is easily reduced by heating, etc. In other words, it was found that PBTTT-C16 has a low doping efficiency, and a conductor material obtained by using PBTTT-C16 has low conductivity.

[0007] It is therefore an object of the present disclosure to provide a conductive material having high electrical conductivity. Another object of the present disclosure is to provide a method for producing a conductive material having high electrical conductivity. Another object of the present disclosure is to provide an electronic device comprising a conductor material having high electrical conductivity. [Means for solving the problem]

[0008] As a result of intensive research by the present inventors to solve the above problems, they have found that a conjugated polymer compound having an electron-donating group containing a heteroatom in a side chain is easily oxidized and, after being oxidized, is difficult to be reduced, and that a conductor material obtained by doping a conjugated polymer compound having an electron-donating group containing a heteroatom in a side chain with a dopant containing a specific anion has excellent electrical conductivity. The present disclosure has been completed based on these findings.

[0009] That is, the present disclosure provides a conductor material having a configuration in which a conjugated polymer compound having an electron-donating group containing a heteroatom in its side chain is doped with a dopant containing an anion selected from a nitrogen anion, a boron anion, a phosphorus anion, and an antimony anion, and a counter cation.

[0010] The present disclosure also provides a method for preparing a compound according to the present invention, wherein the anion is represented by the following formula (1): [ka] (In the formula, R 1 , R 2 R may be the same or different and represents an electron-withdrawing group. 1 , R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom. The conductive material is provided with an anion represented by the formula:

[0011] The present disclosure also provides the conductive material, wherein the anion is an anion represented by the following formula (1a): [ka] (In the formula, R 3 , R 4 R may be the same or different and represent a halogen atom or a haloalkyl group. 3 , R 4 may be bonded to each other to form a haloalkylene group.

[0012] The present disclosure also provides the conductive material, wherein the conjugated polymer compound is a polymer compound having a repeating unit represented by the following formula (2): [ka] (In the formula, L 1 ~L 4 are the same or different and represent elements of Groups 13 to 16; D 1 ~D 4 are the same or different and each represents an electron donating group containing a hetero atom or a hydrogen atom. 1 ~D 4 At least one of the groups is an electron donating group containing a heteroatom.

[0013] The present disclosure also provides the conductive material, wherein the electron-donating group containing a heteroatom is a group represented by the following formula (d): [ka] (In the formula, D represents at least one heteroatom selected from the elements of Groups 14 to 16; R 5 represents an aliphatic hydrocarbon group having 5 to 30 carbon atoms. The bond marked with a wavy line in the formula bonds to the main chain of the conjugated polymer compound.

[0014] The present disclosure also provides a method for producing a conductor material, comprising doping a conjugated polymer compound having an electron-donating group containing a heteroatom in a side chain with a dopant containing an anion selected from a nitrogen anion, a boron anion, a phosphorus anion, and an antimony anion, and a counter cation to obtain the conductor material.

[0015] The present disclosure also provides a method for producing the conductive material, wherein the anion is an anion represented by the following formula (1): [ka] (In the formula, R 1 , R 2 R may be the same or different and represents an electron-withdrawing group. 1 , R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom.

[0016] The present disclosure also provides a method for producing the conductive material, wherein the anion is an anion represented by the following formula (1a): [ka] (In the formula, R 3 , R 4 R may be the same or different and represent a halogen atom or a haloalkyl group. 3 , R 4 may be bonded to each other to form a haloalkylene group.

[0017] The present disclosure also provides a method for producing the conductive material, wherein the conjugated polymer compound is a polymer compound having a repeating unit represented by the following formula (2): [ka] (In the formula, L 1 ~L 4 are the same or different and represent elements of Groups 13 to 16; D 1 ~D 4 are the same or different and each represents an electron donating group containing a hetero atom or a hydrogen atom. 1 ~D 4At least one of the groups is an electron donating group containing a heteroatom.

[0018] The present disclosure also provides a method for producing the conductive material, wherein the electron-donating group containing a heteroatom is a group represented by the following formula (d): [ka] (In the formula, D represents at least one heteroatom selected from the elements of Groups 14 to 16; R 5 represents an aliphatic hydrocarbon group having 5 to 30 carbon atoms. The bond marked with a wavy line in the formula bonds to the main chain of the conjugated polymer compound.

[0019] The present disclosure also provides a method for producing the conductive material, wherein the counter cation contained in the dopant is a radical cation represented by the following formula (3): [ka] [In formula (3), R 11 ~R 13 are the same or different and each represents a monovalent aromatic group or a group represented by the following formula (r), where n represents the valence of the radical cation and is equal to the number of nitrogen atoms (n) in the formula. [ka] (In formula (r), Ar 1 , Ar 2 , Ar 3 are the same or different and represent a divalent aromatic group; Ar 4 , Ar 5 , Ar 6 , Ar 7 are the same or different and each represents a monovalent aromatic group represented by the following formula (sb) which may have a substituent. s and t are the same or different and each represents an integer of 0 or more. The bond marked with a wavy line in the formula is bonded to the nitrogen atom in formula (3). [ka] (In formula (sb), Ar 8 , Ar 9are the same or different and represent a divalent aromatic group; Ar 10 , Ar 11 , Ar 12 , Ar 13 are the same or different and each represents a monovalent aromatic group. u and v are the same or different and each represents an integer of 0 or more. The bond marked with a wavy line in the formula bonds to a monovalent aromatic group.

[0020] The present disclosure also provides an electronic device comprising the conductive material. Effect of the Invention

[0021] The conductor material of the present disclosure has a high doping amount and is difficult to dedope. Therefore, it has high electrical conductivity. The conductor material also has high crystallinity. Furthermore, the conductor material is highly flexible. It can be formed into a film by a simple method and can easily be made large in area. Therefore, the conductor material can be suitably used for manufacturing electronic devices that are lightweight, thin, flexible, large in area, etc. while suppressing costs. Furthermore, electronic devices comprising the conductive material can be inexpensively realized that are highly conductive and highly stable (stable against heat, water, electricity, etc.), as well as lightweight, flexible, thin, and large in area. [Brief description of the drawings]

[0022] [Figure 1] FIG. 2 is a diagram showing ultraviolet-visible-near infrared absorption spectra of the conductor materials (=conjugated polymer compounds after doping with a dopant) obtained in the examples and comparative examples. [Diagram 2] FIG. 2 is a diagram showing the ultraviolet-visible-near infrared absorption spectrum of the conjugated polymer compound (= the conjugated polymer compound before doping with a dopant) used in the examples and comparative examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] [Conductor material] The conductive material of the present disclosure has a configuration in which a dopant containing an anion selected from a nitrogen anion, a boron anion, a phosphorus anion, and an antimony anion and a counter cation is doped into a conjugated polymer compound having an electron-donating group containing a heteroatom in its side chain (or as its side chain).

[0024] The conductive material is preferably a p-type conductive material.

[0025] The conductive material preferably has a structure in which the anion is stored in gaps in a crystal structure of a conjugated polymer compound having an electron-donating group containing a hetero atom in a side chain, thereby giving the conductive material high crystallinity and suppressing dedoping.

[0026] The conductive material exhibits high electrical conductivity. The electrical conductivity of the conductive material is, for example, 250 S / cm or more, preferably 280 S / cm or more, particularly preferably 300 S / cm or more, most preferably 305 S / cm or more, and particularly preferably 310 S / cm or more. Therefore, the conductive material can be suitably used as an electronic device material or an electrode material for a secondary battery.

[0027] The conductive material has excellent storage stability and can maintain high conductivity for a long period of time. For example, the decrease in conductivity after storage for 14 days at room temperature (25° C.) [(conductivity before storage−conductivity after storage for 14 days) / conductivity before storage×100] is 5% or less, preferably 3% or less, and particularly preferably 1% or less. The rate of decrease in conductivity after storage for 56 days at room temperature (25°C) [(conductivity before storage-conductivity after storage for 56 days) / conductivity before storage x 100] is 20% or less, preferably 15% or less, and particularly preferably 10% or less.

[0028] In addition, the conductive material is highly flexible. It can be formed into a film by a simple method (e.g., injection molding, extrusion molding, casting, powder molding, etc.), and can be easily made into a large-area film. Therefore, the conductive material can be suitably used for manufacturing electronic devices that are lightweight, thin, flexible, large-area, etc., while suppressing costs.

[0029] [Method of manufacturing conductor materials] The conductive material can be produced, for example, by doping a conjugated polymer compound having an electron-donating group containing a heteroatom in a side chain with a dopant containing an anion selected from a nitrogen anion, a boron anion, a phosphorus anion, and an antimony anion and a counter cation.

[0030] The method of doping the conjugated polymer compound with a dopant includes a method of forming a coating film containing the dopant (the dopant coating film has a thickness of, for example, 10 to 200 nm, preferably 30 to 100 nm) on the surface of the conjugated polymer compound by a dry process or a wet process.

[0031] The dry process method includes a method of attaching a dopant to the surface of the conjugated polymer compound (for example, a film, sheet, coating film, etc. having a thickness of about 10 to 500 nm, which is made of a conjugated polymer compound having an electron-donating group containing a hetero atom in its side chain) by vacuum deposition method, sputtering method, etc.

[0032] The wet process may be performed by immersing the conjugated polymer compound in a composition in which a dopant is dissolved and / or dispersed in a solvent, or by applying the composition to the surface of the conjugated polymer compound, and then removing the solvent. After drying, an annealing treatment may be performed as necessary.

[0033] When the conjugated polymer compound is doped with a dopant, the counter cation constituting the dopant extracts electrons from the conjugated polymer compound, thereby generating holes as charge carriers and exhibiting electrical conductivity.

[0034] When the counter cation extracts an electron from the conjugated polymer, it is converted into a neutral compound, which is then removed from the conjugated polymer system.

[0035] When the counter cation is converted into a neutral compound, the anion is released from the ionic bond with the counter cation. Then, the anion is stably stored in the gaps of the crystal structure of the conjugated polymer compound. This enhances the crystallinity of the conjugated polymer compound and suppresses dedoping.

[0036] (Dopant) The dopant comprises an anion selected from a nitrogen anion, a boron anion, a phosphorus anion, and an antimony anion, and a counter cation. The dopant may be a metal compound or a metal complex.

[0037] The dopant acts as a P-type dopant.

[0038] (anion) The anion is an anion selected from nitrogen anions, boron anions, phosphorus anions, and antimony anions.

[0039] As the anion, among them, nitrogen anion is preferable in terms of its excellent dedoping suppression effect, because after being released from the ionic bond with the counter cation, it is stably stored in the gaps of the crystal structure of the conjugated polymer compound, thereby exerting the effect of increasing the crystallinity of the conjugated polymer compound.

[0040] Therefore, the anion is preferably an anion represented by the following formula (1). [ka] (In the formula, R 1 , R 2 R may be the same or different and represents an electron-withdrawing group. 1 , R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom.

[0041] Examples of the electron-withdrawing group include a nitro group, a cyano group, (C 1-5 ) acyl group, carboxyl group, (C 1-5) alkoxycarbonyl group, halo(C 1-5 ) alkyl group, sulfo group, (C 1-5 ) alkylsulfonyl group, halosulfonyl group, halo(C 1-5 ) alkylsulfonyl groups, etc.

[0042] R 1 , R 2 Among them, a halosulfonyl group, a haloalkylsulfonyl group, or R 1 and R 2 are preferably linked together to form a sulfonyl-haloalkylene-sulfonyl group.

[0043] Examples of the halosulfonyl group include a fluorosulfonyl group and a chlorosulfonyl group.

[0044] Examples of the haloalkylsulfonyl group include fluoroalkylsulfonyl groups (e.g., fluoro C groups such as fluoromethylsulfonyl group, trifluoroethylsulfonyl group, trifluoropropylsulfonyl group, and pentafluoropropylsulfonyl group). 1-5 Alkyl sulfonyl groups; perfluoro C such as trifluoromethylsulfonyl group, pentafluoroethylsulfonyl group, pentafluoropropylsulfonyl group, and nonafluorobutylsulfonyl group 1-5 alkylsulfonyl group), chloroalkylsulfonyl group (e.g., chloro C such as chloromethylsulfonyl group) 1-5 alkylsulfonyl groups).

[0045] R 1 and R 2 Examples of the haloalkylene group in the sulfonyl-haloalkylene-sulfonyl group formed by bonding with each other include fluoroalkylene groups (e.g., perfluoro C groups such as tetrafluoroethylene, hexafluoropropane-1,3-diyl, and octafluorobutane-1,4-diyl groups). 1-5 alkylene groups), chloroalkylene groups (e.g., perchloro C 1-5 alkylene groups, etc.

[0046] As the anion, an anion represented by the following formula (1a) is particularly preferable. [ka] (In the formula, R 3 , R 4 R may be the same or different and represent a halogen atom or a haloalkyl group. 3 , R 4 may be bonded to each other to form a haloalkylene group.

[0047] Examples of the haloalkyl group include fluoroalkyl groups (e.g., fluoro C groups such as fluoromethyl, trifluoroethyl, trifluoropropyl, and pentafluoropropyl groups). 1-5 Alkyl groups; perfluoro C such as trifluoromethyl, pentafluoroethyl, pentafluoropropyl, and nonafluorobutyl groups 1-5 alkyl group), chloroalkyl group (e.g., chloro C such as chloromethyl group) 1-5 alkyl group).

[0048] Examples of the haloalkylene group include fluoroalkylene groups (e.g., perfluoro C groups such as tetrafluoroethylene, hexafluoropropane-1,3-diyl, and octafluorobutane-1,4-diyl groups). 1-5 alkylene groups), chloroalkylene groups (e.g., perchloro C 1-5 alkylene groups, etc.

[0049] (Counter cation) The counter cation is not particularly limited as long as it is a cation that acts to extract electrons from the conjugated polymer compound. Among them, a radical cation represented by the following formula (3) is preferable because it has excellent oxidizing power and easily extracts electrons from the conjugated polymer compound. In particular, a compound represented by the following formula (3), in which R 11 ~R 13 At least one of the above is a group represented by the following formula (r): [ka] [In formula (3), R 11 ~R 13 are the same or different and each represents a monovalent aromatic group or a group represented by the following formula (r), and n represents the valence of the radical cation and is equal to the number (n) of nitrogen atoms in formula (3). [ka] (In formula (r), Ar 1 , Ar 2 , Ar 3 are the same or different and represent a divalent aromatic group; Ar 4 , Ar 5 , Ar 6 , Ar 7 are the same or different and each represents a monovalent aromatic group represented by the following formula (sb) which may have a substituent. s and t are the same or different and each represents an integer of 0 or more. The bond marked with a wavy line in the formula is bonded to the nitrogen atom in formula (3). [ka] (In formula (sb), Ar 8 , Ar 9 are the same or different and represent a divalent aromatic group; Ar 10 , Ar 11 , Ar 12 , Ar 13 are the same or different and each represents a monovalent aromatic group. u and v are the same or different and each represents an integer of 0 or more. The bond marked with a wavy line in the formula bonds to a monovalent aromatic group.

[0050] When s, t, u, and v are each an integer of 2 or greater, there will be a plurality of groups shown in the parentheses, and these groups may be the same or different.

[0051] Each of s, t, u, and v represents an integer of 0 or more, for example, 0 to 5, preferably 0 to 3, and particularly preferably 0 to 2. When the values ​​of s, t, u, and v are large, the doping efficiency to the conjugated polymer compound is improved, and the crystallinity of the conjugated polymer compound after doping tends to be improved.

[0052] The monovalent aromatic group is a group obtained by removing one hydrogen atom from the structural formula of an aromatic compound [more specifically, a group obtained by removing one hydrogen atom bonded to a carbon atom constituting an aromatic compound (a carbon atom or a heteroatom when the aromatic compound is an aromatic heterocycle)].

[0053] The divalent aromatic group is a group obtained by removing two hydrogen atoms from the structural formula of an aromatic compound [more specifically, a group obtained by removing two hydrogen atoms bonded to carbon atoms constituting the aromatic compound (carbon atoms or heteroatoms when the aromatic compound is an aromatic heterocycle)].

[0054] The aromatic compounds include aromatic hydrocarbons and aromatic heterocycles.

[0055] The aromatic hydrocarbons include, for example, aromatic hydrocarbon rings having 6 to 14 carbon atoms, such as benzene and naphthalene, and structures in which two or more of the aromatic hydrocarbon rings are bonded via a single bond or a linking group.

[0056] Examples of the linking group include C 1-5 Examples of such bonds include an alkylene group, a carbonyl group (-CO-), an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO-), an amide bond (-CONH-), and a carbonate bond (-OCOO-).

[0057] As the aromatic hydrocarbon, at least one selected from the aromatic hydrocarbons represented by the following formulas (ar-1) to (ar-6) is preferable. [ka]

[0058] Examples of the aromatic heterocycle include a monocyclic aromatic heterocycle having, as ring-constituting atoms, a carbon atom and at least one heteroatom (e.g., an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, etc.), and a fused ring in which one or more aromatic hydrocarbon rings are fused to the monocyclic aromatic heterocycle. Specific examples thereof include pyrrole, furan, thiophene, phosphole, pyrazole, imidazole, oxazole, isoxazole, thiazole, indole, benzofuran, benzothiophene, isoindole, isobenzofuran, benzophosphole, benzimidazole, benzoxazole, benzothiazole, benzisoxazole, indazole, benzisothiazole, benzotriazole, purine, pyridine, phosphinine, pyrimidine, pyrazine, pyridazine, triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, hexazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, pteridine, phthalazine, acridine, 4aH-phenoxazine, and carbazole.

[0059] The monovalent aromatic group and the divalent aromatic group may have a substituent. Examples of the substituent include a halogen atom, 1-5 Alkyl groups, oxo groups, hydroxyl groups, substituted oxy groups (e.g., C 1-5 Alkoxy group, C 1-5 acyloxy group, etc.), carboxyl group, substituted oxycarbonyl group (e.g., C 1-5 alkoxycarbonyl group), substituted or unsubstituted carbamoyl group, cyano group, nitro group, amino group, substituted amino group (e.g., mono- or di-C 1-5 Alkylamino group, mono or di C 1-5 As the substituent, a halogen atom is preferable, and a bromine atom is particularly preferable.

[0060] Furthermore, the monovalent aromatic group may have, in addition to the above-mentioned substituents, for example, a group represented by the following formula (sb-1). [ka] [In the formula, Ar 14 , Ar 15 are the same or different and represent a monovalent aromatic group. The bond marked with a wavy line in the formula is bonded to a carbon atom constituting an aromatic compound (when the aromatic compound is an aromatic heterocycle, it is bonded to a carbon atom or a heteroatom).

[0061] In the above formula, Ar 14 , Ar 15 Examples of the monovalent aromatic group in include the same as those mentioned above.

[0062] (Method of producing dopant) For example, a nitrogen anion represented by the formula (1) (hereinafter, sometimes referred to as "nitrogen anion (1)") and a nitrogen anion represented by the formula (3), 11 ~R 13 and a radical cation which is the same or different and is a monovalent aromatic group (hereinafter, may be referred to as "radical cation (3a)") can be produced through the following step [1].

[0063] Step [1]: In the presence of an oxidizing agent, an ionic compound containing a nitrogen anion (1) is reacted with an amine compound corresponding to the above radical cation (3a).

[0064] The ionic compounds and the amine compounds may each be used alone or in combination of two or more.

[0065] The ionic compound may, for example, be an ionic compound containing a nitrogen anion and a monovalent metal ion. The metal ion may, for example, be Li + , Na + Alkali metals such as Mg 2+ , Ca 2+ Alkaline earth metals such as Cu + , Ag + , Au + and the like transition metals.

[0066] The ionic compound may be, for example, TFSI, such as silver bis(trifluoromethanesulfonyl)imide (AgTFSI). - Preferred are monovalent metal salts of the formula:

[0067] Examples of the amine compound include tris(halophenyl)amines such as tris(p-bromophenyl)amine.

[0068] The amount of the ionic compound used is, for example, about 1 to 5 moles per mole of the amine compound.

[0069] The oxidizing agent may be, for example, NOPF6, iron trichloride (FeCl3), a halogen element (e.g., iodine I 2、 Bromine (Br2), chlorine (Cl2), etc. These can be used alone or in combination of two or more.

[0070] The amount of the oxidizing agent used is, for example, about 1 to 5 moles per mole of the amine compound.

[0071] The reaction in step [1] can be carried out in the presence of a solvent. Examples of the solvent include nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; water; alcohol solvents such as methanol; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; ether solvents such as diethyl ether, THF, and dioxane; and ester solvents such as ethyl acetate. These can be used alone or in combination of two or more.

[0072] The reaction atmosphere in step [1] is not particularly limited as long as it does not inhibit the reaction, and may be, for example, any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.

[0073] The reaction temperature in the step [1] is, for example, about −70 to 60° C. The reaction time is, for example, about 0.5 to 5 hours.

[0074] After completion of the reaction, the obtained reaction product can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of these.

[0075] As a cation, the formula (3) is represented, and R in the formula (3) is 11 ~R 13 In the case of producing a dopant containing a radical cation in which at least one of the groups is represented by formula (r) (hereinafter, may be referred to as "radical cation (3b)"), an amine compound corresponding to the radical cation (3b) may be used in place of the amine compound corresponding to the radical cation (3a) in the above step [1].

[0076] An amine compound corresponding to the radical cation (3b) can be produced, for example, by subjecting a triarylamine halide to a coupling reaction (e.g., a Sholl-type coupling reaction) using an oxidizing agent such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ).

[0077] (Conjugated polymer compounds having electron-donating groups containing heteroatoms in their side chains) The conjugated polymer compound having an electron donating group containing a heteroatom in the side chain is preferably a π-conjugated polymer compound having an electron donating group containing a heteroatom in the side chain. The conjugated polymer compound having the side chain is more easily oxidized and more difficult to dedoped than the conjugated polymer compound not having the side chain. In the present disclosure, a conductor material having excellent conductivity is realized by using a conjugated polymer compound having an electron donating group containing a heteroatom in the side chain as a semiconductor to be doped with the above-mentioned dopant. In addition, the "conjugated polymer compound" in this specification includes an oligomer.

[0078] As the main chain of the conjugated polymer compound, among them, a heterocyclic conjugated polymer compound is preferable in terms of having high crystallinity, and in particular, a heterocyclic conjugated polymer compound containing a nitrogen atom or a sulfur atom as a heteroatom is preferable, and in particular, a conjugated polymer compound containing a heterocycle containing a sulfur atom is preferable, and in particular, a conjugated polymer compound containing a thiophene ring structure such as a thiophene ring, a benzothiophene ring, or a thienothiophene ring is preferable.

[0079] The conjugated polymer compound is preferably a polymer compound having a repeating unit represented by the following formula (2). [ka] (In the formula, L 1 ~L 4 are the same or different and represent elements of Groups 13 to 16; D 1 ~D 4 are the same or different and each represents an electron donating group containing a hetero atom or a hydrogen atom. 1 ~D 4 At least one of the groups is an electron donating group containing a heteroatom.

[0080] As the conjugated polymer compound, a polymer compound having a repeating unit represented by the following formula (2a) or (2b) is particularly preferred, and a polymer compound having a repeating unit represented by the following formula (2b) is particularly preferred. [ka]

[0081] In the above formula, L 1 ~L 4 are the same or different and represent elements of Groups 13 to 16; D 1 ~D 4 are the same or different and each represents an electron donating group containing a hetero atom or a hydrogen atom. 1 ~D 4 At least one of the groups is an electron donating group containing a heteroatom.

[0082] Examples of the elements in Groups 13 to 16 include a boron atom, a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom. Among these, elements in Groups 15 and 16 are preferred, and a sulfur atom is particularly preferred.

[0083] The electron donating group containing a hetero atom includes, for example, a group containing at least one hetero atom selected from the Groups 14 to 16 of elements.

[0084] Among them, the electron donating group containing a heteroatom is preferably a group represented by the following formula (d): A conjugated polymer compound having a group represented by the following formula (d) in a side chain can stably store anions released from ionic bonds with counter cations in gaps in the crystal structure constituted by the side chain, thereby suppressing dedoping and enabling a high conductivity state to be stably maintained over time. [ka] (In the formula, D represents at least one heteroatom selected from the elements of Groups 14 to 16; R 5 represents an aliphatic hydrocarbon group having 5 to 30 carbon atoms. The bond marked with a wavy line in the formula bonds to the main chain of the conjugated polymer compound.

[0085] The at least one heteroatom selected from the Groups 14 to 16 elements includes, for example, a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, etc. Among these, a Group 15 element or a Group 16 element is preferred, and an oxygen atom is particularly preferred.

[0086] R 5 Examples of the aliphatic hydrocarbon group having 5 to 30 carbon atoms include alkyl groups having 5 to 30 carbon atoms, such as a pentyl group, a hexyl group, a decyl group, a dodecyl group, a hexadecyl group, and a nonadecyl group; and alkenyl groups having 5 to 30 carbon atoms (preferably having 10 to 30 carbon atoms, more preferably having 10 to 20 carbon atoms, particularly preferably having 10 to 18 carbon atoms, and most preferably having 12 to 18 carbon atoms), such as an oleyl group.

[0087] R5 The aliphatic hydrocarbon group having 5 to 30 carbon atoms in the formula (I) is preferably an alkyl group having 5 to 30 carbon atoms, more preferably an alkyl group having 5 to 20 carbon atoms, particularly preferably an alkyl group having 10 to 20 carbon atoms, most preferably an alkyl group having 10 to 18 carbon atoms, and particularly preferably an alkyl group having 12 to 15 carbon atoms.

[0088] The content of the side chains in a conjugated polymer compound having an electron-donating group containing a hetero atom in the side chain is, for example, 1 to 4 (preferably 2 to 4, particularly preferably 2 to 3) per repeating unit (preferably the repeating unit represented by the above formula (2)).

[0089] (Method for producing a conjugated polymer compound having an electron-donating group containing a heteroatom in the side chain) As a conjugated polymer compound having an electron-donating group containing a heteroatom in a side chain, for example, a conjugated polymer compound having a repeating unit represented by the following formula (2a) can be produced via the following reactions (I) and (II). [ka]

[0090] D in the above formula 1 ~D 4 , L 1 ~L 4 is the same as above. X represents a halogen atom.

[0091] In reaction (I), a compound represented by the above formula (a) is reacted with a compound represented by the above formula (a') to obtain a compound represented by the above formula (b).

[0092] The reaction (I) is preferably carried out in the presence of a silver catalyst and / or a base, and more preferably in the presence of a palladium complex and / or a ligand.

[0093] Examples of the silver catalyst include silver salts such as silver oxide, silver carbonate, silver nitrate, silver sulfate, silver cyanide, silver chloride, silver bromide, silver iodide, silver acetate, silver benzoate, and silver lactate; silver complexes such as silver acetylacetonate, etc. These may be used alone or in combination of two or more.

[0094] The amount of the silver catalyst used is, for example, about 0.05 to 5.0 moles per mole of the total of the compound represented by the formula (a) and the compound represented by the formula (a').

[0095] Examples of the base include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-s-butylamine, tri-t-butylamine, diisopropylethylamine, dimethylcyclohexylamine, dicyclohexylethylamine, tribenzylamine, N-methylpiperidine, N,N-dimethylaniline, N,N-diethylaniline, 1,4-diazabicyclo[2.2.2]octane, tetramethylethylenediamine, 1,4-dimethylpiperazine, N-methylpyrrolidine, N-methylmorpholine, 1-methyl-2,2,6,6-tetramethylpiperidine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-ene, and the like. Examples of suitable bases include organic bases such as butyl ether, pyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, and 2,6-di-t-butylpyridine; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide; alkali metal carbonates such as sodium bicarbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate; alkali metal phosphates such as potassium phosphate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; metal amides such as lithium diisopropylamide; and alkali metal halides such as potassium fluoride, potassium iodide, sodium fluoride, and cesium fluoride. These may be used alone or in combination of two or more.

[0096] The amount of the base used is, for example, about 0.5 to 5.0 moles per mole of the compound represented by the above formula (a) and the compound represented by the above formula (a').

[0097] Examples of the palladium catalyst include zero-valent palladium compounds such as tetrakistriphenylphosphinepalladium, bis(1,5-cyclooctadiene)palladium, bis(triphenylphosphine)(maleic anhydride)palladium, tris(dibenzylideneacetone)dipalladium, and (1,5-cyclooctadiene)(maleic anhydride)palladium; and divalent palladium compounds such as palladium acetate, palladium propionate, palladium carbonate, palladium benzoate, palladium acetylacetonate, palladium chloride, palladium sulfate, palladium nitrate, lithium palladium chloride, bisbenzonitrile palladium chloride, bistriphenylphosphinepalladium chloride, bistriphenylphosphinepalladium acetate, π-allylpalladium chloride, π-allylpalladium acetate, and sodium tetrachloropalladate. These can be used alone or in combination of two or more.

[0098] The amount of the palladium catalyst used is, for example, about 1 to 10 mol % of the compound represented by the above formula (a) and the compound represented by the above formula (a').

[0099] Reaction (I) can be carried out in the presence of a solvent. Examples of the solvent include nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; water; alcohol solvents such as methanol; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; ether solvents such as diethyl ether, THF, and dioxane; ester solvents such as ethyl acetate; dimethylformamide and dimethylsulfoxide. These can be used alone or in combination of two or more.

[0100] The reaction atmosphere for reaction (I) is not particularly limited as long as it does not inhibit the reaction, and may be, for example, any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.

[0101] The reaction temperature for reaction (I) is, for example, about 30 to 100° C. The reaction time is, for example, about 0.5 to 5 hours.

[0102] Reaction (II) is a cross-coupling reaction between the compound represented by the above formula (b) and the compound represented by the above formula (c). As the cross-coupling reaction, for example, Stille cross-coupling reaction, Kumada cross-coupling reaction, Negishi cross-coupling reaction, Suzuki cross-coupling reaction, etc. can be used. Through this reaction, a conjugated polymer compound having a repeating unit represented by the above formula (2a) is obtained.

[0103] The compound represented by the above formula (c) can be selected and used depending on the type of cross-coupling reaction to be used. For example, in the case of using a Stille cross-coupling reaction, the compound represented by the formula (c) is an organotin compound, and R a is a trialkylstannyl group (SnR3 group; R is, for example, an alkyl group having 1 to 3 carbon atoms). In addition, when the Kumada cross-coupling reaction is used, the compound represented by the formula (c) is a magnesium compound, and R a is a magnesium halide group (-MgX group; X represents a halogen atom). When the Negishi cross-coupling reaction is used, the compound represented by the formula (c) is a zinc compound, and R a is a ZnX group (X represents a halogen atom). When the Suzuki cross-coupling reaction is used, the compound represented by the formula (c) is a boron compound, and R a is a BY2 group (Y is, for example, a hydroxyl group).

[0104] The amount of the compound represented by the above formula (c) used is, for example, about 1.0 to 1.5 moles per mole of the compound represented by the above formula (b).

[0105] The reaction (II) is preferably carried out in the presence of a palladium catalyst and / or ligand.

[0106] Examples of the palladium catalyst include Pd(PPh3)4, Pd(dba)2, Pd2(dba)3, Pd2(dba)3·CHCl3, Pd(t-Bu3P)2, and Pd(acac)2. These may be used alone or in combination of two or more.

[0107] The amount of the palladium catalyst used is, for example, about 0.5 to 10 mol % of the compound represented by the above formula (b).

[0108] The ligand is preferably a phosphine ligand. Examples of the phosphine ligand include trialkylphosphines such as trimethylphosphine and tri(t-butyl)phosphine; tricycloalkylphosphines such as tri(cyclohexyl)phosphine; and aromatic phosphines such as tri(o-tolyl)phosphine, dimethylphenylphosphine, and diphenyl-2-pyridinylphosphine. These can be used alone or in combination of two or more.

[0109] The amount of the ligand used is, for example, about 1 to 15 mol % of the compound represented by the above formula (b).

[0110] The reaction (II) can be carried out in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, trifluorotoluene, chlorobenzene, anisole, benzonitrile, nitrobenzene, and ethyl benzoate; aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; haloalkanes such as carbon tetrachloride, chloroform, dichloromethane, and 1,2-dichloroethane; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; nitriles such as acetonitrile and propionitrile; chain or cyclic ethers such as diethyl ether, dibutyl ether, dimethoxyethane, dioxane, and tetrahydrofuran; and organic acids such as acetic acid. These can be used alone or in combination of two or more.

[0111] The reaction atmosphere for reaction (II) is not particularly limited as long as it does not inhibit the reaction, and may be, for example, any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.

[0112] The reaction temperature for reaction (II) is, for example, room temperature (25° C.) to about 200° C. The reaction time is, for example, about 1 to 72 hours.

[0113] As a conjugated polymer compound having an electron-donating group containing a heteroatom in a side chain, for example, a conjugated polymer compound having a repeating unit represented by the following formula (2b) can be produced via the following reactions (III) and (IV). [ka]

[0114] D in the above formula 1 ~D 4 , L 1 ~L 4 , X, R a is the same as above.

[0115] In the reaction (III), the compound represented by the above formula (d) is reacted with the compound represented by the above formula (d') to obtain the compound represented by the above formula (e).

[0116] The reaction (III) is preferably carried out in the presence of a copper catalyst and / or a base.

[0117] Examples of the copper catalyst include monovalent or divalent copper halides such as copper iodide (I), copper iodide (II), copper bromide (I), copper bromide (II), copper chloride (I), copper chloride (II), copper fluoride (I), and copper fluoride (II); copper oxide (I), copper oxide (II), copper sulfate (I), copper sulfate (II), copper carbonate (I), copper carbonate (II), copper acetate (I), copper acetate (II), copper nitrate (I), copper nitrate (II), copper methanesulfonate (I), copper methanesulfonate (II), copper trifluoromethanesulfonate (I), copper trifluoromethanesulfonate (II), copper cyanide (I), and copper cyanide (II) are examples of monovalent or divalent protonic acid copper salts. These can be used alone or in combination of two or more.

[0118] The amount of the copper catalyst used is, for example, about 0.05 to 1 mole per mole of the compound represented by the above formula (d) and the compound represented by the above formula (d').

[0119] The base may be the same as the base usable in reaction (I). The base may be used alone or in combination of two or more kinds.

[0120] The amount of the base used is, for example, about 0.5 to 5.0 moles per mole of the compound represented by the above formula (d) and the compound represented by the above formula (d').

[0121] The reaction (III) can be carried out in the presence of a solvent. Examples of the solvent include the same solvents as those usable in the reaction (I). The solvent can be used alone or in combination of two or more.

[0122] The reaction atmosphere for reaction (III) is not particularly limited as long as it does not inhibit the reaction, and may be, for example, any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.

[0123] The reaction temperature for reaction (III) is, for example, about −100 to 10° C. The reaction time is, for example, about 0.5 to 5 hours.

[0124] Reaction (IV) is a cross-coupling reaction between the compound represented by formula (e) and the compound represented by formula (c). Reaction (IV) can be carried out in the same manner as reaction (II), except that the compound represented by formula (e) is used instead of the compound represented by formula (b).

[0125] [Electronic Devices] The electronic device of the present disclosure includes the above-mentioned conductive material.

[0126] Examples of the electronic device include switching elements, diodes, transistors, photoelectric conversion devices, solar cells, and photoelectric conversion elements (eg, solar cell elements, organic electroluminescence elements, etc.).

[0127] The electronic device includes the above-mentioned conductive material, and therefore has high electrical conductivity and high stability (stability against heat, water, electricity, etc.) In addition, it is possible to realize a lightweight, flexible, thin, and large-area electronic device at low cost.

[0128] The above configurations and combinations thereof of the present disclosure are merely examples, and additions, omissions, substitutions, and modifications of configurations are possible as appropriate without departing from the spirit and scope of the present disclosure. EXAMPLES

[0129] Hereinafter, the present disclosure will be described more specifically with reference to examples. However, the present disclosure is not limited to these examples and is limited only by the claims.

[0130] Preparation Example 1 (Preparation of Dopant) Silver bis(trifluoromethanesulfonyl)imide (AgTFSI, 3.51 mmol), tris(4-bromophenyl)amine (2.51 mmol), and diethyl ether (100 mL) were mixed and stirred for 20 minutes, then cooled to -36°C. A mixture of iodine (2.51 mmol) / diethyl ether (30 mL) was added dropwise thereto over 15 minutes, and then the temperature was raised to room temperature. The precipitate was collected by filtration and dried under reduced pressure at room temperature for 2 hours to obtain dopant (1) represented by the following formula.

[0131] [ka]

[0132] Preparation Example 2 (Preparation of Conjugated Polymer Compound 1 Having an Electron-Donating Group Containing a Heteroatom in the Side Chain) In the presence of toluene in an amount to give a substrate concentration of 0.5 M and p-toluenesulfonic acid monohydrate in an amount of 5 mol % of the substrate, 3-methoxythiophene as a substrate was reacted with 1.1 molar equivalents of 1-tridecanol under reflux for 4 hours to give 3-tridecyloxythiophene (yield: 92%).

[0133] In the presence of THF in an amount to give a substrate concentration of 0.5 M, 3-tridecyloxythiophene as a substrate was reacted with 1.0 molar equivalent of NBS at 0° C. for 30 minutes to obtain 2-bromo-4-tridecyloxythiophene (yield: 97%).

[0134] In the presence of THF in an amount to give a substrate concentration of 0.1 M, 2-bromo-4-tridecyloxythiophene as a substrate was mixed with 1 molar equivalent of lithium diisopropylamide and 1 molar equivalent of copper(II) chloride at -78°C, and then the mixture was heated to 25°C. The mixture was then reacted for 12 hours while maintaining the temperature at 25°C to obtain 5,5'-dibromo-3,3'-tridecyloxy-2,2'-bithiophene (yield: 73%).

[0135] In the presence of chlorobenzene at a substrate concentration of 0.05 M, 2.0 mol % of Pd2(dba)3·CHCl3 as the substrate, and 8.0 mol % of tri(o-tolyl)phosphine as the substrate, 5,5'-dibromo-3,3'-tridecyloxy-2,2'-bithiophene as the substrate and 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene were reacted under microwave irradiation. This produced conjugated polymer compound 1 having a repeating unit represented by the following formula (2-1).

[0136] [ka]

[0137] Preparation Example 3 (Preparation of Conjugated Polymer Compound 2 Having an Electron-Donating Group Containing a Heteroatom in the Side Chain) 3-Tridecyloxythiophene was obtained in the same manner as in Preparation Example 2.

[0138] In the presence of THF in an amount to give a substrate concentration of 0.5 M, 3-tridecyloxythiophene as a substrate was reacted with 1.0 molar equivalent of NBS at 0°C for 30 minutes to obtain 2-bromo-3-tridecyloxythiophene (yield: >99%).

[0139] In the presence of THF in an amount to give a substrate concentration of 0.1 M, 2-bromo-3-tridecyloxythiophene as a substrate was mixed with 2 molar equivalents of silver nitrate, 2 molar equivalents of potassium fluoride, and 5 mol% of PdCl2(phCN)2 at room temperature, and then the mixture was heated to 70°C and reacted for 3 hours while maintaining the temperature at 70°C to obtain 5,5'-dibromo-4,4'-tridecyloxy-2,2'-bithiophene (yield: 73%).

[0140] In the presence of chlorobenzene at a substrate concentration of 0.05 M, 2.0 mol % of Pd2(dba)3·CHCl3 as the substrate, and 8.0 mol % of tri(o-tolyl)phosphine as the substrate, 5,5'-dibromo-4,4'-tridecyloxy-2,2'-bithiophene as the substrate and 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene were reacted under microwave irradiation. This produced conjugated polymer compound 2 having a repeating unit represented by the following formula (2-2).

[0141] [ka]

[0142] Example 1 The conjugated polymer compound 1 obtained in Preparation Example 1 and o-dichlorobenzene were stirred at 150° C. for 1 hour in a nitrogen atmosphere to obtain a solution 1 containing the conjugated polymer compound 1 at a concentration of 0.5 mass %. The obtained solution 1 was spin-coated (500 rpm x 5 sec, then 3000 rpm x 60 sec) onto a glass substrate equipped with electrodes [Cr (3 nm) / Au (30 nm)], dried at 150°C for 30 min, and further annealed at 180°C for 30 min to obtain a film 1 with an average thickness of 50 nm.

[0143] The obtained film 1 was immersed for 10 minutes at 60° C. in an acetonitrile solution (dopant concentration: 1.5 mmol / L) of the dopant (1) obtained in Preparation Example 1. After immersion, it was dried for 10 minutes at 80° C. to obtain a conductive material (1).

[0144] Example 2 A conductor material (2) was obtained in the same manner as in Example 1, except that the conjugated polymer compound 2 obtained in Preparation Example 2 was used instead of the conjugated polymer compound 1 obtained in Preparation Example 1.

[0145] Comparative Example 1 A conductor material (3) was obtained in the same manner as in Example 1, except that a conjugated polymer compound 3 (product name "PBTTT-C14", manufactured by Sigma-Aldrich Corporation) having a repeating unit represented by the following formula (2-3) was used instead of the conjugated polymer compound 1 obtained in Preparation Example 1.

[0146] [ka]

[0147] (Doping efficiency evaluation) The ultraviolet-visible-near infrared (UV-Vis-NIR) absorption spectra of the conductor materials (1) to (3) obtained in the examples and comparative examples were measured in the range of 200 to 2700 nm at 1 nm intervals using an ultraviolet-visible-near infrared spectrophotometer (manufactured by JASCO). The results are shown in Figure 1. In addition, the absorption spectrum of each of the conjugated polymer compounds before doping with the conductor materials (1) to (3) was also measured in the same manner. The results are shown in FIG.

[0148] 1 and 2, the conjugated polymer compounds 1 and 2 show a greater reduction in the peak near 500 nm derived from the conjugated polymer compound before doping with a dopant, and an increase in the peak near 1200 to 2500 nm derived from the conjugated polymer compound after doping with a dopant, compared to the conjugated polymer compound 3. This shows that the conjugated polymer compounds 1 and 2 are more easily oxidized than the conjugated polymer compound 3, and that the conductor materials (1) and (2) have superior doping efficiency compared to the conductor material (3).

[0149] (Conductivity evaluation) The electrical conductivity (S) and electrical conductivity (S / cm) of the conductive material (1) (doped film thickness: 64.3 nm) were measured under the following conditions using a Keithley 2612B SourceMeter manufactured by Keithley. Measurement conditions Sweep voltage: -0.1 to 0.1 V (0.01 V / step) Wiring width (W): 612 μm Channel length (L): 500, 200, or 100 μm

[0150] The results are shown in the table below. [Table 1]

[0151] The electrical conductivity (S) and electrical conductivity (S / cm) of the conductor material (2) (doped film thickness: 33 nm) were measured in the same manner as in the (electrical conductivity evaluation) of the conductor material (1) except that the wiring width (W) was set to 2000 μm. The results are shown in the table below. [Table 2]

[0152] From Tables 1 and 2, it can be seen that an electronic device including conductive material (1) or conductive material (2) can obtain a stable high conductivity even when the channel length (L) is changed.

[0153] (Evaluation of electrical conductivity stability) The electrical conductivity of the conductor material (1) was measured immediately after preparation (storage period 0 days) and after storage at room temperature (25°C) for 14 days, 28 days, 42 days, or 56 days in the same manner as in (Evaluation of electrical conductivity). The results are shown in Table 3 below.

[0154] [Table 3]

[0155] From Table 3, it can be seen that the conductor material of the present disclosure is inhibited from dedoping over time and can maintain high conductivity even after long-term storage.

[0156] In summary, the configuration of the present disclosure and its variations are set forth below. [1] A conductive material having a configuration in which a dopant containing an anion selected from a nitrogen anion, a boron anion, a phosphorus anion, and an antimony anion and a counter cation is doped into a conjugated polymer compound having an electron-donating group containing a heteroatom in its side chain. [2] The conductive material according to [1], wherein the anion is an anion represented by formula (1): [3] The conductive material according to [1], wherein the anion is an anion represented by formula (1a): [4] The conductive material according to any one of [1] to [3], wherein the counter cation is a radical cation represented by formula (3). [5] The conductive material according to any one of [1] to [4], wherein the conjugated polymer compound is a π-conjugated polymer compound having an electron-donating group containing a heteroatom in a side chain. [6] The conductive material according to any one of [1] to [4], wherein the conjugated polymer compound is a heterocyclic conjugated polymer compound. [7] The conductive material according to any one of [1] to [4], wherein the conjugated polymer compound is a heterocyclic conjugated polymer compound containing a nitrogen atom or a sulfur atom as a heteroatom. [8] The conductive material according to any one of [1] to [4], wherein the conjugated polymer compound is a conjugated polymer compound containing a thiophene ring structure. [9] The conductive material according to any one of [1] to [4], wherein the conjugated polymer compound is a polymer compound having a repeating unit represented by formula (2).

[10] The conductive material according to any one of [1] to [4], wherein the conjugated polymer compound is a polymer compound having a repeating unit represented by formula (2a) or a polymer compound having a repeating unit represented by formula (2b).

[11] The conductive material according to any one of [1] to

[10] , wherein the electron-donating group containing a heteroatom is a group represented by formula (d):

[12] The conductive material according to any one of [1] to

[11] , wherein the conjugated polymer compound is a polymer compound having a repeating unit represented by formula (2), and the content of electron-donating groups containing a heteroatom is 1 to 4 per repeating unit represented by formula (2).

[13] The conductive material according to any one of [1] to

[12] , which is a p-type conductive material.

[14] The conductive material according to any one of [1] to

[13] , which has a conductivity of 250 S / cm or more under the following measurement conditions: <Measurement conditions> Conductor material thickness: 64.3 nm Sweep voltage: -0.1 to 0.1 V (0.01 V / step) Wiring width: 612μm Channel length: 500μm

[15] The conductive material according to any one of [1] to

[14] , which has a decrease in electrical conductivity of 5% or less when stored at 25°C for 14 days.

[16] The conductive material according to any one of [1] to

[15] , which has a decrease in electrical conductivity of 20% or less when stored at 25° C. for 56 days.

[17] A method for producing a conductive material according to any one of [1] to

[16] , comprising doping a conjugated polymer compound having an electron-donating group containing a heteroatom in a side chain with a dopant containing an anion selected from a nitrogen anion, a boron anion, a phosphorus anion, and an antimony anion, and a counter cation, to obtain the conductive material according to any one of [1] to

[16] .

[18] The method for producing a conductive material according to

[17] , wherein the anion is an anion represented by formula (1):

[19] The method for producing a conductive material according to

[17] , wherein the anion is an anion represented by formula (1a):

[20] The method for producing a conductive material according to any one of

[17] to

[19] , wherein the conjugated polymer compound is a π-conjugated polymer compound having an electron-donating group containing a heteroatom in a side chain.

[21] The method for producing a conductive material according to any one of

[17] to

[19] , wherein the conjugated polymer compound is a heterocyclic conjugated polymer compound.

[22] The method for producing a conductive material according to any one of

[17] to

[19] , wherein the conjugated polymer compound is a heterocyclic conjugated polymer compound containing a nitrogen atom or a sulfur atom as a heteroatom.

[23] The method for producing a conductive material according to any one of

[17] to

[19] , wherein the conjugated polymer compound is a conjugated polymer compound containing a thiophene ring structure.

[24] The method for producing a conductive material according to any one of

[17] to

[19] , wherein the conjugated polymer compound is a polymer compound having a repeating unit represented by formula (2).

[25] The method for producing a conductive material according to any one of

[17] to

[19] , wherein the conjugated polymer compound is a polymer compound having a repeating unit represented by formula (2a) or a polymer compound having a repeating unit represented by formula (2b).

[26] The method for producing a conductive material according to any one of

[17] to

[25] , wherein the electron-donating group containing a heteroatom is a group represented by formula (d):

[27] The method for producing a conductive material according to any one of

[17] to

[26] , wherein the counter cation contained in the dopant is a radical cation represented by formula (3).

[28] An electronic device comprising the conductive material according to any one of [1] to

[16] . [Industrial Applicability]

[0157] The conductor material of the present disclosure has a high doping amount and is difficult to dedo. It also has high crystallinity and is highly flexible. It can be formed into a film by a simple method and can be easily made large in area. Therefore, the conductor material can be suitably used for manufacturing electronic devices that are lightweight, thin, flexible, large in area, etc. while suppressing costs.

Claims

1. A conductive material having a configuration in which a dopant including an anion represented by the following formula (1) and a counter cation which is a radical cation represented by the following formula (3) is doped into a conjugated polymer compound having an electron-donating group containing a heteroatom represented by the following formula (d) in its side chain. 【Chemistry 1】 (In the formula, R 1 and R 2 are the same or different and each represents an electron-withdrawing group. R 1 and R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom.) 【Chemistry 2】 In formula (3), R 11 to R 13 are the same or different and each represents a monovalent aromatic group or a group represented by the following formula (r), and n represents the valence of the radical cation and is equal to the number (n) of nitrogen atoms in the formula. 【Chemistry 3】 (In formula (r), Ar 1 , Ar 2 , and Ar 3 are the same or different and each represents a divalent aromatic group, and Ar 4 , Ar 5 , Ar 6 , and Ar 7 are the same or different and each represents a monovalent aromatic group represented by formula (sb) below which may have a substituent. s and t are the same or different and each represents an integer of 0 or more. The bond marked with a wavy line in the formula bonds to the nitrogen atom in formula (3).) 【Chemistry 4】 (In formula (sb), Ar 8 and Ar 9 are the same or different and represent a divalent aromatic group, Ar 10 , Ar 11 , Ar 12 and Ar 13 are the same or different and represent a monovalent aromatic group, and u and v are the same or different and represent an integer of 0 or more. The bond marked with a wavy line in the formula bonds to the monovalent aromatic group.) 【Chemistry 5】 (In the formula, D represents at least one heteroatom selected from the elements of Groups 14 to 16, and R 5 represents an aliphatic hydrocarbon group having 5 to 30 carbon atoms. The bond indicated by the wavy line in the formula bonds to the main chain of the conjugated polymer compound.)

2. The conductive material according to claim 1 , wherein the anion is an anion represented by the following formula (1a): 【Chemistry 6】 (In the formula, R ３ , R ４ R may be the same or different and represents a halogen atom or a haloalkyl group. ３ , R ４ may be bonded to each other to form a haloalkylene group.

3. The conductive material according to claim 1 or 2, wherein the conjugated polymer compound is a polymer compound having a repeating unit represented by the following formula (2): 【Chemistry 7】 (In the formula, L １ ~L ４ are the same or different and represent elements of Groups 13 to 16; D １ ~D ４ are the same or different and each represents an electron donating group containing a hetero atom or a hydrogen atom. １ ~D ４ At least one of the groups is an electron donating group containing a heteroatom.

4. A method for producing a conductor material, comprising doping a conjugated polymer compound having, in a side chain, an electron-donating group containing a heteroatom represented by the following formula (d), with a dopant containing an anion represented by the following formula (1) and a counter cation which is a radical cation represented by the following formula (3), to obtain the conductor material described in any one of claims 1 to 3. 【Chemistry 8】 (In the formula, D represents at least one heteroatom selected from the elements of Groups 14 to 16, and R 5 represents an aliphatic hydrocarbon group having 5 to 30 carbon atoms. The bond indicated by the wavy line in the formula bonds to the main chain of the conjugated polymer compound.) 【Chemistry 9】 (In the formula, R 1 and R 2 are the same or different and each represents an electron-withdrawing group. R 1 and R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom.) 【Chemistry 10】 In formula (3), R 11 to R 13 are the same or different and each represents a monovalent aromatic group or a group represented by the following formula (r), and n represents the valence of the radical cation and is equal to the number (n) of nitrogen atoms in the formula. 【Chemistry 11】 (In formula (r), Ar 1 , Ar 2 , and Ar 3 are the same or different and each represents a divalent aromatic group, and Ar 4 , Ar 5 , Ar 6 , and Ar 7 are the same or different and each represents a monovalent aromatic group represented by formula (sb) below which may have a substituent. s and t are the same or different and each represents an integer of 0 or more. The bond marked with a wavy line in the formula bonds to the nitrogen atom in formula (3).) 【Chemistry 12】 (In formula (sb), Ar 8 and Ar 9 are the same or different and represent a divalent aromatic group, Ar 10 , Ar 11 , Ar 12 and Ar 13 are the same or different and represent a monovalent aromatic group, and u and v are the same or different and represent an integer of 0 or more. The bond marked with a wavy line in the formula bonds to the monovalent aromatic group.)

5. The method for producing a conductive material according to claim 4 , wherein the anion is an anion represented by the following formula (1a): 【Chemistry 13】 (In the formula, R ３ , R ４ R may be the same or different and represents a halogen atom or a haloalkyl group. ３ , R ４ may be bonded to each other to form a haloalkylene group.

6. The method for producing a conductive material according to claim 4 or 5, wherein the conjugated polymer compound is a polymer compound having a repeating unit represented by the following formula (2): 【Chemistry 14】 (In the formula, L １ ~L ４ are the same or different and represent elements of Groups 13 to 16; D １ ~D ４ are the same or different and each represents an electron donating group containing a hetero atom or a hydrogen atom. １ ~D ４ At least one of the groups is an electron donating group containing a heteroatom.

7. An electronic device comprising the conductive material according to any one of claims 1 to 3.

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