JP2020015877A - Organic polymer and method for producing the same as well as use thereof - Google Patents

Abstract

To provide a novel organic polymer having high mobility (electric mobility or carrier mobility) and a method for producing the same.SOLUTION: There is provided an organic polymer having a donor unit (D) and an acceptor unit (A), in which the donor unit (D) includes at least a donor unit (D1) represented by the following formula (I). (where a ring A and a ring B each independently represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, n represents an integer of 0 or 1 to 6, Rto Reach independently represents a substituent, ato aeach independently represents an integer of 0 to 2, a ring C represents a benzene ring subjected to orthocondensation sequentially nonlinearly with adjacent benzene rings according to the number of n.)SELECTED DRAWING: None

Description

  The present invention includes a novel organic polymer (semiconductor polymer) useful for forming an organic semiconductor used for a semiconductor element (for example, a field effect transistor, a photoelectric conversion element, and the like), a method for manufacturing the same, and the organic polymer. The present invention relates to a composition, an organic semiconductor, a method for producing the same, and a semiconductor device (or electronic device).

  As a typical material for forming an organic semiconductor, a highly planarized aromatic condensed ring compound such as a metal phthalocyanine compound or a polyacene compound such as pentacene is known. Organic semiconductors formed of these low-molecular compounds are generally formed by forming a film on a substrate by a vacuum high-temperature process such as vapor deposition. In recent years, attention has been focused on printed electronics that can form a film more easily and efficiently (or with energy savings) than the vacuum high-temperature process and can cope with an increase in area. In printed electronics, compared to the low-molecular compounds, not only the moldability or film-forming properties (for example, easy adjustment of ink viscosity), but also the mechanical properties (film strength, etc.) and heat resistance of the formed film. Therefore, organic polymers are suitable, and organic polymers having various structures are being developed.

  For example, WO 2017/170245 (Patent Document 1) discloses a repeating unit represented by the following formula (I) (a repeating unit in which an aromatic ring is ortho-condensed in a zigzag manner; hereinafter, simply referred to as a zigzag unit). ) Is disclosed.

(Wherein, ring A and ring B each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle, n represents 0 or an integer of 1 to 6, and R ^{1 to} R ^{2 + n} each independently represent And a1 to a (2 + n) each independently represent an integer of 0 to 2, and a ring C is sequentially non-adjacent to an adjacent benzene ring according to the number of n. A benzene ring which is ortho-condensed linearly is shown).

  In Examples of this document, an organic polymer having a repeating unit (zigzag-like unit) in which the rings A and B are thiophene rings and n is 2 in the above formula (I) is prepared. A semiconductor element is manufactured by forming a film on a substrate by a spin coating method. However, the mobility (carrier mobility) μ of the obtained organic polymer was not sufficient.

WO 2017/170245 (Claims, Examples)

  Accordingly, an object of the present invention is to provide a novel organic polymer having high mobility (electric mobility or carrier mobility) and a method for producing the same, a composition and an organic semiconductor containing the organic polymer, a method for producing the same, and An electronic device including an organic semiconductor is provided.

Another object of the present invention is to provide an organic material that can be oriented with high orientation (molecular orientation or crystallinity) [or low π stack distance d _π ] even when a film is formed by a simple film forming method such as a spin coating method. An object of the present invention is to provide a polymer and a method for producing the same, a composition and an organic semiconductor including the organic polymer, a method for producing the same, and an electronic device including the organic semiconductor.

  Still another object of the present invention is to provide an organic polymer capable of achieving both high orientation and high solubility in an organic solvent and a method for producing the same, a composition containing the organic polymer, an organic semiconductor and a method for producing the same, and An electronic device including an organic semiconductor is provided.

  Another object of the present invention is to provide a method for producing the organic polymer simply or efficiently.

  The present inventors have conducted intensive studies to achieve the above object, and as a result, the organic polymer having zigzag-like units described in Examples of Patent Document 1 is not oriented between molecules in film formation by spin coating. I discovered that. As a result of further studies by the present inventors, when the donor unit (D) containing a predetermined zigzag unit and the acceptor unit (A) are combined, the orientation between molecules is improved, and the mobility is improved. Have been found to be effectively improved, and the present invention has been completed.

  That is, the organic polymer of the present invention is an organic polymer having a donor unit (D) and an acceptor unit (A), and the donor unit (D) is represented by at least the following formula (I). The donor unit (D1).

(Wherein, ring A and ring B each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle, n represents 0 or an integer of 1 to 6, and R ^{1 to} R ^{2 + n} each independently represent A ^{1 to} a ^{2 + n} each independently represent an integer of 0 to 2; and ring C is arranged in a non-linear sequence with respect to an adjacent benzene ring in accordance with the number of n. A benzene ring ortho-condensed in the same manner).

  The donor unit (D1) has a unit represented by at least one of the following formulas (I-1) to (I-5) (particularly, a unit represented by the formula (I-3)). It may be.

(Wherein, R ^{1 to} R ⁶ each independently represent an alkyl group, an aryl group, an alkoxy group, or an alkylthio group, and a ^{1 to} a ⁶ each independently represent an integer of 0 to 2, Ring A and ring B are the same as described above).

In the formula (I-3), at least one of R ^{1 to} R ⁴ is a linear or branched C _4-34 alkyl group or a linear or branched C _4-34 alkoxy group, A ^{1 to} a ⁴ may be each independently 0 or 1, and at least one of a ^{1 to} a ⁴ may be 1.

  In the formula (I), the ring A and the ring B may be an aromatic ring selected from a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, and a benzene ring.

  The acceptor unit (A) may include a unit (A1) having a nitrogen atom and an aromatic heterocyclic skeleton containing a group 16 atom of the periodic table. The unit (A1) may include a unit represented by at least one formula selected from the following formulas (III-1) to (III-5).

(Wherein, rings E ¹ and E ² are each independently an aromatic ring, Z ^{1 to} Z ⁵ are each independently an oxygen atom, a sulfur atom or a selenium atom, R ^A1 , R ^A2 and R ^A3 are Each independently represents an alkyl group, aryl group, alkoxy group, alkylthio group or halogen atom, m1, m2 and m3 each independently represent an integer of 0 or more).

In the formula (III-1), the ring E ¹ may be a benzene ring, a naphthalene ring, a pyridine ring, a pyridazine ring, an isoquinoline ring, a phthalazine ring or a quinoxaline ring, and Z ¹ is an oxygen atom or a sulfur atom. R ^A1 may be an alkyl group, an alkoxy group or a halogen atom, and m1 may be an integer of about 0-2.

  The organic polymer may be a block copolymer or an alternating copolymer of the donor unit (D) and the acceptor unit (A). The donor unit (D) may include a unit having at least one substituent selected from a linear or branched alkyl group and a linear or branched alkoxy group, The sex unit (A) may include a unit having no linear or branched alkyl group and no linear or branched alkoxy group.

  The present invention also includes a method for producing the organic polymer by subjecting a compound containing the donor unit (D) and a compound containing the acceptor unit (A) to a coupling reaction. The coupling reaction may be a Suzuki coupling reaction, and the reaction may be performed under microwave irradiation.

  In addition, the present invention provides an organic semiconductor containing the organic polymer (for example, in addition to the organic polymer, further includes a substrate, the organic polymer is edge-on orientation or face-on orientation with respect to the substrate A composition comprising the organic polymer and a solvent; a method of applying the composition to a substrate and removing the solvent to produce the organic semiconductor; and the organic semiconductor. Electronic devices including semiconductors are also included.

Since the novel organic polymer of the present invention combines a donor unit (D) containing a predetermined zigzag unit and an acceptor unit (A), the orientation between molecules is improved to achieve high mobility. it can. Further, even when the film is formed by a simple film forming method such as a spin coating method, the film can be oriented with high orientation (molecular orientation or crystallinity) [or low π stack distance d _π ]. Further, it is possible to achieve both high orientation and high solubility in an organic solvent, which are contradictory characteristics. According to the method of the present invention, the organic polymer can be easily or efficiently produced.

FIG. 1 is a diagram showing a relationship between a two-dimensional diffraction image in a thin film X-ray analysis of a film formed by spin-coating the compound obtained in Example 1 and an annealing temperature, and FIG. A two-dimensional diffraction image at 100 ° C., (b) a two-dimensional diffraction image at an annealing temperature of 150 ° C., (c) a two-dimensional diffraction image at an annealing temperature of 200 ° C., and (d) a two-dimensional diffraction image at an annealing temperature of 240 ° C. It is a two-dimensional diffraction image. FIG. 2 is a diagram showing a relationship between a two-dimensional diffraction image in a thin film X-ray analysis of a film obtained by forming the compound obtained in Comparative Example 1 and a film forming method, and FIG. 2B is a two-dimensional diffraction image when the film is formed, and FIG. FIG. 3 is a schematic diagram of an element for measuring transistor characteristics.

  The organic polymer (semiconductor polymer or π-conjugated polymer) of the present invention has a donor (electron-donating or electron-rich) unit (D) and an acceptor (electron-accepting, electron-deficient or electron-deficient) unit. A) a donor / acceptor type polymer (or DA type polymer) having a unit (A);

[Donor unit (D)]
The donor unit (D) contains at least a first donor unit (or zigzag unit) (D1) represented by the following formula (I).

(Wherein, ring A and ring B each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle, n represents 0 or an integer of 1 to 6, and R ^{1 to} R ^{2 + n} each independently represent A ^{1 to} a ^{2 + n} each independently represent an integer of 0 to 2; and ring C is arranged in a non-linear sequence with respect to an adjacent benzene ring in accordance with the number of n. A benzene ring ortho-condensed in the same manner).

In the formula (I), Ring A and Ring B each independently represent an aromatic hydrocarbon ring (arene ring) or an aromatic heterocycle (heteroarene ring). Examples of the aromatic hydrocarbon ring, a benzene ring; fused bicyclic or tetracyclic C _10-20 arene ring, for example, bicyclic C _10-16 arene ring such as a naphthalene ring; tricyclic arene ring (e.g., anthracene, Condensed tricyclic _C12-16 arene ring such as phenanthrene). Preferred aromatic hydrocarbon rings are benzene rings, naphthalene rings, especially benzene rings.

  The aromatic heterocyclic ring includes a single ring or a condensed ring having at least one hetero atom as a ring constituent atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, a selenium atom, a phosphorus atom, a silicon atom, a titanium atom, a zinc atom, and a germanium atom. The aromatic heterocycle may have multiple heteroatoms, for example, the same or different heteroatoms. Preferred heteroatoms may be heteroatoms selected from oxygen, sulfur, nitrogen and selenium, preferably oxygen, sulfur and especially oxygen. The heterocycle having a hetero atom may be a 3- to 10-membered ring, and is usually a 5- or 6-membered ring. Such a heterocycle includes an arene ring such as a benzene ring (for example, the above-mentioned arene ring and the like). ) May be condensed.

  Preferred aromatic heterocycles may be a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring and the like.

  The ring A and the ring B are usually an aromatic heterocycle (preferably a furan ring, a thiophene ring, particularly a thiophene ring) in many cases. The types of the ring A and the ring B may be different from each other, but are usually the same in many cases. When the types of the ring A and the ring B are the same, the condensed position of the adjacent benzene ring in the ring A and the ring B may be different from each other, but usually the same.

  n represents 0 or an integer of 1 to 6, usually 0 or 1 to 5 (for example, 0 or 1 to 4), and preferably about 1 to 3 (for example, 2 or 3). Further, the benzene ring represented by ring C is ortho-condensed to the adjacent benzene ring in a non-linear (preferably zigzag) manner sequentially according to the number of n. One or more ring C (benzene ring) is different from an anthracene ring, a naphthacene ring, a pentacene ring or the like which is ortho-condensed linearly, and is ortho-condensed non-linearly in a major axis direction to benzene rings adjacent to each other. And it may be ortho-condensed in a W-type or U-type form that may be moderate, such as a dibenzo [a, j] anthracene ring or a pentaphene ring, Benzene ring may share a 1,2-position carbon atom and a 3,4-position carbon atom and may be ortho-condensed in a zigzag form. The preferred form of ortho-condensation is a zigzag form. That is, a phenanthrene ring is interposed between the ring A and the ring B in the compound of n = 1, a chrysene ring is interposed in the compound of n = 2, and a picene ring is interposed in the compound of n = 3. The form is preferred.

Representative examples of the substituent represented by R ^{1 to} R ^{2 + n} include, for example, a halogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heterocyclic group, and a hydroxyl group. , Alkoxy, alkylthio, haloalkoxy, haloalkylthio, cycloalkyloxy, cycloalkylthio, aryloxy, arylthio, carboxyl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, sulfonyl , An alkylsulfonyl group, a haloalkylsulfonyl group, an amino group, an N-substituted amino group, an acyl group, an acyloxy group, an amide group, a nitro group, a cyano group, a silyl group, an alkylsilyl group, and an alkylsilylethynyl group.

Examples of the halogen atom represented by R ^{1 to} R ^{2 + n} include a fluorine, chlorine, bromine or iodine atom. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, i-butyl, s-butyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, and n. -Octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, 3-hexyltetradecyl, 3-octyltridecyl, 5-decylheptadecyl, and the like. Examples thereof include a chain or branched C _1-36 alkyl group. The alkyl group may usually be a linear or branched _C4-34 alkyl group, and in order to increase the solubility in an organic solvent, a long-chain alkyl group, for example, a linear or branched Advantageously, it is a _C6-32 alkyl group, preferably a straight-chain or branched-chain _C6-30 alkyl group (e.g. a straight-chain or branched-chain _C8-28 alkyl group). For imparting high solubility, branched alkyl groups are advantageous.

Examples of the haloalkyl group include halogen atoms such as chloromethyl group, trichloromethyl group, trifluoromethyl group, pentafluoroethyl group, perchloroethyl group, perfluoroisopropyl group, and perfluorobutyl group (fluorine, chlorine, bromine atom, etc.). And the like, and a linear or branched C _1-36 alkyl group (e.g., a halo C _1-12 alkyl group, preferably a halo C _1-6 alkyl group).

The alkyl group and / or the haloalkyl group may have a substituent. Examples of such a substituent include an alkoxy group (eg, a C _1-10 alkoxy group such as a methoxy group and an ethoxy group).

Examples of the alkenyl group include, for example, a C _2-30 alkenyl group such as a vinyl group, an allyl group, a 2-butenyl group, and a 4-pentenyl group. Usually, a linear or branched C _3-18 alkenyl group is exemplified. For example, it may be a linear or branched C _4-16 alkenyl group. The alkynyl groups include an ethynyl group, 2-propynyl group, 1-like _{C 2-30} alkynyl groups such as pentynyl group. Examples typically linear or branched _{C 3-18} alkynyl group, for example, It may be a linear or branched C _4-16 alkynyl group.

Examples of the cycloalkyl group include a C _3-10 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the aryl group include a C _6-12 aryl group such as a phenyl group and a naphthyl group, and a bi C _6-12 aryl group such as a biphenyl group. Examples of the aralkyl group include a C _6-12 aryl-C _1-4 alkyl group such as a benzyl group and a phenylethyl group (phenethyl group).

  As the heterocycle corresponding to the heterocyclic group, an aromatic heterocycle, for example, pyridine, pyrazine, quinoline, naphthyridine, quinoxaline, phenazine, phenanthroline, nitrogen-containing heterocycle such as carbazole, furan, oxygen-containing heterocycle such as benzofuran, Examples thereof include a sulfur-containing heterocycle such as thiophene, benzothiophene, dibenzothiophene, and thienothiophene; a selenium-containing heterocycle such as selenophene and benzoselenophene; and a heterocycle having a plurality of heteroatoms such as thiazole and benzothiazole.

Examples of the alkoxy group include a linear or branched C _1-32 alkoxy group corresponding to the alkyl group, for example, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a hexadecyloxy group, and a 3-octyltri group. Examples thereof include a decyloxy group and a 5-decylheptadecyloxy group. The alkoxy group may usually be a linear or branched C _4-36 alkoxy group (for example, a linear or branched C _4-34 alkoxy group), and may be a long-chain alkoxy group, for example, Even a linear or branched C _6-32 alkoxy group, preferably a linear or branched C _6-30 alkoxy group (for example, a linear or branched C _8-28 alkoxy group). Good. Examples of the alkylthio group include a linear or branched _C4-36 alkylthio group corresponding to the above alkoxy group. In order to enhance solubility in an organic solvent, an alkoxy group (for example, a long-chain alkoxy group) and an alkylthio group (for example, a long-chain alkylthio group) are also useful.

Examples of the haloalkoxy group include a haloalkoxy group corresponding to the haloalkyl group, for example, a halogen atom such as a chloromethoxy group, a trichloromethoxy group, a trifluoromethoxy group, a trifluoroethoxy group, a perfluoroisopropoxy group, and a perfluorobutoxy group. Examples thereof include a linear or branched C _1-36 alkoxy group (for example, a halo C _1-12 alkoxy group, preferably a halo C _1-6 alkoxy group) having (for example, a fluorine, chlorine, or bromine atom). Examples of the haloalkylthio group include a haloalkylthio group corresponding to the haloalkoxy group.

Examples of the cycloalkyloxy group include, for example, a C _3-10 cycloalkyloxy group such as a cyclopentyloxy group, a cyclohexyloxy group, and a cyclooctyloxy group, and the cycloalkylthio group corresponds to the cycloalkyloxy group. A C _3-10 cycloalkylthio group can be exemplified.

Examples of the aryloxy group include a C _6-12 aryloxy group such as a phenoxy group and a naphthoxy group, and examples of the arylthio group include a C _6-12 arylthio group corresponding to the aryloxy group.

Examples of the alkoxycarbonyl group include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a t-butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, and a 3-octyltridecyloxycarbonyl group. And a linear or branched C _1-36 alkoxy-carbonyl group such as a 5-decylheptadecyloxycarbonyl group.

Examples of the cycloalkoxycarbonyl group include a C _3-10 cycloalkyloxy-carbonyl group such as a cyclohexyloxycarbonyl group, and examples of the aryloxycarbonyl group include a C _6-12 aryloxy group such as a phenoxycarbonyl group. -Carbonyl group and the like. Examples of the alkylsulfonyl group include a linear or branched C _1-4 alkylsulfonyl group such as a methylsulfonyl group, and examples of the haloalkylsulfonyl group include a chloromethylsulfonyl group and a trifluoromethylsulfonyl group. And a straight-chain or branched-chain haloC _1-4 alkylsulfonyl group.

Examples of the N-substituted amino group include N-mono C _1-6 alkylamino groups such as N-methylamino group and N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, And N, N-diC _1-6 alkylamino groups such as N, N-dibutylamino group.

Examples of the acyl group include a _C1-30 alkyl-carbonyl group such as an acetyl group and a propionyl group, and a _C6-10 aryl-carbonyl group such as a benzoyl group. Examples of the acyloxy group include a C _1-30 alkyl-carbonyloxy group such as an acetyloxy group and a propionyloxy group, and a C _6-10 aryl-carbonyloxy group such as a benzoyloxy group.

The alkyl silyl group, for example, mono- to tri-C _1-4 alkylsilyl group such as trimethylsilyl group. Examples of the alkyl silyl ethynyl group, for example, mono- to tri-C _1-4 alkylsilyl such as trimethylsilyl ethynyl group An ethynyl group can be exemplified.

The substituents R ^{1 to} R ^{2 + n} may be, for example, an electron-accepting group such as a halogen atom, a cyano group, a haloalkyl group, a haloalkoxyl group, and a haloalkylsulfonyl group, but improve the donor property (electron-donating property). From the point of view, an embodiment in which the substituents R ^{1 to} R ^{2 + n} are replaced with an electron-donating group such as an alkyl group, an alkoxy group, an N-substituted amino group, or a hydrogen atom instead of the substituents R ^{1 to} R ^{2 + n} (that is, the coefficient a ^{1 to} a ^{2 + n} are preferably 0 or 1).

The types of these substituents R ^{1 to} R ^{2 + n} may be the same or different, may be different depending on the position of a benzene ring interposed between ring A and ring B, or may be the same. Among these substituents, in order to increase the solubility in an organic solvent, the above-mentioned alkyl group (linear or branched long-chain alkyl group), alkoxy group (linear or branched long-chain alkoxy group) Particularly, an alkyl group is preferable. In addition, an aryl group may contribute to carrier mobility.

The alkyl group is preferably a branched alkyl group from the viewpoint of improving solubility, and more preferably a branched C _10-40 alkyl group (for example, a branched C _16-34 alkyl group). group), more preferably a branched chain _{C 18-30} alkyl group (e.g., 3-octyl - tridecyl group, 5-decyl - branched _{C 20-28} alkyl groups such as heptadecyl), particularly branched-chain _{C 21 -26} alkyl group (e.g., 4-octyl - tetradecyl, 5-octyl - branched _{C 22-24} alkyl groups such as pentadecyl, especially 4-octyl - branched _{C 22} alkyl group such as tetradecyl group) preferable.

The branched structure of the branched alkyl group is not particularly limited, but is usually a branched alkyl group having one branch point in many cases. The position of the branch point in the branched alkyl group is not particularly limited. However, from the viewpoint of excellent balance between solubility and orientation and easy compatibility between high moldability and mobility, the positions of the 2- to 8-positions (for example, 2 It is preferable to have a branch point at (〜 to 6-position), more preferably 3 to 5-position, especially 4-position. Further, in the branched alkyl group having one branch point, it is preferable that the carbon numbers of the two linear alkyl groups extending from the branch point to the terminal are substantially the same, and in the two linear alkyl groups, The difference in the number of carbon atoms may be, for example, about 0 to 6, preferably about 0 to 4, and more preferably about 0 to 2. Specific examples of the two linear alkyl groups include a linear C _6-16 alkyl group, preferably a linear C _7-14 alkyl group, and more preferably a linear C ₈ alkyl group such as a dodecyl group. _It may be a _-12 alkyl group (especially, a linear C _8-10 alkyl group such as an octyl group and a decyl group).

The coefficients a ^{1 to} a ^{2 + n} each independently represent an integer of 0 to 2, and are usually 0 or 1 in many cases. Further, all of a ^{1 to} a ^{2 + n} may be simultaneously “0” (that is, unsubstituted), but usually, at least one of a ^{1 to} a ^{2 + n} is 1 or 2, that is, a ^{1 to} a ^{2 + n.} Are not all “0” at the same time, and often have at least one of the substituents R ^{1 to} R ^{2 + n} . Depending on the values of the coefficients a ^{1 to} a ^{2 + n} , the types of the substituents R ^{1 to} R ^{2 + n} may be the same or different. For example, the substituents on the same benzene ring may be the same or different, and the substituents on different benzene rings may be the same or different.

The substituent may be substituted on any benzene ring interposed between ring A and ring B. The substitution position of the substituents R ^{1 to} R ^{2 + n} with respect to a predetermined benzene ring interposed between the ring A and the ring B is not particularly limited. The substituent is a benzene ring adjacent to the ring A and a benzene ring adjacent to the ring B (the benzene rings located at both ends of the condensed benzene ring excluding the rings A and B in the formula (I)). Often have.

  The specific donor unit (D1) represented by the formula (I) is, for example, a unit represented by at least one of the following formulas (I-1) to (I-5). Is also good.

(Wherein, ring A and ring B are the same as described above, and R ^{1 to} R ⁶ and a ^{1 to} a ⁶ are the same as those of R ^{1 to} R ^{2 + n} and a ^{1 to} a ^{2 + n} (where n is an integer of 0 to 4)) Correspondingly the same).

R ^{1 to} R ⁶ are each independently often an alkyl group, an aryl group, an alkoxy group, or an alkylthio group (particularly, an alkyl group or an alkoxy group), and a ^{1 to} a ⁶ are each independently It is often 0 or 1.

  The donor unit (D1) may be contained alone or in combination of two or more. A polymer having such a donor unit (D1) has high carrier mobility and is useful as an organic semiconductor. Among these donor units (D1), from the viewpoints of carrier mobility, productivity (or moldability), etc., a unit represented by the above formula (I-2) having a phenanthrene ring and a chrysene ring are usually provided. The unit represented by the formula (I-3), the unit represented by the formula (I-4) having a picene ring, and the like are commonly used. The unit represented by the formula (I-3) is useful. Typically, for example, it may be a unit represented by the following formula (I-3).

(In the formula, at least one of R ^{1 to} R ⁴ is a linear or branched C _4-34 alkyl group or a linear or branched C _4-34 alkoxy group, and a ^{1 to} a ⁴ are Each independently represents 0 or 1, at least one of a ^{1 to} a ⁴ is 1, and ring A and ring B are the same as described above).

  Furthermore, specific examples of the unit represented by the formula (I-3) having a chrysene ring include units represented by the following formulas (I-3a) to (I-3i).

(In the formula, ^Ra represents a hydrogen atom, an alkyl group or an acyl group, and R ^{1 to} R ⁴ and a ^{1 to} a ⁴ are the same as described above.).

Examples of the alkyl group represented by ^Ra include a linear or branched C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Examples of the acyl group include a linear or branched C _1-4 alkyl-carbonyl group such as an acetyl group and a propionyl group.

In the formulas (I-3) and (I-3a) to (I-3i), at least one of R ^{1 to} R ⁴ is a long-chain alkyl group (for example, a linear or branched C _{4 -32} alkyl group) and / or a long-chain alkoxy group (for example, a linear or branched C _4-32 alkoxy group), and a ^{1 to} a ⁴ each independently represent 0 or 1 are ^shown, at least one of a 1 ~a ⁴ is a 1 ^(i.e., does not a 1 ~a ⁴ is 0 at the same time) often. Such a long-chain alkyl group and / or long-chain alkoxy group is often substituted on a benzene ring adjacent to the ring A and the ring B. That ^is, of a 1 ~a ^4, often ^{a 1} and ^{a 4} are 1.

  Representative units of the unit represented by the formula (I-3) include, for example, the following formulas (I-3a1), (I-3b1), (I-3c1) or (I-3d1) [preferably the formula (I-3d1)] (I-3c1) or (I-3d1)].

(Wherein, R ¹ and R ⁴ represent a linear or branched C _6-30 alkyl group or a linear or branched C _6-30 alkoxy group).

  The first donor unit (D1) may be used alone or in combination of two or more. That is, the first donor unit (D1) belongs to the category represented by the formula (I) and may include a plurality of units of different types. For example, the first unit (D1) has a coefficient n (number of benzene rings). A plurality of units selected from different units [for example, a unit represented by the formula (I-2), a unit represented by the formula (I-3), a unit represented by the formula (I-5), and the like] It may include a unit having a different vertical arrangement (for example, a unit represented by the formula (I-3a1) and a unit represented by the formula (I-3b1)).

The donor unit (D) includes, in addition to the first donor unit (D1) represented by the formula (I), another unit having a donor property (second donor unit) (D2). May be. As the second donor unit (D2), for example, a substituent such as a thiophene unit, a dibenzothiophene unit, or a benzodithiophene unit [for example, a group exemplified as the substituents R ^{1 to} R ^{2 + n} in the formula (I); Similar substituents] may be used. These donor units may be contained alone or in combination of two or more. Among the second donor units (D2), a donor unit represented by the following formula (II-1) is generally used.

(In the formula, R ^D1 represents a substituent, and k represents an integer of 0 to 2.)

In the formula (II-1), examples of the substituent R ^D1 include the same substituents as the substituents R ^{1 to} R ^{2 + n} in the formula (I), including preferred embodiments. Usually, an alkyl group or an alkoxy group (for example, , A linear or branched long-chain alkyl group, or a linear or branched long-chain alkoxy group) in many cases.

  The coefficient k is often 0 or 1.

  The ratio of the donor unit (D1) represented by the formula (I) is selected from the range of, for example, about 10 to 100 mol% (for example, 30 to 100 mol%) based on the entire donor unit (D). In order to increase the carrier mobility, for example, 50 to 100 mol%, preferably 60 to 100 mol% (for example, 70 to 99 mol%), more preferably 80 to 100 mol% (for example, 85 to 95 mol%) Mol%), in particular, about 90 to 100 mol% (for example, 95 to 100 mol%, preferably substantially 100 mol%).

[Acceptor unit (A)]
The acceptor unit (A) is not particularly limited as long as it is a structural unit having an acceptor property (electron accepting property, electron deficiency or electron deficiency), and a conventional acceptor unit can be used. As a typical acceptor unit (A), for example, a unit (A1) having an aromatic heterocyclic skeleton containing a nitrogen atom and a Group 16 (or Group 6B) atom of the periodic table [First acceptor unit (A1) Also referred to].

  The first acceptor unit (A1) is not particularly limited as long as it has a nitrogen atom and an aromatic heterocyclic skeleton containing a Group 16 atom of the periodic table. Examples of Group 16 atoms in the periodic table include an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, and a polonium atom (preferably an oxygen atom, a sulfur atom or a selenium atom, more preferably an oxygen atom or a sulfur atom, particularly a sulfur atom ).

  The aromatic heterocyclic skeleton contained in the first acceptor unit (A1) usually has a 5- or 6-membered heterocyclic ring (preferably a 5-membered heterocyclic ring) containing a nitrogen atom and an atom of Group 16 of the periodic table (or an internal ring thereof). S) is often a skeleton. That is, the aromatic heterocyclic skeleton may be the 5- or 6-membered heterocyclic skeleton, but may include a plurality of aromatic rings (the arene ring) including the 5- or 6-membered heterocyclic ring (particularly, the 5-membered heterocyclic ring). And / or heteroarene ring) may be a fused and / or fused ring (or linked by a single bond) polycyclic heterocyclic skeleton (in particular, a fused polycyclic heterocyclic skeleton in which the plurality of rings are fused). Good.

  Typical first acceptor units (A1) include units represented by the following formulas (III-1) to (III-5).

(Wherein, rings E ¹ and E ² are each independently an aromatic ring, Z ^{1 to} Z ⁵ are each independently a Group 16 atom of the periodic table, R ^A1 , R ^A2 and R ^A3 are each independently And the substituents, m1, m2 and m3 each independently represent an integer of 0 or more).

In formula (III-1), as the periodic table Group 16 atoms represented by Z ^1, for example, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, such as polonium atom. Preferred atoms Z ^1, an oxygen atom, a sulfur atom or a selenium atom, among others oxygen or sulfur atom (in particular, a sulfur atom) are particularly preferred.

The aromatic ring represented by E ¹ is not particularly limited as long as it can be condensed with a 5-membered heterocyclic ring containing atom Z ¹ and two nitrogen atoms, ie, as long as it has two carbon atoms adjacent to each other. It may be a hydrogen ring (arene ring) or an aromatic heterocycle (heteroarene ring).

As the aromatic hydrocarbon ring (arene ring), for example, a monocyclic arene ring such as a benzene ring; a condensed polycyclic arene ring [for example, an indene ring, an indane ring, a naphthalene ring, a tetralin ring, an azulene ring, an indacene ring] , Acenaphthylene ring, biphenylene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, fluoranthene ring, aceanthrylene ring, acephenanthrylene ring, naphthacene ring, chrysene ring, pyrene ring, triphenylene ring, pentacene ring, pentaphene ring And a C _9-30 fused polycyclic arene ring such as a picene ring and a perylene ring]. Preferred aromatic hydrocarbon rings include a C _6-22 arene ring (eg, a C _6-18 arene ring), and more preferably a C _6-14 arene ring (eg, a C _6-10 arene such as a benzene ring or a naphthalene ring) Ring), especially a benzene ring.

Examples of the aromatic heterocyclic ring (heteroarene ring) include, for example, a monocyclic heteroarene ring [for example, a nitrogen (N) -containing monocyclic heteroarene ring (for example, a pyrrole ring, an imidazole ring, a pyrazole ring, Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, etc.); oxygen (O) -containing monocyclic heteroarene ring (eg, furan ring, pyran ring, etc.); sulfur (S) -containing monocyclic heteroarene ring (eg, A monocyclic heteroarene ring containing two or more heteroatoms (eg, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a thiazine ring, a thiadiazine ring, etc.); C _2-5 monocyclic heteroarene ring, etc.]; polycyclic heterolane ring [eg, nitrogen (N) -containing polycyclic heteroarene ring (eg, indolizine ring, i Indole ring, 3H-indole ring, isoindole ring, 1H-indazole ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, carbazole ring, 4aH A carbazole ring, a β-carboline ring, an acridine ring, a phenanthridine ring, a phenazine ring, a phenanthroline ring, a perimidine ring, etc.); an oxygen (O) -containing polycyclic heteroarene ring (eg, benzofuran ring, isobenzofuran ring, chromene Ring, chroman ring, isochroman ring, xanthene ring, etc.); sulfur (S) -containing polycyclic heteroarene ring (eg, benzothiophene ring, thienothiophene ring, thianthrene ring, etc.); Cyclic heteroarene ring (eg, Enofuran ring, phenoxazine ring, a phenothiazine ring, phenoxathiin ring, such as C _6-20 polycyclic heteroarene ring such as phenarsazine ring)] and the like. Preferred heteroarene rings include a C _2-13 heteroarene ring (eg, a nitrogen (N) -containing monocyclic or polycyclic C _2-13 heteroarene ring and the like), and more preferably a C _3-9 heteroarene ring ( In particular, it may be a nitrogen (N) -containing monocyclic or bicyclic _C3-9 heteroarene ring such as a pyridine ring, a pyridazine ring, an isoquinoline ring, a phthalazine ring, and a quinoxaline ring).

Preferred ring E ¹ includes a C _6-14 arene ring, a nitrogen (N) -containing C _3-10 heteroarene ring and the like, and among them, a C _6-10 arene ring, a nitrogen (N) -containing monocyclic or A bicyclic C _4-8 heteroarene ring (particularly a C _6-10 arene ring such as a benzene ring) is preferred. More specifically, the ring E ¹ is a benzene ring, a naphthalene ring, a pyridine ring, a pyridazine ring, an isoquinoline ring, a phthalazine ring, aromatic ring selected from a quinoxaline ring (particularly, benzene ring) is preferably.

Incidentally, the aromatic ring represented by E ^1, condensation position between 5 membered heterocyclic ring containing atoms Z ¹ and two nitrogen atoms is not particularly limited.

Examples of the substituent represented by R ^A1 include the same groups as the groups exemplified as R ^{1 to} R ^{2 + n} in the formula (I). Preferred examples of the substituent R ^A1 include an alkyl group, an aryl group, an alkoxy group, an alkylthio group, and a halogen atom. Among them, a long-chain alkyl group (for example, a linear or branched C _6-36 alkyl group) And the like, a long-chain alkoxy group (for example, a linear or branched C _6-36 alkoxy group), and a halogen atom are preferable, and a halogen atom (particularly, a fluorine atom) is preferable.

Coefficients m1 can be appropriately selected depending on the kind of ring ^{E 1,} for example, an integer of 0 to 4 (e.g., an integer of 0 to 3), preferably an integer of 0 to 2 (e.g., 0 or 1), more preferably May be 0. When m1 is 2 or more, the types of the two or more substituents ^RA1 may be the same or different from each other.

  Representative examples of the unit represented by the formula (III-1) include units represented by the following formulas (III-1a) to (III-1g).

(Wherein Z ¹ , R ^A1 and m1 are the same as described above, including preferred embodiments).

  The acceptor unit (A) may contain the units represented by the formulas (III-1a) to (III-1g) alone or in combination of two or more. Among the units represented by the formulas (III-1a) to (III-1g), the units represented by the formulas (III-1a) and (III-1b) [particularly the units represented by the formula (III-1a)] are preferable. .

In formula (III-2), the periodic table Group 16 atom represented by Z ² include the same atoms including Z ¹ and preferred embodiments of the formula (III-1). Also, two atoms Z ² may be the same or different from each other, usually, it is often the same.

The aromatic ring represented by E ² can be condensed at two places with a 5-membered heterocyclic ring containing the atom Z ² and two nitrogen atoms, that is, as long as it has two or more pairs of two carbon atoms adjacent to each other. It is not limited, and may be an aromatic hydrocarbon ring (arene ring) or an aromatic heterocyclic ring (heteroarene ring).

As the aromatic hydrocarbon ring (arene ring), for example, a monocyclic arene ring such as a benzene ring; a condensed polycyclic arene ring [for example, an indene ring, an indane ring, a naphthalene ring, a tetralin ring, an azulene ring, an indacene ring] , Acenaphthylene ring, biphenylene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, fluoranthene ring, aceanthrylene ring, acephenanthrylene ring, naphthacene ring, chrysene ring, pyrene ring, triphenylene ring, pentacene ring, pentaphene ring And a C _9-30 fused polycyclic arene ring such as a picene ring and a perylene ring]. Preferred aromatic hydrocarbon rings include a C _6-22 arene ring (eg, a C _6-18 arene ring), and more preferably a C _6-14 arene ring (eg, a C _6-10 arene such as a benzene ring or a naphthalene ring) Ring, etc.), especially a naphthalene ring.

As the aromatic heterocycle (heteroarene ring), for example, a polycyclic heterolane ring [eg, a nitrogen (N) -containing polycyclic heteroarene ring (eg, an indolizine ring, an indole ring, a 3H-indole ring, an isoindole) Ring, 1H-indazole ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, 4aH-carbazole ring, β-carboline ring, acridine ring, Anthridine ring, phenazine ring, phenanthroline ring, perimidine ring, etc.); oxygen (O) -containing polycyclic heteroarene ring (eg, benzofuran ring, isobenzofuran ring, chromene ring, chroman ring, isochroman ring, xanthene ring); Sulfur (S) -containing polycyclic heteroarene ring (eg If, benzothiophene ring, etc. thianthrene ring); polycyclic heteroarene ring containing two or more hetero atoms (e.g., a phenoxazine ring, a phenothiazine ring, phenoxathiin ring, C such as phenarsazine ring) _{6- 20} polycyclic heteroarene rings, etc.]. A preferred heteroarene ring may be a C _6-13 heteroarene ring (eg, a nitrogen (N) -containing monocyclic or polycyclic C _6-13 heteroarene ring).

Preferred examples of the ring E ² include a C _6-14 arene ring and the like, and among them, a C _6-10 arene ring such as a benzene ring and a naphthalene ring (particularly a naphthalene ring) is preferable.

Incidentally, the aromatic ring represented by E ^2, the condensation position of the 5-membered heterocyclic ring containing atoms Z ² and the two nitrogen atoms is not particularly limited.

Examples of the substituent represented by R ^A2, for example, the same groups as exemplified as ^R 1 ^{~R 2 + n} in the formula (I). Preferred substituents ^RA2 include an alkyl group, an aryl group, an alkoxy group, an alkylthio group, a halogen atom and the like, and among them, a long-chain alkyl group (for example, a linear or branched _C6-36 alkyl group) And the like, a long-chain alkoxy group (for example, a linear or branched C _6-36 alkoxy group), and a halogen atom are preferable, and a halogen atom (particularly, a fluorine atom) is preferable.

Factor m2 can be appropriately selected depending on the kind of ring ^{E 2,} for example, an integer of 0 to 4 (e.g., an integer of 0 to 3), preferably an integer of 0 to 2 (e.g., 0 or 1), more preferably May be 0. When m2 is 2 or more, the types of the two or more substituents ^RA2 may be the same or different from each other.

  Typical examples of the unit represented by the formula (III-2) include a unit represented by the following formula (III-2a).

(Wherein, m2a represents 0 or 1, ^{Z 2} and ^{R A2} are as defined above, including the preferred embodiments, respectively).

  In the formula (III-2a), m2a is preferably 0. Further, the two m2a may be the same or different from each other.

In formula (III-3), the periodic table Group 16 atom represented by Z ³ include the same atoms including Z ¹ and preferred embodiments of the formula (III-1).

In formula (III-4), periodic table Group 16 atom represented by Z ⁴ include the same atoms including Z ¹ and preferred embodiments of the formula (III-1). Also, two atoms Z ⁴ may be the same or different from each other, usually, it is often the same.

In formula (III-5), the periodic table Group 16 atom represented by Z ⁵ include the same atoms including Z ¹ and preferred embodiments of the formula (III-1). Also, two atoms Z ⁵ may be the same or different from each other, usually, it is often the same.

Examples of the substituent represented by R ^A3, for example, the same groups as exemplified as ^R 1 ^{~R 2 + n} in the formula (I). Preferred substituents ^RA3 include an alkyl group, an aryl group, an alkoxy group, an alkylthio group, a halogen atom and the like, and among them, a long-chain alkyl group (for example, a linear or branched _C6-36 alkyl group) And a long-chain alkoxy group (eg, a linear or branched C _6-36 alkoxy group).

The coefficient m3 is 0 or 1, preferably 0. Two m3's may be the same or different from each other. When both m3 are 1, the types of the two substituents ^RA3 may be the same or different from each other.

  These first acceptor units (A1) may be used alone or in combination of two or more. Among these first acceptor units (A1), a unit represented by the formula (III-1) is preferable, and a unit represented by the formula (III-1a) is particularly preferable.

The acceptor unit (A) does not necessarily need to include the first acceptor unit (A1), and may include another acceptor unit (also referred to as a second acceptor unit (A2)). . The second acceptor unit (A2) may have, for example, a substituent [for example, the same substituent as the group exemplified as the substituents R ^{1 to} R ^{2 + n} in the formula (I)]. Examples include units having an aromatic hydrocarbon ring skeleton in which at least a 5-membered carbon ring is fused, such as a cyclopenta [h, i] aceanthrylene unit (a unit represented by the following formula).

  The acceptor unit (A) may be formed of a single unit or a combination of two or more units, and at least one selected from a first acceptor unit (A1) and a second acceptor unit (A2) (In particular, the first acceptor unit (A1)).

  The ratio of the first acceptor unit (A1) [particularly, the unit represented by the formula (III-1) such as the formula (III-1a)] is, for example, based on the entire acceptor unit (A). , 10 to 100 mol% (for example, 30 to 100 mol%). In order to increase carrier mobility, for example, 50 to 100 mol%, preferably 60 to 100 mol% (for example, 70 to 100 mol%) To 99 mol%), more preferably about 80 to 100 mol% (for example, 85 to 95 mol%), particularly about 90 to 100 mol% (for example, 95 to 100 mol%, preferably substantially 100 mol%). It may be.

  As long as the effects of the invention are not impaired, the organic polymer of the present invention may contain other conjugated units and / or non-conjugated units that do not belong to the donor unit (D) and the acceptor unit (A) (for example, alkylene units). Unit etc.). The ratio of such a unit is, for example, 10 mol% or less (for example, 0 to 5 mol%), preferably 1 mol% or less (for example, 0.01 to 0.1 mol%), based on the entire constitutional unit of the organic polymer. (Approximately 1 mol%), and is preferably substantially not contained.

  The organic polymer of the present invention is a copolymer containing at least a donor unit (D) (also simply referred to as a D unit) and an acceptor unit (A) (also simply referred to as an A unit). And a random copolymer of A units, but from the viewpoint that orientation (or crystallinity) is easily improved by intermolecular interaction, a form in which each unit is regularly arranged (or having a repeating unit) Form), and usually, preferably an alternating copolymer or a block copolymer (a copolymer represented by the following formula (1)).

[-(D) _q- (A) _r- ] _p (1)
(Wherein (D) is a D unit, (A) is an A unit, the number of repetitions p is an integer of 2 or more, and the numbers of repetitions q and r each independently represent an integer of 1 or more, and the same applies hereinafter).

  The alternating copolymer may be any copolymer as long as D units and A units are alternately arranged, and in the formula (1), q and r are both 1. In the alternating copolymer, a plurality of repeating D units and A units may include a plurality of types of units, but from the viewpoint of improving intermolecular interaction, both are usually formed of a single unit. (For example, the following formula (i)).

[-(D1)-(A1)-] _p (i)
(In the formula, (D1) represents the first donor unit (D1), (A1) represents the first acceptor unit (A1) (the same applies hereinafter, and the repetition number p is the same as described above).

  In the block copolymer, at least one of the D unit and the A unit may be bonded or connected to each other to form a block, and in the formula (1), at least one of q and r may be repeated. It is a copolymer having a number of 2 or more. As a typical organic polymer of the block copolymer, for example, a block copolymer represented by the following formula (ii) or (iii) may be used.

[-(D1) _q1- (A1) _r1- ] _p (ii)
(In the formula, the numbers of repetitions q1 and r1 each independently represent an integer of 1 or more, at least one of q1 and r1 is 2 or more, and (D1), (A1) and p are the same as above.)

[-((D2) _q2- (D1) _q1- (D2) _q2 )-(A1) _r1- ] _p (iii)
(Wherein (D2) is the second donor unit (D2), the numbers of repetitions q1, q2 and r1 each independently represent an integer of 1 or more, and (D1), (A1) and p are the same as above. ).

  Among these copolymers, from the viewpoint of improving the intermolecular interaction, the organic polymer is preferably an alternating copolymer (particularly, a copolymer represented by the formula (i)).

  Since the organic polymer of the present invention is a DA polymer and has high orientation (or crystallinity) due to intermolecular interaction, the solubility, which is a contradictory property, tends to decrease. Therefore, from the viewpoint of achieving a good balance between high orientation and high solubility, the organic polymer is selected from linear or branched long-chain alkyl groups, and linear or branched long-chain alkoxy groups. It preferably contains a unit having at least one substituent. In the present specification and claims, unless otherwise specified, the term “long chain” means that the number of carbon atoms forming a substituent is, for example, 4 or more (eg, 6 to 50), preferably 8 or more ( For example, 10 to 46), more preferably 12 or more (for example, 16 to 40), particularly 18 or more (for example, about 22 to 32).

  Such a substituent may be substituted on at least one (particularly, any one) unit of the D unit and the A unit, and usually, the D unit (particularly, the first donor unit (D1) ) Has the substituent, and the A unit often does not have the substituent. Both the D unit and the A unit may have the substituent, but the orientation (or crystallinity) may be reduced due to steric hindrance between adjacent substituents.

[Method for producing DA polymer]
The organic polymer of the present invention is usually synthesized (or polymerized) by subjecting a compound containing a D unit and / or an A unit to a conventional coupling reaction to connect the units (or to form a bond between the units). )it can. Therefore, the organic polymer is a compound having both a D unit and an A unit (for example, a (D)-(A) type dimer, (A)-(D)-(A) type, (D)-( A)-(D) multimers or oligomers such as type trimers) may be synthesized through a homocoupling reaction. However, from the viewpoint of productivity and the like, a compound having D units and an A unit are usually used. In many cases, the compound is synthesized by performing a cross-coupling reaction with a compound having the compound.

  In addition, the compound having a D unit and / or an A unit may be a monomer (or a monomer) having a D unit or an A unit, or may be a multimer (or an oligomer) of a dimer or more. . The oligomer may include a single unit or a plurality of units selected from D units and A units. When a plurality (for example, three or more) units are included, the arrangement or order is not particularly limited.

  Further, the compound having a D unit and / or an A unit has a reactive group that can be coupled depending on the type of the coupling reaction. The reactive group may be bonded or substituted at a position (usually two bonding positions) connecting the compound (or unit). The compound having a D unit and / or an A unit may have both reactive groups out of a pair of reactive groups that can be coupled. However, from the viewpoint of productivity or procureability, the compound is usually used. , A compound having a D unit has one reactive group (a first reactive group), and the other reactive group (a second reactive group) that can be coupled to the reactive group is an A unit In many cases.

  Therefore, typical methods for producing the organic polymer of the present invention include, for example, a compound having a D unit represented by the following formula (2D) and a compound having an A unit represented by the following formula (2A). And a method of synthesizing an organic polymer represented by the formula (1) by a cross-coupling reaction.

(Wherein X ¹ each independently represents a first reactive group, X ² each independently represents a second reactive group that can be coupled to the first reactive group, (D), (D) A), p, q and r are the same as above).

  The coupling reaction is not particularly limited, and a conventional coupling reaction, for example, a coupling reaction using a palladium catalyst (for example, a palladium (0) catalyst) (for example, Negishi coupling reaction, Hiyama coupling reaction, Suzuki- Miyaura coupling reaction (Suzuki coupling reaction), Migita-Kosugi-Stille coupling reaction (Stille coupling reaction) and the like; coupling reaction using a nickel catalyst (for example, nickel (0) catalyst) (for example, Kumada-Tamao-Corriu coupling reaction, etc .; Coupling reaction using an iron catalyst (eg, iron (III) catalyst) (eg, Kochi-Furstner coupling reaction, etc.); Copper catalyst (eg, , Copper (I) catalyst, etc.) (eg, Ullmann reaction) Coupling reactions without using a transition metal catalyst (e.g., coupling reaction using an organic catalyst, a coupling reaction using a one-electron catalyst, such as a coupling reaction using a radical species), and the like.

  When a polymer is prepared by a coupling reaction using a metal catalyst, it is difficult to completely remove the metal catalyst from the obtained polymer. , Ppm or ppb order), it is known that the semiconductor characteristics deteriorate. From such a viewpoint, among these coupling reactions, a coupling reaction not using a metal catalyst (for example, a transition metal catalyst) is preferable. In addition, among these coupling reactions, from the viewpoint of productivity and the like, a coupling reaction using a palladium (0) catalyst or a nickel (0) catalyst, preferably a Suzuki-Miyaura coupling reaction, a Migita-Kosugi-Stile A coupling reaction using a palladium (0) catalyst such as a coupling reaction (particularly a Suzuki-Miyaura coupling reaction) is preferred. In the Suzuki-Miyaura coupling reaction, a nickel catalyst may be used instead of the palladium catalyst.

The first and second reactive groups X ¹ and X ² can be appropriately selected according to the coupling reaction. In the case of synthesizing by a Suzuki-Miyaura coupling reaction, examples of one reactive group (for example, the first reactive group X ¹ ) include a halogen atom or a fluorinated alkane sulfonyloxy group. Examples of the halogen atom include an iodine atom, a bromine atom and a chlorine atom (preferably an iodine atom and a bromine atom). Examples of the fluorinated alkanesulfonyloxy group include a _C1-4 alkanesulfonyloxy group such as a trifluoromethanesulfonyloxy group (group [-OTf]). One of these reactive groups (for example, the first reactive group X ¹ ) may be used alone or in combination of two or more. Among these one reactive groups (for example, the first reactive group X ¹ ), a halogen atom (for example, an iodine atom or a bromine atom) is preferable, and a bromine atom is generally used.

In the Suzuki-Miyaura coupling reaction, the other reactive group (for example, the second reactive group X ² ) capable of coupling with the one reactive group (for example, the first reactive group X ¹ ) includes , Boron-containing groups. Examples of the boron-containing group include a boronic acid group or a dihydroxyboryl group (group [—B (OH) ₂ ]); a boronic ester group [eg, a dialkoxyboryl group (eg, a dimethoxyboryl group, a diisopropoxyboryl group) , A diboroxyboryl group or other di-C _1-4 alkoxyboryl group, etc.), a cyclic boronic ester group (for example, a pinacolatoboryl group (group [—Bpin]), a 1,3,2-dioxaborinan-2-yl group, 5 , 5-dimethyl-1,3,2-dioxaborinan-2-yl group and the like). These other reactive groups (for example, the second reactive group X ² ) may be used alone or in combination of two or more. The other reactive group (e.g., a second reactive group ^{X 2)} of, usually, group [-B _(OH) 2], and a group [-Bpin] is generic.

When the synthesis is performed by the Migita-Kosugi-Stille coupling reaction, one reactive group (for example, the first reactive group X ¹ ) is exemplified as one reactive group in the Suzuki-Miyaura coupling reaction, for example. It may be the same as the halogen atom or the fluorinated alkanesulfonyloxy group including the preferred embodiment. One of these reactive groups can be used alone or in combination of two or more. In the Migita-Kosugi-Stille coupling reaction, the other reactive group (for example, the second reactive group X ² ) capable of coupling with the one reactive group is a trialkylstannyl group (for example, , A tri-C _1-6 alkylstannyl group such as a trimethylstannyl group and a tri-n-butylstannyl group, and preferably a tri-C _1-4 alkylstannyl group such as a tri-n-butylstannyl group). . These other reactive groups can be used alone or in combination of two or more.

The first and second reactive groups X ¹ and X ² may be either a typical reactive groups described above. For example, Suzuki - in Miyaura coupling reaction, a first reactive group X ¹ is a halogen atom or a fluorinated alkane sulfonyloxy group, the second reactive group X ² is a also good a boron-containing group; first reactive group X ¹ is a boron-containing group, the second reactive group X ² may be a halogen atom or a fluorinated alkane sulfonyloxy group.

  As the compound having a D unit represented by the formula (2D), for example, a compound in which q is 1 and (D) is formed by the first donor unit (D1), that is, a compound represented by the following formula (2D) -I) and the like. The compound having a D unit represented by the formula (2D) can be used alone or in combination of two or more.

(Wherein, ring A, ring B, ring C, n, R ^{1 to} R ^{2 + n} and a ^{1 to} a ^{2 + n} are the same as those in the above formula (I) including preferred embodiments, and X ¹ represents a preferred embodiment) The same applies to the formula (2D).

  As the compound having an A unit represented by the formula (2A), for example, a compound in which r is 1 and (A) is formed of the first acceptor unit (A1), that is, a compound represented by the following formula (2A) And a compound having the first acceptor unit (A1) such as a compound represented by -III-1). In addition, the compound having the A unit represented by the formula (2A) can be used alone or in combination of two or more.

(Wherein, ring E ¹ , Z ¹ , R ^A1 , and m1 are the same as those in formula (III-1) including preferred embodiments, and X ² is the same as in formula (2A) including preferred embodiments. Is).

  The ratio of the compound having the D unit represented by the formula (2D) to the compound having the A unit represented by the formula (2A) is, for example, the former / the latter (molar ratio) = 1 / 0.8. It may be about 1 / 1.2 (for example, 1 / 0.9 to 1 / 1.1).

In the case of synthesis by a Suzuki-Miyaura coupling reaction, the reaction is carried out in the presence of a palladium catalyst, a nickel catalyst (for example, Ni (dppf) or the like), usually in the presence of a palladium catalyst. As the palladium catalyst, a conventional coupling catalyst, e.g., palladium (0) catalyst {e.g., tetrakis (triphenylphosphine) palladium _{(0) [Pd (PPh 3} ) 4], bis (tri -t- butylphosphine) palladium (0) palladium (0) -phosphine complex such as [Pd (P (t-Bu) ₃ ) ₂ ]; palladium (II) catalyst {for example, bis (triphenylphosphine) palladium (II) dichloride [PdCl _{2 (PPh 3)} 2], bis (tri -o- tolyl phosphine) palladium (II) dichloride _{[PdCl 2 (P (o-} tolyl) 3) 2], [1,1'- bis (diphenylphosphino) ferrocene] palladium (II) dichloride _{[PdCl 2 (dppf)],} [1,2- bis (diphenylphosphino I Roh) ethane] palladium (II) dichloride _{[PdCl 2 (dppe)],} [1,3- bis (palladium such as diphenylphosphino) propane] palladium (II) dichloride _[PdCl 2 (dppp)] (II) - And phosphine complexes. When a palladium (II) catalyst is used, the reaction is started by being reduced to a zero-valent complex by a reducing compound (for example, a phosphine, an amine, an organometallic reagent, and the like described later) in the reaction system.

These catalysts can be used alone or in combination of two or more. Of these catalysts, typically, Pd palladium such as _{(PPh 3) 4 (0)} - phosphine complex is generic. The ratio of the catalyst is, for example, 0.01 to 0.1 mol (for example, 0.02 to 0.08 mol) in terms of metal per 1 mol of the compound having the D unit represented by the formula (2D). ).

The palladium catalyst may be prepared by adding a palladium catalyst precursor, a ligand and a reaction system. Examples of the palladium catalyst precursor include a palladium (0) catalyst precursor {eg, tris (dibenzylideneacetone) dipalladium (0) chloroform complex [Pd ₂ (dba) ₃ .CHCl ₃ ], bis (dibenzylideneacetone) Palladium (0) -dba complex such as palladium (0) [Pd (dba) ₂ ]; palladium (II) catalyst precursor {eg, palladium (II) acetate [Pd (OAc)], palladium (II) chloride [PdCl ₂ ], bis (acetonitrile) palladium (II) dichloride [PdCl ₂ (CH ₃ CN) ₂ ], bis (benzonitrile) palladium (II) dichloride [PdCl ₂ (PhCN) ₂ ], allyl palladium (II) chloride dimer _{[(PdCl (allyl)) 2} ], tetrachloropalladate Um (II) Sodium [NaPdCl _4], etc.} and the like. These palladium catalyst precursors can be used alone or in combination of two or more. Usually, a palladium (0) -dba complex such as Pd ₂ (dba) ₃ .CHCl ₃ is widely used.

  Examples of the ligand include phosphines (eg, triarylphosphines such as triphenylphosphine and tolylphosphine, trialkylphosphines such as tri-t-butylphosphine, and tricycloalkylphosphines such as tricyclohexylphosphine); Nitrogen-containing heterocyclic carbene (for example, imidazole carbene such as 1,3-diisopropylimidazolium tetrafluoroborate and 1,3-di-t-butylimidazol-2-ylidene) and the like. These ligands can be used alone or in combination of two or more. Usually, phosphines such as triphenylphosphine are widely used. The ratio of the palladium catalyst precursor and the ligand may be about the same as the molar ratio (or equivalent ratio) in the target palladium catalyst.

  The Suzuki-Miyaura coupling reaction may be usually performed in the presence of a base. As the base, usually, an inorganic base, for example, a metal hydroxide (eg, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, an alkaline earth metal hydroxide such as barium hydroxide, Thallium (I) hydroxide, etc.), metal carbonates or bicarbonates (eg, alkali metal carbonates or bicarbonates such as sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, thallium (I) carbonate, etc.), Metal phosphates (eg, alkali metal phosphates such as tripotassium phosphate), metal fluorides (eg, alkali metal fluorides such as potassium fluoride and cesium fluoride), metal alkoxides (eg, sodium methoxy) Alkali metal alkoxides such as sodium ethoxide, etc.), metal organic acid salts (eg potassium acetate) Alkali metal acetate such as beam) and the like.

  These bases can be used alone or in combination of two or more. Usually, metal phosphates such as tripotassium phosphate are widely used. The ratio of the base may be, for example, about 0.1 to 50 mol (for example, 1 to 25 mol) based on 1 mol of the compound having the D unit represented by the formula (2D).

  The coupling reaction may be performed in the absence or presence of a solvent inert to the reaction. Examples of the solvent include hydrocarbons (eg, aliphatic hydrocarbons (hexane, dodecane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), alcohols (Such as methanol and ethanol), ethers (such as cyclic ethers such as dioxane and tetrahydrofuran, and chain ethers such as diethyl ether and diisopropyl ether), ketones (such as acetone and methyl ethyl ketone), esters (such as ethyl acetate), and nitrile (Such as acetonitrile and benzonitrile), amides (such as N, N-dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone), sulfoxides (such as dimethylsulfoxide), and water. These solvents may be used alone or as a mixed solvent. Among these solvents, a mixed solvent of water and hydrocarbons (eg, water and aromatic hydrocarbons), a mixed solvent of water and ethers (water, THF, and the like) are generally used.

  The coupling reaction may be performed in the presence or absence of a phase transfer catalyst. Examples of the phase transfer catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide and trioctylmethylammonium chloride. Specifically, for example, Aliquat (registered trademark) 336 (manufactured by Sigma Aldrich) or the like can be used.

  These phase transfer catalysts can be used alone or in combination of two or more. Usually, trioctylmethylammonium chloride and the like are widely used. The ratio of the phase transfer catalyst is, for example, about 0.01 to 3 mol (for example, 0.1 to 1 mol) with respect to 1 mol of the compound having the D unit represented by the formula (2D). Good.

  The coupling reaction may be performed in an atmosphere of an inert gas (for example, nitrogen; a rare gas such as helium or argon). The reaction temperature may be, for example, about 50 to 200 ° C, preferably about 70 to 150 ° C. The reaction time is not particularly limited, and may be, for example, about 1 minute to 5 days, preferably about 30 minutes to 3 days.

  The coupling reaction is generally performed under heating, and may be performed under microwave irradiation. When reacting under microwave irradiation, the reaction temperature may be the same as the above range. The irradiation time (or reaction time) may be, for example, about 10 minutes to 3 hours (for example, 20 minutes to 1 hour). As described above, in the present invention, when the Suzuki-Miyaura coupling reaction is performed under irradiation with microwaves, the reaction time is significantly shortened and the yield is high with higher yield as compared with the case where the reaction is performed without irradiation with microwaves. Organic polymers can be prepared. Therefore, the reaction yield is, for example, 50% or more (for example, 55 to 100%), preferably 60% or more (for example, 65 to 99%), and more preferably 70% or more (for example, 85 to 98.5%). Degree). When an aromatic hydrocarbon such as toluene is used as the solvent, the yield may be more easily improved in some cases.

  After completion of the reaction, if necessary, the reaction mixture is purified by a conventional separation and purification method, such as washing, extraction, concentration, decantation, reprecipitation, chromatography, a method combining these, and the organic polymer is separated and purified. You may. If necessary, the organic polymer may be fractionated into one or a plurality of components having a predetermined molecular weight by operations such as chromatography and extraction.

  The compound having a D unit represented by the formula (2D) can be synthesized by a conventional method, for example, a method according to Patent Document 1 or Example 10 of WO 2010/024388. Specifically, for example, a compound represented by the following formula (2D-I-3) may be prepared by the following method.

(Wherein, R ^b is an alkyl group, X ³ is a halogen atom, and ring A, ring B, R ^{1 to} R ⁴ , a ^{1 to} a ^4, and X ¹ are the same as described above, including preferred embodiments) .

(Synthesis of compound represented by formula (5-I-3))
The compound represented by the formula (5-I-3) is prepared by lithiating a predetermined portion of the ring A and the ring B of the compound represented by the formula (3-I-3) with a lithiating agent (4a). lithium silylating agent or protective agent: silylated with ^{_(R b} 3 SiCl _R b is an alkyl group shows a) (4b), to protect the predetermined portion with a silyl group (-SiR ^b _3). In this example, n-butyllithium (n-BuLi) is used as a lithiating agent, triisopropylsilyl chloride (TIPSCl) is used as a silylating agent, and an alkylsilyl group is has introduced (-SiR ^b _3).

  The compound represented by the formula (3-I-3) can be prepared according to Patent Document 1 or WO 2010/024388 (for example, Example 10), and typically, the compound represented by the formula (I And compounds corresponding to the units represented by -3a) to (I-3i). These compounds can be used alone or in combination of two or more.

Examples of the lithiating agent (4a) include conventional lithiating agents such as alkyllithium (eg, C _1-6 alkyllithium such as methyllithium, n-butyllithium, s-butyllithium, and t-butyllithium); Aryl lithium (phenyllithium, etc.), lithium amides (lithium diisopropylamide (LDA), lithium-2,2,6,6-tetramethylpiperidine (LiTMP), lithium-bis (trimethylsilyl) amide (LHMDS), etc.) No. The lithiating agents may be used alone or in combination of two or more. The amount of the lithiating agent used may be about 1 to 5 equivalents (for example, 1.5 to 3 equivalents) to the compound represented by the formula (3-I-3).

  The lithiation reaction may be performed in the presence of a solvent inert to the reaction. As the solvent, for example, ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran (THF) and dioxane), and aliphatic or alicyclic hydrocarbons (such as cyclohexane) may be used. Usually, THF, cyclohexane and the like are widely used. The reaction is carried out in an atmosphere of an inert gas (nitrogen; rare gas such as helium, argon, etc.) at a temperature of about -100 ° C to 30 ° C (normally -80 ° C to 0 ° C), and a reaction time of 1 minute to 12 hours (normally) , 10 to 60 minutes). After completion of the reaction, if necessary, the reaction solution may be purified by a conventional separation and purification means, but the reaction solution containing the obtained lithiated product may be subjected to the next silylation reaction without purification.

Examples of the silylating agent (4b) (or protecting agent) include tri-linear or branched C such as trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride (TIPSCl), tributylsilyl chloride, and triisobutylsilyl chloride. Examples thereof include _1-6 alkylsilyl halide. These silylating agents can be used alone or in combination of two or more. The amount of the silylating agent used may be about 1 to 5 equivalents (for example, 1.5 to 3 equivalents) to the compound represented by the formula (3-I-3).

  The silylation reaction is carried out in a solvent similar to the lithiation reaction described above, under an inert atmosphere, at a temperature of about -100 ° C to 40 ° C (normally -80 ° C to 30 ° C), for a reaction time of 1 to 48 hours (usually 12 hours). ~ 24 hours). After completion of the reaction, the product may be purified by a conventional separation and purification means (column chromatography, filtration, recrystallization, etc.).

(Synthesis of compound represented by formula (7-I-3))
The compound represented by the formula (5-I-3) is boronated with a boronating agent or a boron compound (6) to prepare a compound represented by the formula (7-I-3). In this example, the iridium catalyst [bis (1,5-cyclooctadiene) di-μ-methoxydiiridium (I) complex: Ir (OMe) (COD) ₂ ] and 4,4′-di-t-butyl- In the presence of 2,2'-bipyridyl (dtbpy), 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bis-1,3,2-dioxa Using a boronate [(Bpin) ₂ ], predetermined portions of a benzene ring adjacent to ring A and a benzene ring adjacent to ring B are borated.

  For boration of the compound represented by the formula (5-I-3), a conventional boration method using a catalyst such as an iridium catalyst, a rhenium catalyst, and a rhodium catalyst, for example, an iridium catalyst and a bipyridyl ligand, A method using a ligand such as a diimine ligand or a phosphine ligand (such as triphenylphosphine) is exemplified. These catalysts and ligands can be used alone or in combination of two or more. The amount of the catalyst such as the iridium catalyst may be about 0.1 to 10 mol% (for example, 2 to 8 mol%) based on the compound represented by the formula (5-I-3). The amount of a ligand such as a bipyridyl ligand may be about 1.5 to 5 times the mol of the catalyst.

As the boronating agent or the boron compound (6), a compound capable of forming a boronic acid ester, for example, (BPin) ₂ , or a conventional compound, for example, diboronic acid, pinacol borane, or the like can be used. The boron compound (6) can be used alone or in combination of two or more. The amount of the boron compound (6) used may be about 1.1 to 5 equivalents (for example, 1.5 to 3 equivalents) to the compound represented by the formula (5-I-3).

  The boration reaction is carried out in an inert solvent such as the organic solvent and alicyclic hydrocarbons (eg, cyclohexane) under an inert atmosphere at a temperature of about 30 to 120 ° C. (eg, 50 to 100 ° C.) for a reaction time of It may be performed for about 1 to 36 hours (normally, 18 to 24 hours). After completion of the reaction, the product may be purified by conventional separation and purification means (filtration, washing, etc.).

Synthesis of the compound represented by the formula (9-I-3) The compound represented by the formula (7-I-3) is reacted with a halogenating agent (8) to give a compound having a halogen atom introduced therein ( The compound represented by 9-I-3) can be prepared. In this example, the compound represented by the formula (7-I-3) is reacted with copper (II) bromide.

In the formula (9-I-3), examples of the halogen atom represented by X ³ include a chlorine, bromine, iodine atom and the like, and usually, it is often bromine. Two halogen atoms X ³ may be different from each other, but typically are the same.

Examples of the halogenating agent (8) include copper (II) halides such as copper (II) chloride, copper (II) bromide, and copper (II) iodide [Cu (X ³ ) ₂ (II)]. Can be exemplified. The use amount of the halogenating agent (8) such as copper halide may be about 2 to 10 equivalents (for example, 5 to 8 equivalents) to the compound represented by the formula (7-I-3). .

  In the halogenation reaction, a solvent inert to the reaction, for example, a mixed solvent of water and a water-soluble solvent (cyclic ethers, alcohols such as methanol, amides such as N-methyl-2-pyrrolidone (NMP), etc.) And so on. Usually, a mixed solvent of alcohols, amides and water (for example, a mixed solvent of methanol, NMP and water, etc.) is widely used. The reaction may be performed under an inert atmosphere at a temperature of about 30 to 120 ° C. (eg, 50 to 100 ° C.) for a reaction time of about 5 to 48 hours (generally, 18 to 24 hours). After completion of the reaction, the product may be purified by conventional separation and purification means (filtration, extraction, washing, etc.).

Synthesis of the compound represented by the formula (11-I-3) Using the Negishi coupling reaction, the compound represented by the formula (9-I-3) is reacted with the alkylating agent (10) in the presence of a catalyst. And the compound represented by the formula (11-I-3) can be prepared. In this example, in the presence of a palladium catalyst (1,1′-bis (diphenylphosphino) ferrocene) dichloropalladium (II) dichloromethane complex (PdCl ₂ (dppf) CH ₂ Cl ₂ ), the compound represented by the formula (9-I-3) ) And a zinc reagent [alkyl zinc halide lithium chloride such as R ¹ -ZnCl LiCl and / or R ⁴ -ZnCl LiCl (R ¹ and R ⁴ are alkyl groups) Shown)) to introduce an alkyl group.

The alkylating agent (10), for example, Grignard reagents, alkyl zinc halides, dialkyl zinc, lithium zincate or magnesium zincate ^{[M +} _R 1 3 Zn ^- and / or _{^{M + R 4 3 Zn - (}} M is lithium or magnesium And R ¹ and R ⁴ represent an alkyl group.)], And a conventional alkylating agent such as an alkylating metal can be used. These alkylating agents (10) can be used alone or in combination of two or more. As the alkylating agent, a zinc reagent (lithium zincate or magnesium zincate) is often used.

The zinc reagent includes, for example, an alkyl magnesium halide (10A), a zinc compound (10B) (eg, a zinc halide such as zinc chloride), and a lithium compound (10C) (a lithium halide such as lithium chloride). May be formed. As the alkyl magnesium halide (10A), an alkyl magnesium halide (chloride, bromide, iodide) corresponding to R ¹ and R ⁴ can be used. The amount of the alkyl magnesium halide (10A) used may be, for example, about 1.5 to 10 equivalents (for example, 2 to 5 equivalents) to the compound represented by the formula (9-I-3). The amount of each of the zinc compound (10B) and the lithium compound (10C) may be, for example, about 0.8 to 1.2 times the molar amount of the alkyl magnesium halide (10A). The amount of the alkylating agent or zinc reagent (10) to be used may be about 1.5 to 5 equivalents (for example, 2 to 3 equivalents) relative to the compound represented by the formula (9-I-3). .

  The reaction for preparing the zinc reagent is carried out, for example, in a solvent inert to the reaction (such as ethers such as diethyl ether and THF) under an inert atmosphere at a reaction temperature of 10 to 70 ° C (for example, room temperature of about 20 to 25 ° C). ), The reaction may be performed for about 10 minutes to 12 hours. The obtained reaction solution may be purified as necessary, or may be subjected to a coupling reaction without purification.

  Examples of the palladium catalyst include the above catalysts and the palladium catalyst exemplified in the Suzuki-Miyaura coupling reaction. In addition, you may use together the above-mentioned ligand, for example, a phosphine ligand (triphenylphosphine), etc. as a ligand. The catalysts and ligands can be used alone or in combination of two or more. The amount of the palladium catalyst used may be, for example, about 1 to 50 mol% (for example, 5 to 25 mol%) based on the compound represented by the formula (9-I-3).

  The Negishi coupling reaction is carried out in the presence of a solvent inert to the reaction (for example, a cyclic ether such as THF) under an inert atmosphere at a reaction temperature of about 30 to 120 ° C (for example, 50 to 100 ° C). It can be performed for about 1 to 48 hours (usually 12 to 24 hours). After completion of the reaction, the product may be purified by a conventional separation and purification means (extraction, washing, column chromatography, etc.).

Synthesis of Compound Represented by Formula (13-I-3) The compound represented by the formula (13-I-3) in which X ¹ in the formula (2D-I) corresponds to a hydrogen atom is represented by the formula (11-I-3) It can be prepared by subjecting the compound represented by -3) to a deprotection reaction. For the deprotection reaction, conventional deprotecting agents (12) such as acids and bases, for example, alkali metal carbonates such as potassium carbonate, fluoride ions such as tetrabutylammonium fluoride (TBAF) and the like can be used. The deprotecting agent (12) can be used alone or in combination of two or more. Usually, TBAF or the like is widely used. The use amount of the deprotecting agent (12) may be about 1 to 10 equivalents (for example, 2 to 5 equivalents) to the compound represented by the formula (11-I-3).

  The deprotection reaction is carried out in an inert atmosphere in the presence of a solvent inert to the reaction (for example, cyclic ethers such as THF) at a reaction temperature of about -20 ° C to 50 ° C (eg, -10 ° C to 30 ° C). And a reaction time of about 10 minutes to 12 hours (usually, 30 minutes to 3 hours). After completion of the reaction, the reaction product may be purified by conventional separation and purification means (filtration, washing, column chromatography, etc.).

Synthesis of the compound represented by the formula (2D-I-3) The compound represented by the formula (2D-I-3) is obtained by converting the compound represented by the formula (13-I-3) into a lithiating agent (14a) And reacting the resulting lithiated product with a halogenating agent (14b).

  As the lithiation agent (14a), the same lithiation agent as the lithiation agent (4a) can be used, and it can be used alone or in combination of two or more. The amount of the lithiating agent used may be about 1.5 to 10 equivalents (for example, 2 to 5 equivalents) to the compound represented by the formula (13-I-3).

  The lithiation reaction may be performed in the presence of an inert solvent (such as a cyclic ether such as THF) as in the lithiation reaction. The reaction may be carried out under an inert gas atmosphere at a temperature of about -100 to 30C (normally -80 to -10C) and for a reaction time of about 1 minute to 12 hours (generally 1 to 3 hours). After completion of the reaction, if necessary, the reaction solution may be purified by a conventional separation and purification means, but the reaction solution containing the obtained lithiated product may be subjected to the next halogenation reaction without purification.

  As the halogenating agent (14b), a conventional halogen compound, for example, a halogenated alkane such as 1,2-dibromo-1,1,2,2-tetrachloroethane, a simple halogen such as chlorine, bromine, or iodine is used. it can. Usually, halogenated alkanes and the like are widely used. The amount of the halogenating agent (14b) used is about the same as the amount of the lithiating agent (14a) used. The halogenation reaction is carried out in the presence of a solvent inert to the reaction (for example, cyclic ethers such as THF) in an inert atmosphere at a reaction temperature of about -50 ° C to 50 ° C (for example, -30 ° C to 30 ° C). The reaction may be performed for about 10 minutes to 48 hours (usually, 12 to 24 hours).

  In each of the above reaction steps, after completion of the reaction, a predetermined compound is purified by a conventional separation and purification method, for example, filtration, concentration, crystallization or precipitation, recrystallization, extraction, washing, chromatography, a method combining these, and the like. The compound may be separated and purified and used for the subsequent reaction, or a predetermined compound may be used for the subsequent reaction without separation and purification from the reaction mixture.

  In the above reaction scheme, the production of a compound in which n is 2 in the formula (2D-I) has been described. For a compound in which n is 0 to 1, or 3 or more, the compound is represented by the formula (3-I-3). It can be prepared by using a zigzag compound corresponding to a unit having a desired n in the formula (I) instead of the compound represented by the formula (I). In addition, such a zigzag-like compound may be prepared with reference to Patent Document 1 and International Publication No. 2010/024388 (for example, Example 10).

[Characteristics of organic polymer (DA type polymer)]
The molecular weight of the organic polymer of the present invention is not particularly limited. For example, when measured by gel permeation chromatography (GPC), the number average molecular weight Mn is 500 to 5,000,000 (for example, 1000 to 1,000,000) in terms of polystyrene, It may be preferably about 3000 to 500000 (for example, 5000 to 100000), more preferably about 8000 to 50000 (for example, 10,000 to 25000), and the weight average molecular weight Mw is 1,000 to 100,000,000 (for example, 3000 to 1,000,000); It may be preferably 5,000 to 100,000 (e.g., 10,000 to 80,000), more preferably about 20,000 to 50,000, and usually 30,000 to 300,000 (e.g., 50,000 to 250,000), preferably From 100,000 to 200,000 (e.g., from 120000 to 180000) may be about. The molecular weight distribution (Mw / Mn) is, for example, 1 to 20 (for example, 1.1 to 10), preferably 1.2 to 8 (for example, 1.3 to 5), and more preferably 1.4 to 3 (for example). For example, it may be about 1.5 to 2), and usually about 1.5 to 15 (for example, 6 to 8). The degree of polymerization DPn is, for example, about 3 to 100 (for example, 5 to 50), preferably about 7 to 30 (for example, 10 to 25), and more preferably about 11 to 23 (for example, 17 to 21). Is also good.

The organic polymer of the present invention has a high heat resistance, a 5% mass defect temperature _{T 95} can be measured by TG-DTA (thermogravimetric-differential thermal analyzer), for example, 200 to 600 ° C. ( For example, the temperature may be about 300 to 500 ° C), preferably about 350 to 450 ° C.

  The organic polymer (semiconductor polymer or π-conjugated polymer) of the present invention has a first donor unit (D1), which is expected to have low orientation (or crystallinity) [a plurality of adjacent benzene rings have a zigzag shape. To a zigzag-like unit which is ortho-condensed to), surprisingly, it exhibits extremely excellent orientation (or crystallinity). Therefore, even if the film is formed by a simple method such as spin coating, High orientation can be maintained. Therefore, high mobility can be realized, and it can be effectively used as an organic semiconductor.

Organic polymer distance (interplanar distance) d _[pi between [pi stack (polymer film or an organic semiconductor), for example, 3.3～3.7A (e.g., 3.35～3.6A), preferably 3 .4～3.55A (e.g., it may be about 3.4～3.5A. Note that the d _[pi common organic semiconductor polymers between .π stack is about 3.4~3.75Å If the distance (interplanar distance) d _[pi is too large, the mobility may be lowered. Further, the distance between the lamellar structure (interplanar distance) d _l is the side chain or substituents of organic polymer [e.g., R ^{1 to} R ^{2 + n} (especially, a long-chain alkyl group or the like)], for example, about 10 to 50 ° (for example, 15 to 40 °), preferably about 20 to 35 ° (for example, 25 to 30 °). The distance between the surfaces may be described in, for example, an example described later. It can be measured by thin film X-ray analysis as.

  In addition, although the organic polymer has high orientation (or crystallinity), the introduction of an alkyl group or the like into the side chain can increase the solubility in an organic solvent, and can achieve high orientation and dissolution. And the film forming property can be improved. Therefore, the present invention also includes a composition containing an organic polymer and an organic solvent. Such a composition is useful for forming a thin film of an organic semiconductor, and a thin film (organic semiconductor thin film) can be formed by a simple method such as printing or coating (coating).

[Use of organic polymer (DA type polymer)]
The organic polymer of the present invention has excellent semiconductor properties and film-forming properties as described above, and can be effectively used as an organic semiconductor. The organic semiconductor may include at least the organic polymer, and may include a conventional semiconductor material, an additive, and the like, as needed, in a range that does not impair the carrier transportability.

Such semiconductor materials include, for example, acenes (eg, naphthacene, chrysene, pyrene, pentacene, picene, perylene, hexacene, heptacene, dibenzopentacene, coronene, tetrabenzopentacene, ovalene, etc.); phthalocyanines (eg, phthalocyanine (Eg, copper phthalocyanine), naphthalocyanine, subphthalocyanine); carbazoles [eg, 1,3,5-tris [2,7- (N, N- (p-methoxyphenyl) amino) -9H-carbazole-9] -Yl] benzene (SGT405) and the like]; thiophenes [for example, 2,5-bis [4- (N, N-bis (p-methoxyphenyl) amino] phenyl] -3,4-ethylenedioxythiophene (H101) ), 2,3,4,5-tetrakis [4- (N, N- [(P-methoxyphenyl) amino) phenyl] thiophene (H111) and the like]; tetracarboxylic diimides [for example, 1,4,5,8-naphthalenetetracarboxylic diimide, 2,3,6,7-naphthalenetetra Carboxylic acid diimide, 2,3,6,7-anthracenetetracarboxylic acid diimide and the like]; triptycenes [for example, 2,6,14-tris [5 ′-(4- (N, N-bis (p-methoxyphenyl) ) Amino) phenyl) -thiophen-2'-yl] triptycene (T103) etc.]; polyacetylenes (trans-polyacetylene etc.); polyparaphenylenes (polyparaphenylene, polyparaphenylenevinylene etc.) ); Polypyrroles (such as poly (pyrrole-2,5-diyl)); [E.g., poly (3-methylthiophen-2,5-diyl), poly (3-hexylthiophen-2,5-diyl) (P3HT), poly [N-9'-heptadecanyl-2,7-carbazole -Alt-5,5- (4 ', 7'-di-2-thienyl-2', 1 ', 3'-benzothiadiazole)] (PCDTBT), poly [N-9'-heptadecanyl-2,7- Carbazole-alt-3,6-bis (thiophen-5-yl) -2,5-dioctyl-2,5-dihydropyrrolo [3,4] pyrrole-1,4-dione] (PCBTDPP), poly [2, 6- (4,4-bis- (2-ethylhexyl) -4H-cyclopenta [2,1-b; 3,4-b ′] dithiophene) -alt-4,7- (2,1,3-benzothiadiazole )] (PCPDTBT) etc.]; Litriarylamines [eg, poly [bis (phenyl-4-yl)-(2,4,6-trimethylphenyl) -amine] (PTAA), poly [bis (phenyl-4-yl)-(4-butyl Phenyl) -amine] (PolyTPD) and the like]; polyfluorenes [for example, poly [9,9-dioctylfluorene-co-bis-N, N '-(4-butylphenyl) -bis-N, N'-phenyl] 1,4-phenylenediamine] (PFB), etc.] an organic polymer semiconductor materials, such as; the carbon material [e.g., fullerenes _{(eg, C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene, C 84} fullerene ), Graphenes (graphene, graphene oxide, etc.), carbon nanotubes (single-walled carbon nanotubes (SWNT) An inorganic semiconductor material such as multi-walled carbon nanotubes (MWNT), etc.), etc.] and the like. These conventional semiconductor materials can be used alone or in combination of two or more.

  Examples of the additive include a leveling agent, an adhesion improver (such as a silane coupling agent), and a dopant. These additives can be used alone or in combination of two or more.

  In the organic semiconductor of the present invention, the ratio of the organic polymer (DA polymer) is, for example, 10% by weight or more (for example, 30 to 100% by weight), or preferably 50% by weight, based on the entire organic semiconductor. % (Eg, 70 to 99.9% by weight), more preferably about 80% by weight (eg, 90 to 99% by weight), and substantially 100% by weight (the organic polymer (D -A type polymer) only).

  The organic semiconductor (organic semiconductor thin film or organic semiconductor layer) of the present invention may be formed by a dry process such as a vacuum evaporation method or a sputtering method, but the organic polymer (DA type polymer) has a high solubility. May be formed by a wet process (such as coating). The wet process includes a film forming step of applying a composition (or a solution) containing the organic polymer and a solvent to at least one surface of a substrate (or a substrate) and removing the solvent. .

The substrate (or substrate) is not particularly limited, and may be, for example, a glass plate, a silicon wafer, or a plastic film (for example, a transparent resin film such as a polyethylene terephthalate film). These substrates may have one or more functional layers (for example, a conductive layer such as ITO, an insulating layer such as SiO ₂ ), a self-assembly such as β-phenethyltrimethoxysilane (β-PTS) on the surface, if necessary. Monolayer (SAM) or the like may be formed.

The composition may be prepared by a conventional method, for example, by mixing an organic polymer and a solvent to dissolve the organic polymer and, if necessary, filtering. As the solvent, for example, aromatic hydrocarbons (eg, benzene, toluene, xylene, anisole, etc.); halogenated hydrocarbons (eg, halo C _1-6 alkanes such as dichloromethane, chloroform, 1,2-dichloroethane, etc.) chlorobenzene, dichlorobenzene); alcohols (e.g., methanol, ethanol, 2-propanol, n- butanol, _{C 1-6} alkane monool such as t- butanol; such _{C 2-4} alkanediol such as ethylene glycol), ethers (Chain ethers such as diethyl ether and diisopropyl ether, cyclic ethers such as tetrahydrofuran and dioxane); glycol ethers [eg, cellosolves (eg, methyl cellosolve), carbitols (eg, methyl carbitol) , Triethylene glycol monomethyl ether, and propylene glycol monomethyl ether (poly) C _2-4 alkylene glycol mono C _1-4 alkyl ether, ethylene glycol dimethyl ether, (poly) C _2-4 alkylene glycol such as dipropylene glycol dimethyl ether di C _1-4, such as alkyl ethers]; glycol ether acetates [e.g., cellosolve acetates (e.g., C _1-4 alkyl cellosolve acetate, such as methyl cellosolve acetate), carbitol acetates (e.g., such as methyl carbitol acetate C _1-4, such as alkyl carbitol acetate), propylene glycol monomethyl ether acetate, dipropylene glycol monobutyl ether acetate Etc. (poly) C _2-4 alkylene glycol mono C _1-4 alkyl ether acetates such as over preparative]; ketones (acetone, chain ketones such as methyl ethyl ketone, cyclic ketones such as cyclohexanone), esters (ethyl acetate, etc. Acetates, lactate esters such as methyl lactate, etc.); carbonates (chain carbonates such as dimethyl carbonate, cyclic carbonates such as ethylene carbonate, propylene carbonate, etc.); nitriles (acetonitrile, propionitrile, benzonitrile, etc.); Amides (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.); sulfoxides (dimethylsulfoxide, etc.); and mixed solvents thereof. Usually, aromatic hydrocarbons, halogenated hydrocarbons (eg, o-dichlorobenzene, etc.) are widely used.

  In the composition (or solution), the concentration (solid content concentration) of the organic polymer can be selected according to a coating method and the like, and is, for example, 0.001 to 20% by weight (for example, 0.01 to 10% by weight). Preferably, it may be about 0.1 to 5% by weight (for example, 0.5 to 3% by weight), particularly about 0.6 to 2% by weight (for example, 0.7 to 1.3% by weight).

  The coating method is not particularly limited, and a conventional coating method, for example, an air knife coating method, a roll coating method, a gravure coating method, a blade coating method, a bar coating method, a die coating method, a dip coating method, a spray coating method, a spin coating method , A casting method, an edge casting method, a drop casting method, a screen printing method, an ink jet printing method, a compression orientation method, and the like. Usually, a spin coating method, an edge casting method, a drop casting method, an ink jet printing method and the like are generally used, and a spin coating method and the like are preferable from the viewpoint of easy film formation (or productivity).

  The organic semiconductor (layer) can be formed by removing the solvent by a conventional drying method, for example, natural drying, drying by heat treatment, or the like. The temperature in the heat treatment may be, for example, about 30 to 100 ° C, preferably about 40 to 80 ° C. Moreover, you may dry under reduced pressure as needed.

  Further, the obtained coating film (organic semiconductor thin film) may be subjected to an annealing treatment as needed. The annealing temperature can be selected, for example, from the range of about 50 to 400 ° C (for example, 80 to 380 ° C), for example, 100 to 360 ° C (for example, 150 to 350 ° C), preferably 200 to 340 ° C (for example, 250-330 ° C.), more preferably about 280-320 ° 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, about 2 to 4 hours). Note that the annealing treatment may be performed in an air atmosphere, may be performed in an inert gas atmosphere such as nitrogen or a rare gas (such as helium or argon), or may be performed in an inert gas (particularly argon) atmosphere. Is preferred.

  The thickness of the organic semiconductor (layer) thus obtained may be, for example, about 1 to 5000 nm, preferably about 30 to 1000 nm, and more preferably about 50 to 500 nm, depending on the application.

  The organic semiconductor of the present invention may be an n-type semiconductor, a p-type semiconductor, or an intrinsic semiconductor. Since the organic semiconductor of the present invention has a high mobility (carrier mobility or electric mobility) of electrons and / or holes (holes), semiconductors such as electronic devices such as switching elements, rectifiers (diodes), and transistors are used. It can be used as a material for an element, a photoelectric conversion device, or a material for a photoelectric conversion element (such as a solar cell element and an organic electroluminescence (EL) element).

  In the organic semiconductor of the present invention, the organic polymer (DA type polymer) may be face-on oriented (or in-plane oriented) with respect to the substrate, but is usually edge-on oriented (or out-of-plane). Orientation). Therefore, it can be effectively used as an organic thin film transistor.

Such an organic thin film transistor includes a gate electrode layer, a gate insulating layer, a source / drain electrode layer, and an organic semiconductor layer. According to the stacked structure of these layers, the organic thin film transistor can be classified into a top gate type and a bottom gate type (top contact type, bottom contact type). For example, by forming an organic semiconductor film on a gate electrode (such as a p-type silicon wafer on which an oxide film is formed) and forming source / drain electrodes (gold electrodes) on the organic semiconductor film, a top-contact type electric field is formed. An effect transistor can be manufactured. Further, a carrier injection layer (dopant layer) may be formed between the source / drain electrode layer and the organic semiconductor layer. Such carrier injection layers include, for example, TCNQs such as tetracyanoquinonedimethane (TCNQ) and 2,3,5,6-tetrafluorotetracyanoquinonedimethane (F ₄ TCNQ), and iron (III) chloride. Metal halides, fullerenes and the like.

Since the organic semiconductor of the present invention contains the organic polymer (DA type polymer), both high mobility and high solubility can be achieved. Therefore, the mobility of the case of manufacturing a field effect transistor using an organic semiconductor of the present invention, in the drain voltage Vd = -150 V, for example, 0.001~10cm ² / Vs (e.g., 0.005～1Cm ² / Vs), preferably about 0.008 to 0.5 cm ² / Vs (for example, about 0.01 to 0.1 cm ² / Vs).

  In the field-effect transistor, the threshold voltage Vth at a drain voltage Vd of -150 V may be, for example, -100 V or more and less than 0 V (for example, about -70 to -0.01 V), and preferably -60. It may be about -0.1V. Note that the mobility and the threshold voltage Vth may be measured by a method described in an embodiment described later.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

  [Synthesis Example 1] (Synthesis of zigzag low molecular weight compound)

  Except that 3-bromofuran is used instead of 3-bromothiophene, the target compound (3-1) (chryseno) is prepared according to the method described in Synthesis Examples 1 to 5 of WO2017 / 170245 (Patent Document 1). [2,1-b: 8,7-b '] difuran) was prepared.

¹ H-NMR (400 MHz, TCE-d ₂ , 100 ° C.): δ (ppm) 8.86 (d, 2H, J = 9.2 Hz), 8.72 (d, 2H, J = 9.2 Hz), 8.33 (d, 2H, J = 9.2 Hz), 7.87 (d, 2H, J = 9.2 Hz), 7.83 (d, 2H, J = 1.6 Hz), 7.37 (d , 2H, J = 1.6 Hz).

  [Synthesis Example 2] (Silylation step)

  Under an argon atmosphere, while stirring a white suspension of compound (3-1) (100 mg, 0.324 mmol) / tetrahydrofuran (THF, 5 mL) at -78 ° C, 1.55 M n- as a lithiating agent (4a) was used. Butyllithium (n-BuLi) cyclohexane solution (0.44 mL, 0.681 mmol) was added dropwise. The resulting light green suspension was further stirred at −78 to 0 ° C. for 15 minutes, lowered to −78 ° C. again, and triisopropylsilyl chloride (TIPSCl) (131 mg, 0.681 mmol) as a silylating agent (4b). Was added, and the mixture was stirred for 19 hours while the temperature was naturally raised to room temperature. Methanol was added to the light green suspension, and the crude product obtained by filtration was purified by column chromatography with n-hexane to give the target compound (5-1) as a light yellow solid (87 mg, 94%, two-step yield). ).

¹ H-NMR (400 MHz, TCE-d ₂ , 100 ° C.): δ (ppm) 8.85 (d, 2H, J = 9.2 Hz), 8.68 (d, 2H, J = 9.2 Hz), 8.37 (d, 2H, J = 9.2 Hz), 7.87 (d, 2H, J = 9.2 Hz), 7.61 (s, 2H), 1.44-1.54 (m, 6H) ), 1.23 (d, 36H, J = 7.2 Hz).

  [Synthesis Example 3] (Boronization step)

Under an argon atmosphere, a suspension of compound (5-1) (1.3 g, 2.1 mmol) / cyclohexane (30 mL) was stirred at room temperature, and bis (1,5-cyclooctadiene) di-μ-methoxy was stirred. Diiridium (I) complex ([Ir (OMe) (COD)] ₂ , 69 mg, 0.11 mmol), 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy, 56 mg, 0.2 mmol) ), 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bis-1,3,2-dioxaboronate [(4) Bpin) ₂ ] (1.2 g, 4.6 mmol). The resulting suspension was further stirred at 80 ° C. for 22 hours. The reaction mixture was diluted with methanol, filtered, and washed with methanol to obtain the desired compound (7-1) (1.5 g, 83% yield).

¹ H-NMR (400 MHz, TCE-d ₂ , 100 ° C.): δ (ppm) 9.09 (s, 2H), 9.00 (d, 2H, J = 9.2 Hz), 8.35 (d, 2H, J = 9.2 Hz), 7.57 (s, 2H), 1.43-1.51 (m, 6H), 1.45 (s, 24H), 1.26 (d, 36H, J = 7.2 Hz).

  [Synthesis Example 4] (Halogenation step)

  Halogenation is performed while stirring a suspension of compound (7-1) (1.4 g, 1.6 mmol) / N-methylpyrrolidone (120 mL) / methanol (40 mL) / water (20 mL) at room temperature under an argon atmosphere. Copper (II) bromide (2.4 g, 10.6 mmol) as agent (8) was added. The resulting dark green suspension was stirred at 80 ° C. for 21 hours. After methanol was added to the reaction mixture at 0 ° C., the mixture was stirred, filtered, and washed with methanol to obtain the target compound (9-1) as a solid (1.1 g, 90% yield).

¹ H-NMR (400 MHz, TCE-d ₂ , 100 ° C.): δ (ppm) 8.83 (s, 2H), 8.77 (d, 2H, J = 9.2 Hz), 8.33 (d, 2H, J = 9.2 Hz), 7.65 (s, 2H), 1.45-1.55 (m, 6H), 1.24 (d, 36H, J = 7.2 Hz).

  [Synthesis Example 5] (Coupling step by Negishi coupling)

(R ^1a represents a 5-decyl-heptadecyl group; the same applies hereinafter)

Under an argon atmosphere, while stirring a 0.11 M 5-decyl-heptadecyl magnesium bromide-diethyl ether solution (9 mL, 0.98 mmol) / tetrahydrofuran (12 mL) solution at 0 ° C., 1.0 M zinc (II) chloride- After adding a tetrahydrofuran solution (0.97 mL, 0.97 mmol) and a 0.5 M lithium chloride-tetrahydrofuran solution (1.95 mL, 0.97 mmol), the white suspension was stirred at room temperature for 30 minutes, and a clear zinc solution was added. A reagent (alkyl zinc chloride lithium chloride: R ^1a -ZnCl LiCl) (compound (10)) was prepared.

Compound (9-1) (303 mg, 0.389 mmol), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex (PdCl ₂ (dppf) were added to a zinc reagent (compound (10)). ) _CH 2 _Cl 2, was added 31.8mg, 0.0389mmol) at room temperature. The resulting black suspension was stirred at 70 ° C. for 18 hours. Water was added to the obtained black suspension, and the organic layer was extracted with chloroform and washed with water. The crude product obtained by concentrating the extract under reduced pressure was purified by silica gel column chromatography (hexane) to obtain the target compound (11-1) as a transparent liquid (420 mg, 78% yield).

¹ H-NMR (400 MHz, TCE-d ₂ , 100 ° C.): δ (ppm) 8.78 (d, 2H, J = 9.2 Hz), 8.44 (s, 2H), 8.29 (d, 2H, J = 9.2 Hz), 7.58 (s, 2H), 3.19 (t, 4H, J = 7.6 Hz), 1.94 (quint, 4H, J = 7.6 Hz), 44-1.55 (m, 10H), 1.20-1.38 (m, 122H), 0.87 (t, 12H, J = 6.8 Hz).

  [Synthesis Example 6] (Desilylation step)

  Under an argon atmosphere, a compound (11-1) (400 mg, 0.29 mmol) / tetrahydrofuran (20 mL) solution was stirred at 0 ° C., and 1.0 M tetrabutylammonium fluoride (TBAF) was used as a deprotecting agent (12). -A solution of tetrahydrofuran (0.87 mL, 0.87 mmol) was added. The resulting white suspension was stirred at room temperature for 1.5 hours. Water and methanol were added to the reaction mixture, and the mixture was further stirred at 0 ° C., and the crude product obtained by filtration was purified by column chromatography (hexane) to give the target compound (13-1) as a white solid (131 mg, (42% yield).

¹ H-NMR (400 MHz, TCE-d ₂ , 100 ° C.): δ (ppm) 8.80 (d, 2H, J = 9.2 Hz), 8.48 (s, 2H), 8.26 (d, 2H, J = 9.2 Hz), 7.82 (d, 2H, J = 2.0 Hz), 7.35 (d, 2H, J = 2.0 Hz), 3.19 (t, 4H, J = 7) 1.6 Hz), 1.94 (quint, 4H, J = 7.6 Hz), 1.44-1.55 (m, 4H), 1.20-1.43 (m, 86H), 0.87 (t , 12H, J = 6.8 Hz).

  [Synthesis Example 7] (Halogenation step)

  Under an argon atmosphere, while stirring the compound (13-1) (130 mg, 0.122 mmol) / THF (3 mL) solution at -78 ° C, n-butyllithium (n-BuLi) / A normal hexane solution (1.55 M, 0.17 mL, 0.268 mmol) was added dropwise, and the mixture was stirred at −78 to −20 ° C. for 2 hours. To this light brown solution, a 1,2-dibromo-1,1,2,2-tetrachloroethane (87 mg, 0.268 mmol) / THF (3 mL) solution as a halogenating agent (14b) was added at −20 ° C. The mixture was stirred for 17 hours while being naturally raised to room temperature. After adding water to the reaction solution and diluting with chloroform, the organic layer was extracted with chloroform, dried over magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane) to obtain a white solid compound (2D-1) (95 mg, 64% yield).

¹ H-NMR (400 MHz, TCE-d ₂ , 100 ° C.): δ (ppm) 8.77 (d, 2H, J = 9.2 Hz), 8.44 (s, 2H), 8.17 (d, 2H, J = 9.2 Hz), 7.29 (s, 2H), 3.15 (t, 4H, J = 7.6 Hz), 1.92 (quint, 4H, J = 7.6 Hz), 44-1.54 (m, 4H), 1.20-1.39 (m, 86H), 0.872 (t, 12H, J = 7.2 Hz).

  [Example 1] (Suzuki coupling polymerization)

Under an argon atmosphere, compound (2D-1) (85 mg, 0.069 mmol), compound (2A-1) [4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl) -2,1,3-benzothiadiazole, manufactured by Tokyo Chemical Industry Co., Ltd., 27 mg, 0.069 mmol], tris (dibenzylideneacetone) dipalladium (0) chloroform complex (Pd ₂ (dba) ₃ CHCl) _3, 2.0 mg, 0.002 mmol), triphenylphosphine _{(PPh 3, 2.1mg, 0.008mmol)} , Aliquat ( registered trademark) 336 (Sigma Aldrich Corporation, 1 drop), tripotassium phosphate aqueous 2M (K ₃ PO ₄ , 0.17 mL, 0.327 mmol) and toluene (Tol, 2 mL) were added, and the mixture was stirred at 130 ° C. for 27 hours using an oil bath. The reaction mixture was reprecipitated in methanol, and the resulting precipitate was subjected to extraction (or washing) of impurities using a Soxhlet extractor in the order of methanol and acetone. Extraction of the washed precipitate with hexane resulted in no residue. The target compound (1-1) was obtained as a reddish brown solid (77 mg, 98% yield) by removing hexane from the obtained hexane solution.

When the obtained target compound (1-1) was measured by GPC (gel permeation chromatography) in terms of polystyrene, the number average molecular weight Mn was 13477, the weight average molecular weight Mw was 23713, and the molecular weight distribution Mw / Mn was 1.76. The polymerization degree DPn was 11.2. Further, when the obtained desired compound 5% mass defect temperature _{T 95} in (1-1) was measured by TG-DTA (thermogravimetric-differential thermal analyzer), it was 385 ° C..

[Example 2] (Suzuki coupling polymerization using microwave)
Under an argon atmosphere, compound (2D-1) (122 mg, 0.1 mmol), compound (2A-1) (39 mg, 0.1 mmol), tetrakistriphenylphosphine palladium (0) complex (Pd (PPh ₃ ) ₄ , 5 .8mg, 0.005mmol), Aliquat (registered trademark) 336 (Sigma Aldrich Corporation, 1 drop), tripotassium phosphate aqueous _{2M (K 3 PO 4, 1mL} , 2.0mmol), THF (1.0mL) Was added and mixed, and the mixture was heated and stirred for 40 minutes using a microwave irradiation apparatus (“Initiator +” manufactured by Biotage Japan, Inc., conditions: 130 ° C.). The obtained reaction mixture was washed and extracted in the same manner as in Example 1 to obtain the desired compound (1-1) (91 mg, yield 76%). When the obtained target compound (1-1) was measured by GPC (gel permeation chromatography) in terms of polystyrene, the number average molecular weight Mn was 18625, the weight average molecular weight Mw was 37935, the molecular weight distribution Mw / Mn was 2.0, The polymerization degree DPn was 15.5.

[Example 3]
The desired compound (1-1) was obtained in the same manner as in Example 2 except that toluene (1.6 mL) was used instead of THF (1.0 mL) (114 mg, 94% yield). When the obtained target compound (1-1) was measured by GPC (gel permeation chromatography) in terms of polystyrene, the number average molecular weight Mn was 16,460, the weight average molecular weight Mw was 38358, the molecular weight distribution Mw / Mn was 2.3, The polymerization degree DPn was 13.8.

[Comparative Example 1]
Second fraction (B) described in Example 4 of WO2017 / 170245 (Patent Document 1) (compound represented by the following formula, degree of polymerization DPn: 9.9, number average molecular weight Mn: 9175) , Weight average molecular weight Mw: 14662, molecular weight distribution Mw / Mn: 1.6).

(Wherein, R ¹¹ represents a 3-octyltridecyl group).

[Synthesis Example 8]
In place of chryseno [2,1-b: 8,7-b '] difuran (the compound (3-1)), chryseno [2,1-b: 8,7-b'] dithiophene (the following compound (3 -2), and an alkylating agent (10) in a Negishi coupling reaction [synthesized according to Synthesis Examples 1 to 5 of WO 2017/170245 (Patent Document 1)] [alkyl zinc chloride lithium chloride: R ^1a- ZnCl LiCl (wherein, R ^1a represents a 5-decyl-heptadecyl group)] and R ^1b (wherein, R ^1b represents a 5-octyl-pentadecyl group) instead of the alkyl group R ^1a. In accordance with Synthesis Examples 1 to 7 (reacted with each reagent having the same molar ratio), except that lithium zinc chloride (R ^1b -ZnCl LiCl) prepared and used was introduced, Is Compound (2D-2) was prepared.

(Wherein, R ^1b represents a 5-octyl-pentadecyl group; the same applies hereinafter).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.84 (d, 2H, J = 9.2 Hz), 8.52 (s, 2H), 8.38 (d, 2H, J = 9) .2 Hz), 8.10 (s, 2H), 3.07 (t, 4H, J = 7.6 Hz), 1.93 (quint, 4H, J = 7.6 Hz), 1.42-1.52 (M, 4H), 1.17-1.40 (m, 70H), 0.87 (t, 12H, J = 7.2 Hz).

  [Example 4] (Suzuki coupling polymerization)

Under an argon atmosphere, compound (2D-2) (114 mg, 0.1 mmol), compound (2A-1) (39 mg, 0.1 mol), tetrakistriphenylphosphine palladium (0) complex (Pd (PPh ₃ ) ₄ , 12 mg , 0.01 mmol), Aliquat® 336 (Sigma Aldrich, 1 drop), 2M aqueous potassium carbonate (K ₂ CO ₃ , 1 mL, 2 mmol), THF (1.6 mL), and mix. The mixture was heated and stirred for 40 minutes using a wave irradiation device (“Initiator +” manufactured by Biotage Japan, Inc., conditions: 130 ° C.). The obtained reaction mixture was washed and extracted in the same manner as in Example 1 to obtain the desired compound (1-2) (95 mg, 85% yield). When the obtained target compound (1-2) was measured by GPC (gel permeation chromatography) in terms of polystyrene, the number average molecular weight Mn was 13,267, the weight average molecular weight Mw was 51352, the z average molecular weight Mz was 638208, and the molecular weight distribution Mw. / Mn was 3.9 and the degree of polymerization DPn was 11.9.

[Synthesis Example 9]
In place of chryseno [2,1-b: 8,7-b '] difuran (the compound (3-1)), chryseno [2,1-b: 8,7-b'] dithiophene (the following compound (3 -2), and an alkylating agent (10) in a Negishi coupling reaction [synthesized according to Synthesis Examples 1 to 5 of WO 2017/170245 (Patent Document 1)] [alkyl zinc chloride lithium chloride: R ^1a- ZnCl LiCl (wherein, R ^1a represents a 5-decyl-heptadecyl group)] and R ^1c (wherein, R ^1c represents a 4-octyl-tetradecyl group) in place of the alkyl group R ^1a. According to Synthesis Examples 1 to 7 (reacted with each reagent having the same molar ratio) except that lithium zinc chloride (R ^1c -ZnCl LiCl) prepared and used was introduced. Is Compound (2D-3) was prepared.

(Wherein, R ^1c represents a 4-octyl-tetradecyl group; the same applies hereinafter).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.85 (d, 2H, J = 9.2 Hz), 8.53 (s, 2H), 8.39 (d, 2H, J = 9) .2 Hz), 8.10 (s, 2H), 3.05 (t, 4H, J = 7.6 Hz), 1.92 (quint, 4H, J = 7.6 Hz), 1.33-1.49 (M, 6H), 1.18-1.34 (m, 64H), 0.86 (t, 12H, J = 7.2 Hz).

  [Example 5] (Suzuki coupling polymerization)

Under an argon atmosphere, compound (2D-3) (112 mg, 0.1 mmol), compound (2A-1) (39 mg, 0.1 mol), tetrakistriphenylphosphine palladium (0) complex (Pd (PPh ₃ ) ₄ , 12 mg , 0.01 mmol), Aliquat® 336 (Sigma Aldrich, 1 drop), 2M aqueous potassium carbonate (K ₂ CO ₃ , 1 mL, 2 mmol), THF (1.6 mL), and mix. The mixture was heated and stirred for 40 minutes using a wave irradiation device (“Initiator +” manufactured by Biotage Japan, Inc., conditions: 130 ° C.). The obtained reaction mixture was washed and extracted in the same manner as in Example 1 to obtain the desired compound (1-3) (52 mg, 46 (% yield). The obtained desired compound (1-3) ) Was measured by GPC (gel permeation chromatography) in terms of polystyrene. The number average molecular weight Mn was 12995, the weight average molecular weight Mw was 84204, the z average molecular weight Mz was 386585, the molecular weight distribution Mw / Mn was 6.5, and the degree of polymerization was calculated. DPn was 11.6.

[Example 6]
In the same manner as in Example 5, the target compound (1-3) was obtained (32 mg, 29% yield). When the obtained target compound (1-3) was measured by GPC (gel permeation chromatography) in terms of polystyrene, the number average molecular weight Mn was 21,624, the weight average molecular weight Mw was 155918, the z average molecular weight Mz was 1461778, and the molecular weight distribution Mw. / Mn was 7.2 and the degree of polymerization DPn was 19.3.

[Thin film X-ray analysis]
(Sample preparation)
A silicon (Si) substrate provided with a silicon dioxide (SiO ₂ ) insulating film (500 nm in thickness) was ultrasonically cleaned with acetone and 2-propanol for 3 minutes each, and dried at 120 ° C. for 30 minutes. Subsequently, UV ozone treatment was performed for 30 minutes. A self-assembled monolayer (SAM) of decyltriethoxysilane (DTS) was formed on the cleaned substrate surface by a vapor method.

  Using the compound (1-1) obtained in Example 1, a solution of the compound (1-1) / orthodichlorobenzene (oDCB) at a concentration of 1.0% by weight dissolved at 80 ° C. on the surface of the monomolecular film. Was dropped, and the film was formed by a spin coating method (at a rotation speed of 500 rpm and a rotation time of 5 s, and further at a rotation speed of 2,000 rpm and a rotation time of 30 s), and then (a) 100 ° C., (b) 150 ° C. After annealing at (c) 200 ° C. or (d) 240 ° C. for 30 minutes, it was dried under vacuum at 100 ° C. for 12 hours to form a coating film.

  Samples using the compound obtained in Comparative Example 1 were prepared by a spin coating method and a compression alignment method capable of improving the molecular orientation compared to the spin coating method. The sample prepared by the spin coating method was prepared in the same manner as the sample of Example 1 except that the compound obtained in Comparative Example 1 was used instead of the compound (1-1) obtained in Example 1. . The annealing was performed at 150 ° C. for 30 minutes.

  In the sample prepared by the compression orientation method, a self-assembled monolayer (SAM) of perfluorodecyltrichlorosilane (F-SAM) is formed on the surface of the substrate subjected to the above-mentioned cleaning treatment by an evaporation method, and the surface of the monomolecular film is formed. Was added dropwise at 120 ° C. to a solution of the compound obtained in Comparative Example 1 at a concentration of 0.01% by weight / orthodichlorobenzene (oDCB), which was subjected to a compression alignment method [ionic liquid: EMIM-TFSI (1-ethyl-3). -Methylimidazolium bis (trifluoromethanesulfonyl) imide), coating temperature: 140 ° C., coating speed: 2 mm / sec, drying time: 20 sec], and after drying at 200 ° C. for 1 hour in an argon atmosphere. Then, the substrate was washed in acetonitrile for 3 hours and further annealed at 150 ° C. for 1 hour in an argon atmosphere.

(Measurement condition)
Measurement facility: SPring-8
Wavelength: 1.00Å
Incident angle: 0.12 °
Exposure time: 60 seconds Direct beam: X = 57, Y = 587 pixels
Camera length: 175.1 mm

  FIG. 1 (spin coating) shows the measurement results (two-dimensional diffraction image) of the compound (1-1) obtained in Example 1, and FIG. 2 ((a) spin coating) shows the measurement results of the sample obtained in Comparative Example 1. And (b) compression orientation).

As is clear from FIG. 1, in the compound (1-1) obtained in Example 1, the edge-on (edge-on) orientation [the planar skeleton of the molecule (main chain plane) is perpendicular to the substrate]. Orientation]. More specifically, peaks (100), (200), (300), (400), and (500) are observed on the qz axis indicating the property in the direction perpendicular to the substrate, and the distance between the planes (lamella distance) d _l between the structures are 27.5Å at any annealing temperature is considered to correspond to the alkyl group represented by R ^1a. Further, a peak of (010) is observed on the qxy axis indicating the property of the direction parallel to the substrate (plane direction of the substrate), and the inter-plane distance (distance between π stacks) d _π is 3. 45 ° (annealing temperature: 100 ° C., 200 ° C., 240 ° C.) or 3.47 ° (150 ° C.). Since d _{π of} a general organic semiconductor polymer is about 3.4 to 3.75 °, the compound (1-1) has a small d _π even when the film is formed by a spin coating method in which the orientation cannot be improved so much. It was found that the compound was extremely excellent in orientation (or crystallinity). Further, it was found that as the annealing temperature increased, each peak appeared more clearly, and the orientation could be further improved.

  On the other hand, in the compound obtained in Comparative Example 1, in the sample formed by spin coating, as shown in FIG. 2A, although peaks such as (100) and (200) are slightly observed, ) Was not observed, indicating that the molecules were not very oriented.

When the orientation is improved by compression orientation, peaks of (100), (200), (300) and (010) are observed as in the case of compound (1-1), as shown in FIG. , D ₁ was 25.3 ° and d _π was 3.9 °, indicating that edge-on orientation was achieved. Even when formed by the compression orientation method, the distance d _π between the π stacks was relatively large.

[Transistor characteristics]
(Element using polymer of Example 1)
A silicon (Si) substrate provided with a silicon dioxide (SiO ₂ ) insulating film (thickness: 500 nm) was subjected to ultrasonic cleaning in the order of acetone and 2-propanol for 3 minutes each, and then dried at 120 ° C. for 30 minutes. Subsequently, UV ozone treatment was performed for 30 minutes. A self-assembled monolayer (SAM) of β-phenethyltrichlorosilane (β-PTS) was formed on the surface of the substrate subjected to the UV ozone treatment by a vapor method.

A 2.0% by weight solution of the compound (1-1) / ortho-dichlorobenzene (oDCB) obtained in Example 1 dissolved at 70 ° C. was dropped onto the surface of the monomolecular film, and the solution was spin-coated (rotation). After forming the film at a number of 1000 rpm and a rotation time of 30 s), the film was annealed at 100 ° C. for 30 minutes in an argon atmosphere and dried at 60 ° C. under reduced pressure for 12 hours. The dried film surface Place the metal mask, as the carrier injection layer, tetrafluoro tetracyanoquinodimethane _(F 4 -TCNQ) (thickness of about 2 nm), vacuum evaporation as a source electrode and a drain electrode, a gold (thickness 40 nm) As a result, a device element (top contact-bottom gate type, channel length 200 μm, channel width 2 mm) was manufactured. FIG. 3 shows a schematic diagram of the device.

The carrier mobility μ and the threshold voltage Vth of the manufactured device element were measured using a semiconductor parameter analyzer (model number “keithley 4200”, manufactured by Keithley Instruments Co., Ltd.), and when the drain voltage Vd = −100 V, μ = 1.1 × 10 ⁻² cm ² / Vs, Vth = −33 V, and μ = 1.3 × 10 ⁻² cm ² / Vs, Vth = −58 V at a drain voltage Vd = −150 V.

(Device using the polymer of Comparative Example 1)
On the other hand, for the compound obtained in Comparative Example 1, an element was prepared by the method described in Example 5 of International Publication No. WO2017 / 170245 (Patent Document 1), and the carrier mobility μ was measured. It was 6.9 × 10 ⁻³ cm ² / Vs, and the mobility was lower than that of the device manufactured using Example 1.

(Element Using Polymer of Example 4)
A silicon (Si) substrate provided with a silicon dioxide (SiO ₂ ) insulating film (thickness: 500 nm) was subjected to ultrasonic cleaning in the order of acetone and 2-propanol for 3 minutes each, and then dried at 120 ° C. for 30 minutes. Subsequently, UV ozone treatment was performed for 30 minutes. A self-assembled monolayer (SAM) of β-phenethyltrichlorosilane (β-PTS) was formed on the surface of the substrate subjected to the UV ozone treatment by a vapor method.

A solution of the compound (1-2) / orthodichlorobenzene (oDCB) obtained in Example 4 having a concentration of 2.0% by weight dissolved at 70 ° C. was dropped on the surface of the monomolecular film, and the solution was spin-coated (rotation). After forming the film at a number of 1000 rpm and a rotation time of 30 s), the film was annealed at 300 ° C. for 30 minutes in an argon atmosphere and dried at 100 ° C. under reduced pressure for 12 hours. The dried film surface Place the metal mask, as the carrier injection layer, tetrafluoro tetracyanoquinodimethane _(F 4 -TCNQ) (thickness of about 2 nm), vacuum evaporation as a source electrode and a drain electrode, a gold (thickness 40 nm) As a result, a device element (top contact-bottom gate type, channel length 200 μm, channel width 2 mm) was manufactured. FIG. 3 shows a schematic diagram of the device.

The carrier mobility μ and the threshold voltage Vth of the fabricated device element were measured using a semiconductor parameter analyzer (model “keithley 4200”, manufactured by Keithley Instruments Co., Ltd.), and when the drain voltage Vd = −100 V, μ = 1.6 × 10 ⁻² cm ² / Vs, Vth = −55 V, and μ = 2.0 × 10 ⁻² cm ² / Vs, Vth = −89 V at a drain voltage Vd = −150 V.

  Further, an element was formed by a drop casting method instead of the spin coating method. Specifically, the compound (1-3) obtained in Example 5 having a concentration of 0.1% by weight dissolved at room temperature (about 25 ° C.) / Orthodichlorobenzene was dissolved on the surface of the monomolecular film of the substrate on which the SAM was formed. The (oDCB) solution was added dropwise, and a film was formed at 120 ° C. using a hot plate, and then dried under reduced pressure at 40 ° C. for 12 hours. Thereafter, the device element shown in FIG. 3 was manufactured in the same manner as the element manufactured by the spin coating method.

The carrier mobility μ and the threshold voltage Vth of the fabricated device element were measured using a semiconductor parameter analyzer (model number “keithley 4200”, manufactured by Keithley Instruments Co., Ltd.), and when the drain voltage Vd was −150 V, μ = 1.8 × 10 ⁻² cm ² / Vs and Vth = −62 V.

(Element Using Polymer of Example 5)
A silicon (Si) substrate provided with a silicon dioxide (SiO ₂ ) insulating film (thickness: 500 nm) was subjected to ultrasonic cleaning in the order of acetone and 2-propanol for 3 minutes each, and then dried at 120 ° C. for 30 minutes. Subsequently, UV ozone treatment was performed for 30 minutes. A self-assembled monolayer (SAM) of decyltriethoxysilane (DTS) was formed on the surface of the substrate subjected to the UV ozone treatment by a vapor method.

A solution of the compound (1-3) / orthodichlorobenzene (oDCB) obtained in Example 5 having a concentration of 1.0% by weight dissolved at 70 ° C. was dropped on the surface of the monomolecular film, and the solution was spin-coated (rotation). (Number: 1000 rpm, rotation time: 30 s), and then annealed at 300 ° C. for 3 hours in an argon atmosphere. The dried film surface Place the metal mask, as the carrier injection layer, tetrafluoro tetracyanoquinodimethane _(F 4 -TCNQ) (thickness of about 2 nm), vacuum evaporation as a source electrode and a drain electrode, a gold (thickness 40 nm) As a result, a device element (top contact-bottom gate type, channel length 200 μm, channel width 2 mm) was manufactured. FIG. 3 shows a schematic diagram of the device.

The carrier mobility μ and the threshold voltage Vth of the fabricated device element were measured using a semiconductor parameter analyzer (model “keithley 4200”, manufactured by Keithley Instruments Co., Ltd.), and when the drain voltage Vd = −100 V, μ = 5.1 × 10 ⁻² cm ² / Vs, Vth = −30 V, and μ = 5.7 × 10 ⁻² cm ² / Vs, Vth = −51 V at a drain voltage Vd = −150 V.

(Element Using Polymer of Example 6)
A silicon (Si) substrate provided with a silicon dioxide (SiO ₂ ) insulating film (thickness: 500 nm) was subjected to ultrasonic cleaning in the order of acetone and 2-propanol for 3 minutes each, and then dried at 120 ° C. for 30 minutes. Subsequently, UV ozone treatment was performed for 30 minutes. A self-assembled monolayer (SAM) of β-phenethyltrichlorosilane (β-PTS) was formed on the surface of the substrate subjected to the UV ozone treatment by a vapor method.

A solution of the compound (1-3) / orthodichlorobenzene (oDCB) obtained in Example 6 having a concentration of 1.0% by weight dissolved at room temperature (about 25 ° C.) was dropped on the surface of the monomolecular film, and the solution was spin-dried. After forming a film by a coating method (rotation speed: 1000 rpm, rotation time: 30 s), annealing was performed at 300 ° C. for 3 hours in an argon atmosphere. The dried film surface Place the metal mask, as the carrier injection layer, tetrafluoro tetracyanoquinodimethane _(F 4 -TCNQ) (thickness of about 2 nm), vacuum evaporation as a source electrode and a drain electrode, a gold (thickness 40 nm) As a result, a device element (top contact-bottom gate type, channel length 200 μm, channel width 2 mm) was manufactured. FIG. 3 shows a schematic diagram of the device.

The carrier mobility μ and the threshold voltage Vth of the manufactured device element were measured using a semiconductor parameter analyzer (model number “keithley 4200”, manufactured by Keithley Instruments Co., Ltd.), and when the drain voltage Vd = −100 V, μ = 7.3 × 10 ⁻² cm ² / Vs, Vth = −32 V, and μ = 8.0 × 10 ⁻² cm ² / Vs, Vth = −53 V at a drain voltage Vd = −150 V.

  Since the organic polymer compound of the present invention is excellent in solubility and mobility in an organic solvent, an organic semiconductor containing the compound can be used in various electronic devices, for example, a rectifying element (diode), a switching element, or a transistor (organic). It can be effectively used as an organic semiconductor device such as a thin film transistor (for example, a junction transistor (bipolar transistor), a field effect transistor (unipolar transistor), etc.) and a photoelectric conversion element (solar cell element, organic EL element, etc.). In particular, since the compound can be edge-on-oriented with respect to the substrate, it can be suitably used as a transistor.

Claims (16)

An organic polymer having a donor unit (D) and an acceptor unit (A), wherein the donor unit (D) contains at least the donor unit (D1) represented by the following formula (I). Organic macromolecules.
(Wherein, ring A and ring B each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle, n represents 0 or an integer of 1 to 6, and R ^{1 to} R ^{2 + n} each independently represent A ^{1 to} a ^{2 + n} each independently represent an integer of 0 to 2; and ring C is arranged in a non-linear sequence with respect to an adjacent benzene ring in accordance with the number of n. A benzene ring which is ortho-condensed is shown.) The organic polymer according to claim 1, wherein the donor unit (D1) has a unit represented by at least one of the following formulas (I-1) to (I-5).
(Wherein, R ^{1 to} R ⁶ each independently represent an alkyl group, an aryl group, an alkoxy group, or an alkylthio group, and a ^{1 to} a ⁶ each independently represent an integer of 0 to 2, Ring A and ring B are the same as in claim 1.) The organic polymer according to claim 1 or 2, wherein the donor unit (D1) has a unit represented by the following formula (I-3).
(In the formula, at least one of R ^{1 to} R ^{4 represents} a linear or branched C _4-34 alkyl group or a linear or branched C _4-34 alkoxy group, and a ^{1 to} a ⁴ Each independently represents 0 or 1, at least one of a ^{1 to} a ⁴ is 1, and ring A and ring B are the same as in claim 1)   In the formula (I), the ring A and the ring B are aromatic rings selected from a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, and a benzene ring. .   The organic polymer according to any one of claims 1 to 4, wherein the acceptor unit (A) includes a unit (A1) having a nitrogen atom and an aromatic heterocyclic skeleton containing a group 16 atom of the periodic table. The unit (A1) having a nitrogen atom and an aromatic heterocyclic skeleton containing a Group 16 atom of the periodic table is a unit represented by at least one formula selected from the following formulas (III-1) to (III-5) The organic polymer according to claim 5, comprising:
(Wherein, rings E ¹ and E ² are each independently an aromatic ring, Z ^{1 to} Z ⁵ are each independently an oxygen atom, a sulfur atom or a selenium atom, R ^A1 , R ^A2 and R ^A3 are Each independently represents an alkyl group, aryl group, alkoxy group, alkylthio group or halogen atom, m1, m2 and m3 each independently represent an integer of 0 or more.) In the formula (III-1), ring E ¹ is a benzene ring, a naphthalene ring, a pyridine ring, a pyridazine ring, an isoquinoline ring, a phthalazine ring or a quinoxaline ring, Z ¹ is an oxygen atom or a sulfur atom, and R ^A1 is an alkyl The organic polymer according to claim 6, which is a group, an alkoxy group or a halogen atom, and m1 is an integer of 0 to 2.   The organic polymer according to any one of claims 1 to 7, which is a block copolymer or an alternating copolymer of the donor unit (D) and the acceptor unit (A).   The donor unit (D) contains a unit having at least one substituent selected from a linear or branched alkyl group and a linear or branched alkoxy group, and the acceptor unit (A) Contains a unit having no linear or branched alkyl group and no linear or branched alkoxy group, The organic polymer according to any one of claims 1 to 8.   The method for producing an organic polymer according to any one of claims 1 to 9, wherein a compound containing a donor unit (D) and a compound containing an acceptor unit (A) are subjected to a coupling reaction.   The production method according to claim 10, wherein the coupling reaction is a Suzuki coupling reaction, and the reaction is performed under microwave irradiation.   An organic semiconductor comprising the organic polymer according to claim 1.   The organic semiconductor according to claim 12, further comprising a substrate, wherein the organic polymer according to any one of claims 1 to 9 is edge-on or face-on oriented with respect to the substrate.   A composition comprising the organic polymer according to claim 1 and a solvent.   14. The method for producing an organic semiconductor according to claim 12 or 13, wherein the composition according to claim 14 is applied to a substrate, and the solvent is removed.   An electronic device comprising the organic semiconductor according to claim 12.