WO2012050102A1

WO2012050102A1 - Polymeric compound, organic semiconductor material, and organic transistor

Info

Publication number: WO2012050102A1
Application number: PCT/JP2011/073372
Authority: WO
Inventors: 宏樹寺井
Original assignee: 住友化学株式会社
Priority date: 2010-10-13
Filing date: 2011-10-12
Publication date: 2012-04-19
Also published as: JP2012082345A; TW201229085A

Abstract

[Problem] To provide a polymeric compound which increases the field effect mobility of an organic transistor when used in an active layer (organic semiconductor layer) of the organic transistor. [Solution] A polymeric compound containing a structural unit represented by formula (1) (wherein R¹ represents an alkyl group, an aryl group, or a heteroaryl group; and R² represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, or a heteroaryl group) and a structural unit represented by formula (2-1) or (2-2) (wherein Z¹ represents -CR⁵=CR⁶-, -S-, -O-, -Se-, or -NR⁷-; R³, R⁴, R⁵, and R⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a halogen atom, a cyano group, or a nitro group; R⁷ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group; and Z² represents =S=, =CR⁵-CR⁶=, or =Se=).

Description

Polymer compound, organic semiconductor material and organic transistor

The present invention relates to a polymer compound useful as an organic semiconductor material and an organic transistor using the same.

Since organic transistors using organic semiconductor materials are expected to be lighter, have lower manufacturing costs and can be manufactured at lower temperatures than conventional transistors using inorganic semiconductor materials, they are actively researched and developed. Has been done.

The field effect mobility, which is one of the performances of organic transistors, greatly depends on the carrier mobility of the organic semiconductor material contained in the active layer. Therefore, it is considered to use various organic semiconductor materials for the active layer of the organic transistor. ing.

For example, in Non-Patent Document 1, an organic transistor is manufactured using the following polymer compound as an organic semiconductor material, and transistor characteristics are measured.

However, an organic transistor using the polymer compound as an organic semiconductor material has a field effect mobility of about 1.0 × 10 ⁻³ cm ² / Vs, and the field effect mobility is not necessarily high enough. is there.

The present invention solves the above-mentioned conventional problems, and the object of the present invention is to provide a polymer compound that increases the field effect mobility of an organic transistor when used in an active layer (organic semiconductor layer) of the organic transistor. Is to provide.

That is, the present invention has the formula

(1)

[Wherein, R ¹ represents an alkyl group, an aryl group, or a heteroaryl group. R ² represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or a heteroaryl group. ]
And the structural unit represented by

[Wherein Z ¹ represents —CR ⁵ ═CR ⁶ —, —S—, —O—, —Se— or —NR ⁷ —. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a halogen atom, a cyano group or a nitro group. R ⁷ represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. Z ² represents = S =, = CR ⁵ -CR ⁶ = or = Se =. ]
The polymer compound containing the structural unit represented by these is provided.

In one embodiment, the polymer compound has the formula

[Wherein R ¹ and R ² represent the same meaning as described above. a represents an integer of 1 to 4. b represents an integer of 0 to 4. c represents an integer of 1 to 4. A plurality of R ¹ may be the same or different. A plurality of R ² may be the same or different. ]
It has the structural unit represented by these.

The present invention also provides an organic semiconductor material containing the polymer compound. In the present invention, the “organic semiconductor material” means a material containing an organic compound exhibiting semiconductor behavior.

The present invention also provides an organic semiconductor element having an organic layer containing the organic semiconductor material. In the present invention, the “organic semiconductor element” means a semiconductor element having an organic layer containing an organic semiconductor material.

The present invention also provides an organic transistor having a source electrode, a drain electrode, a gate electrode, and an active layer, wherein the active layer includes the organic semiconductor material.

Since the organic transistor containing the polymer compound of the present invention in the active layer exhibits high field effect mobility, the present invention is extremely useful.

It is a schematic cross section which shows an example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention. It is a schematic cross section which shows the other example of the organic transistor of this invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant descriptions are omitted.

In the present specification, the “structural unit” means a unit structure present in one or more polymer compounds. The “structural unit” is preferably contained in the polymer compound as a “repeating unit” (that is, a unit structure present in two or more in the polymer compound).

<Polymer compound>
(First structural unit)
The polymer compound of the present invention includes a structural unit represented by the formula (1) (hereinafter sometimes referred to as “first structural unit”). The first structural unit may be contained alone or in combination of two or more in the polymer compound.

In formula (1), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group. R ² represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or a heteroaryl group.

Here, the alkyl group may be linear or branched, and may be a cycloalkyl group. The alkyl group usually has 1 to 60 carbon atoms, preferably 1 to 20 carbon atoms. Among the alkyl groups, a linear alkyl group and a branched alkyl group are preferable, and a linear alkyl group is more preferable.

Specific examples of the alkyl group include a straight chain alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, and an n-octadecyl group, Examples thereof include branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group and 3,7-dimethyloctyl group, and cycloalkyl groups such as cyclopentyl group and cyclohexyl group.

The alkyl group may have a substituent, and examples of the substituent that the alkyl group may have include an alkoxy group, an aryl group, and a halogen atom. Specific examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.

The alkoxy group may have a substituent, and the number of carbon atoms of the alkoxy group excluding the substituent is usually 1-20. The alkoxy group may be linear or branched, and may be a cycloalkoxy group.

Specific examples of the alkoxy group include n-butyloxy group, n-hexyloxy group, 2-ethylhexyloxy group, 3,7-dimethyloctyloxy group, n-dodecyloxy group and the like.

Among the alkoxy groups, linear alkyloxy groups such as n-butyloxy group, n-hexyloxy group, n-dodecyloxy group and the like are preferable.

The alkylthio group may have a substituent, and the alkylthio group excluding the substituent usually has 1 to 20 carbon atoms. The alkylthio group may be linear or branched, and may be a cycloalkylthio group.

Specific examples of the alkylthio group include n-butylthio group, n-hexylthio group, 2-ethylhexylthio group, 3,7-dimethyloctylthio group, n-dodecylthio group and the like.

Among the alkylthio groups, linear alkylthio groups such as n-butylthio group, n-hexylthio group, and n-dodecylthio group are preferable.

An aryl group is an atomic group obtained by removing one hydrogen atom directly bonded to an aromatic ring from an aromatic hydrocarbon compound, a group having a benzene ring, a group having a condensed ring, an independent aromatic ring or two condensed rings. These include groups directly attached. The aryl group usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms. Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2- Examples include a fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, and a 4-phenylphenyl group.

The aryl group may have a substituent. Examples of the substituent that the aryl group may have include an alkyl group, an alkoxy group, an alkylthio group, a heteroaryl group, and a halogen atom. Examples of the aryl group having a substituent include a 4-hexylphenyl group, a 3,5-dimethoxyphenyl group, and a pentafluorophenyl group. When the aryl group has a substituent, the substituent is preferably an alkyl group.

A heteroaryl group is an atomic group obtained by removing one hydrogen atom directly bonded to an aromatic ring from a heterocyclic compound having aromaticity, a group having a condensed ring, an independent heteroaromatic ring or a condensed ring 2 Includes groups in which more than one are directly bonded. The heteroaryl group usually has 2 to 60 carbon atoms, and preferably 3 to 20 carbon atoms. Heteroaryl groups include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-oxazolyl group, 2-thiazolyl group, 2-imidazolyl group 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group and the like.

The heteroaryl group may have a substituent. Examples of the substituent that the heteroaryl group may have include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, and a halogen atom. Examples of the heteroaryl group having a substituent include a 5-octyl-2-thienyl group and a 5-phenyl-2-furyl group. When the heteroaryl group has a substituent, the substituent is preferably an alkyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ¹ is preferably an alkyl group from the viewpoint of improving the solubility of the polymer compound and facilitating device fabrication.

R ² is preferably a hydrogen atom, an alkyl group or an alkylthio group from the viewpoint of facilitating the device preparation by improving the synthesis of the compound containing the first structural unit and the solubility of the polymer compound, An alkyl group is more preferable, and a hydrogen atom is more preferable.

Examples of the first structural unit include a structural unit represented by the formula (1-001) to a structural unit represented by the formula (1-010). Among these, from the viewpoint of ease of synthesis, a structural unit represented by the formula (1-001) is preferable.

[In the formulas (1-001) to (1-010), R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or a heteroaryl group, and R ^a represents an alkyl group, an aryl group or Represents a heteroaryl group. A plurality of R may be the same or different. A plurality of R ^a may be the same or different.]

From the viewpoint of improving the carrier mobility of the polymer compound, the polymer compound may include a structural unit represented by the formula (3) including the first structural unit or a structural unit represented by the formula (4). preferable.

In formula (3) and formula (4), a represents an integer of 1 to 4. From the viewpoint of ease of synthesis, 1 or 2 is preferable.

In the formulas (3) and (4), b represents an integer of 0 to 4. From the viewpoint of ease of synthesis, 0 to 2 is preferable.

In the formulas (3) and (4), c represents an integer of 1 to 4. From the viewpoint of ease of synthesis, 1 or 2 is preferable.

From the viewpoint of ease of synthesis, a and c are preferably the same.

Examples of the structural unit represented by the formula (3) include a structural unit represented by the formula (3-001) to a structural unit represented by the formula (3-014). Among these, a structural unit represented by the formula (3-001) to a structural unit represented by the formula (3-005) are preferable.

[In the formulas (3-001) to (3-014), R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or a heteroaryl group, and R ^a represents an alkyl group, an aryl group or Represents a heteroaryl group. A plurality of R may be the same or different. A plurality of R ^a may be the same or different.]

Examples of the structural unit represented by the formula (4) include a structural unit represented by the formula (4-001) to a structural unit represented by the formula (4-014). Among these, a structural unit represented by formula (4-001) to a structural unit represented by formula (4-005) are preferable.

[In the formulas (4-001) to (4-014), R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or a heteroaryl group, and R ^a represents an alkyl group, an aryl group or Represents a heteroaryl group. A plurality of R may be the same or different. A plurality of R ^a may be the same or different.]

From the viewpoint of ease of synthesis, the structural unit represented by the formula (3) is preferable to the structural unit represented by the formula (4).

(Second structural unit)
The polymer compound of the present invention includes a structural unit represented by the formula (2-1) or a structural unit represented by the formula (2-2) (hereinafter referred to as a structural unit or a formula represented by the formula (2-1)). (2-2) may be referred to as “second structural unit”). The second structural unit may be contained alone or in combination of two or more in the polymer compound.

In Formula (2-1) and Formula (2-2), Z ¹ represents —CR ⁵ ═CR ⁶ —, —S—, —O—, —Se— or —NR ⁷ —. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a halogen atom, a cyano group or a nitro group. R ⁷ represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. Z ² represents = S =, = CR ⁵ -CR ⁶ = or = Se =. Definitions and specific examples of alkyl groups, aryl groups, and heteroaryl groups represented by R ³ , R ⁴ , R ^5, and R ⁶ include the alkyl groups, aryl groups, and heteroaryl groups represented by R ¹ described above. Definitions and examples are the same. Examples of the halogen atom represented by R ³ , R ⁴ , R ⁵ and R ⁶ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ⁷ are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ¹ described above.

The polymer compound of the present invention preferably contains a structural unit represented by the formula (2-1).

Z ¹ is preferably —S— from the viewpoint of increasing the carrier mobility of the polymer compound of the present invention.

Examples of the second structural unit include a structural unit represented by the formula (2-001) to a structural unit represented by the formula (2-006).

[In the formulas (2-001) to (2-006), R ^a represents an alkyl group, an aryl group or a heteroaryl group, and R ^b represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group or an aryl group. Represents a heteroaryl group or a halogen atom. A plurality of R ^a may be the same or different. A plurality of R ^b may be the same or different.]

The second structural unit is a structure that relatively accepts electrons compared to the first structural unit.
Therefore, in the polymer having the second structural unit in the polymer compound, the second structural unit is polarized relatively negatively, and the first structural unit is polarized relatively positively. As a result, it is presumed that an electrostatic attractive force is generated between the polymer compounds, and intermolecular carrier movement is promoted.

(Other structural units)
The polymer compound of the present invention includes a first structural unit, a second structural unit, a structural unit represented by the formula (3), and a structural unit other than the structural unit represented by the formula (4) (hereinafter referred to as “other structures”). May be referred to as “unit”.). Other structural units may be contained alone or in combination of two or more in the polymer compound.

Examples of the other structural unit include a divalent aromatic group, a group represented by the formula —CR ^c ═CR ^c —, and a group represented by the formula —C≡C—.

A divalent aromatic group is an atomic group obtained by removing two hydrogen atoms from an aromatic ring, and a group having a benzene ring, a group having a condensed ring, an independent aromatic ring or two or more condensed rings are directly bonded. Contains groups. Divalent aromatic groups include phenylene group, naphthalenediyl group, anthracenediyl group, phenanthenediyl group, tetracenediyl group, pyrenediyl group, pentacenediyl group, perylenediyl group, fluorenediyl group, oxadiazolediyl group, thiadiazole Diyl group, oxazole diyl group, thiazole diyl group, thiophene diyl group, bithiophene diyl group, terthiophene diyl group, quaterthiophene diyl group, pyrrole diyl group, frangyl group, selenophene diyl group, pyridine diyl group, pyrazine diyl group, Pyrimidinediyl group, triazinediyl group, benzothiophenediyl group, benzopyrrolediyl group, benzofuranyl group, quinolinediyl group, isoquinolinediyl group, thienothiophenediyl group, benzodithio Enjiiru group, and the like. The divalent aromatic group may have a substituent.

-CR ^{^c} = CR ^c - in the group represented by, ^{R c} each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a cyano group. The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ^c are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ¹ described above.

From the viewpoint of increasing the carrier mobility of the polymer compound of the present invention, the other structural unit is preferably a divalent aromatic group, and may have a phenylenediyl group which may have a substituent, or a substituent. A fluorenediyl group which may have a thiophene diyl group which may have an alkyl group, an aryl group or a heteroaryl group as a substituent, a thienothiophene diyl group which may have a substituent, a substituent The benzodithiophenediyl group which may be present is more preferable, and the group represented by the following formula (A-001) to the group represented by the formula (A-005) is particularly preferable.

[Wherein, R ^b represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, or a halogen atom. A plurality of R ^b may be the same or different. R ^d represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. A plurality of R ^d may be the same or different. ]

The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ^d are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ¹ described above.

The polymer compound of the present invention is preferably a conjugated polymer compound. In the present invention, the “conjugated polymer compound” means a polymer compound in which all monomers constituting the polymer compound are conjugated with a part or the whole of the structure. .

When the polymer compound of the present invention is composed of the first structural unit, the second structural unit, and another structural unit, from the viewpoint of increasing the carrier mobility of the polymer compound, the polymer compound has a total of structural units. The total of the first structural unit and the second structural unit is preferably 50 mol% or more, and more preferably 70 mol% or more.

The polymer compound of the present invention comprises at least one structural unit selected from the group consisting of a structural unit represented by formula (3) and a structural unit represented by formula (4), a second structural unit, and other structural units. In the case of consisting of structural units, from the viewpoint of increasing the carrier mobility of the polymer compound, the structural unit represented by the formula (3) and the formula (4) are represented with respect to the total of the structural units of the polymer compound. The total of the structural unit and the second structural unit is preferably 50 mol% or more, and more preferably 70 mol% or more.

The polymer compound of the present invention includes a first structural unit, a structural unit represented by the formula (3), a structural unit represented by the formula (4), a second structural unit, and other structural units. Examples thereof include compounds P01 to P12. The total of each structural unit is 100 mol%.

[Table 1]

In the polymer compound of the present invention, if a group active in the polymerization reaction remains at the end of the molecular chain, the carrier mobility of the polymer compound may be lowered. Therefore, the molecular chain terminal is preferably a stable group such as an aryl group or a heteroaryl group.

The polymer compound of the present invention may be any type of copolymer, such as a block copolymer, a random copolymer, an alternating copolymer, or a graft copolymer.

From the viewpoint of increasing the carrier mobility of the polymer compound, the structural unit represented by formula (3) or the structural unit represented by formula (4), and the structural unit or formula represented by formula (2-1) It is more preferable that the copolymer is an alternating copolymer with the structural unit represented by (2-2), and the structural unit represented by the formula (3) and the structural unit represented by the formula (2-1) or the formula (2-1) It is more preferable that the copolymer be an alternating copolymer with the structural unit represented by 2-2).

The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as “GPC”) of the polymer compound of the present invention is usually 1 × 10 ³ to 1 × 10 ⁸ .

From the viewpoint of forming a good thin film during thin film production, the number average molecular weight is preferably 2 × 10 ³ or more.

The number average molecular weight is preferably 1 × 10 ⁶ or less from the viewpoint of enhancing the solubility in a solvent and facilitating the production of a thin film.

<Method for producing polymer compound>
The production method of the polymer compound of the present invention is not particularly limited, and examples thereof include a method using a reductive coupling reaction using a Ni catalyst, a method using a Stille coupling reaction, and a method using a Suzuki coupling reaction. . From the viewpoint of easy synthesis of the compound and the ability to obtain an alternating copolymer compound, a method using a Stille coupling reaction and a Suzuki coupling reaction is preferred.

The polymer compound of the present invention includes, for example, a monomer that is a raw material for a structural unit including a first structural unit, a monomer that is a raw material for a second structural unit, and, if necessary, a raw material for another structural unit. It is manufactured by copolymerizing with the monomer which becomes. Here, specific examples of the structural unit including the first structural unit include the first structural unit, the structural unit represented by the formula (3), or the formula (4).

The monomer that is a raw material of the structural unit including the first structural unit is, for example, a compound in which a halogen atom is bonded to the bond of the structural unit including the first structural unit. This compound is produced by halogenating a compound in which a hydrogen atom is bonded to a bond of a structural unit including the first structural unit.

Halogenation of a compound in which a hydrogen atom is bonded to a bond of a structural unit including the first structural unit may be performed by dissolving the compound in a suitable solvent and reacting with a halogenating agent. As the solvent, chloroform, tetrahydrofuran, dimethylformamide, acetic acid and the like can be used. As the halogenating agent, N-bromosuccinimide (NBS), bromine, N-iodosuccinimide (NIS), N-chlorosuccinimide (NCS) Etc. can be used.

In this case, the monomer used as the raw material of the second structural unit is, for example, an alkyl metal group such as a trialkylstannyl group, a dihydroxyboryl group (—B (OH) ₂ ), or a bond of the second structural unit, It is a compound in which a group obtained by removing a hydroxyl group from boric acid diester is bonded.

A compound in which an alkyl metal group, dihydroxyboryl group, or a group obtained by removing a hydroxyl group from a boric acid diester is bonded to the bond of the second structural unit is a compound in which a hydrogen atom is bonded to the bond of the second structural unit. , Dihydroxyborylation or boric acid diesterification.

Alkyl metalation of a compound in which a hydrogen atom is bonded to the bond of the second structural unit is obtained by dissolving a compound in which a hydrogen atom is bonded to the bond of the second structural unit in an appropriate solvent and alkylating in the presence of a base. What is necessary is just to make it react. As the solvent, diethyl ether, tetrahydrofuran (THF), hexane, heptane, toluene or the like can be used, and as the base, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide or the like can be used. As the alkyl metallizing agent, trimethyltin chloride, tributyltin chloride or the like can be used.

Dihydroxyborylation or boric acid diesterification of a compound in which a hydrogen atom is bonded to the bond of the second structural unit is performed by dissolving the compound in which the hydrogen atom is bonded to the bond of the second structural unit in an appropriate solvent, and the presence of a base. What is necessary is just to make trialkyl borate react below. As the solvent, diethyl ether, tetrahydrofuran (THF), hexane, heptane, toluene or the like can be used, and as the base, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide or the like can be used. As the trialkyl borate, trimethyl borate, triisopropyl borate, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and the like can be used.

The monomer used as the raw material for the other structural unit is, for example, a group obtained by removing a hydroxyl group from a halogen atom, an alkali metal group, a dihydroxyboryl group, or a boric acid diester at the bond of the group exemplified as the other structural unit. It is a bound compound. These compounds are obtained by halogenating, alkylating, dihydroxyborating, or boric acid diester a compound in which a hydrogen atom is bonded to a bond of a group exemplified as another structural unit using the same method as described above. Manufactured by.

Next, a compound in which a halogen atom is bonded to the bond of the structural unit including the first structural unit, and a group in which the hydroxyl group is removed from the alkali metal group, dihydroxyboryl group, or boric acid diester bond to the bond of the second structural unit And, if necessary, a compound in which a group obtained by removing a hydroxyl group from a halogen atom, an alkali metal group, a dihydroxyboryl group, or a boric acid diester is bonded to a bond of a group exemplified as another structural unit. The polymer compound of the present invention is obtained by dissolving in a solution and heating in the presence of a transition metal complex and, if necessary, a phosphine compound and a base, and reacting.

At that time, the reaction amount of the monomer as the raw material of the structural unit containing the first structural unit and the monomer as the raw material of the second structural unit is 30/70 to 70/30, preferably 35 in terms of molar ratio. / 65 to 65/35, more preferably 40/60 to 60/40. When the ratio of the reaction amount of both monomers is less than 40 mol%, the molecular weight of the polymer compound is low, and the field effect mobility may be low.

In the case of using the monomer as a raw material for other structural units in the above reaction, the amount used is 50 mol% or less, preferably 30 mol% or less based on the total amount of monomers. It is.

Solvents include aromatic hydrocarbon solvents such as toluene and benzene, ether solvents such as tetrahydrofuran and anisole, 1-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetonitrile, etc. And a transition metal complex includes Pd ₂ (dba) ₃ (where dba represents trans, trans-dibenzylideneacetone), Pd (dba) ₂ , tetrakis (Triphenylphosphine) palladium, palladium (II) acetate, dichlorobis (triphenylphosphine) palladium, bis (1,5-cyclooctadiene) nickel (0) and the like can be used. As the phosphine compound, tri-n -Butylphosphine, tri-ter -Butylphosphine, tricyclohexylphosphine, triphenylphosphine, tristolylphosphine (the tolyl group in the compound may be an orthotolyl group, a metatolyl group or a paratolyl group), tris (methoxyphenyl) phosphine (a methoxyphenyl group in the compound) May be an orthomethoxyphenyl group, a metamethoxyphenyl group or a paramethoxyphenyl group), (2-biphenylyl) di-tert-butylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3- Bis (diphenylphosphino) propane, 1,1′-bis (diphenylphosphino) ferrocene and the like can be used, and as the base, sodium carbonate, potassium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide, hydroxide Lithium, vinegar Potassium, and sodium acetate. The reaction temperature is adjusted to 0 to 200 ° C. in consideration of the stability of the compound and the reaction time. In this case, the reaction time is 30 minutes to 100 hours.

Thereafter, purification operations such as reprecipitation, Soxhlet washing, extraction, silica gel column purification, gel permeation chromatography purification and the like are performed to obtain the polymer compound of the present invention.

<Organic semiconductor element>
Since the polymer compound of the present invention has high carrier mobility, it can be used as an organic semiconductor material, for example, in an organic layer of an organic semiconductor element. Examples of the organic semiconductor element include an organic transistor, an organic solar battery, and an organic electroluminescence element. The polymer compound of the present invention is particularly useful as a charge transport material for organic transistors.

<Organic semiconductor materials>
The organic semiconductor material may contain one kind of the polymer compound of the present invention alone, or may contain two or more kinds. The organic semiconductor material may further contain a low molecular compound or a polymer compound having carrier transportability in addition to the polymer compound of the present invention in order to enhance carrier transportability. When the organic semiconductor material contains a component other than the polymer compound of the present invention, the polymer compound of the present invention is preferably contained in an amount of 30% by mass or more, and more preferably 50% by mass or more. When the content of the polymer compound of the present invention is less than 30% by mass, it may be difficult to form a thin film or to obtain good charge mobility.

Compounds having carrier transport properties include arylamine derivatives, stilbene derivatives, oligothiophenes and derivatives thereof, low molecular compounds such as oxadiazole derivatives, fullerenes and derivatives thereof, polyvinylcarbazole and derivatives thereof, polyaniline and derivatives thereof, polythiophene And polymer derivatives thereof, such as polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, and polyfluorene and derivatives thereof.

The organic semiconductor material may contain a polymer compound material as a polymer binder in order to improve its characteristics. As the polymer binder, those that do not excessively lower the carrier transportability are preferable.

Examples of polymer binders include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof , Polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

<Organic transistor>
The organic transistor has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path The thing which has is mentioned. Examples of the organic transistor having such a configuration include a field effect organic transistor and a static induction organic transistor.

A field effect organic transistor usually has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path. The organic transistor having an active layer and an insulating layer disposed between the gate electrode. In particular, an organic transistor in which a source electrode and a drain electrode are provided in contact with an active layer and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween is preferable.

The electrostatic induction organic transistor usually has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path And the gate electrode is provided in the active layer. In particular, an organic transistor in which a source electrode, a drain electrode, and the gate electrode are provided in contact with the active layer is preferable.

The gate electrode may be a structure that can form a current path flowing from the source electrode to the drain electrode and that can control the amount of current flowing through the current path with a voltage applied to the gate electrode, and is, for example, a comb electrode.

FIG. 1 is a schematic cross-sectional view showing an example of an organic transistor (field-effect organic transistor) of the present invention. An organic transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the substrate 1 at a predetermined interval, and a source electrode 5 and a drain electrode 6 so as to cover the substrate 1. Formed on the insulating layer 3 so as to cover the active layer 2 formed on the insulating layer 3, the insulating layer 3 formed on the active layer 2, and the insulating layer 3 on the region between the source electrode 5 and the drain electrode 6. The gate electrode 4 is provided.

FIG. 2 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the substrate 1 so as to cover the source electrode 5, a source electrode 5, and a predetermined electrode The drain electrode 6 formed on the active layer 2 with an interval, the insulating layer 3 formed on the active layer 2 and the drain electrode 6, and the insulating layer on the region between the source electrode 5 and the drain electrode 6 And a gate electrode 4 formed on the insulating layer 3 so as to cover 3.

FIG. 3 is a schematic cross-sectional view showing another example of the organic transistor (field effect type organic transistor) of the present invention. The organic transistor 120 shown in FIG. 3 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. A source electrode 5 and a drain electrode 6 formed on the insulating layer 3 with a predetermined interval so as to cover a part of the region of the insulating layer 3 formed, and a part of the source electrode 5 and the drain electrode 6 And an active layer 2 formed on the insulating layer 3 so as to cover the surface.

FIG. 4 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention. An organic transistor 130 shown in FIG. 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. The source electrode 5 formed on the insulating layer 3 so as to cover a part of the region of the insulating layer 3 formed on the active layer 3 and the active formed on the insulating layer 3 so as to cover a part of the source electrode 5 A layer 2 and a drain electrode 6 formed on the insulating layer 3 at a predetermined interval so as to cover a part of the active layer 2 are provided.

FIG. 5 is a schematic sectional view showing another example of the organic transistor (electrostatic induction type organic transistor) of the present invention. The organic transistor 140 shown in FIG. 5 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the source electrode 5, and a plurality of active transistors 2 with a predetermined interval on the active layer 2. The formed gate electrode 4 and the active layer 2a formed on the active layer 2 so as to cover the gate electrode 4 (the material constituting the active layer 2a is the same as or different from that of the active layer 2). And a drain electrode 6 formed on the active layer 2a.

FIG. 6 is a schematic cross-sectional view showing another example of the organic transistor (field effect type organic transistor) of the present invention. The organic transistor 150 shown in FIG. 6 includes a substrate 1, an active layer 2 formed on the substrate 1, a source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval, and a source electrode. 5 and an insulating layer 3 formed on the active layer 2 so as to cover a part of the drain electrode 6, a region of the insulating layer 3 in which the source electrode 5 is formed in the lower portion, and a drain electrode 6 are formed in the lower portion. And a gate electrode 4 formed on the insulating layer 3 so as to partially cover each region of the insulating layer 3.

FIG. 7 is a schematic cross-sectional view showing another example of the organic transistor (field-effect organic transistor) of the present invention. The organic transistor 160 shown in FIG. 7 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. An active layer 2 formed so as to cover the region of the insulating layer 3 formed on the active layer 2, a source electrode 5 formed on the active layer 2 so as to cover a part of the active layer 2, and one of the active layers 2 A source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval are provided so as to cover the portion.

FIG. 8 is a schematic cross-sectional view showing another example of the organic transistor (field-effect organic transistor) of the present invention. An organic transistor 170 shown in FIG. 8 has a gate electrode 4, an insulating layer 3 formed on the gate electrode 4, an active layer 2 formed on the insulating layer 3, and a predetermined interval on the active layer 2. A source electrode 5 and a drain electrode 6 formed in this manner. In this case, the gate electrode 4 also serves as the substrate 1.

In the above-described organic transistor of the present invention, the active layer 2 and / or the active layer 2a is composed of a film containing the polymer compound of the present invention, and a current path (channel) between the source electrode 5 and the drain electrode 6 is formed. ) The gate electrode 4 controls the amount of current passing through the current path (channel) by applying a voltage.

Such a field effect organic transistor can be produced by a known method, for example, a method described in JP-A-5-110069. The electrostatic induction organic transistor can be manufactured by a known method such as the method described in Japanese Patent Application Laid-Open No. 2004-006476.

The material of the substrate 1 may be any material that does not hinder the characteristics of the organic transistor. As the substrate, a glass substrate, a flexible film substrate, or a plastic substrate can be used.

The material of the insulating layer 3 may be any material having high electrical insulation, and SiO _x , SiN _x , Ta ₂ O ₅ , polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass, photoresist, and the like can be used. From the viewpoint of lowering the voltage, it is preferable to use a material having a high dielectric constant.

When the active layer 2 is formed on the insulating layer 3, the surface of the insulating layer 3 is treated with a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the active layer 2. It is also possible to form the active layer 2 after the modification.

In the case of an organic field effect transistor, charges such as electrons and holes generally pass near the interface between the insulating layer and the active layer. Therefore, the state of this interface greatly affects the mobility of the transistor. Therefore, as a method for improving the interface state and improving the properties, control of the interface with a silane coupling agent has been proposed (for example, Surface Chemistry, 2007, Vol. 28, No. 5, p. 242-248). ).

Examples of silane coupling agents include alkylchlorosilanes (octyltrichlorosilane (OTS), octadecyltrichlorosilane (ODTS), phenylethyltrichlorosilane, etc.), alkylalkoxysilanes, fluorinated alkylchlorosilanes, fluorinated alkylalkoxy. Examples thereof include silylamine compounds such as silanes and hexamethyldisilazane (HMDS). Further, the surface of the insulating layer may be subjected to ozone UV treatment or O ₂ plasma treatment before treatment with the surface treatment agent.

By such treatment, the surface energy of the silicon oxide film used as the insulating layer can be controlled. Further, the surface treatment improves the orientation of the film constituting the active layer on the insulating layer, and high charge transportability (mobility) can be obtained.

The gate electrode 4 includes metals such as gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum, low-resistance polysilicon, low-resistance amorphous silicon, tin oxide, indium oxide, indium / tin oxide. A material such as (ITO) can be used.
These materials may be used alone or in combination of two or more. Note that a highly doped silicon substrate can be used as the gate electrode 4. A highly doped silicon substrate has not only the performance as a gate electrode but also the performance as a substrate. When the gate electrode 4 having such a performance as a substrate is used, the substrate 1 may be omitted in the organic transistor in which the substrate 1 and the gate electrode 4 are in contact with each other.

The source electrode 5 and the drain electrode 6 are preferably made of a low resistance material, and particularly preferably made of gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum or the like. These materials may be used alone or in combination of two or more.

In the organic transistor, a layer composed of another compound may be interposed between the source electrode 5 and the drain electrode 6 and the active layer 2. Such layers include low molecular compounds having electron transport properties, low molecular compounds having hole transport properties, alkali metals, alkaline earth metals, rare earth metals, complexes of these metals with organic compounds, iodine, bromine, Halogens such as chlorine and iodine chloride, sulfur oxide compounds such as sulfuric acid, sulfuric anhydride, sulfur dioxide and sulfate, nitric oxide compounds such as nitric acid, nitrogen dioxide and nitrate, halogenated compounds such as perchloric acid and hypochlorous acid, Examples thereof include layers made of aromatic thiol compounds such as alkyl thiol compounds, aromatic thiols, and fluorinated alkyl aromatic thiols.

In addition, after manufacturing the organic transistor as described above, it is preferable to form a protective film on the organic transistor in order to protect the element. Thereby, an organic transistor is interrupted | blocked from air | atmosphere and the fall of the characteristic of an organic transistor can be suppressed. Further, when a display device to be driven is formed on an organic transistor, the protective film can also reduce the influence on the organic transistor in the formation process.

Examples of the method for forming the protective film include a method of covering the organic transistor with a UV curable resin, a thermosetting resin, an inorganic SiON _x film, or the like. In order to effectively block the atmosphere, it is preferable to form a protective film after the organic transistor is manufactured without exposing the organic transistor to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

An organic field effect transistor, which is a kind of organic transistor configured as described above, can be applied as a pixel drive switching element of an active matrix drive type liquid crystal display or an organic electroluminescence display. And since the organic field effect transistor of embodiment mentioned above is equipped with the active compound which contains the high molecular compound of this invention as an active layer, and the charge transport property improved by it, the field effect mobility is provided. Is expensive. Therefore, it is useful for manufacturing a display having a sufficient response speed.

Hereinafter, examples will be shown to describe the present invention in more detail, but the present invention is not limited to these examples.

(NMR analysis)
The NMR measurement was performed by dissolving the compound in deuterated chloroform and using an NMR apparatus (Varian, INOVA300).

(Mass spectrometry)
Mass spectrometry was determined using a mass spectrometer (AccuTOF TLC JMS-T100TD, manufactured by JEOL Ltd.).

(Molecular weight analysis)
The number average molecular weight and the weight average molecular weight of the polymer compound were determined using gel permeation chromatography (GPC, manufactured by Shimadzu Corporation, trade name: LC-10AD). The polymer compound to be measured was dissolved in tetrahydrofuran and injected into GPC. Tetrahydrofuran was used for the mobile phase of GPC. As the column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. A UV detector (manufactured by Shimadzu Corporation, trade name: SPD-M10A) was used as the detector.

Synthesis example 1
(Synthesis of 3-dodecylthiothiophene)

A flask was charged with 25 g (0.22 mol) of 3-methoxythiophene, 2.5 g (11 mmol) of paratoluenesulfonic acid monohydrate, 44 g (0.22 mol) of dodecanethiol, and 250 mL of toluene. Stir for hours. The reaction solution was added to water, and the toluene layer was extracted. After the toluene solution was washed with water, the solvent was distilled off with an evaporator to obtain a liquid. The obtained liquid was diluted with n-hexane, and the diluted solution was purified with a silica gel column using n-hexane as a developing solvent, and an n-hexane solution was recovered. Thereafter, n-hexane was evaporated to obtain 3-dodecylthiothiophene. The yield was 55 g and the yield was 88%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.32 (m, 1H), 7.11 (m, 1H), 7.02 (m, 1H), 2.84 (t, 2H), 1.62 ( m, 2H), 1.15-1.40 (m, 18H), 0.88 (t, 3H)

Synthesis example 2
(Synthesis of 2-bromo-3-dodecylthiothiophene)

The flask was charged with 55 g (0.19 mol) of 3-dodecylthiothiophene and 165 mL of chloroform and stirred at 0 ° C. To the reaction solution, 34 g (0.19 mol) of N-bromosuccinimide was added little by little. Thereafter, the reaction solution was stirred at 0 ° C. for 3 hours. Thereafter, the reaction solution was added to an aqueous sodium thiosulfate solution, and the chloroform layer was extracted. After the chloroform solution was washed with water, the solvent was distilled off with an evaporator to obtain a liquid. The obtained liquid was diluted with n-hexane and purified with a silica gel column using n-hexane as a developing solvent to recover an n-hexane solution. Thereafter, n-hexane was evaporated to obtain 2-bromo-3-dodecylthiothiophene. The yield was 70 g and the yield was 95%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.25 (d, 1H), 6.92 (d, 1H), 2.85 (t, 2H), 1.56 (m, 2H), 1.15 1.50 (m, 18H), 0.88 (t, 3H)

Synthesis example 3
(Synthesis of Compound 1)

To a flask in which the gas in the flask was replaced with nitrogen, 1.0 g (2.8 mmol) of 2-bromo-3-dodecylthiothiophene, 5,5′-bis (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolan-2-yl) -2,2'-bithiophene, 20 mL of tetrahydrofuran, 50 mg of tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphonium tetra 64 mg of fluoroborate was added. To the reaction solution, 5.5 mL of a 2 mol / L potassium carbonate aqueous solution was dropped and refluxed for 5 hours. Thereafter, the reaction solution was concentrated, the concentrated reaction solution was poured into water, toluene was further added, and the toluene layer was extracted. After the toluene solution was washed with water, the solvent was distilled off with an evaporator to obtain a liquid. The obtained liquid was diluted with n-hexane and purified with a silica gel column using n-hexane as a developing solvent to recover an n-hexane solution. Thereafter, n-hexane was evaporated to obtain Compound 1. The yield was 1.7 g and the yield was 90%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.29 (m, 2H), 7.18 (m, 2H), 7.15 (m, 2H), 7.04 (m, 2H), 2.87 ( t, 4H), 1.61 (m, 4H), 1.15-1.50 (m, 36H), 0.88 (t, 6H)

Synthesis example 4
(Synthesis of Compound 2)

In a flask, 1.7 g (2.4 mmol) of Compound 1 and 50 mL of chloroform were added and stirred at 0 ° C. To the reaction solution, 0.88 g (5.0 mmol) of N-bromosuccinimide was added and stirred at 0 ° C. for 8 hours. Thereafter, the reaction solution was added to an aqueous sodium thiosulfate solution, and the chloroform layer was extracted. After the chloroform solution was washed with water, the solvent was distilled off with an evaporator to obtain a liquid. The obtained liquid was diluted with n-hexane and purified with a silica gel column using n-hexane as a developing solvent to recover an n-hexane solution. Thereafter, n-hexane was evaporated to obtain Compound 2. The yield was 1.9 g, and the yield was 91%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.19 (d, 2H), 7.12 (d, 2H), 6.99 (s, 2H), 2.84 (t, 4H), 1.61 ( m, 4H), 1.15-1.50 (m, 36H), 0.88 (t, 6H)

Synthesis example 5
(Synthesis of Compound 4)

4.8 g (6.6 mmol) of Compound 1 and 96 mL of diethyl ether were placed in a flask where the gas in the flask was replaced with argon, and cooled to −70 ° C. After dropping 5.6 mL of a 2.6 mol / L n-butyllithium hexane solution into the reaction solution, the mixture was stirred at room temperature (25 ° C.) for 1 hour. Again, the reaction solution was cooled to −70 ° C., and 4.7 g (14 mmol) of tributyltin chloride was added dropwise. Thereafter, the reaction solution was stirred at room temperature (25 ° C.) for 3 hours. Thereafter, the solvent in the reaction solution was distilled off with an evaporator to obtain a liquid. The obtained liquid was diluted with n-hexane and purified with an alumina column using n-hexane as a developing solvent to recover an n-hexane solution. Thereafter, n-hexane was evaporated to obtain Compound 3.

In a flask where the gas in the flask was replaced with nitrogen, the entire amount of Compound 3 obtained by the above method, 7.2 g (20 mmol) of 2-bromo-3-dodecylthiothiophene, 200 mL of toluene, tetrakis (triphenylphosphine) 0.15 g of palladium was added, and the reaction solution was refluxed for 8 hours. The reaction solution was poured into water and the toluene layer was extracted. After the toluene solution was washed with water, the solvent was distilled off with an evaporator to obtain a solid. The obtained solid was diluted with n-hexane and purified with a silica gel column using n-hexane as a developing solvent to recover an n-hexane solution. Thereafter, n-hexane was evaporated to obtain a solid. The solid was recrystallized using 2-propanol to obtain Compound 4. The yield was 8.0 g and the yield was 94%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.35 (m, 2H), 7.31 (s, 2H), 7.16-7.21 (m, 4H), 7.04 (m, 2H), 2.91 (t, 4H), 2.87 (t, 4H), 1.50-1.70 (m, 8H), 1.10-1.50 (m, 72H), 0.87 (t, 12H)

Synthesis Example 6
(Synthesis of Compound 5)

In a flask, 8.0 g (6.2 mmol) of Compound 4 and 50 mL of chloroform were added and stirred at 0 ° C. To the reaction solution, 2.3 g (13 mmol) of N-bromosuccinimide was added. Thereafter, the reaction solution was stirred at 0 ° C. for 8 hours. The reaction solution was added to an aqueous sodium thiosulfate solution, and the chloroform layer was extracted. After the chloroform solution was washed with water, the solvent was distilled off with an evaporator to obtain a solid. The obtained solid was diluted with n-hexane and purified with a silica gel column using n-hexane as a developing solvent to recover an n-hexane solution. Thereafter, n-hexane was evaporated to obtain Compound 5. The yield was 7.0 g and the yield was 78%.

MS 1455.91

Example 1
(Synthesis of Compound 6)

Into a flask where the gas in the flask was replaced with nitrogen, 0.20 g (0.22 mmol) of

compound

2, 4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2 was added. -Yl) -2,1,3-benzothiadiazole 0.079 g (0.20 mmol), tetrahydrofuran 14 mL, tris (dibenzylideneacetone) dipalladium 4.1 mg, tri-tert-butylphosphonium tetrafluoroborate 5 .2 mg was added and stirred. 1.1 mL of 2 mol / L potassium carbonate aqueous solution was dropped into the reaction solution, and the mixture was refluxed for 15 minutes. To the reaction solution, 35 mg of phenylboronic acid and 14 mL of chlorobenzene were added and refluxed for 30 minutes. Next, 1.0 g of sodium N, N-diethyldithiocarbamate trihydrate was added to the reaction solution, and the mixture was refluxed for 3 hours. Thereafter, the reaction solution was poured into water, toluene was added, and the toluene layer was extracted. After the toluene solution was washed with an acetic acid aqueous solution and water, the toluene solution was added dropwise to acetone to obtain a precipitate. The precipitate was dissolved in chloroform and purified with a silica gel column using chloroform as a developing solvent. The purified chloroform solution was added dropwise to methanol, and the precipitate was filtered to obtain Compound 6. The yield was 0.18 g, the number average molecular weight in terms of polystyrene was 2.5 × 10 ³ , and the weight average molecular weight was 5.3 × 10 ³ .

Example 2
(Synthesis of Compound 7)

Into a flask where the gas in the flask was replaced with nitrogen, 0.30 g (0.21 mmol) of

compound

5 and 4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2 were added. -Yl) -2,1,3-benzothiadiazole 0.076 g (0.20 mmol), tetrahydrofuran 19 mL, tris (dibenzylideneacetone) dipalladium 3.8 mg, tri-tert-butylphosphonium tetrafluoroborate 4 .8 mg was added and stirred. 1.0 mL of 2 mol / L potassium carbonate aqueous solution was dripped at the reaction liquid, and it was made to recirculate | reflux for 30 minutes. To the reaction solution, 32 mg of phenylboronic acid and 19 mL of chlorobenzene were added and refluxed for 30 minutes. Next, 1.0 g of sodium N, N-diethyldithiocarbamate trihydrate was added to the reaction solution, and the mixture was refluxed for 3 hours. Thereafter, the reaction solution was poured into water, toluene was added, and the toluene layer was extracted. After the toluene solution was washed with an acetic acid aqueous solution and water, the organic layer was dropped into acetone to obtain a precipitate. The precipitate was dissolved in chlorobenzene and purified with a silica gel column using chlorobenzene as a developing solvent. The purified chlorobenzene solution was added dropwise to methanol, and the precipitate was filtered to obtain Compound 7. The yield was 0.13 g, the polystyrene-equivalent number average molecular weight was 4.0 × 10 ³ , and the weight average molecular weight was 6.3 × 10 ³ .

Example 3
(Production and Evaluation of Organic Transistor 1)
An organic transistor 1 having a structure shown in FIG. 8 was prepared using a solution containing Compound 6 as a charge transporting compound.
The surface of the heavily doped n-type silicon substrate serving as the gate electrode was thermally oxidized to form a silicon oxide film (hereinafter referred to as “thermal oxide film”). The thermal oxide film functions as an insulating layer. Next, a source electrode and a drain electrode were formed on the thermal oxide film by a photolithography process. The source electrode and the drain electrode had a chromium (Cr) layer and a gold (Au) layer from the thermal oxide film side, and had a channel length of 20 μm and a channel width of 2 mm. The substrate on which the thermal oxide film, the source electrode, and the drain electrode thus obtained were ultrasonically cleaned with acetone, and UV ozone treatment was performed with an ozone UV cleaner. Thereafter, the surface of the thermal oxide film was modified with β-phenethyltrichlorosilane, and the surfaces of the source electrode and the drain electrode were modified with pentafluorobenzenethiol. Next, an organic semiconductor layer was formed by spin-coating 0.5 wt% of an orthodichlorobenzene solution of Compound 6 on the surface-treated thermal oxide film, source electrode and drain electrode at a rotation speed of 1000 rpm. Thereafter, the organic semiconductor layer was heated at 230 ° C. for 1 hour to manufacture the organic transistor 1.

The transistor characteristics were measured by changing the gate voltage Vg and the source-drain voltage Vsd of the organic transistor 1 obtained. The field effect mobility was 3.8 × 10 ⁻³ cm ² / Vs.

Example 4
(Production and Evaluation of Organic Transistor 2)
Organic transistor 2 was produced in the same manner as in Example 3 except that compound 7 was used instead of compound 6.

The transistor characteristics were measured by changing the gate voltage Vg and the source-drain voltage Vsd of the organic transistor 2 obtained. The field effect mobility was 2.4 × 10 ⁻³ cm ² / Vs.

1 ... substrate,
2, 2a ... active layer,
3. Insulating layer,
4 ... Gate electrode,
5 ... Source electrode,
6 ... drain electrode,
100, 110, 120, 130, 140, 150, 160, 170 ... Organic transistors.

Claims

formula

(1)
[Wherein, R 1 represents an alkyl group, an aryl group, or a heteroaryl group. R 2 represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or a heteroaryl group. ]
And the structural unit represented by

[Wherein Z 1 represents —CR 5 ═CR 6 —, —S—, —O—, —Se— or —NR 7 —. R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a halogen atom, a cyano group or a nitro group. R 7 represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. Z 2 represents = S =, = CR 5 -CR 6 = or = Se =. ]
A polymer compound comprising a structural unit represented by:
formula

[Wherein R 1 and R 2 represent the same meaning as described above. a represents an integer of 1 to 4. b represents an integer of 0 to 4. c represents an integer of 1 to 4. A plurality of R 1 may be the same or different. A plurality of R 2 may be the same or different. ]
The high molecular compound of Claim 1 containing the structural unit represented by these.
The polymer compound according to claim 2, wherein a and c are the same.
The polymer compound according to any one of claims 1 to 3, comprising a structural unit represented by the formula (2-1).
The polymer compound according to any one of claims 1 to 4, wherein Z 1 is -S-.
The polymer compound according to any one of claims 1 to 5, which is a conjugated polymer compound.
A structural unit represented by formula (3) or a structural unit represented by formula (4) and a structural unit represented by formula (2-1) or a structural unit represented by formula (2-2) The polymer compound according to any one of claims 2 to 6, which is an alternating copolymer.
The polymer compound according to any one of claims 1 to 7, which has a polystyrene-reduced number average molecular weight of 2 × 10 3 to 1 × 10 6 .
An organic semiconductor material comprising the polymer compound according to any one of claims 1 to 8.
An organic semiconductor element having an organic layer containing the organic semiconductor material according to claim 9.
An organic transistor having a source electrode, a drain electrode, a gate electrode, and an active layer, wherein the active layer includes the organic semiconductor material according to claim 9.