DOPANT AND CONDUCTIVE COMPOSITION AND METHOD FOR MANUFACTURING SAME - Patent application

Abstract

A novel dopant according to the present disclosure contains an anion represented by formula (1) and a counter cation. In formula (1), each of R1 and R2 represents at least one group selected from among a nitro group, a cyano group, an acyl group, a carboxyl group, an alkoxycarbonyl group, a haloalkyl group, a sulfo group, an alkyl sulfonyl group, a halosulfonyl group and a haloalkyl sulfonyl group, or alternatively, R1 and R2 may combine with each other to form a –SO2-L-SO2- group (wherein L represents a haloalkylene group). The counter cation may be a radical cation represented by formula (2). (In the formula, R1 and R2 represent electron-withdrawing groups which may combine with each other to form a hetero ring; and each of R3 to R5 represents a hydrogen atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group.) This dopant is able to form an electroconductive composition that has a high conductivity.

Description

[Technical field]

[0001] The present disclosure relates to a novel dopant capable of forming a conductive composition exhibiting high conductivity (electrical conductivity or electrical conductivity), a conductive composition containing the dopant and a conductive organic compound and a method for producing the same, an electronic device containing the conductive composition, and a novel ionic compound useful as a dopant and a method for producing the same. [Background technology]

[0002] Organic electronic materials (organic semiconductor materials or conductive organic compounds) such as conductive polymer compounds (or π-conjugated polymer compounds) are used as materials for various electronic devices, taking advantage of their light weight, flexibility, and moldability (or productivity). Organic semiconductor materials are usually doped with a dopant to impart or develop high electrical conductivity. Dopants include donors (electron donors or N-type dopants) that inject electrons as carriers, and acceptors (electron acceptors or P-type dopants) that extract electrons and inject holes. Donors include, for example, alkali metals, alkaline earth metals, quaternary ammoniums, and quaternary phosphoniums, while acceptors include halogens, Lewis acids, protonic acids, transition metal halides, and organic compounds.

[0003] A representative acceptor (electron acceptor dopant) is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), which is widely used in the field of organic semiconductors. For example, Non-Patent Document 1 describes an example in which F4TCNQ is subjected to molecular implantation doping of PBTTT-C16 (poly[2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene]) to prepare a P-type organic semiconductor composition. [Prior art documents] [Non-patent literature]

[0004] [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]

[0005] In Non-Patent Document 1, PBTTT-C16 is oxidized to F4TCNQ and becomes a radical cation state, forming holes, while the radical anion of the reduced F4TCNQ is stored in PBTTT-C16. However, since this radical anion of F4TCNQ is unstable, not only is it easily oxidized to the radical cation and returns to a neutral state, but F4TCNQ also has a low oxidizing power itself and escapes (sublimes) due to the influence of heat, etc., and this leads to a low doping efficiency (the ratio of generated carriers to the doped amount). If the doping efficiency is low, a large amount of dopant is required to increase the carrier concentration (or conductivity), but if the amount of dopant (impurity) is too large, it will obstruct the charge path (or conductive path) and cause a decrease in conductivity, so the conductivity cannot be sufficiently improved.

[0006] To improve conductivity, it is important that conductive organic compounds such as PBTTT-C16 are regularly arranged with high crystallinity, but F4TCNQ is stored in an unstable state, so the crystallinity of PBTTT-C16 may decrease after doping, and the crystal structure of PBTTT-C16 may be disturbed when F4TCNQ is released. Furthermore, if the crystallinity decreases, it becomes difficult to suppress molecular fluctuation and maintain the polymer assembly structure (or crystal structure), so there is a risk of the stability (durability in high temperature environments) decreasing.

[0007] Accordingly, an object of the present disclosure is to provide a novel dopant capable of forming a conductive composition exhibiting high conductivity, a conductive composition containing the dopant and a method for producing the same, and an electronic device containing the conductive composition.

[0008] Another object of the present disclosure is to provide a dopant capable of suppressing a decrease in crystallinity of a doped conductive organic compound (or maintaining or improving the crystallinity) and forming a conductive composition exhibiting high stability, a conductive composition containing this dopant and a method for producing the same, and an electronic device containing this conductive composition.

[0009] It is still another object of the present disclosure to provide a dopant exhibiting high doping efficiency, a conductive composition containing the dopant and a method for producing the same, and an electronic device containing the conductive composition.

[0010] Another object of the present disclosure is to provide novel ionic compounds useful as dopants and methods for making the same. [Means for solving the problem]

[0011] As a result of intensive research to achieve the above object, the inventors have found that the conductivity of a conductive composition can be effectively improved by using an ionic compound composed of a nitrogen anion having a specific chemical structure and a counter cation as a dopant, and have completed the present invention.

[0012] That is, the novel dopant of the present disclosure contains an anion represented by the following formula (1) and a counter cation.

[0013] [ka]

[0014] (In the formula, R 1 and R 2 each independently represents an electron-withdrawing group, R 1 and R 2 may be bonded to each other to form a heterocycle).

[0015] In the formula (1), R 1 and R 2may be at least one group selected from a nitro group, a cyano group, an acyl group, a carboxyl group, an alkoxycarbonyl group, a haloalkyl group, a sulfo group, an alkylsulfonyl group, a halosulfonyl group, and a haloalkylsulfonyl group, or R 1 and R 2 and may be bonded to each other to form a sulfonyl-haloalkylene-sulfonyl group (a haloalkylenedisulfonyl group or a group [--SO2-L-SO2-] (wherein L represents a haloalkylene group)).

[0016] In the formula (1), R 1 and R 2 may be a fluorosulfonyl group or a fluoroalkylsulfonyl group (e.g., a perfluoroalkylsulfonyl group), or R 1 and R 2 and may be bonded to each other to form a sulfonyl-fluoroalkylene-sulfonyl group (a fluoroalkylenedisulfonyl group or a group [—SO 2 -L—SO 2 -] (wherein L represents a fluoroalkylene group (for example, a perfluoroalkyl group)).

[0017] The counter cation may be a radical cation represented by the following formula (2):

[0018] [ka]

[0019] (In the formula, R 3 ~R 5 each independently represents a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group).

[0020] In the formula (2), R 3 ~R 5 may be an aryl group which may have a substituent, and the substituent may be a group selected from a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a nitro group, an amino group, and a substituted amino group.

[0021] The present disclosure includes a conductive composition including the dopant and a conductive organic compound. The conductive organic compound may be a conductive polymer having a heterocycle (a conductive heteropolymer or a heterocyclic conductive polymer). The conductive organic compound may be a conductive polymer having at least a constitutional unit represented by the following formula (3).

[0022] [ka]

[0023] (In the formula, X 1 represents an oxygen atom or a sulfur atom, and R 6 represents a substituent, and n represents an integer of 0 to 2).

[0024] The present disclosure also encompasses a method for doping the conductive organic compound with the dopant to produce the conductive composition, and an electronic device including the conductive composition.

[0025] Furthermore, the present disclosure encompasses an ion pair (or ionic compound) comprising an anion represented by the following formula (1a) and a radical cation represented by the following formula (2a):

[0026] [ka]

[0027] (In the formula, R 1a and R 2a each independently represents a fluorine atom or a fluoroalkyl group (e.g., a perfluoroalkyl group), R 1a and R 2a may be bonded to each other to form a fluoroalkylene group (eg, a perfluoroalkylene group).

[0028] [ka]

[0029] (In the formula, R 3a ~R 5a each independently represents a substituent, and m3 to m5 each independently represent an integer of 0 to 5).

[0030] The present disclosure also encompasses a method for producing the ion pair (or ionic compound) containing the anion represented by formula (1a) and the radical cation represented by formula (2a), by reacting an ionic compound containing an anion represented by formula (1a) and a monovalent metal ion [in particular, an ionic compound composed of an anion represented by formula (1a) and a monovalent metal ion] with a neutral compound corresponding to the radical cation represented by formula (2a) in the presence of an oxidizing agent.

[0031] In this specification and claims, the term "dopant" refers to an additive (an oxidizing agent (acceptor) or a reducing agent (donor)) for forming organic electronic materials, including not only organic semiconductors but also organic thermoelectric materials. Effect of the Invention

[0032] In the present disclosure, an ionic compound containing a nitrogen anion having a specific chemical structure is used as a dopant, so that a conductive composition exhibiting high conductivity can be formed. In addition, the dopant of the present disclosure can suppress the decrease in crystallinity of a conductive organic compound (or maintain or improve the crystallinity) even when doped, and can form a conductive composition exhibiting high stability (durability in a high-temperature environment). Furthermore, the dopant of the present disclosure also exhibits high doping efficiency, so that it can efficiently dope even highly crystalline conductive organic compounds that are usually difficult to dope. In addition, the present disclosure can provide a novel ionic compound useful as a dopant. [Brief description of the drawings]

[0033] [Figure 1]FIG. 1 shows ultraviolet-visible-near infrared (UV-Vis-NIR) absorption spectra of the conductive compositions obtained in Example 2 and Comparative Example 1, and PBTTT-C14 not doped with a dopant. [Diagram 2] FIG. 2 shows the results of measuring the X-ray rocking curves of the conductive compositions obtained in Example 3 and Comparative Example 2, and PBTTT-C14 not doped with a dopant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] [Dopant] The novel dopant (P-type dopant) of the present disclosure is an ionic compound (also called a salt, ion pair, ionic substance, or heteropolar compound) containing an anion represented by the above formula (1) and a counter cation, and may be a metal complex or metal compound. In particular, the dopant is preferably composed of an anion represented by the above formula (1) and a counter cation. In the monovalent anion represented by formula (1), two electron-withdrawing groups R 1 and R 2 Since the anion has a chemical structure in which the negative charge in the nitrogen anion is delocalized, it is relatively stable even when used alone.

[0035] When the dopant of the present disclosure is doped into a conductive organic compound as a P-type dopant, the counter cation is converted into a corresponding electrically neutral compound (or atom) by the electrons received from the conductive organic compound, and is stabilized. Therefore, the anion represented by formula (1) is released from the ionic bond with the counter cation, and the anion exists alone in a state stored or embedded in the conductive organic compound (for example, in a crystal). Unlike conventional dopants such as F4TCNQ, the anion represented by formula (1) is relatively stable even when alone as described above, and therefore can exist stably in the composition without donating electrons to the conductive organic compound in a radical cation state. Therefore, the doping efficiency is high, and the conductivity can be effectively improved.

[0036] In addition, although the reason is not clear, perhaps because the anion represented by formula (1) is stable, unexpectedly, it is possible to suppress the decrease in crystallinity of the conductive organic compound after doping (or to maintain or improve the crystallinity), thereby further improving the conductivity and forming a conductive composition that exhibits high stability.

[0037] The dopant of the present disclosure is an electron-withdrawing group R 1 and R 2 It is easier to change (or chemically modify) the type of cation or the type of counter cation compared to conventional dopants, and it is easier to control (or tune) the LUMO of the dopant depending on the HOMO of the conductive organic compound to which it is combined by doping.

[0038] The anion represented by formula (1) is preferable because it is a closed-shell, soft base. In the present specification and claims, soft acid or base and hard acid or base refer to the definition (or classification) of acids and bases in HSAB (hard and soft acids and bases). In order to obtain energy gain derived from Coulomb interaction by efficient shielding of charges (to allow the anion represented by formula (1) and the conductive organic compound having holes to exist stably in the conductive composition after doping), it is considered desirable for ions of similar size and shape to form a pair. Therefore, it is preferable that the anion that forms a pair with the doped conductive organic compound (especially the conductive polymer compound) having a delocalized hole is large in size.

[0039] (anion represented by formula (1))

[0040] [ka]

[0041] (In the formula, R 1 and R 2 each independently represents an electron-withdrawing group, R 1 and R2 may be bonded to each other to form a heterocycle).

[0042] In the formula (1), R 1 and R 2 Examples of the electron-withdrawing group represented by the formula (I) include a nitro group, a cyano group, an acyl group, a carboxyl group, an alkoxycarbonyl group (C such as a methoxycarbonyl group), 1-6 Alkoxy-carbonyl group, haloalkyl group (perhaloalkyl group such as trifluoromethyl group and trichloromethyl group), sulfo group, alkylsulfonyl group (methylsulfonyl group, etc.) 1-6 alkylsulfonyl groups, halosulfonyl groups, and haloalkylsulfonyl groups.

[0043] R 1 and R 2 means that they are bonded together to form a heterocycle (or R 1 and R 2 When forming a heterocycle, the two electron-withdrawing groups exemplified above bonded to the nitrogen may be bonded (or substituted) directly or with a divalent linking group (an alkylene group, a haloalkylene group, an ether group, an ester group, a group combining these, etc.) to form a ring. Representative R 1 and R 2 Examples of the divalent group formed by bonding together include a sulfonyl-haloalkylene-sulfonyl group (a haloalkylene disulfonyl group or a group [-SO2-L-SO2-] (wherein L is a haloalkylene group)).

[0044] These electron-withdrawing groups R 1 and R 2 Among these, a halosulfonyl group, a haloalkylsulfonyl group, or R 1 and R 2and a group in which the two are bonded together, [-SO2-L-SO2-] (wherein L represents a haloalkylene group), is preferred. Examples of the halosulfonyl group include a fluorosulfonyl group and a chlorosulfonyl group. Examples of the haloalkylsulfonyl group include a fluoroalkylsulfonyl group [e.g., a fluoromethylsulfonyl group, a trifluoroethylsulfonyl group, a trifluoropropylsulfonyl group, a pentafluoropropylsulfonyl group, a perfluoroalkylsulfonyl group (e.g., a perfluoroC group such as a trifluoromethylsulfonyl group, a pentafluoroethylsulfonyl group, a heptafluoropropylsulfonyl group, or a nonafluorobutylsulfonyl group]. 1-6 Fluoro C such as alkylsulfonyl groups 1-6 alkylsulfonyl groups, etc.]; chloroalkylsulfonyl groups (e.g., chloroC such as chloromethylsulfonyl groups); 1-6 alkylsulfonyl groups, etc.

[0045] In the group [-SO2-L-SO2-], examples of the haloalkylene group represented by L include fluoroalkylene groups (e.g., perfluoroalkylene groups, specifically, perfluoro C groups such as tetrafluoroethylene groups, hexafluoropropane-1,3-diyl groups, and octafluorobutane-1,4-diyl groups). 2-4 Alkylene groups, etc.), chloroalkylene groups (perchloro C 2-4 alkylene groups, perchloroalkylene groups, etc.

[0046] More preferred R 1 and R 2 Examples of the fluorosulfonyl group include fluoroalkylsulfonyl groups (e.g., perfluoroalkylsulfonyl groups), and R 1 and R 2 and are bonded to each other to form a group [-SO2-L-SO2-] (wherein L is a fluoroalkylene group (perfluoro C 2-4 and perfluoroalkylene groups such as alkylene groups. 1-4Examples include perfluoroalkylsulfonyl groups such as alkylsulfonyl groups, and among these, perfluoro C 1-3 Perfluoro C such as alkylsulfonyl groups, especially trifluoromethylsulfonyl groups 1-2 An alkylsulfonyl group is preferred.

[0047] In addition, when a heterocycle is not formed, the group R 1 and R 2 The types of may be different from each other, but usually, it is preferable that they are the same.

[0048] Representative examples of the anion represented by formula (1) include an anion represented by the following formula (1a):

[0049] [ka]

[0050] (In the formula, R 1a and R 2a each independently represents a fluorine atom or a fluoroalkyl group; R 1a and R 2a may be bonded to each other to form a fluoroalkylene group).

[0051] In the formula (1a), R 1a and R 2a Examples of the fluoroalkyl group represented by the formula (I) include fluoroalkyl groups [e.g., fluoromethyl group, trifluoroethyl group, trifluoropropyl group, pentafluoropropyl group, perfluoroalkyl groups (e.g., perfluoro C groups such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, and nonafluorobutyl group]. 1-6 Fluoro C such as alkyl groups 1-6 alkyl group, etc.], chloroalkyl group (e.g., chloromethyl group, etc.) 1-6 Alkyl groups, etc.

[0052] R 1a and R2a means that they are bonded together to form a heterocycle (or R 1a and R 2a and may be bonded to each other to form a fluoroalkylene group. Examples of such a fluoroalkylene group include perfluoroalkylene groups (e.g., perfluoro C groups such as tetrafluoroethylene, hexafluoropropane-1,3-diyl, and octafluorobutane-1,4-diyl groups). 2-4 Fluoro C such as alkylene groups 2-4 An alkylene group is exemplified.

[0053] Preferred groups R 1a and R 2a Examples of the alkyl groups include fluorine atoms and perfluoroalkyl groups (perfluoro C 1-4 alkyl group, etc.), R 1a and R 2a and a perfluoroalkylene group (perfluoro C 2-4 Alkylene groups, etc.) are preferred, and perfluoro C 1-3 Examples of perfluoroalkyl groups include alkyl groups and perfluoroalkyl groups, particularly trifluoromethyl groups. 1-2 An alkyl group is preferred.

[0054] In addition, when a ring is not formed, the group R 1a and R 2a The types of may be different from each other, but usually, it is preferable that they are the same.

[0055] Specific examples of the anion represented by formula (1) or (1a) include R 1a and R 2a is a fluorine atom, i.e., a bis(fluorosulfonyl)imide anion [i.e., the formula [(FSO2)2N - ] anion (FSI - or FSA - Also called)];R 1a and R 2a Perfluoroalkyl group (Perfluoro C 1-4an anion which is an alkyl group, etc.), more specifically, a bis(trifluoromethanesulfonyl)imide anion [i.e., an anion represented by the formula [(CF3SO2)2N - ] or the formula [Tf2N - ] anion (TFSI - or TFSA - )], N-trifluoromethanesulfonyl-N-nonafluorobutanesulfonylimide anion [i.e., the anion represented by the formula [CF3SO2-N - -SO2C4F9] anion], bis(nonafluorobutanesulfonyl)imide anion [i.e., an anion represented by the formula [(C4F9SO2)2N - ], etc.; R 1a and R 2a and a perfluoroalkylene group (perfluoro C 2-4 alkylene group, etc.), more specifically, a hexafluoropropane-1,3-di(sulfonyl)imide anion [i.e., in formula (1a), R 1a and R 2a and an anion in which the divalent group formed by bonding R 1a and R 2a is a fluorine atom or a perfluoroalkyl group (perfluoro C 1-4 The anion R is preferably an alkyl group, 1a and R 2a Perfluoro C 1-3 More preferred are anions which are alkyl groups, especially TFSI. - R 1a and R 2a Perfluoro C 1-2 Anions which are alkyl groups are preferred.

[0056] (Counter cation) The counter cation may be a cation having a valence of 2 or more (polyvalent), but is usually a monovalent cation. In addition, since the anion represented by the formula (1) is a soft base, the counter cation is preferably a soft acid. Furthermore, the counter cation may be a non-radical cation, but is preferably a radical cation. When the counter cation is a radical cation, it is easy to receive electrons from the conductive organic compound with high oxidizing power (easy to inject holes) during doping, and it can effectively improve the doping efficiency, and after receiving electrons and becoming neutral, it can often exist stably in the composition. Examples of such counter cations include radical cations represented by the following formula (2).

[0057] [ka]

[0058] (In the formula, R 3 ~R 5 each independently represents a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group).

[0059] In the formula (2), R 3 ~R 5 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include a linear or branched C alkyl group such as a methyl group, an ethyl group, an n-butyl group, and a t-butyl group. 1-6 Examples of the cycloalkyl group include a C alkyl group such as a cyclopentyl group and a cyclohexyl group. 3-10 Examples of the aryl group include C aryl groups such as phenyl, 1-naphthyl, and 2-naphthyl groups. 6-14 BiC such as aryl group and biphenylyl group 6-10 Examples of the aralkyl group include C aryl groups such as benzyl groups and phenethyl groups. 6-14 Aryl-C 1-6Among these hydrocarbon groups, alkyl groups and aryl groups are preferred, and aryl groups are more preferred.

[0060] R 3 ~R 5 The heterocyclic group represented by the formula (I) may be aromatic or non-aromatic, and may be, for example, a heterocyclic group containing at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic group may be a monocyclic heterocyclic group, or a polycyclic heterocyclic group in which a monocyclic heterocyclic ring is condensed with one or more heterocyclic rings and / or hydrocarbon rings (aromatic hydrocarbon rings or non-aromatic hydrocarbon rings) (ortho-condensed, ortho-peri-condensed, etc.). The rings forming the heterocyclic group (in the case of a polycyclic heterocyclic group, the rings condensed with each other) are often 5- to 7-membered rings, preferably 5- or 6-membered rings.

[0061] Representative examples of heterocyclic groups include heterocyclic groups containing a nitrogen atom as a heteroatom [e.g., 5- or 6-membered monocyclic heterocyclic groups containing a nitrogen atom, such as a pyrrolyl group, an imidazolyl group, a pyridyl group, or a pyrazinyl group; polycyclic heterocyclic groups having a 5- or 6-membered ring containing a nitrogen atom, such as an indolyl group, a quinolyl group, an isoquinolyl group, a quinazolyl group, a carbazolyl group, a carbolinyl group, a phenanthridinyl group, an acridinyl group, a phenazinyl group, or a naphthyridinyl group]; heterocyclic groups containing an oxygen atom as a heteroatom [e.g., 5- or 6-membered monocyclic heterocyclic groups containing an oxygen atom, such as a furyl group; an isobenzofuranyl group, or a chromenyl group]. heterocyclic groups containing a sulfur atom as a heteroatom [for example, a 5- or 6-membered monocyclic heterocyclic group containing a sulfur atom, such as a thienyl group; a 5- or 6-membered polycyclic heterocyclic group containing a sulfur atom, such as a benzothienyl group, a thianthrenyl group, a thienothienyl group, and the like]; heterocyclic groups containing different heteroatoms [for example, a 5- or 6-membered monocyclic heterocyclic group containing different heteroatoms, such as a morpholinyl group, an isothiazolyl group, an isoxazolyl group, and the like; a 5- or 6-membered polycyclic heterocyclic group containing different heteroatoms, such as a phenoxathiinyl group, and the like].

[0062] R 3 ~R 5 The hydrocarbon group or heterocyclic group represented by R may each be aromatic. 3 ~R 5 The hydrocarbon group or heterocyclic group represented by the formula (I) may have one or more substituents. Examples of the substituents include linear or branched C alkyl groups such as halogen atoms (fluorine, chlorine, bromine, iodine, etc.), alkyl groups (methyl, ethyl, n-butyl, t-butyl, etc.), and the like. 1-6 Alkyl groups, hydroxyl groups, alkoxy groups (methoxy groups, t-butoxy groups, etc.) 1-6 Alkoxy groups, acyl groups (formyl groups, acetyl groups, etc.) 1-8 C such as alkylcarbonyl group and benzoyl group 6-12 Aryl-carbonyl group, alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.) 1-6 Examples of the substituents include an alkoxy-carbonyl group, a cyano group, a nitro group, an amino group, a substituted amino group (a mono- or dialkylamino group such as a dimethylamino group, a mono- or diacylamino group such as an acetylamino group, etc.). These substituents may be used alone or in combination of two or more. Among these substituents, halogen atoms, alkyl groups, alkoxy groups, etc. are often used, and halogen atoms (particularly bromine atoms) are preferred.

[0063] The number of substitutions of the substituents can be selected depending on the type of the hydrocarbon group or heterocyclic group to be substituted, and may be selected, for example, from an integer range of about 0 to 6 (e.g., 0 to 5), preferably an integer of 0 to 4 (e.g., 0 to 3), and more preferably an integer of about 1 to 2 (particularly 1). The substitution position may be any position, but when the substituent is substituted on a phenyl group as a hydrocarbon group, it is preferable that the substituent is substituted at least at the p-position.

[0064] Preferred R 3 ~R 5Examples of the alkyl group include a hydrocarbon group which may have a substituent, and more preferably, an aryl group which may have a substituent (a C group which may have a substituent such as a phenyl group, a naphthyl group, or a biphenyl group). 6-14 aryl group, etc.), and more preferably C 6-12 Aryl groups, especially optionally substituted C 6-10 R may be an aryl group, particularly preferably a phenyl group. 3 ~R 5 Preferably, the hydrocarbon group (particularly an aryl group such as a phenyl group) has at least the above-mentioned substituent. The preferred substituents, number of substitutions and substitution positions for the hydrocarbon group (particularly an aryl group such as a phenyl group) are the same as those in the above-mentioned preferred embodiments.

[0065] R 3 ~R 5 Specifically, haloaryl groups (mono- or trihalo C such as p-chlorophenyl, p-bromophenyl, and p-iodophenyl groups) 6-10 aryl groups, etc.), alkylaryl groups (e.g., mono- or tri-C such as p-methylphenyl and dimethylphenyl groups) 1-4 Alkyl C 6-10 aryl groups, etc.), alkoxyaryl groups (e.g., mono- or tri-C such as p-methoxyphenyl groups, etc. 1-4 Alkoxy C 6-10 Among them, haloaryl groups (mono or dihalo C 6-10 aryl group, and the like), and more preferably a monohaloaryl group (particularly a p-halophenyl group such as a p-bromophenyl group, and the like).

[0066] In addition, R 3 ~R 5 may be the same or different, but it is usually preferred that they are the same.

[0067] Representative radical cations represented by the formula (2) include trialkylaminium radical cations, tricycloalkylaminium radical cations, triarylaminium radical cations, and triarylalkylaminium radical cations, and the radical cation represented by the following formula (2a) is particularly preferred.

[0068] [ka]

[0069] (In the formula, R 3a ~R 5a each independently represents a substituent, and m3 to m5 each independently represent an integer of 0 to 5).

[0070] In the formula (2a), R 3a ~R 5a The substituent represented by the formula (2) is R 3 ~R 5 The substituents, including preferred embodiments, are the same as those exemplified as the substituents that may be possessed by the hydrocarbon group or heterocyclic group represented by the following formula:

[0071] The number of substitutions represented by m3 to m5 may be, for example, an integer of 0 to 4 (e.g., 0 to 3), preferably an integer of about 1 or 2 (particularly 1), and is usually not less than 1. The numbers of substitutions m3 to m5 may be different from one another, but are usually preferably the same.

[0072] When m3 to m5 are 1 or more, the substituents R 3a ~R 5a The types of m3 to m5 may be different from each other, but are usually preferably the same. 3a ~R 5a The types may be the same or different from each other.

[0073] When m3 to m5 are 1 or more, the corresponding substituent R 3a ~R5a The substitution position of may be any position, but it is preferable that it is substituted at least at the p-position relative to the phenyl group.

[0074] Specific examples of the radical cation represented by formula (2) or (2a) include triphenylamine; tris(halophenyl)amines [e.g., tris(mono- or dihalophenyl)amines such as tris(p-chlorophenyl)amine, tris(p-bromophenyl)amine, tris(p-iodophenyl)amine, tris(m-bromophenyl)amine, and tris(o-bromophenyl)amine]; tris(alkylphenyl)amines [e.g., tris(mono- or dihalophenyl)amines such as tris(p-methylphenyl)amine and tris(pt-butylphenyl)amine]; 1-4 tris(alkoxyphenyl)amines [e.g., tris(mono or diC such as tris(p-methoxyphenyl)amine, tris(pt-butoxyphenyl)amine, etc. 1-4 Examples of the radical cations include the radical cations of the corresponding neutral compounds (amine compounds) such as tris(halophenyl)amine and tris(alkoxy-phenyl)amine. Among these, tris(halophenyl)amine and tris(monohalophenyl)amine are preferred, and tris(p-halophenyl)amine and tris(p-bromophenyl)amine are more preferred.

[0075] The dopant of the present disclosure may contain an anion represented by the formula (1) and a counter cation, and the anion represented by the formula (1) [or formula (1a)] and the counter cation (for example, a radical cation represented by the formula (2) or formula (2a)) may each be contained alone or in combination of two or more. Usually, the dopant is often composed of only the anion represented by the formula (1) and the counter cation [particularly, only the anion represented by the formula (1) [or formula (1a)] and the counter cation alone].

[0076] A representative dopant of the present disclosure is an ionic compound composed of a combination of an anion represented by the above formula (1a) and a radical cation represented by the above formula (2a) as a counter cation. Note that such an ionic compound combining an anion represented by the above formula (1a) and a radical cation represented by the above formula (2a) is a novel substance.

[0077] Specifically, in formula (1a), R 1a and R 2a is a fluorine atom or a perfluoroalkyl group (perfluoro C 1-6 anions such as alkyl groups, and R 1a and R 2a and a perfluoroalkylene group (perfluoro C 2-4 An anion selected from the group consisting of cyclic anions such as alkylene groups, e.g., FSI - , TFSI - and hexafluoropropane-1,3-di(sulfonyl)imide anion, etc., which are specific examples of the anion represented by formula (1) or (1a) above; and a radical cation represented by formula (2a) above [for example, a radical cation corresponding to an amine compound selected from triphenylamine, tris(halophenyl)amine, tris(alkylphenyl)amine, and tris(alkoxyphenyl)amine, which are specific examples of the radical cation represented by formula (2) or (2a) above]. 1a and R 2a Perfluoroalkyl group (Perfluoro C 1-4 An ionic compound combining an anion such as an alkyl group and a radical cation of a tris(halophenyl)amine [e.g., tris(monohalophenyl)amine] is preferred, and TFSI is even more preferred. - and a tris(p-halophenyl)amine such as tris(p-bromophenyl)amine.

[0078] (Manufacturing method) The method for producing the dopant (or ionic compound) of the present disclosure is not particularly limited, and the dopant may be produced, for example, by a method in which an ionic compound containing an anion represented by formula (1) [particularly formula (1a)] and a monovalent metal ion is reacted with a neutral compound corresponding to a predetermined counter cation, specifically, a neutral compound (or a corresponding amine compound) corresponding to a radical cation represented by formula (2) [particularly formula (2a)], in the presence of an oxidizing agent.

[0079] The monovalent metal ion may be, for example, an alkali metal ion, but is usually a transition metal ion, for example, Cu + , Ag + , Au + The monovalent metal ions may be used alone or in combination of two or more. The preferred monovalent metal ion is Ag. + may be also possible.

[0080] The ionic compound containing the anion represented by formula (1) [particularly formula (1a)] and the monovalent metal ion may contain the anion represented by formula (1) [particularly formula (1a)] and the monovalent metal ion, and the anion represented by formula (1) [or formula (1a)] and the monovalent metal ion may each be contained alone or in combination of two or more. Usually, it is often composed of only the anion represented by formula (1) and the monovalent metal ion [particularly, only the anion represented by the formula (1) [or formula (1a)] and the monovalent metal ion alone].

[0081] Examples of ionic compounds containing an anion represented by formula (1) [particularly formula (1a)] and a monovalent metal ion include monovalent metal salts of the anions specifically exemplified as the anion represented by formula (1) or (1a), such as TFSI, e.g., silver bis(trifluoromethanesulfonyl)imide (AgTFSI). - The ionic compounds containing an anion represented by formula (1) [particularly formula (1a)] and a monovalent metal ion can be used alone or in combination of two or more kinds.

[0082] Examples of neutral compounds (or corresponding amine compounds) corresponding to the radical cation represented by formula (2) [particularly formula (2a)] include amine compounds corresponding to the radical cations specifically exemplified by those represented by formula (2) or (2a), such as tris(halophenyl)amine [e.g., tris(p-bromophenyl)amine, etc.].

[0083] The ratio of the ionic compound composed of the anion represented by formula (1) [particularly formula (1a)] and the monovalent metal ion may be, for example, about 1 to 5 mol (e.g., 1.1 to 3 mol), and preferably about 1.2 to 2 mol (e.g., 1.3 to 1.5 mol), relative to 1 mol of the neutral compound corresponding to the radical cation represented by formula (2) [particularly formula (2a)].

[0084] The oxidizing agent may be any oxidizing agent capable of one-electron oxidation of the neutral compound to form a radical cation represented by the corresponding formula (2) [particularly formula (2a)], and examples thereof include halogen alone (chlorine Cl2, bromine Br2, iodine I2, etc.), halogen acids [for example, hypohalite salts (for example, hypohalite alkali metal salts such as sodium hypochlorite NaClO, etc.), halite salts (for example, chlorite alkali metal salts such as sodium chlorite NaClO2, etc.), halogen acid salts (for example, halogen acid alkali metal salts such as potassium bromate KBrO3, etc.), perhalogen acid salts (for example, perhalogen acid alkali metal salts such as potassium metaperiodate KIO4, etc.)], etc. These oxidizing agents can be used alone or in combination of two or more kinds. Among these oxidizing agents, halogen alone (particularly iodine I2) is preferred.

[0085] The proportion of the oxidizing agent may be, for example, about 1 to 5 mol (e.g., 1 to 3 mol), preferably about 1 to 2 mol (e.g., 1 to 1.5 mol), and more preferably about 1 mol, relative to 1 mol of the neutral compound corresponding to the radical cation represented by formula (2) [particularly formula (2a)].

[0086] The reaction may be carried out in the presence of a solvent. Examples of the solvent include aprotic solvents and other solvents inert to the reaction, such as ethers (e.g., chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, etc.). Chain ethers such as diethyl ether are often used.

[0087] The reaction may be generally carried out in an inert gas atmosphere (nitrogen gas, rare gas, etc.) or with stirring. The reaction temperature may be, for example, from -70°C to +60°C (for example, from -50°C to +40°C), preferably from about -40°C to +30°C. The reaction time may be, for example, from 1 minute to 1 hour (for example, from 5 to 30 minutes), preferably from about 10 to 20 minutes. After the reaction is completed, the product may be separated and purified by a conventional separation and purification means, for example, filtration, drying, extraction, recrystallization, reprecipitation, or a combination of these.

[0088] [Conductive composition] The conductive composition of the present disclosure includes the dopant of the present disclosure and a conductive organic compound (or an organic semiconductor compound). The conductive composition may include a dopant (second dopant) different from the dopant of the present disclosure (first dopant), but usually does not substantially include a second dopant (conventional dopant such as F4TCNQ). The first dopant may be used alone or in combination of two or more kinds, and usually is used alone.

[0089] (Conductive organic compound) The conductive organic compound may be a conductive low molecular weight compound or a conductive high molecular weight compound. In the present specification and claims, the term "conductive organic compound" ("conductive low molecular weight compound" and "conductive high molecular weight compound") refers to a compound that exhibits the properties of a semiconductor or a conductor (or a good conductor) when doped with the dopant of the present disclosure [or has a conductivity (electrical conductivity or electrical conductivity) of, for example, 10 -10S / cm or more], and a compound that exhibits insulating properties when it is alone (before doping or in an undoped state) without a dopant [for example, a compound with a conductivity of 10 -10 This term is used to include substances with a density of less than 100 S / cm.

[0090] Representative examples of the conductive low molecular weight compound include acenes (e.g., naphthacene, chrysene, pyrene, pentacene, picene, perylene, hexacene, heptacene, dibenzopentacene, coronene, tetrabenzopentacene, ovalene, etc.); phthalocyanines (e.g., phthalocyanine (copper phthalocyanine, etc.), naphthalocyanine, subphthalocyanine, etc.); carbazoles [e.g., 1,3,5-tris[2,7-(N,N-(p-methoxyphenyl)amino)-9H-carbazol-9-yl]benzene (SGT405), etc.]; thiophenes [e.g., 2,5-bis[4-(N,N-bis(p-methoxyphenyl)amino] )phenyl]-3,4-ethylenedioxythiophene (H101), 2,3,4,5-tetrakis[4-(N,N-bis(p-methoxyphenyl)amino)phenyl]thiophene (H111), etc.]; tetracarboxylic acid diimides [for example, 1,4,5,8-naphthalenetetracarboxylic acid diimide, 2,3,6,7-naphthalenetetracarboxylic acid diimide, 2,3,6,7-anthracenetetracarboxylic acid diimide, etc.]; triptycenes [for example, 2,6,14-tris[5'-(4-(N,N-bis(p-methoxyphenyl)amino)phenyl)-thiophen-2'-yl]triptycene (T103), etc.].

[0091] Representative examples of conductive polymer compounds (or conjugated polymer compounds) include aliphatic conjugated polymer compounds (e.g., polyacetylene such as trans-polyacetylene, polyphenylacetylene, etc.); aromatic conjugated polymer compounds [e.g., poly(p-phenylene), poly(m-phenylene), polyfluorene, etc.]; heterocyclic conjugated polymer compounds [e.g., polypyrroles (e.g., poly(pyrrole-2,5-diyl)), polythiophenes [e.g., polythiophene, polyalkylthiophene, poly[5,5'-bis(3-alkyl-2-thienyl)-2,2'-bithiophene] (or PQT), poly[2,5 ... poly(3,4-ethylenedioxythiophene) (or PEDOT), etc.); heteroatom-containing conjugated polymer compounds [e.g., polyaniline, polyazobenzene, polytriarylamines (e.g., poly[bis(4-phenyl)-(2,4,6-trimethylphenyl)-amine] (or PTAA), etc.)]; ladder-type (or double-chain) conjugated polymer compounds [e.g., polyacene, polyphenanthrene, etc.]; mixed conjugated polymer compounds [e.g., poly(p-phenylenevinylene), poly(p-phenylene sulfide), etc.].

[0092] These conductive organic compounds may be commercially available or may be prepared by a conventional method. These conductive organic compounds may be used alone or in combination of two or more. Among them, conductive polymer compounds are preferred because of their excellent moldability (productivity) and heat resistance in the production of electronic devices and the like. Conductive polymer compounds may be used alone or in combination of two or more, and usually, a single conductive polymer compound is often used. The conductive organic compound (or conductive polymer compound) in the conductive composition of the present disclosure is usually capable of forming a P-type organic semiconductor, and among the conductive polymer compounds, conductive polymer compounds having at least a heterocycle such as a heterocyclic conjugated polymer compound are preferred.

[0093] The conductive polymer compound having a heterocycle may be a conjugated polymer compound containing at least a structural unit having a heterocycle in the molecular structure (particularly in the main chain). The heterocycle may be a monocyclic heterocycle, or a polycyclic heterocycle in which a monocyclic heterocycle is condensed with one or more rings [heterocycle and / or hydrocarbon ring (aromatic hydrocarbon ring or non-aromatic hydrocarbon ring)] (ortho-condensation, ortho-peri-condensation, etc.). The rings forming the heterocycle (in the case of a polycyclic heterocycle, the rings condensed with each other) are often 5- to 7-membered rings, preferably 5- or 6-membered rings.

[0094] Examples of the heteroatom forming the heterocycle include a nitrogen atom, an oxygen atom, and a sulfur atom. These heteroatoms may be contained alone or in combination of two or more in the heterocycle. Among these heteroatoms, a nitrogen atom and a sulfur atom are preferred, and a sulfur atom is more preferred. The heterocycle may be a heterocycle containing an oxygen atom such as a furan ring, a heterocycle containing a nitrogen atom such as a pyrrole ring, and the like, but is preferably a heterocycle containing at least a sulfur atom as a heteroatom such as a thiophene ring, a benzothiophene ring, a thienothiophene ring, or a benzothiadiazole ring [particularly, a heterocycle having a thiophene ring structure (including or containing) such as a thiophene ring, a benzothiophene ring, or a thienothiophene ring].

[0095] Representative examples of such structural units having a heterocycle include structural units represented by the following formula (3).

[0096] [ka]

[0097] (In the formula, X 1 represents an oxygen atom or a sulfur atom, and R 6 represents a substituent, and n represents an integer of 0 to 2).

[0098] In the formula (3), preferred X 1 is a sulfur atom.

[0099] R 6 Examples of the substituent represented by the formula (I) include linear or branched C alkyl groups such as hexyl, octyl, 2-ethylhexyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups. 1-20 Alkyl groups, etc.), alkoxy groups (e.g., hexyloxy, octyloxy, 2-ethylhexyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, and other linear or branched C 1-20 Among these, linear or branched C 6-18 Alkyl groups such as alkyl groups are preferred.

[0100] The number of substitutions n is often 0 or 1, and is preferably 1 from the viewpoint of solubility. When n is 2, the two groups R 6 The types may be the same or different from each other.

[0101] Specific examples of the constitutional unit (or divalent group) represented by the formula (3) include 3-C alkyl groups such as thiophene-2,5-diyl group, 3-alkylthiophene-2,5-diyl group (for example, 3-hexylthiophene-2,5-diyl group), 6-18 alkylthiophene-2,5-diyl group, etc. These constitutional units represented by the formula (3) may be used alone or in combination of two or more kinds.

[0102] The conductive polymer compound having a heterocycle preferably contains at least a constitutional unit represented by the above formula (3), and more preferably contains a constitutional unit represented by the following formula (3A) from the viewpoint of high crystallinity and easy improvement of conductivity. Normally, when the crystallinity of a conductive organic compound is high, it is difficult to dope (doping efficiency is easily reduced), and therefore it is difficult to improve the conductivity, but the dopant of the present disclosure has excellent doping efficiency even for conductive organic compounds with high crystallinity, and therefore can effectively improve the conductivity.

[0103] [ka]

[0104] (In the formula, X 1a and X 1b represents an oxygen atom or a sulfur atom, and R 6a and R 6b represents a substituent, n1 and n2 represent integers of 0 to 2, and X 2a and X 2b represents an oxygen atom or a sulfur atom, and R 7a and R 7b represents a hydrogen atom or a substituent).

[0105] In the formula (3A), preferred X 1a and X 1b is a sulfur atom. X 1a and X 1b The types may be different from each other, but are usually the same.

[0106] R 6a and R 6b The substituent represented by the formula (3) is R 6 The substitution numbers n1 and n2 are often 0 or 1, and are preferably 1 from the viewpoint of solubility. n1 and n2 may be different from each other, but are usually the same. When n1 and n2 are 1, R 6a , R 6b The substitution positions of are X 1a , X 1b Although it may be either the 3-position or the 4-position of the 5-membered heterocycle containing 2a and X 2b The position is often close to a condensed heterocyclic ring containing

[0107] When n1 and n2 are 1 to 2, R 6a and R 6b The types of R may be different from each other, but are usually the same. Also, when n1 and n2 are 2, the two R 6a , two R 6b The types may be the same or different from each other.

[0108] Preferred X 2a and X 2b is a sulfur atom. X 2a and X 2b The types may be different from each other, but are usually the same.

[0109] R 7a and R 7b The substituent represented by the formula (3) is R 6 The same groups as those mentioned above, including preferred embodiments thereof, are also included. 7a and R 7b is a hydrogen atom.

[0110] Representative examples of the structural unit (or divalent group) represented by the formula (3A) include structural units represented by the following formula (3a) (such as structural units having 2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene).

[0111] [ka]

[0112] (In the formula, R 6a and R 6b is the same as the above formula (3A) including preferred embodiments.

[0113] Specific examples of the structural unit represented by formula (3a) include R 6a and R 6b R is a dodecyl group. 6a and R 6b R is a structural unit that is a tetradecyl group; 6a and R 6b R is a structural unit that is a hexadecyl group; 6a and R 6b 2,5-bis(3-C 6-20 (R alkylthiophene-2-yl)thieno[3,2-b]thiophene 6a and R 6b C6-20 The structural units represented by the formula (3A) or (3a) may be used alone or in combination of two or more kinds.

[0114] In the conductive polymer compound having a heterocycle, the proportion of a structural unit (such as the structural unit represented by the formula (3)) having a heterocycle [preferably a heterocycle containing at least a sulfur atom as a heteroatom, particularly a heterocycle having a thiophene ring structure] relative to the total structural units may be, for example, about 10 mol % or more (e.g., 30 mol % or more), preferably 50 mol % or more (e.g., 70 mol % or more), and more preferably 90 mol % or more (e.g., substantially 100 mol %).

[0115] The proportion of the structural units (or divalent groups) represented by the formula (3) may be, for example, about 10 to 100 mol % (for example, 30 to 90 mol %), and preferably about 50 to 80 mol % (for example, 60 to 70 mol %), relative to the total structural units. The proportion of the structural units represented by the formula (3A) [particularly (3a)] may be, for example, about 10 mol % or more (for example, 30 mol % or more), preferably 50 mol % or more (for example, 70 mol % or more), and more preferably 90 mol % or more (for example, substantially 100 mol %), relative to the total structural units.

[0116] Representative examples of conductive polymer compounds having a heterocycle include the above-mentioned heterocyclic conjugated polymer compounds, and among these, polythiophenes such as polythiophene, polyalkylthiophene, PQT, PBTTT, and PEDOT are preferred.

[0117] Examples of polythiophenes include poly(thiophene-2,5-diyl). Examples of polyalkylthiophenes include poly(3-C) such as poly(3-methylthiophene-2,5-diyl), poly(3-hexylthiophene-2,5-diyl) (or P3HT), poly(3-octylthiophene-2,5-diyl) (or P3OT), and poly(3-dodecylthiophene-2,5-diyl) (or P3DDT). 1-18 Examples of PQT include poly[5,5'-bis(3-C alkylthiophene-2,5-diyl)-2,2'-bithiophene] (or PQT-C12), etc. 1-18 Examples of PBTTT include poly[2,5-bis(3-C alkyl-2-thienyl)-2,2'-bithiophene], such as poly[2,5-bis(3-dodecylthiophene-2-yl)thieno[3,2-b]thiophene] (or PBTTT-C12), poly[2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene] (or PBTTT-C14), and poly[2,5-bis(3-hexadecylthiophene-2-yl)thieno[3,2-b]thiophene] (or PBTTT-C16). 1-18 (alkylthiophene-2-yl)thieno[3,2-b]thiophene] and the like.

[0118] The conductive polymer compounds having a heterocycle (particularly polythiophenes) may be used alone or in combination of two or more. Among them, polythiophene, polyalkylthiophene, PQT, PBTTT, etc. are preferred, and PBTTT is more preferred.

[0119] The molecular weight of the conductive polymer compound is not particularly limited, and for example, when measured by gel permeation chromatography (GPC), the number average molecular weight Mn may be about 500 to 5,000,000 (e.g., 5,000 to 100,000), preferably about 10,000 to 50,000 (e.g., 15,000 to 40,000), and more preferably about 20,000 to 30,000 (e.g., 23,000 to 27,000), in terms of polystyrene, and the molecular weight distribution or PDI (Mw / Mn) may be, for example, about 1 to 20 (e.g., 1.1 to 10), preferably about 1.2 to 5 (e.g., 1.3 to 3), and more preferably about 1.5 to 2.5 (e.g., 1.6 to 2). If Mn is too large, the solubility may decrease, and the moldability may decrease, and if it is too small, the heat resistance and mechanical properties may decrease.

[0120] In the conductive composition, the total amount of the dopant and the conductive organic compound of the present disclosure may be, for example, 50% by mass or more (for example, 80% by mass or more), preferably 90% by mass or more (substantially 100% by mass). If the proportion of the dopant is too small, the carrier density may not be improved and the conductivity may not be improved sufficiently, and if the proportion is too large, the crystallinity of the conductive organic compound may decrease and the conductivity may decrease. Since the dopant of the present disclosure has high doping efficiency, even a small amount can effectively improve the carrier density and conductivity.

[0121] The conductive composition may contain conventional additives within a range that does not impair the effects of the present disclosure. Examples of additives include leveling agents and adhesion improvers (such as silane coupling agents). These additives may be used alone or in combination of two or more. The proportion of the additives may be, for example, 30 parts by mass or less (e.g., 10 parts by mass or less), preferably 5 parts by mass or less (e.g., 0 to 1 part by mass) relative to 100 parts by mass of the total amount of the dopant and the conductive organic compound.

[0122] In addition, the conductive composition may not contain a solvent, but may contain a solvent as necessary in order to form a thin film or film of an organic semiconductor by a simple method such as printing or coating.

[0123] Examples of the solvent include aromatic hydrocarbons (e.g., benzene, toluene, xylene, anisole, etc.); halogenated hydrocarbons (e.g., halo-C hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane); 1-6 Alkanes, chlorobenzene, dichlorobenzene; alcohols (e.g., methanol, ethanol, 2-propanol, n-butanol, t-butanol, etc.) 1-6 Alkane monools; C such as ethylene glycol 2-4 Alkanediols, etc.; ethers (chain ethers such as diethyl ether and diisopropyl ether, cyclic ethers such as tetrahydrofuran and dioxane, etc.); glycol ethers [for example, (poly)C such as cellosolves (methyl cellosolve, etc.), carbitols (methyl carbitol, etc.), triethylene glycol monomethyl ether, and propylene glycol monomethyl ether] 2-4 Alkylene glycol mono C 1-4 Alkyl ethers; (poly)C such as ethylene glycol dimethyl ether and dipropylene glycol dimethyl ether 2-4 Alkylene glycol di-C 1-4 alkyl ethers, etc.]; glycol ether acetates [e.g., cellosolve acetates (e.g., methyl cellosolve acetate, etc. C 1-4 Alkyl cellosolve acetates, carbitol acetates (e.g., methyl carbitol acetate, etc.) 1-4 (Poly)C such as alkyl carbitol acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monobutyl ether acetate 2-4 Alkylene glycol mono C 1-4alkyl ether acetates, etc.; ketones (chain ketones such as acetone and methyl ethyl ketone, cyclic ketones such as cyclohexanone, etc.); esters (acetate esters such as ethyl acetate, lactate esters such as methyl lactate, etc.); carbonates (chain carbonates such as dimethyl carbonate, cyclic carbonates such as ethylene carbonate and propylene carbonate, etc.); nitriles (acetonitrile, propionitrile, benzonitrile, etc.); amides (N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.); sulfoxides (dimethyl sulfoxide, etc.); and mixed solvents thereof. Usually, aromatic hydrocarbons and halogenated hydrocarbons (for example, o-dichlorobenzene, etc.) are often used.

[0124] When the conductive composition contains a solvent, it may be prepared by mixing each component with the solvent and then filtering as necessary. The solid content concentration in the conductive composition (solution or dispersion) can be selected depending on the application method, and may be, for example, about 0.001 to 20 mass% (e.g., 0.01 to 10 mass%), preferably 0.1 to 5 mass% (e.g., 0.5 to 3 mass%), and particularly about 0.6 to 2 mass% (e.g., 0.7 to 1.3 mass%).

[0125] (Method of manufacturing conductive composition) The method for producing a conductive composition containing a dopant and the conductive organic compound of the present disclosure includes at least a doping step of doping the conductive organic compound with the dopant. The conductive organic compound to be subjected to the doping step does not necessarily have to be formed into a predetermined shape, and may be formed into a predetermined shape after or during the doping step, but is usually formed into a predetermined shape (e.g., a membrane or film) in advance before the doping step.

[0126] A conventional molding method can be used for forming into a predetermined shape, and when forming into a thin film or film, for example, it may be formed by a dry process such as a vacuum deposition method or a sputtering method, or it may be formed by a wet process (coating, etc.). In terms of moldability (or productivity), a wet process is preferred.

[0127] In the wet process, a composition (solution or dispersion) containing at least the conductive organic compound and the solvent is printed or applied (or coated) onto at least one surface of a base material (or substrate), and the solvent is removed from the resulting coating to form a film.

[0128] The base material (or substrate) is not particularly limited, and may be, for example, a glass plate, a silicon wafer, a plastic film (for example, a transparent resin film such as a polyethylene terephthalate film), etc. If necessary, one or more functional layers (for example, a conductive layer such as ITO, an insulating layer such as SiO2, a self-assembled monolayer (SAM) such as β-phenethyltrimethoxysilane (β-PTS), etc.) may be formed on the surface of these base materials.

[0129] The printing or coating method is not particularly limited, and may be a conventional method such as air knife coating, roll coating, gravure coating, blade coating, bar coating, die coating, dip coating, spray coating, spin coating, casting, edge casting, drop casting, screen printing, inkjet printing, compression orientation, etc. Usually, spin coating, edge casting, drop casting, inkjet printing, etc. are often used, and from the viewpoint of ease of film formation (or productivity), spin coating, etc. are preferred.

[0130] The solvent can be removed from the resulting coating by a conventional method such as natural drying, drying under heating and / or reduced pressure, or spin drying (or spin drying), to form a thin film or film. These drying methods may be used alone or in combination of two or more. When drying is performed by heating, the heating temperature may be, for example, about 30 to 100°C, and preferably about 40 to 80°C.

[0131] The obtained thin film or film may be subjected to an annealing treatment. The annealing temperature may be selected from the range of, for example, about 50 to 400°C (for example, 80 to 380°C), and may be, for example, about 100 to 360°C (for example, 150 to 350°C), preferably about 200 to 340°C (for example, 250 to 330°C), and more preferably about 280 to 320°C. The annealing time may be, for example, about 10 minutes to 12 hours, preferably about 30 minutes to 8 hours, and more preferably about 1 to 6 hours (for example, 2 to 4 hours). The annealing may be performed in an air atmosphere or in an inert gas atmosphere such as nitrogen gas or rare gas (helium, argon, etc.), and is preferably performed in an inert gas (particularly argon) atmosphere.

[0132] The doping method is not particularly limited, and a conventional method can be used, for example, a gas phase doping method, a liquid phase doping method in which a conductive organic compound (such as a membrane or film-like conductive organic compound) is impregnated into a dopant solution, an electrochemical doping method in which a conductive organic compound is immersed in an electrolyte solution containing a dopant and electrolysis is performed, an ion implantation method, an induced doping method, and the like.

[0133] Among these, the liquid phase doping method is often used. The solvent for preparing the dopant solution used in the liquid phase doping method is not particularly limited as long as it can dissolve or disperse the dopant, and examples thereof include the solvents exemplified in the section on the conductive composition, and usually, polar solvents such as nitriles (acetonitrile, etc.) are often used. The concentration of the dopant solution may be selected from a range of, for example, about 0.01 to 100 mmol / L (for example, 0.1 to 10 mmol / L), and may be, for example, about 0.3 to 5 mmol / L (for example, 0.5 to 2 mmol / L), preferably about 0.5 to 1.5 mmol / L (for example, 0.8 to 1.2 mmol / L). In order to efficiently dope (to shift the equilibrium), the amount of dopant used in the dopant solution is usually in large excess relative to the conductive organic compound (or the repeating unit of the conductive polymer compound).

[0134] Impregnation (or immersion) of the conductive organic compound (such as a membrane or film-like conductive organic compound) into the dopant solution may be performed while heating as necessary. The heating temperature may be equal to or lower than the boiling point of the dopant solution, for example, 20 to 60° C. (e.g., 30 to 50° C.), preferably about 35 to 45° C. The impregnation time may be, for example, 1 minute to 12 hours (e.g., 5 to 30 minutes), preferably about 10 to 20 minutes.

[0135] After impregnating the conductive organic compound in the dopant solution, the obtained conductive composition may be dried by the above-mentioned conventional method to remove the solvent. For example, when the conductive organic compound is in the form of a membrane or film, it is often heated and dried after spin drying. The rotation speed in spin drying may be, for example, about 500 to 5000 rpm (for example, 1000 to 2000 rpm), and the time may be about 1 second to 1 hour (for example, 5 to 60 seconds). In addition, the temperature in heat drying may be, for example, about 40 to 300°C (for example, 60 to 100°C), and the time may be, for example, about 1 minute to 12 hours (for example, 5 to 30 minutes).

[0136] When the conductive composition contains the above-mentioned additives, these additives may be mixed with the conductive organic compound before, after or during the doping step.

[0137] The thickness (average thickness) of the thin film or thin membrane thus obtained may be appropriately selected depending on the application, and may be, for example, about 1 to 5000 nm, preferably about 30 to 1000 nm, and more preferably about 50 to 500 nm.

[0138] (Characteristics of Conductive Compositions and Electronic Devices) The conductive composition of the present disclosure exhibits high conductivity, and may be, for example, about 10 to 10,000 S / cm (e.g., 100 to 5,000 S / cm), preferably about 300 to 3,000 S / cm (e.g., 500 to 2,500 S / cm), and more preferably about 1,000 to 2,000 S / cm (e.g., 1,200 to 1,800 S / cm). Note that in this specification and claims, the conductivity can be measured by the method described in the examples below.

[0139] The conductive composition of the present disclosure may usually be a P-type semiconductor, and since it has high conductivity as described above, it can be used as a material for forming electronic devices, for example, semiconductor elements such as switching elements, rectifier elements (diodes), and transistors, photoelectric conversion elements (solar cell elements, organic electroluminescence (EL) elements, etc.), thermoelectric conversion elements, etc.

[0140] Each feature disclosed herein may be combined with any other feature disclosed herein. EXAMPLES

[0141] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples.

[0142] [Synthesis of ionic compounds] Example 1

[0143] [ka]

[0144] Silver bis(trifluoromethanesulfonyl)imide [AgTFSI, 1.36 g, 3.51 mmol], tris(4-bromophenyl)amine (1.21 g, 2.51 mmol), and diethyl ether (Et2O, 100 mL) were mixed and stirred for 20 minutes, then cooled to -36°C. A mixture of iodine (I2, 0.64 g, 2.51 mmol) / Et2O (30 mL) was added dropwise over 15 minutes, and the temperature was raised to room temperature. The precipitate was collected by filtration and dried under reduced pressure at room temperature for 1 hour to obtain a crude product (1.77 g, 93% yield) as a deep purple solid. The crude product obtained was dissolved in dry methylene chloride (CH2Cl2, 90 mL), filtered, and the filtrate obtained was poured into dry Et2O (360 mL) at -26°C. The mixture was then heated to room temperature, and the precipitate was again collected by filtration and dried under reduced pressure at room temperature for 2 hours to obtain the target product (an ionic compound of the anion represented by formula (1a-1) and the cation represented by formula (2a-1) (also called TPA-TFSI), 1.41 g, 74% yield) as a deep purple solid. The results of elemental analysis are shown below.

[0145] Anal. Calcd for C20H12Br3F6N2O4S2: C 31.52; H 1.59; N 3.68. Found: C 31.55; H 1.80; N 3.80.

[0146] [UV-Vis-NIR spectrum measurement] Example 2 The ionic compound (TPA-TFSI) obtained in Example 1 was liquid-phase doped into a polymer compound having a repeating unit represented by the following formula (3a-1) ("PBTTT-C14" manufactured by Aldrich, Mn = 25 × 300, PDI = 1.8) to prepare a measurement sample (conductive composition) by the method described below.

[0147] [ka]

[0148] (Wherein, R is an n-tetradecyl group (group -C 14 H 29 ) indicates.

[0149] That is, a 1% by mass solution of PBTTT-C14 in orthodichlorobenzene was spin-coated onto a glass substrate (500 rpm, 5 seconds, then 2000 rpm, 60 seconds) to prepare a spin-coated film with an average thickness of 40 to 100 nm. The obtained spin-coated film was immersed in a 1 mmol / L dopant solution (a solution of the ionic compound obtained in Example 1 in acetonitrile) at a temperature of 40° C. for 15 minutes. After immersion, the film was spin-dried (1500 rpm, 30 seconds), and then dried at a temperature of 80° C. for 10 minutes to prepare a measurement sample (conductive composition).

[0150] The ultraviolet-visible-near infrared (UV-Vis-NIR) absorption spectrum of the obtained measurement sample was measured in the range of 200 to 2700 nm at 1 nm intervals using an ultraviolet-visible-near infrared spectrophotometer (manufactured by JASCO). The measurement results are shown in Figure 1. For reference, Figure 1 also shows the spectrum of only PBTTT-C14 not doped with a dopant as the measurement sample.

[0151] Comparative Example 1 The ultraviolet-visible-near infrared (UV-Vis-NIR) absorption spectrum was measured in the same manner as in Example 2, except that 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) was used instead of the ionic compound obtained in Example 1. The measurement results are shown in FIG.

[0152] As is clear from FIG. 1, in Example 2, the peak at around 500 nm derived from neutral PBTTT-C14 is greatly reduced, and the absorption at around 1200 to 2500 nm derived from PBTTT-C14 radical cation is greatly increased, compared to Comparative Example 1 in which F4-TCNQ is doped. Therefore, in Example 2, the doping efficiency was higher than that in Comparative Example 1 in which F4-TCNQ is doped. It is considered that the sharp absorption at around 400 nm in Comparative Example 1 indicates the absorption due to neutral F4-TCNQ, and the doublet absorption at around 700 to 1000 nm indicates the absorption of F4-TCNQ anion.

[0153] [X-ray rocking curve measurement] Example 3 The measurement sample (conductive composition) prepared in the same manner as in Example 2 was subjected to X-ray rocking curve measurement using an X-ray diffractometer ("SmartLab" manufactured by Rigaku) ​​with CuKα as the X-ray source. The measurement results are shown in Figure 2. For reference, Figure 2 also shows the measurement results when only PBTTT-C14 not doped with a dopant was used as the sample.

[0154] Comparative Example 2 An X-ray rocking curve was measured in the same manner as in Example 3, except that 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) was used instead of the ionic compound obtained in Example 1. The measurement results are shown in FIG.

[0155] As is clear from Fig. 2, in Example 3, the full width at half maximum (FWHM) was reduced compared to Comparative Example 2 in which F4TCNQ was doped, and it was found that the crystallinity after doping was high. In detail, compared to the case of using PBTTT-C14 alone, the full width at half maximum was reduced by about 2% in Comparative Example 2, whereas it was reduced by about 10% in Example 3. It is considered that this result indicates that the TFSI anion after doping greatly contributed to the improvement of crystallinity.

[0156] [Conductivity measurement] Example 4 A measurement sample was prepared in the same manner as in Example 2, except that a glass substrate equipped with gold electrodes for four-terminal measurement was used instead of a glass substrate. A PBTTT-C14 film was formed and liquid-phase doping was performed on a dopant solution containing the ionic compound of Example 1.

[0157] The conductivity of the obtained measurement sample was measured using a digital multimeter (Keiythley "Keiythley 2000 digital multimeter") under measurement conditions of a current input of 1 μA, and the sample showed a high conductivity of 1500 S / cm.

[0158] Comparative Example 3 The conductivity was measured in the same manner as in Example 4 except that 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) was used instead of the ionic compound obtained in Example 1, and was found to be 250 S / cm. [Industrial Applicability]

[0159] Since the dopant of the present disclosure can effectively improve the conductivity in a conductive composition, the conductive composition containing the dopant of the present disclosure can be effectively used as various electronic devices, for example, organic semiconductor devices such as rectifying elements (diodes), switching elements or transistors (organic thin film transistors) [e.g., junction transistors (bipolar transistors), field effect transistors (unipolar transistors), etc.], photoelectric conversion elements (solar cell elements, organic EL elements, etc.), and thermoelectric conversion elements.

Claims

1. The following formula (1) 【Chemistry 1】 (In the formula, R １ and R ２ each independently represents an electron-withdrawing group; R １ and R ２ may be bonded to each other to form a heterocycle.) A conductive composition comprising a dopant containing an anion represented by the formula: and a counter cation, and a conductive organic compound, The counter cation is represented by the following formula (2): 【Chemistry 2】 (In the formula, R 3 to R 5 each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent.) is a radical cation represented by The conductive organic compound is represented by the following formula (3A): 【Chemistry 3】 (In the formula, X １ａ and X １ｂ represents an oxygen atom or a sulfur atom, R ６ａ and R ６ｂ represents a substituent, n1 and n2 represent integers of 0 to 2, and X ２ａ and X ２ｂ represents an oxygen atom or a sulfur atom, R ７ａ and R ７ｂ represents a hydrogen atom or a substituent.) The conductive composition is a conductive polymer compound containing a structural unit represented by the formula:

2. In formula (1), R １ and R ２ is at least one group selected from a nitro group, a cyano group, an acyl group, a carboxyl group, an alkoxycarbonyl group, a haloalkyl group, a sulfo group, an alkylsulfonyl group, a halosulfonyl group, and a haloalkylsulfonyl group, or R １ and R ２ and are bonded together to form a group [—SO ２ -L-SO ２ 2. The conductive composition according to claim 1, wherein L is a haloalkylene group.

3. In formula (1), R １ and R ２ is a fluorosulfonyl group or a fluoroalkylsulfonyl group, or R １ and R ２ and are bonded together to form a group [—SO ２ -L-SO ２ 3. The conductive composition according to claim 1, wherein L is a fluoroalkylene group.

4. In formula (2), R ３ ~R ５ is an aryl group which may have a substituent, and the substituent is a group selected from a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a nitro group, an amino group and a substituted amino group.

5. A method for producing the conductive composition according to any one of claims 1 to 4, comprising doping the conductive organic compound with the dopant.

6. An electronic device comprising the conductive composition according to any one of claims 1 to 4.

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