JP2023008032A - Conjugated polymer, film-forming composition, organic thin film, and organic semiconductor element - Google Patents

Abstract

To provide: a new conjugated polymer which has all of high carrier mobility, high heat resistance and high solvent solubility; a film-forming composition comprising the polymer; an organic thin film formed from the film-forming composition; and a semiconductor element and an organic thin film transistor element that comprise the organic thin film as an active layer.SOLUTION: A conjugated polymer comprising, as structural units, 7,14-disubstituted bisthieno[2'',3':4,5]thieno[3,2-g:3',2'-g']benzo[1'',2'':4,5:4'',3'';4',5']dithieno[3,2-b:3',2'-b']bis[1]benzothiophene and 5,6-dialkoxy-1,4-bis(2-thienyl)benzothiadiazole can form an organic thin film to form a transistor element to exhibit excellent transistor performance.SELECTED DRAWING: None

Description

The present invention relates to a conjugated polymer containing an oligoheteroacene containing a thienothiophene skeleton and a benzothiadiazole skeleton as structural units, a method for producing the same, and an organic semiconductor device.

Conjugated compounds are used as organic semiconductors in organic thin-film solar cells, organic thin-film transistors, organic EL, etc., and have characteristics not found in inorganic semiconductors, such as energy saving, low cost, solvent solubility, light weight, and flexibility. It can also be used as a coating material applied to (Patent Document 1).

Conjugated compounds such as oligoacenes such as pentacene disclosed in Non-Patent Document 1 and oligoacenes having a thiophene skeleton, a thienothiophene skeleton, etc. disclosed in Non-Patent Document 2 (hereinafter referred to as oligoheteroacenes) are organic. Research on its application to thin film transistors has been carried out. Among them, oligoheteroacenes having a thienothiophene skeleton tend to exhibit high carrier mobility, but problems such as low solvent solubility, low film formability, and low atmospheric stability have been pointed out (Non-Patent Document 3 ), and the development of new conjugated compounds is desired. The polymer containing an oligoheteroacene having a thienothiophene skeleton disclosed in Patent Document 2 is similar to the conjugated polymer of the present invention, but contains a 5,6-dialkoxybenzothiadiazole skeleton as an acceptor unit. There is no description of the conjugated polymer described in the present application characterized by

JP 2017-59668 A JP 2020-111737 A

Polymer Journal, Vol. 49, pp. 23-30, 2017. Chemical Reviews, Vol. 115, pp. 3036-3140, 2015. Tetrahedron Letters, Vol. 55, pp. 5663-5666, 2014.

The present invention provides a new conjugated polymer having high carrier mobility, high heat resistance, and high solvent solubility, a film-forming composition containing the polymer, an organic thin film prepared from the film-forming composition, An object of the present invention is to provide a semiconductor device and an organic thin film transistor device having the organic thin film as an active layer.

In order to solve the above problems, the present inventors conducted extensive studies and found that 7,14-disubstituted bisthieno[2″,3′:4,5]thieno[3,2-g:3′,2 '-g']benzo[1'',2'':4,5:4'',3'';4',5']dithieno[3,2-b:3',2'-b'] A conjugated polymer containing bis[1]benzothiophene and 5,6-dialkoxy-1,4-bis(2-thienyl)benzothiadiazole as structural units has high solvent solubility, high heat resistance, and high It was found to exhibit film forming properties. Furthermore, they also found that an organic thin film can be easily formed using a film-forming composition containing the conjugated polymer, and that an organic thin film transistor element prepared using the organic thin film can be stably driven. was completed.

That is, the present invention consists of the following gists.
[Summary 1]
General formula (1) below

(In the formula, R ¹ represents an alkyl group having 1 to 50 carbon atoms. A plurality of R ¹ may be the same or different.)
A structural unit represented by the following general formula (2)

(In the formula, R ² represents a hydrogen atom or an alkyl group having 1 to 50 carbon atoms. A plurality of R ² may be the same or different. R ³ represents an alkoxy group having 1 to 50 carbon atoms. of R ³ may be the same or different.)
A conjugated polymer composed of a divalent heteroaromatic ring connecting group represented by
[Summary 2]
A film-forming composition comprising the conjugated polymer according to Summary 1.
[Summary 3]
An organic thin film produced by using the film-forming composition according to Summary 2.
[Summary 4]
An organic semiconductor device comprising the organic thin film according to summary 3.
[Summary 5]
An organic thin film transistor device comprising the organic thin film according to Summary 4.

The conjugated polymer of the present invention is an organic semiconductor having both high solvent solubility and heat resistance, and can efficiently drive an organic thin film transistor element having this as an active layer.

It is a figure which shows the structure by the cross-sectional shape of an organic thin-film transistor element.

The present invention will be described in detail below.

The alkyl group having 1 to 50 carbon atoms represented by R ¹ and R ² may be linear, branched or cyclic, and may be a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group. group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, dodriacontyl group, tritriacontyl group, tetratriacontyl group, pentatria Contyl group, hexatriacontyl group, tetracontyl group, hentetracontyl group, dotetracontyl group, tritetracontyl group, tetratetracontyl group, linear alkyl group such as pentacontyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, 2- dodecyltetradecyl group, 2-dodecylhexadecyl group, 2-tetradecylhexadecyl group, 3-decylpentadecyl group, 3-dodecylheptadecyl group, 3-tetradecylnonacosyl group, 4-decylhexadecyl group, 4 Examples include branched alkyl groups such as -dodecyloctadecyl group and 4-tetradecylicosyl group, and cyclic alkyl groups such as cyclopentyl group and cyclohexyl group.

The alkoxy group having ¹ to 50 carbon atoms represented by R3 may be linear, branched or cyclic, and may be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group group, nonadecyloxy group, icosyloxy group, henicosyloxy group, docosyloxy group, tricosyloxy group, tetracosyloxy group, pentacosyloxy group, hexacosyloxy group, heptacosyloxy group, octacosyloxy group group, nonacosyloxy group, triacontyloxy group, hentriacontyloxy group, dodriacontyloxy group, tritriacontyloxy group, tetratriacontyloxy group, pentatriacontyloxy group, hexatriacontyloxy group, straight-chain alkoxy groups such as tetracontyloxy group, hentetracontyloxy group, dotetracontyloxy group, tritetracontyloxy group, tetratetracontyloxy group, pentacontyloxy group, isopropoxy group, 1- (2-methylpropyl)oxy group, 2-butyloxy group, tert-butoxy group, 2-ethylhexyloxy group, 3,7-dimethyloctyloxy group, 2-decyltetradecyloxy group, 2-dodecyltetradecyloxy group, Examples include branched alkoxy groups such as 2-dodecylhexadecyloxy group and 2-tetradecylhexadecyloxy group, and cyclic alkoxy groups such as cyclopentyloxy group and cyclohexyloxy group.

As a group represented by R ¹ , the solubility of the conjugated polymer containing the general formulas (1) and (2) of the present invention (hereinafter referred to as "the conjugated polymer of the present invention"), and the carrier An alkyl group having 6 to 50 carbon atoms is preferable, and an alkyl group having 6 to 34 carbon atoms is more preferable, from the viewpoint of high mobility, such as a hexyl group, an octyl group, a decyl group, an undecyl group, a nonadecyl group, an icosyl group, and a henicosyl group. , 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, 2-dodecyltetradecyl group, 2-dodecylhexa Decyl group, 2-tetradecylhexadecyl group, 3-decylpentadecyl group, 3-dodecylheptadecyl group, 3-tetradecylnonacocyl group, 4-decylhexadecyl group, 4-dodecyloctadecyl group, or 4-tetra A decylicosyl group is more preferable, and a nonadecyl group, a henicosyl group, a 2-decyltetradecyl group, a 2-decyltetradecyl group, a 2-dodecylhexadecyl group, a 4-dodecyloctadecyl group and a 2-tetradecylhexadecyl group are particularly preferable. preferable.

The group represented by R ² is preferably a hydrogen atom or an alkyl group having 4 to 50 carbon atoms, such as a hydrogen atom or 4 to 34 carbon atoms, from the viewpoint of high solubility and carrier mobility of the conjugated polymer of the present invention. Alkyl groups of more preferably hydrogen atom, butyl group, pentyl group, hexyl group, octyl group, decyl group, nonadecyl group, icosyl group, henicosyl group, 2-decyltetradecyl group, 2-dodecylhexadecyl group, 2- Tetradecylhexadecyl group, 2-decyltetradecyloxy group, 2-dodecyltetradecyloxy group, 2-dodecylhexadecyloxy group or 2-tetradecylhexadecyloxy group are more preferable, hydrogen atom, hexyl group, octyl group , a decyl group, a 2-decyltetradecyl group or a 2-decyltetradecyl group is particularly preferred.

R ³ is preferably an alkoxy group having 4 to 50 carbon atoms, more preferably an alkoxy group having 4 to 30 carbon atoms, from the viewpoint of high solubility and carrier mobility of the conjugated polymer of the present invention. group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, 2-hexyldecyloxy group, 2-octyldodecyloxy group, 2-decyltetradecyloxy group, A 2-dodecyltetradecyloxy group, a 2-dodecylhexadecyloxy group or a 2-tetradecylhexadecyloxy group is more preferable, and a hexyloxy group, an octyloxy group, a 2-hexyldecyloxy group and a 2-decyltetradecyloxy group. is particularly preferred.

Next, the conjugated polymer of the present invention will be explained.

The conjugated polymer of the present invention has the following general formula (1)

(Wherein, R ¹ has the same meaning as described above.) and a divalent structural unit represented by the following general formula (2)

(In the formula, R ² and R ³ have the same meanings as defined above.).

Specific structural units represented by general formula (1) can be exemplified by formulas (1-2) to (1-17), but the present invention is not limited thereto.

The structural unit represented by the general formula (1) is preferably the formula (1-2) to the formula (1-14) in terms of the film-forming properties and carrier mobility of the conjugated polymer of the present invention. Formulas (1-2) to (1-12) are more preferred, and formulas (1-10) to (1-12) are particularly preferred.

Specific structural units represented by general formula (2) can be exemplified by formulas (2-1) to (2-80), but the present invention is not limited thereto.

The structural unit represented by the general formula (1) has a high film-forming property and carrier mobility of the conjugated polymer of the present invention, and is represented by formulas (2-1) to (2-6) and formula (2). -7) to formula (2-14), formula (2-15) to formula (2-20), formula (2-29) to formula (2-44), formula (2-53) to formula (2- 58), formula (2-67) to formula (2-72), formula (2-81) to formula (2-86) are preferable, formula (2-3), formula (2-5), formula (2 -8), formula (2-10), formula (2-12), formula (2-16), formula (2-41), and formula (2-81) are more preferred.

In the conjugated polymer of the present invention, the order of the structural units is not particularly limited as long as it contains the structural units represented by the general formulas (1) and (2). Examples include alternating, random, and gradient. be done. A conjugated polymer in which the structural units represented by the general formula (1) and the general formula (2) are alternately repeated is preferable in terms of film formability and mobility. That is, general formula (3)

(wherein R ¹ , R ² and R ³ have the same meanings as above).

As the conjugated polymer of the present invention represented by the general formula (3), in terms of high film-forming properties and carrier mobility, specifically formulas (3-1) to (3-84)

A conjugated polymer represented by a structural unit represented by is preferable, and formulas (3-1) to (3-10), formulas (3-13) to formulas (3-38), and formulas (3-41 ) to formula (3-66), formula (3-69) to formula (3-94), formula (3-97) to formula (3-160) are more preferable, formula (3-29), formula (3 -31), formula (3-34), formula (3-36), formula (3-45), and formula (3-138) are particularly preferred.

The left end of the structural unit is called the head, and the right end is called the tail. There is no particular restriction on the regioregularity, but for example, a head-to-tail structure is preferred.

The molecular weight of the conjugated polymer of the present invention is preferably 2,000 to 2,000,000, more preferably 4,000 to 300,000, more preferably 6,000, for high solubility and high mobility. ~150,000 is particularly preferred. In the present invention, the molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene.

The terminal structure of the conjugated polymer of the present invention is not particularly limited. , a halogen atom such as an iodine atom, an aromatic group such as a phenyl group and a thienyl group, and the like, and the structures at both terminals may be the same or different.

Next, the conjugated polymer of the present invention can be produced, for example, by referring to the method described in literature (JP-A-2020-111737, etc.).

Next, a method for producing a film-forming composition containing the conjugated polymer of the present invention (hereinafter referred to as "the film-forming composition of the present invention") will be described.

The film-forming composition of the present invention can be prepared by dissolving or dispersing the conjugated polymer of the present invention in a solvent.

The solvent is not particularly limited as long as it can dissolve or disperse the conjugated polymer of the present invention in the solvent. Ether solvents such as tetrahydrofuran, 1,4-dioxane and dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene and tetralin; ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate; Carbonic ester solvents such as fluoroethylene carbonate, ester solvents such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, γ-lactone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and other amide solvents, N,N,N',N'-tetramethylurea (TMU), N,N'-dimethylpropyleneurea (DMPU) and other urea solvents, dimethyl sulfoxide solvents such as sulfoxide (DMSO); alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 2,2,2-trifluoroethanol; Halogen solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, orthodichlorobenzene (o-DCB), nitromethane, water, etc. can be exemplified, and these can be mixed at any ratio. may be used. Among these, aromatic hydrocarbons and halogen solvents are preferable because they have high boiling points and moderate volatilization, and toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3,4-dimethylanisole, chlorobenzene, and o-DCB are more preferable. .

The amount of the solvent used is not particularly limited, and the solvent is added so that the concentration of the conjugated polymer of the present invention is 0.001 to 95% by weight, and the concentration is appropriately selected from 0.01 to 30% by weight. Adding is more preferred.

Methods well known to those skilled in the art such as stirring, shaking, and ball milling can be used for dissolving or dispersing. At this time, heating may be performed.

A binder may be added to the film-forming composition of the present invention to improve film-forming properties. Examples of such binders include polystyrene, poly-α-methylstyrene, polyvinylnaphthalene, poly(ethylene-co-norbornene), polymethylmethacrylate, polytriarylamine, poly(9,9-dioctylfluorene-co- dimethyltriphenylamine) can be exemplified. Although the concentration of the binder is not particularly limited, it is preferably 0.1 to 10.0% by weight from the viewpoint of good coatability.

Next, a method for forming an organic thin film (hereinafter referred to as "the organic thin film of the present invention") using the film-forming composition of the present invention will be described.

The method for forming the organic thin film of the present invention using the film-forming composition of the present invention is not particularly limited. Printing methods such as inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing can be mentioned, and among them, spin coating, drop casting, and inkjet are preferable in terms of efficient film formation.

Although the thickness of the organic thin film of the present invention is not particularly limited, it is preferably 1 nm to 1000 nm, more preferably 10 nm to 500 nm, in terms of high carrier mobility.

The organic thin film of the present invention can be obtained by drying the solvent after film formation. Annealing may be performed at a temperature appropriately selected from the range of 40 to 400° C., if necessary.

A method for producing an organic thin film transistor device containing the condensed ring polymer compound of the present invention in the active layer (hereinafter referred to as "organic thin film transistor device of the present invention") will be described.

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

FIG. 1 shows the structure of an element included in the organic thin film transistor element of the present invention. Here, (A) is a bottom gate-top contact type, (B) is a bottom gate-bottom contact type, (C) is a top gate-top contact type, and (D) is a top gate-bottom contact type. 1 is an active layer, 2 is a substrate, 3 is a gate electrode, 4 is a gate insulating layer, 5 is a source electrode, and 6 is a drain electrode.

Substrates include, for example, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, cellulose triacetate plastic substrates, glass, quartz, aluminum oxide, silicon, hydrated silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, indium tin Inorganic substrates such as oxides, and metal substrates such as gold, copper, chromium, titanium, and aluminum can be used. Among these, glass, silicon, and highly doped silicon are preferred, and glass is more preferred, in terms of good transistor performance.

As the gate electrode, for example, inorganic electrodes such as aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, chromium, graphene, carbon nanotubes, or doped and organic electrodes such as conductive polymer (PEDOT-PSS). Among these, an inorganic electrode is preferred because of its good conductivity, and gold is more preferred.

Examples of insulating layers include inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, barium titanate, and bismuth titanate. Insulating layer, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate) , poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, cellulose triacetate, polycyclopentane, polycyclohexane-ethylene copolymer, polyfluorinated cyclopentane, CYTOP, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene Organic insulating layers such as copolymers, parylene N, parylene C, parylene D, parylene HT, and parylene C-UVF can be used. Among these, an organic insulating layer is preferred because of its good insulating properties, and parylene C is more preferred. In addition, these insulating layer surfaces are, for example, octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrichlorosilane, It may be modified with silanes such as phenyltrimethoxysilane, phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid and octylphosphonic acid, and amines such as hexamethyldisilazane. Among these, octadecyltrichlorosilane, octyltrichlorosilane, β-phenethyltrichlorosilane, and octadecylphosphonic acid are preferred in terms of improving the carrier mobility and current on/off ratio of the organic thin film transistor device of the present invention and lowering the threshold voltage. , octylphosphonic acid and hexamethyldisilazane are preferred.

As the source electrode and the drain electrode, electrodes similar to those exemplified for the gate electrode can be exemplified. Among these, an inorganic electrode is preferred because of its good conductivity, and gold is more preferred. Moreover, in order to increase the efficiency of carrier injection, these electrodes can be surface-treated using a surface-treating material. Examples of such surface treatment materials include benzenethiol and pentafluorobenzenethiol.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

The molecular weights and molecular weight distributions of the polymers obtained in Examples were estimated by Gel Permeation Chro-Atography (GPC) measurement. Commercially available reagents were used.
<GPC measurement conditions>
Measuring device: Tosoh Corporation high-speed GPC device HLC-8320GPC EcoSEC
Column: TSKgel SuperMultiporeHZ-H, TSKgel SuperHZ2000
Measurement solvent: THF
Measurement temperature: 25°C
Calibration curve: Polystyrene standard <High temperature GPC measurement conditions>
Measuring device: Tosoh Corporation high temperature GPC device HLC-8321GPC/HT
Column: TSKgel GMH _HR -H(20)HT
Measurement solvent: 1,2,4-trichlorobenzene (TCB)
Measurement temperature: 140°C
Calibration curve: polystyrene standard <TGA measurement conditions>
Measuring device: SII Co., Ltd. EXSTAR6000 TGA/DTA6200
Sample container: aluminum pan Measurement atmosphere: nitrogen T _d3 , T _d5 and T _d10 represent 3%, 5% and 10% weight loss temperatures, respectively.
<DSC measurement conditions>
Measuring device: SII Co., Ltd. EXSTAR6000 DSC6220
Sample container: Aluminum pan Measurement conditions: Nitrogen atmosphere, 10°C/min, 0 to 300°C, the third Heating Scan was used for the results.
[Example 1]

Monomer B (200 mg, 144 μmol) and 4,7-bis(5-bromothiophen-2-yl)-5,6-bis(n-octyloxy)-2,1,3-benzothiadiazole (103 mg, 144 μmol), A mixture of sodium carbonate (76.3 mg, 719 μmol), tri(o-tolyl)phosphine (2.6 mg, 8.6 μmol), tetralin (3.6 mL) and DMSO (0.7 mL) was bubbled with argon for 30 minutes. Pd ₂ (dba) ₃ .CHCl ₃ (3.0 mg, 2.9 μmol) was added to this mixed solution under an argon stream, and the mixture was stirred at 120° C. for 66 hours. After the obtained mixture was cooled to room temperature, it was precipitated in methanol, and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone and hexane to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in chloroform and precipitated in methanol, and the precipitated solid was filtered. The obtained solid was washed with methanol and dried under reduced pressure at 90° C. to obtain black solid (3-29) (207 mg, 85%).
GPC (THF): _Mn = 17000, _Mw = 91000, PDI = 3.01.
GPC (TCB, 140° C.): Mn=2000 g/mol, Mw=7400 g/mol, PDI=3.6.
_Td3 = 312°C, _Td5 = 321°C, _Td10 = 336°C.
No phase transition point was observed by DSC.
[Example 2]

Monomer S (100 mg, 68.3 μmol) and 4,7-bis(5-bromothiophen-2-yl)-5,6-bis(n-octyloxy)-2,1,3-benzothiadiazole (48.8 mg , 68.3 μmol) and toluene (1.7 mL) was bubbled with argon for 30 minutes. Pd(PPh ₃ ) ₄ (1.6 mg, 1.4 μmol) was added to this mixed solution and stirred at 180° C. for 2 hours using a microwave reactor. After the obtained mixture was cooled to room temperature, it was precipitated in methanol, and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, hexane, chloroform and monochlorobenzene to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in o-dichlorobenzene, precipitated in methanol, and the precipitated solid was filtered. The obtained solid was washed with methanol and then dried under reduced pressure at 90° C. to obtain a black solid (3-29) (monochlorobenzene soluble matter: 24 mg, 21%, o-dichlorobenzene soluble matter: 54 mg, 47%).
Monochlorobenzene solubles:
GPC (TCB, 140° C.): Mn=1900 g/mol, Mw=10000 g/mol, PDI=5.5.
_Td3 = 321°C, _Td5 = 331°C, _Td10 = 358°C.
No phase transition point was observed by DSC.
o-dichlorobenzene solubles:
GPC (TCB, 140° C.): Mn=24000 g/mol, Mw=95000 g/mol, PDI=4.0.
_Td3 = 315°C, _Td5 = 325°C, _Td10 = 343°C.
No phase transition point was observed by DSC.
[Example 3]

Monomer S (100 mg, 68.3 μmol) and 4,7-bis(5-bromothiophen-2-yl)-5,6-bis(n-dodecyloxy)-2,1,3-benzothiadiazole (56.5 mg , 68.3 μmol) and tetralin (2.0 mL) was bubbled with argon for 30 minutes. Pd ₂ (dba) ₃ .CHCl ₃ (1.4 mg, 1.4 μmol) and tri(o-tolyl)phosphine (1.7 mg, 5.5 μmol) were added to this mixed solution and heated to 180 using a microwave reactor. C. for 2 hours. After the obtained mixture was cooled to room temperature, it was precipitated in a mixed solution of methanol/1N hydrochloric acid (150 mL/10 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, hexane, chloroform and monochlorobenzene to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in o-dichlorobenzene, precipitated in methanol, and the precipitated solid was filtered. The obtained solid was washed with methanol and then dried under reduced pressure at 90° C. to obtain a black solid (3-31) (monochlorobenzene soluble matter: 67 mg, 55%, o-dichlorobenzene soluble matter: 47 mg, 38%).
Monochlorobenzene solubles:
GPC (TCB, 140° C.): Mn=27000 g/mol, Mw=75000 g/mol, PDI=2.81.
_Td3 = 315°C, _Td5 = 325°C, _Td10 = 343°C.
No phase transition point was observed by DSC.
o-dichlorobenzene solubles:
GPC (TCB, 140° C.): Mn=46000 g/mol, Mw=107000 g/mol, PDI=2.33.
_Td3 = 315°C, _Td5 = 324°C, _Td10 = 341°C.
No phase transition point was observed by DSC.
[Example 4]

Monomer S (100 mg, 68.3 μmol) and 4,7-bis(5-bromothiophen-2-yl)-5,6-bis[(2-hexyldecyl)oxy]-2,1,3-benzothiadiazole ( 64.2 mg, 68.3 μmol) and tetralin (2.0 mL) was bubbled with argon for 30 minutes. Pd ₂ (dba) ₃ .CHCl ₃ (1.4 mg, 1.4 μmol) and tri(o-tolyl)phosphine (1.7 mg, 5.5 μmol) were added to this mixed solution and heated to 180 using a microwave reactor. C. for 2 hours. After the obtained mixture was cooled to room temperature, it was precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/10 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, hexane and chloroform to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in monochlorobenzene. An aqueous solution of sodium N,N-diethyldithiocarbamate (1 g/100 mL) was added to the mixture, and the mixture was stirred at 60° C. for 2 hours, and the organic layer was washed with water. This operation was performed twice in total. Furthermore, an aqueous solution of sodium N,N-diethyldithiocarbamate (1 g/100 mL) was added to the organic layer and the mixture was stirred at room temperature for 24 hours. The organic layer was washed with water and filtered through celite. Thereafter, an aqueous potassium fluoride solution (0.5 g/100 mL) was added to the mixture, and the mixture was stirred at room temperature for 20 hours, and the organic layer was washed with water and filtered through celite. This operation was performed 3 times in total. The obtained mixture was concentrated under reduced pressure, and the solid precipitated in methanol was filtered. The obtained solid was washed with methanol and dried under reduced pressure at 90° C. to obtain black solid (3-34) (46.6 mg, 35%).
GPC (TCB, 140° C.): Mn=33000 g/mol, Mw=85000 g/mol, PDI=2.57.
[Example 5]

Monomer S (100 mg, 68.3 μmol) and 4,7-bis(5-bromothiophen-2-yl)-5,6-bis[(2-decyltetradecyl)oxy]-2,1,3-benzothiadiazole A mixture of (79.5 mg, 68.3 μmol) and tetralin (2.0 mL) was bubbled with argon for 30 minutes. Pd ₂ (dba) ₃ .CHCl ₃ (1.4 mg, 1.4 μmol) and tri(o-tolyl)phosphine (1.7 mg, 5.5 μmol) were added to this mixed solution and heated to 180 using a microwave reactor. C. for 2 hours. After the obtained mixture was cooled to room temperature, it was precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/10 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone and hexane to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in chloroform. An aqueous solution of sodium N,N-diethyldithiocarbamate (1 g/100 mL) was added to the mixture, and the mixture was stirred at 60° C. for 2 hours, and the organic layer was washed with water. This operation was performed twice in total. Furthermore, an aqueous solution of sodium N,N-diethyldithiocarbamate (1 g/100 mL) was added to the organic layer and the mixture was stirred at room temperature for 24 hours. The organic layer was washed with water and filtered through celite. Thereafter, an aqueous potassium fluoride solution (0.5 g/100 mL) was added to the mixture, and the mixture was stirred at room temperature for 20 hours, and the organic layer was washed with water and filtered through celite. This operation was performed 3 times in total. The obtained mixture was concentrated under reduced pressure, and the solid precipitated in methanol was filtered. The obtained solid was washed with methanol and dried under reduced pressure at 90° C. to obtain black solid (3-36) (86.7 mg, 59%).
GPC (THF): Mn = 79000 g/mol, Mw = 1869000 g/mol, PDI = 23.6.
GPC (TCB, 140° C.): Mn=10000 g/mol, Mw=69000 g/mol, PDI=6.90.
[Example 6]

Monomer S (100 mg, 68.3 μmol) and 4,7-bis(5-bromo-4-octyl-thiophen-2-yl)-5,6-bis(n-octyloxy)-2,1,3-benzo A mixture of thiadiazole (64.2 mg, 68.3 μmol) and tetralin (2.0 mL) was bubbled with argon for 30 minutes. Pd ₂ (dba) ₃ .CHCl ₃ (1.4 mg, 1.4 μmol) and tri(o-tolyl)phosphine (1.7 mg, 5.5 μmol) were added to this mixed solution and heated to 180 using a microwave reactor. C. for 2 hours. After the obtained mixture was cooled to room temperature, it was precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/10 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, hexane and chloroform to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in monochlorobenzene. An aqueous solution of sodium N,N-diethyldithiocarbamate (1 g/100 mL) was added to the mixture, and the mixture was stirred at 60° C. for 2 hours, and the organic layer was washed with water. This operation was performed twice in total. Furthermore, an aqueous solution of sodium N,N-diethyldithiocarbamate (1 g/100 mL) was added to the organic layer and the mixture was stirred at room temperature for 24 hours. The organic layer was washed with water and filtered through celite. Thereafter, an aqueous potassium fluoride solution (0.5 g/100 mL) was added to the mixture, and the mixture was stirred at room temperature for 20 hours, and the organic layer was washed with water and filtered through celite. This operation was performed 3 times in total. The obtained mixture was concentrated under reduced pressure, and the solid precipitated in methanol was filtered. The resulting solid was washed with methanol and dried under reduced pressure at 90° C. to obtain black solid (3-45) (64.1 mg, 49%).
GPC (TCB, 140° C.): Mn=32000 g/mol, Mw=68000 g/mol, PDI=2.12.
[Example 7]

Monomer S (84.2 mg, 57.5 μmol) and 4,7-bis(5-bromo-4-octyl-thiophen-2-yl)-5,6-bis(n-octyloxy)-2,1,3 - A mixture of benzothiadiazole (54.0 mg, 57.5 μmol) and tetralin (2.3 mL) was bubbled with argon for 30 minutes. Pd ₂ (dba) ₃ .CHCl ₃ (1.2 mg, 1.1 μmol) and tri(o-tolyl)phosphine (1.4 mg, 4.6 μmol) were added to this mixed solution and heated to 180 using a microwave reactor. C. for 2 hours. After that, 2-(tributylstannyl)thiophene (0.16 mL, 193 mg, 0.517 mmol) was added to the reaction solution and stirred at 180° C. for 10 minutes using a microwave reactor. Furthermore, 2-bromothiophene (0.055 mL, 94 mg, 0.575 mmol) was added and stirred at 180° C. for 10 minutes using a microwave reactor. After the obtained mixture was cooled to room temperature, it was precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/10 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, hexane and chloroform to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in monochlorobenzene. An aqueous solution of sodium N,N-diethyldithiocarbamate (1 g/100 mL) was added to the mixture, and the mixture was stirred at 60° C. for 2 hours, and the organic layer was washed with water. This operation was performed twice in total. Furthermore, an aqueous solution of sodium N,N-diethyldithiocarbamate (1 g/100 mL) was added to the organic layer and the mixture was stirred at room temperature for 24 hours. The organic layer was washed with water and filtered through celite. Thereafter, an aqueous potassium fluoride solution (0.5 g/100 mL) was added to the mixture, and the mixture was stirred at room temperature for 20 hours, and the organic layer was washed with water and filtered through celite. This operation was performed 3 times in total. The obtained mixture was concentrated under reduced pressure, and the solid precipitated in methanol was filtered. The obtained solid was washed with methanol and dried under reduced pressure at 90° C. to obtain black solid (3-45) (45 mg, 41%).
GPC (TCB, 140° C.): Mn=22000 g/mol, Mw=46000 g/mol, PDI=2.09.
[Example 8]

Monomer S (100 mg, 68.3 μmol) and 4,7-bis(5-bromo-4-hexyl-thiophen-2-yl)-5,6-bis(n-hexyloxy)-2,1,3-benzo Thiadiazole (56.5 mg, 68.3 μmol), 2-(tributylstannyl)thiophene (0.65 μL, 760 μg, 2.0 μmol), 2-bromothiophene (0.20 μL, 330 μg, 2.0 μmol) and tetralin (2 .0 mL) of the mixture was bubbled with argon for 30 minutes. Pd ₂ (dba) ₃ .CHCl ₃ (1.4 mg, 1.4 μmol) and tri(o-tolyl)phosphine (1.7 mg, 5.5 μmol) were added to this mixed solution and heated to 180 using a microwave reactor. C. for 2 hours. After that, 2-(tributylstannyl)thiophene (0.20 mL, 230 mg, 0.61 mmol) was added to the reaction solution and stirred at 180° C. for 10 minutes using a microwave reactor. Furthermore, 2-bromothiophene (0.065 mL, 110 mg, 0.68 mmol) was added and stirred at 180° C. for 10 minutes using a microwave reactor. After the obtained mixture was cooled to room temperature, it was precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/10 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, hexane, decane, dodecane and chloroform to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in monochlorobenzene. An aqueous solution of sodium N,N-diethyldithiocarbamate (1 g/100 mL) was added to the mixture, and the mixture was stirred at 60° C. for 2 hours, and the organic layer was washed with water. This operation was performed twice in total. Furthermore, an aqueous solution of sodium N,N-diethyldithiocarbamate (1 g/100 mL) was added to the organic layer and the mixture was stirred at room temperature for 24 hours. The organic layer was washed with water and filtered through celite. After that, an aqueous potassium fluoride solution (0.5 g/100 mL) was added to the mixture, and the mixture was stirred at room temperature for 20 hours. The organic layer was washed with water and then filtered through celite. This operation was performed 3 times in total. The obtained mixture was concentrated under reduced pressure, and the solid precipitated in methanol was filtered. The obtained solid was washed with methanol and dried under reduced pressure at 90° C. to obtain black solid (3-138) (34 mg, 25%).
GPC (THF): Mn = 23000 g/mol, Mw = 439000 g/mol, PDI = 19.1.
GPC (TCB, 140° C.): Mn=10000 g/mol, Mw=14000 g/mol, PDI=1.40.
[Example 9]
A 0.5 wt % o-DCB solution of the conjugated polymer (3-29) synthesized in Example 1 was heated in a glove box under a nitrogen atmosphere to obtain a composition for forming an organic thin film.

After cooling to room temperature, it was filtered through a 0.22 μm filter, so it was confirmed that the compound was kept in a solution state and suitable for film formation.

After forming a parylene C film as a base layer on a glass substrate by a CVD method, a shadow mask having a channel length of 100 μm and a channel width of 500 μm was placed on the parylene C layer, and gold was vapor-deposited under vacuum to form source and drain electrodes. Attached. The above solution was spin-coated under nitrogen in a glovebox. This was heated to 150° C. and held for 15 minutes to prepare an organic thin film (3-29). After forming a parylene C film as a gate insulating film by a CVD method, a silver electrode was prepared by a vapor deposition method to prepare a top gate-bottom contact type organic thin film transistor element (gate electrode is silver, gate insulating layer is parylene C, gold for the source electrode and gold for the drain electrode).

Under the atmosphere, the organic thin film transistor element was connected to a semiconductor parameter analyzer (4200-SCS manufactured by Keithley), and the drain voltage (Vd = -100 V) and the gate voltage (Vg) were scanned from +10 to -100 V in increments of 1 V, The transfer characteristics were evaluated. The organic thin film transistor device exhibited p-type characteristics, and its hole carrier mobility was 0.20 cm ² /Vs. After annealing at 150° C. for 15 minutes, the hole carrier mobility was 0.22 cm ² /Vs. It was confirmed that the material had high heat resistance because the carrier mobility did not decrease even after the heat treatment.
[Reference example 1]

(ref1) to (ref2) were synthesized with reference to JP-A-2020-111737.
[Comparative example]
By repeating the same operation as in Example 9, using (ref1) to (ref2), an organic thin film transistor element was produced. Table 1 shows the carrier mobility.

Since the conjugated polymer provided by the present invention provides high carrier mobility and has excellent solubility in solvents and heat resistance, it is applied as a semiconductor device material represented by organic thin film transistor elements and organic thin film solar cells. There is expected.

(A): Bottom gate-top contact organic thin film transistor (B): Bottom gate-bottom contact organic thin film transistor (C): Top gate-top contact organic thin film transistor (D): Top gate-bottom contact organic thin film transistor 1: Organic semiconductor layer 2: substrate 3: gate electrode 4: gate insulating layer 5: source electrode 6: drain electrode

Claims (7)

General formula (1) below

(In the formula, R ¹ represents an alkyl group having 1 to 50 carbon atoms.)
and a divalent structural unit represented by the following general formula (2)

(In the formula, R ² represents a hydrogen atom or an alkyl group having 1 to 50 carbon atoms. A plurality of R ² may be the same or different. R ³ represents an alkoxy group having 1 to 50 carbon atoms. of R ³ may be the same or different.)
A conjugated polymer composed of a divalent structural unit represented by 2. The conjugated polymer according to claim 1, wherein the structural unit (1) and the structural unit (2) are alternately repeated. 3. The conjugate according to claim 1 or 2, wherein R ¹ is an alkyl group having 6 to 34 carbon atoms, R ² is an alkyl group having 4 to 34 carbon atoms, and R ³ is an alkoxy group having 4 to 30 carbon atoms. system polymer. A film-forming composition comprising the conjugated polymer according to any one of claims 1 to 3. An organic thin film produced using the film-forming composition according to claim 4 . An organic semiconductor device comprising the organic thin film according to claim 5 . An organic thin film transistor device comprising the organic thin film according to claim 6 .

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