WO2017159657A1

WO2017159657A1 - Novel compound and semiconductor material containing same

Info

Publication number: WO2017159657A1
Application number: PCT/JP2017/010129
Authority: WO
Inventors: 翔稲垣; 亜弥石塚; 餌取　秀樹
Original assignee: Dic株式会社
Priority date: 2016-03-18
Filing date: 2017-03-14
Publication date: 2017-09-21
Also published as: JP6494788B2; JPWO2017159657A1; TW201802096A

Abstract

The present invention provides a semiconductor material with which a semiconductor element exhibiting high mobility can be provided by means of a wet deposition method, and a compound with which said semiconductor material can be provided. Provided is a compound represented by general formula (1) (in the formula, Ar represents an optionally substituted aromatic hydrocarbon group or an optionally substituted heteroaromatic group, R¹ represents a hydrogen atom or an acyclic C1-20 alkyl group (-CH₂- in the alkyl group may be substituted by -O-, -R´C=CR´-, -CO-, -OCO-, -COO-, -S-, -SO₂-, -SO-, -NH-, -NR´-, or -C≡C- so that an oxygen atom, sulfur atom, and nitrogen atom do not bond directly to each other, and the hydrogen atom in the alkyl group may be substituted by a halogeno group, a nitrile group, or an aromatic group (R´ represents a C1-20 acyclic or cyclic alkyl group.).), and n represents 0 or 1.).

Description

Novel compound and semiconductor material containing the same

The present invention relates to a novel compound and a semiconductor material containing it.

Transistors using amorphous silicon or polycrystalline silicon as a semiconductor material are widely used as switching elements in liquid crystal display devices and organic EL display devices. However, since these transistors using silicon have a high temperature heat treatment process in their manufacture, they cannot be developed for next-generation flexible display devices using a plastic substrate due to heat resistance problems. In order to solve these problems, an organic transistor using an organic compound as a semiconductor material instead of silicon (hereinafter, a semiconductor material using an organic compound may be referred to as an organic semiconductor material) has been proposed. Yes.

Organic semiconductor materials are plastics with poor heat resistance because they can be formed into inks at low temperatures by coating methods or printing methods (hereinafter, coating methods and printing methods are sometimes referred to as wet film forming methods). It can be applied to a substrate, and is expected to be applied to a flexible display device, and further to a flexible electronic device (for example, an electronic tag or a sensor that is light and flexible). On the other hand, organic semiconductors initially have low mobility (one of the indicators for semiconductor characteristics, the unit is cm ² / Vs) compared to silicon semiconductors, resulting in poor transistor response speed and practical use. There was a problem that it was difficult to make it. However, in recent years, organic semiconductor materials that provide mobility exceeding the mobility of amorphous silicon have been developed in response to this problem.

For example, Non-Patent Document 1 includes 2,6-bis (arylethynyl) benzo [1,2-b: 4,5-b ′] dithiophene (hereinafter referred to as benzo [1,2-b: 4,5-b '] Dithiophene is abbreviated as TBT.) Compounds having a skeleton are described, and it is described that the mobility of a transistor using these compounds reaches 1.2 cm ² / Vs (wet film formation). The semiconductor layer is formed by vacuum deposition instead of the method). As described above, the TBT derivative has high potential from the viewpoint of having high semiconductor characteristics. On the other hand, the compound described in Non-Patent Document 1 has a problem of low solubility in a solvent (solvent) It is difficult to use it for the wet film-forming method when the solubility in is low.

Non-Patent Document 2 describes a compound having a 2,6-diphenyl TBT skeleton, and describes that the mobility of a transistor using this compound is on the order of 10 ⁻² cm ² / Vs. However, these compounds have a low solubility in organic solvents.

Patent Document 1 describes a compound having a 2,6-alkynyl TBT skeleton, and discloses an ethynyl group substituted with a C2-C32 aliphatic hydrocarbon group as an alkynyl group. The compound according to the present invention Is not described, and the mobility of a transistor using these compounds is described as an order of 10 ⁻² cm ² / Vs.

Patent Document 2 discloses a compound represented by the general formula “side chain-aromatic unit-aromatic unit”, but does not describe a compound according to the present invention.

Patent Document 3 discloses a compound represented by the general formula “side chain-aromatic unit-acetylene bond-aromatic unit”, but does not describe a compound according to the present invention.

JP 2008-2558592 A International Publication No. 2012-121393 International Publication No. 2015-137304

As described above, the characteristic of the organic semiconductor material is that a semiconductor element such as a transistor can be provided by a wet film formation method. Therefore, an object of the present invention is to provide a semiconductor material that provides a semiconductor element that exhibits high mobility by a wet film formation method, and further to provide a compound that provides the semiconductor material.

In order to overcome the above problems, the present inventor has intensively studied and found that a TBT derivative having a substituent having a specific structure gives a semiconductor element that exhibits high mobility by a wet film-forming method, thereby completing the present invention. It came to do.

That is, the present invention includes the following items.
1. The compound represented by General formula (1). However, Compound (1-1), Compound (1-2), Compound (1-3), Compound (1-4), Compound (1-5), Compound (1-6), Compound (1-7) , Compound (1-8), Compound (1-9), Compound (1-10), Compound (1-11), Compound (1-12), Compound (1-13), Compound (1-14), Compound (1-15), Compound (1-16), Compound (1-17), Compound (1-18), Compound (1-19), Compound (1-20), Compound (1-21), Compound (1-22), Compound (1-23), Compound (1-24), Compound (1-25), Compound (1-26), Compound (1-27), Compound (1-28), Compound ( 1-29), Compound (1-30), Compound (1-31), Compound (1-32), Compound (1-33), Compound (1-34) Compound (1-35), Compound (1-36), Compound (1-37), Compound (1-38), Compound (1-39), Compound (1-40), Compound (1-41), Compound (1-42), Compound (1-43), Compound (1-44), Compound (1-45), Compound (1-46), Compound (1-47), Compound (1-48), Compound (1-49), Compound (1-50), Compound (1-51), Compound (1-52), Compound (1-53), Compound (1-54), Compound (1-55), Compound ( 1-56), Compound (1-57), Compound (1-58), Compound (1-59), Compound (1-60), and Compound (1-61) are excluded.

(In the formula, Ar represents an heteroaromatic group optionally having a good aromatic hydrocarbon group or a substituent a substituent, R ¹ is 1 carbon atom number of hydrogen atoms or acyclic ~ 20 alkyl groups (wherein —CH ₂ — in the alkyl group is such that —O—, —R′C═CR′—, —CO—, —so that oxygen atoms, sulfur atoms and nitrogen atoms are not directly bonded to each other, OCO—, —COO—, —S—, —SO ₂ —, —SO—, —NH—, —NR′— or —C≡C— may be substituted, and the hydrogen atom in the alkyl group may be halogeno A group, a nitrile group or an aromatic group (wherein R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms), and n is 0 or 1 is represented.)

2.1. A semiconductor material containing the compound described in 1.
3.1. An ink containing the compound described in 1.
4.1. A semiconductor film containing the compound described in 1.
5.1. A semiconductor element having a semiconductor layer containing the compound described in 1.
6.1. A transistor having a semiconductor layer containing the compound described in 1.

According to the present invention, a semiconductor element that exhibits high mobility by a wet film formation method can be provided.

It is a conceptual sectional view of a bottom gate top contact (BGTC) type transistor.

(Compound of the present invention)
Hereinafter, the compound of the present invention will be described.
The compound of the present invention is a TBT derivative represented by the general formula (1).

(Wherein Ar represents an aromatic hydrocarbon group which may have a substituent or a heteroaromatic group which may have a substituent, and R ¹ represents a hydrogen atom or an acyclic carbon atom having 1 to 20 alkyl groups (wherein —CH ₂ — in the alkyl group is such that —O—, —R′C═CR′—, —CO—, —so that oxygen atoms, sulfur atoms and nitrogen atoms are not directly bonded to each other, _{OCO -, - COO -, -} S -, - SO 2 -, - SO -, - NH -, - NR'- or -C≡C- may be substituted with a hydrogen atom in the alkyl group, halogeno A group, a nitrile group or an aromatic group (wherein R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms), and n is 0 or 1 is represented.)

Ar of the compound represented by the general formula (1) will be described.
Ar is not particularly limited as long as it is an aromatic hydrocarbon group that may have a substituent or a heteroaromatic group that may have a substituent.
Phenyl group and substituted phenyl group, naphthyl group and substituted naphthyl group, azulenyl group and substituted azulenyl group, anthracenyl group and substituted anthracenyl group, phenanthryl group and substituted phenanthryl group, An acenaphthylenyl group and a substituted acenaphthylenyl group, an acenaphthenyl group and a substituted acenaphthenyl group, a fluorenyl group and a substituted fluorenyl group, a naphthacenyl group and a substituted naphthaenyl group, a pyrenyl group and a substituted pyrenyl group, A chrycenyl group and a chrycenyl group having a substituent, a perylenyl group and a perylenyl group having a substituent, a monovalent group derived from biphenyl and a monovalent group derived from biphenyl having a substituent, A monovalent group derived from terphenyl and a monovalent group derived from p-terphenyl having a substituent, a monovalent group derived from p-quaterphenyl and a p-quaterphenyl having a substituent Monocyclic or polycyclic aromatic hydrocarbon groups such as monovalent groups;

Pyrrolyl group and substituted pyrrolyl group, imidazolyl group and substituted imidazolyl group, pyrazolyl group and substituted pyrazolyl group, triazolyl group and substituted triazolyl group, tetrazolyl group and substituted tetrazolyl group,
A furyl group and a substituted furyl group, a thienyl group and a substituted thienyl group,
An oxazolyl group and a substituted oxazolyl group, a thiazolyl group and a substituted thiazolyl group, an oxadiazolyl group and a substituted oxadiazolyl group, a thiadiazolyl group and a substituted thiadiazolyl group,

A pyrrolothiazolyl group having a pyrrolothiazolyl group and a substituent, a thienothienyl group having a substituent, and a thienothienyl group having a substituent,
Indolyl group and substituted indolyl group, indolinyl group and substituted indolinyl group, indolizinyl group and substituted indolinyl group, pyrrolopyridazinyl group and substituted pyrrolopyridazinyl group, benzotria Benzotriazolyl group having zolyl group and substituent, benzofuryl group and benzofuryl group having substituent, benzothienyl group and benzothienyl group having substituent, benzoxazolyl group and benzoxazolyl having substituent Group,

Carbazolyl group and substituted carbazolyl group, monovalent group derived from dibenzofuran and monovalent group derived from dibenzofuran having substituent, monovalent group derived from dibenzothiophene and derived from dibenzothiophene having substituent A monovalent group,
Pyridyl group and substituted pyridyl group, pyridazinyl group and substituted pyridazinyl group, pyrimidinyl group and substituted pyrimidinyl group, pyrazinyl group and substituted pyrazinyl group,

A quinolinyl group and a substituted quinolinyl group, an isoquinolinyl group and a substituted isoquinolinyl group, a benzoquinolinyl group and a substituted benzoquinolinyl group,
Monovalent group derived from bithiophene and monovalent group derived from bithiophene having substituent, monovalent group derived from terthiophene and monovalent group derived from terthiophene having substituent, derived from quarterthiophene A monocyclic or polycyclic heteroaromatic group such as a monovalent group derived from a monovalent group and a substituted quarterthiophene having a substituent;
And so on.

The substituent for Ar is not particularly limited as long as it is a commonly used substituent as a substituent for an aromatic compound.
Hydrogen atom, halogeno group, nitro group, nitrile group,
An acyclic or cyclic alkyl group having 1 to 20 carbon atoms (in order to prevent —CH ₂ — in the alkyl group from being directly bonded to an oxygen atom, a sulfur atom and a nitrogen atom, respectively) ′ C═CR′—, —CO—, —OCO—, —COO—, —S—, —SO ₂ —, —SO—, —NH—, —NR′— or —C≡C— In general, a hydrogen atom in the alkyl group may be substituted by a halogeno group, a nitrile group or an aromatic group (wherein R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms). To express.).),
An aromatic group (the aromatic group may be substituted with a halogeno group, a nitro group, a nitrile group, an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, an aromatic group, —CH ₂ — in which —O—, —CR ″ = CR ″ —, —CO—, —OCO—, —COO—, so that oxygen atom, sulfur atom and nitrogen atom are not directly bonded to each other, —S—, —SO ₂ —, —SO—, —NH—, —NR ″ — or —C≡C— may be substituted, and the hydrogen atom in the alkyl group may be a halogeno group, a nitrile group or an aromatic group. It may be substituted with a group (wherein R ″ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms).
Etc.

The substituent for Ar is preferably a hydrogen atom or an acyclic or cyclic alkyl group having 1 to 20 carbon atoms from the viewpoint of developing high mobility, and is preferably a hydrogen atom or non-cyclic group having 1 to 20 carbon atoms. A cyclic alkyl group is more preferable, and a hydrogen atom or a linear alkyl group having 1 to 20 carbon atoms is more preferable.

Ar is preferably a group represented by the general formula (2) from the viewpoint of expressing high mobility in the aromatic group,

(Wherein X ²¹ to X ²⁵ represent a hydrogen atom or an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, and * represents a bond as a monovalent substituent.)

The group represented by the general formula (3) is more preferable.

(Wherein X ³¹ , X ³² , X ³⁴ , and X ³⁵ represent a hydrogen atom, X ³³ represents a hydrogen atom or a linear alkyl group having 1 to 20 carbon atoms, and * represents a monovalent substituent. Represents the bond hand.)

Next, R ¹ of the compound represented by the general formula (1) will be described.
R ¹ represents a hydrogen atom or an acyclic alkyl group having 1 to 20 carbon atoms (in order to prevent —CH ₂ — in the alkyl group from being directly bonded to an oxygen atom, a sulfur atom and a nitrogen atom, respectively). , —R′C═CR′—, —CO—, —OCO—, —COO—, —S—, —SO ₂ —, —SO—, —NH—, —NR′— or —C≡C—. The hydrogen atom in the alkyl group may be substituted with a halogeno group, a nitrile group or an aromatic group (provided that R ′ is an acyclic or cyclic group having 1 to 20 carbon atoms) Represents an alkyl group.).

Specifically, an acyclic alkyl group having 1 to 20 carbon atoms (in order that —CH ₂ — in the alkyl group is not directly bonded to an oxygen atom, a sulfur atom and a nitrogen atom, R′C═CR′—, —CO—, —OCO—, —COO—, —S—, —SO ₂ —, —SO—, —NH—, —NR′— or C≡C— substituted The hydrogen atom in the alkyl group may be substituted with an aromatic group, a halogeno group, or a nitrile group (provided that R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms). And (A-1) a linear or branched alkyl group having 1 to 20 carbon atoms, (A-2) an alkoxy group having 1 to 19 carbon atoms, and (A-3) 2 carbon atoms. To 19 alkoxyalkyl groups, (A-4) alkenyl groups having 2 to 20 carbon atoms, and (A-5) carbon atoms. An alkanoyl group having 2 to 20 carbon atoms, (A-6) an alkanoylalkyl group having 3 to 20 carbon atoms, (A-7) an alkoxycarbonyl group having 2 to 20 carbon atoms, and (A-8) 2 to 2 carbon atoms. 20 alkanoyloxy groups, (A-9) alkylsulfanyl groups having 1 to 19 carbon atoms, (A-10) alkylsulfanylalkyl groups having 2 to 19 carbon atoms, and (A-11) 1 to 19 carbon atoms. (A-12) an alkylsulfonylalkyl group having 2 to 19 carbon atoms, (A-13) an alkylsulfinyl group having 1 to 19 carbon atoms, and (A-14) an alkylsulfonyl group having 2 to 19 carbon atoms. Alkylsulfinylalkyl group, (A-15) alkylamino group having 1 to 19 carbon atoms, (A-16) alkylaminoalkyl group having 2 to 19 carbon atoms, and (A-17) carbon An alkynyl group having 2 to 20 atoms.

Among the above (A-1) to (A-17), from the viewpoint of improving the film formability and mobility of the compound of the present invention, (A-1) a straight chain or branched chain having 1 to 20 carbon atoms An alkyl group, (A-2) an alkoxy group having 1 to 19 carbon atoms, (A-3) an alkoxyalkyl group having 2 to 19 carbon atoms, (A-4) an alkenyl group having 2 to 20 carbon atoms, ( A-9) an alkylsulfanyl group having 1 to 19 carbon atoms, (A-10) an alkylsulfanylalkyl group having 2 to 19 carbon atoms, or (A-17) an alkynyl group having 2 to 20 carbon atoms,
In order to obtain a compound with higher mobility, (A-1) a linear alkyl group having 1 to 20 carbon atoms is more preferred.

(A-1) The linear alkyl group having 1 to 20 carbon atoms is preferably a linear alkyl group having 3 to 12 carbon atoms from the viewpoint of developing high mobility, and has 6 to 10 carbon atoms. A straight chain alkyl group is more preferred.

Specific examples of (A-1) include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl. Group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group Linear alkyl groups such as groups;
Etc. can be mentioned.

About the compound represented by General formula (1), the compound represented by General formula (4) is preferable from a viewpoint of improving a mobility.

(R ⁴¹ and R ^42, which may be the same or different and represent a hydrogen atom or a straight-chain alkyl group having a carbon number of 1 ~ 20, n represents 0 or 1.)

About the compound represented by General formula (1), the compound represented by General formula (5) is preferable from a viewpoint of improving a mobility and improving the solubility to a solvent.

(R ⁵¹ and R ⁵² may be the same or different and each represents a hydrogen atom or a linear alkyl group having 1 to 20 carbon atoms.)

About the compound represented by General formula (5), the compound represented by General formula (6) is preferable from a viewpoint of further improving the solubility to a solvent.

(R ⁶¹ and R ⁶² may be the same or different and each represents a hydrogen atom or a linear alkyl group having 1 to 20 carbon atoms, provided that both R ⁶¹ and R ⁶² are hydrogen atoms. except for.)

Specific compounds of the present invention can include the following compounds, but the compounds of the present invention are not limited thereto.
As specific compounds of the present invention, the case where Ar is a phenyl group, R ¹ is an alkyl group having 1 to 20 carbon atoms, and n is 0 is shown below.

As specific compounds of the present invention, the case where Ar is a phenyl group, R ¹ is an alkyl group having 1 to 20 carbon atoms, and n is 1 is shown below.

As specific compounds of the present invention, the case where Ar is a 4-alkylphenyl group, R ¹ is a hydrogen atom and n is 1 is shown below.

(Method for producing the compound of the present invention)
The manufacturing method of the compound of this invention is demonstrated.
The method for producing the compound of the present invention is not particularly limited as long as it is a method capable of obtaining the compound of the present invention. As shown below, the compound of the present invention can be produced by combining known and commonly used synthetic reactions.

The manufacturing method of the compound of this invention is demonstrated using a manufacturing scheme (S1) type | formula. The production scheme (S1) is an example of a method for producing the compound represented by the general formula (1) when n is 0.

(In the formula, Ar and ^{R 1} have the same meanings as Ar and ^{R 1} in the general formula (1).)

First, unsubstituted TBT is lithiated and then boronated by the action of a boronic ester (first stage). Next, the aryl bromide (Ar—Br) is reacted with Suzuki Miyaura coupling to form Ar (second stage). Finally, after lithiation, the target compound Ar-TBT-R ¹ is obtained by acting alkyl bromide (R ¹ -Br) (third stage).

The manufacturing method of the compound of this invention is demonstrated using a manufacturing scheme (S2) type | formula. The production scheme (S2) is an example of a method for producing the compound represented by the general formula (1) when n is 1.

First, an unsubstituted TBT is lithiated and then iodinated by the action of iodine (first stage). Next, a Sonogashira coupling reaction with arylacetylene (Ar—C≡C—H) is performed to form an arylacetylene (second stage). Finally, after lithiation, the target compound Ar—C≡C-TBT-R ¹ is obtained by reacting with alkyl bromide (R ¹ -Br) or alkyl iodide (R ¹ -I) (3 steps Eye).

(Semiconductor material of the present invention)
The semiconductor material of the present invention will be described.
The compound of the present invention can be used as a semiconductor material for semiconductor devices. The form of the semiconductor material of the present invention is not particularly limited as long as it is a form that can be used for the production of a semiconductor element. Single crystal, polycrystal, powder, amorphous film, polycrystalline film, single crystal film, thin film Solid forms such as; liquid forms such as solutions, dispersions, coating liquids, and inks; and the like. Among them, in view of the feature of the organic semiconductor material that a semiconductor element can be provided by a wet film forming method, a coating liquid or an ink is preferable.
The semiconductor material of the present invention may contain a material other than the compound of the present invention as long as the provided semiconductor element exhibits desired semiconductor characteristics.

(Ink of the present invention)
The ink of the present invention will be described.
The ink of the present invention is a material for forming a semiconductor film containing the compound of the present invention by a wet film-forming method, and further is a semiconductor layer containing the compound of the present invention. It is a material for forming a semiconductor layer included in a semiconductor element by a wet film formation method, and by extension, a material for providing the semiconductor element of the present invention by a wet film formation method.

In addition to the compound of the present invention, the ink of the present invention contains a solvent capable of dissolving or dispersing the compound of the present invention.
Such a solvent is not particularly limited as long as it can dissolve or disperse the compound of the present invention.
Ester solvents such as ethyl acetate, normal propyl acetate, isopropyl acetate, propylene glycol monomethyl ether acetate (PGMAc), 3-methoxy-3-methyl-butyl acetate, ethoxyethyl propionate (EEP), propylene carbonate;

Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-butanol, 3-methoxy-3-methyl-1-butanol, 1,3-butanediol, 1-pentanol, 4- Alcohol solvents such as methyl-2-pentanol, 1-hexanol, cyclohexanol, industrial higher alcohols (eg, Diadol Series (trade name, manufactured by Mitsubishi Chemical));

Hydrocarbon solvents such as pentane, n-hexane, hexane, cyclohexane, methylcyclohexane, n-octane, n-decane, toluene, xylene;
Chlorinated solvents such as dichloromethane and chloroform;

Benzene, toluene, cumene, n-propylbenzene, n-butylbenzene, n-pentylbenzene, o-xylene, m-xylene, p-xylene, p-cymene, 1,4-diethylbenzene, mesitylene, 1,3,5 -Triethylbenzene, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, 2,5-dimethylanisole, 1,3-dimethoxybenzene, 3,5-dimethoxytoluene, 2,4-dimethylanisole, phenetole Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, chlorobenzene, o-dichlorobenzene, trichlorobenzene, tetralin, 1,5-dimethyltetralin, 1-methylnaphthalene, industrial aromatic solvents (for example, Solvesso 100, Solvesso 15 Etc. (trade name, manufactured by Exxon Mobil)) aromatic such solvents;

Tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol diethyl ether (monoglyme), diglyme, triglyme, ethylene glycol monomethyl ether (cellosolve), ethyl cellosolve, propiocellosolve, butyrocellosolve, phenylcellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether , Diethylene glycol propyl ether, diethylene glycol butyl ether, benzyl ethyl ether, ethyl phenyl ether, diphenyl ether, methyl-t-butyl ether, cyclopentyl methyl ether, cyclohexyl methyl ether benzonitryl propylene glycol monomethyl ether, propylene glycol monoethyl ether, pro Glycol monopropyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, diethylene glycol butyl ether, ether solvents such as diethylene glycol ethyl ether;

Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, 2-hexanone, 2-heptanone, 3-heptanone, acetophenone, propiophenone, butyrophenone, cyclohexanone;

Aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, diethylformamide, N-methyl-2-pyrrolidone;
Etc.
In addition, the solvent used for the ink of the present invention may be one type or two or more types.

The ink of the present invention may contain a semiconductor material other than the compound of the present invention as other components depending on the application. Examples of such a semiconductor material include an electron donating material, an electron accepting material, an electron transporting material, a hole transporting material, a light emitting material, and a light absorbing material. *

In addition, the ink of the present invention may contain a polymer compound, a resin, a constitutional component, a surfactant, a release agent, and the like as other components. These components are added as necessary to impart printability and film-forming properties (film-forming ability) to the ink of the present invention.

The resin that can be contained in the ink of the present invention is not particularly limited as long as it is a known and commonly used insulating resin.
Cyanoethyl pullulan, cellulose acetate propionate (CAP), cellulose triacetate (TAC), polyarylate (PAR), polyimide, polyester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetherimide (PEI), polyether Ether ketone (PEEK), polyether sulfone (PES), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polycarbonate (PC), polycycloolefin, polystyrene and polystyrene derivatives, polytetrafluoroethylene (PTFE), poly Paraxylylene derivatives (for example, Parylene series (trade name)), polyvinyl alcohol (PVA), polyvinylphenol (PVP), polyphenylene sulfi (PPS), polymethyl methacrylate (PMMA), acrylic resin, amorphous fluororesin (for example, Cytop series (trade name, manufactured by Asahi Glass)), alkyd resin, urethane resin, epoxy resin, electron beam curable resin (for example, electron Line curable acrylic resin and electron beam curable methacrylic resin), phenoxy resin, phenol resin, fluorine resin, unsaturated polyester resin, polyimide resin, polyvinyl phenol resin, melamine resin, UV curable resin (for example, UV curable resin) And high molecular compounds such as curable acrylic resins and UV-curable methacrylic resins).
The resin contained in the ink of the present invention may be one type or two or more types.
The concentration of the resin in the ink is not particularly limited as long as the semiconductor element using the ink of the present invention exhibits desired semiconductor characteristics, and is usually in the range of 1 to 10% by mass. The range is preferably 3 to 7% by mass.

The constitutional component that can be contained in the ink of the present invention is not particularly limited as long as it is a known and commonly used electrically insulating inorganic fine particle or a known and commonly used electrically insulating pigment. For example,
Aerosil series (trade name, manufactured by Evonik),
Silicia, silo hobic, silo pure, silo page, silo pure, silo sphere, silo mask, silwell, fuji balloon (above, trade name, manufactured by Fuji Silysia), PMA-ST, IPA-ST (above, trade name, Nissan Chemical) Made),
Inorganic fine particles such as NANOBIC3600 series and NANOBIC3800 series (above, trade name, manufactured by BYK Chemie);
Pigments such as EXCEDIC BLUE0565, EXCEDIC RED0759, EXCEDIC YELLOW 0599, EXCEDIC GREEN0358, EXCEDIC YELLOW0648 (above, trade name: manufactured by DIC);
And so on.
The constitutional component contained in the ink of the present invention may be one type or two or more types.
The concentration of the constitutional component in the ink is not particularly limited as long as the semiconductor element using the ink of the present invention exhibits desired semiconductor characteristics, and is usually 0 to 20% by mass of the active component. It is preferable that it is the range of these.

The surfactant that can be contained in the ink of the present invention is not particularly limited as long as it is a known and commonly used electrically insulating surfactant. For example,
Examples thereof include hydrocarbon surfactants, silicone surfactants, and fluorine surfactants. Among them, fluorine-based surfactants having a linear perfluoroalkyl group with a chain length of C6 or more (for example, Megafac F-482, Megafac F-470 (R-08), Megafac F-472SF, Mega Fuck R-30, Mega Fuck F-484, Mega Fuck F-486, Mega Fuck F-172D, Mega Fuck F178RM (above, trade name, manufactured by DIC)) are preferable.
In addition, the surfactant contained in the ink of the present invention may be one type or two or more types.
The concentration of the surfactant in the ink is not particularly limited as long as the semiconductor element using the ink of the present invention exhibits desired semiconductor characteristics, and is usually 0.01 to The range is preferably 5.00% by mass, and more preferably 0.05 to 1.00% by mass in terms of active ingredients.

The release agent that can be contained in the ink of the present invention is not particularly limited as long as it is a known and commonly used electrically insulating silicone compound. For example, dimethyl silicone oil, dimethyl silicone rubber, silicone resin, organic Examples thereof include modified silicone oil, methylphenyl silicone oil, long-chain alkyl-modified silicone oil, a mixture of a fluorine compound and a silicone polymer, and fluorine-modified silicone. Of these, the Granol series (trade name, manufactured by Kyoeisha) and the KF-96L series (trade name, manufactured by Shin-Etsu Chemical) are preferable from the viewpoint of releasability and compatibility with the resin.
In addition, the release agent contained in the ink of the present invention may be one type or two or more types.
The concentration of the release agent in the ink is not particularly limited as long as the semiconductor element using the ink of the present invention exhibits desired semiconductor characteristics. The range is preferably from 0 to 5.0% by mass, and more preferably from 0.0 to 3.0% by mass with respect to the active ingredient.

In addition, the ink of the present invention can contain a leveling agent, a dispersant, an antifoaming agent, and the like as optional components.

The concentration of the compound of the present invention in the ink is not particularly limited as long as the semiconductor element using the ink of the present invention exhibits desired semiconductor characteristics, and is usually 0.01 to 20.00. The range is preferably in the range of mass%, more preferably in the range of 0.05 to 10.00 mass%, and still more preferably in the range of 0.10 to 10.00 mass%.

(Semiconductor element of the present invention)
The semiconductor element of the present invention will be described.
The semiconductor element of the present invention is not particularly limited as long as it is a semiconductor element having a semiconductor layer using the compound of the present invention. For example, diodes; thyristors; photodiodes, solar cells, light receiving elements, etc. Conversion element: Field effect transistor, electrostatic induction transistor, bipolar transistor, thin film transistor, etc .; Organic EL element, light emitting transistor, etc .; Memory; Temperature sensor, chemical sensor, gas sensor, humidity sensor, radiation sensor, bio Sensors such as sensors, blood sensors, immune sensors, artificial retinas, taste sensors, and pressure sensors; logic circuit units such as inverters, ring oscillators, and RFIDs;

(Transistor of the present invention)
The transistor of the present invention will be described.
A transistor is a semiconductor element having a gate electrode, a gate insulating layer, a source electrode, a drain electrode, and a semiconductor layer as essential elements, and is classified into various structures depending on the arrangement of each electrode and each layer.

The structure of the transistor of the present invention is not particularly limited as long as the compound of the present invention is contained as a semiconductor layer. For example, a bottom gate bottom contact (hereinafter abbreviated as BGBC) type transistor, bottom gate top contact ( Hereinafter, BGTC type transistor, top gate bottom contact (hereinafter abbreviated as TGBC) type transistor, top gate top contact (hereinafter abbreviated as TGTC) type transistor, metal base organic transistor (hereinafter abbreviated as MBOT). And an electrostatic induction transistor (hereinafter abbreviated as SIT).

Next, a substrate that is a component of the transistor of the present invention will be described.
The substrate material is not particularly limited as long as it can be processed into a plate shape, a sheet shape, a film shape, etc.
silicon;
Inorganic glass such as quartz glass, soda glass, borosilicate glass, alkali-free glass;
Cellulose acetate propionate (CAP), cellulose triacetate (TAC), polyarylate (PAR), polyimide, polyethylene (PE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetherimide (PEI), polyether Resins and polymer compounds such as ether ketone (PEEK), polyether sulfone (PES), polypropylene (PP), polycarbonate (PC), polycycloolefin, polyphenylene sulfide (PPS), polymethyl methacrylate (PMMA);
Etc.

Among them, from the viewpoint of improving the productivity of the transistor, an inorganic substrate such as a glass plate or a silicon wafer is preferable, and from the viewpoint of obtaining a flexible transistor, a glass sheet, a resin sheet, a plastic film, or the like is used. Preferably, in addition to flexibility, a resin sheet or a plastic film is more preferable from the viewpoint of reducing weight and improving portability and impact resistance.

Next, an electrode which is a component of the transistor of the present invention will be described.
The material for the gate electrode, the source electrode, and the drain electrode is not particularly limited as long as it is a conductive material, and examples thereof include an inorganic conductive material and an organic conductive material.

Examples of inorganic conductive materials include lithium, beryllium, carbon, sodium, magnesium, aluminum, silicon, potassium, calcium, scandium, titanium, chromium, manganese, iron, nickel, copper, zinc, gallium, zirconium, niobium, Molybdenum, silver, tin, antimony, hafnium, tungsten, platinum, gold, graphite, glassy carbon, tin oxide, tin-doped indium oxide (ITO), fluorine-doped zinc oxide, sodium-potassium alloy, molybdenum-tantalum alloy, aluminum-aluminum oxide Mixture, silver-silver oxide mixture, magnesium-aluminum mixture, magnesium-indium mixture, magnesium-silver mixture, magnesium-copper mixture, lithium-aluminum mixture, dope silicon , Mention may be made of carbon paste, silver ink, silver paste, copper ink, a copper paste, nano silver, nano copper.
On the other hand, examples of the organic conductive material include conductive polyaniline, conductive polyaniline derivative, conductive polypyrrole, conductive polypyrrole derivative, conductive polythiophene, conductive polythiophene derivative, polyethylenedioxythiophene and polystyrenesulfonic acid complex ( PEDOT-PSS) and other known and commonly used conductive polymers whose electrical conductivity has been improved by doping;
Charge transfer complexes such as tetrathiafulvalene-tetracyanoquinodimethane complex;
And so on.

Each electrode may be made of one type of conductive material or may be made of two or more types of conductive material. In the case of two or more types, they may be mixed and used. Further, the same conductive material may be used for the gate electrode, the source electrode, and the drain electrode, and different conductive materials may be used for the respective electrodes.

The thickness of the electrode is appropriately determined within a range in which a desired electrical conductivity can be achieved, depending on the type of conductive material used to form the electrode, and is usually in the range of 1 nm to 1 μm. Preferably, it is in the range of 10 nm to 200 nm, more preferably in the range of 20 nm to 100 nm.

The shape of the source electrode and the drain electrode is not particularly limited as long as the source electrode and the drain electrode are formed so as to oppose each other with a substantially constant interval (this interval corresponds to the channel length (L)).

The channel length (L) is usually preferably in the range of 0.1 μm to 1 mm, more preferably in the range of 0.5 μm to 200 μm, and still more preferably in the range of 1 μm to 100 μm.

Examples of the electrode forming method include known and commonly used methods as described in "Basics of Materials Science No. 6 Basics of Organic Transistors (Aldrich)", and a desired shape (pattern) and a desired It is not particularly limited as long as it can form a thick electrode, for example,
First, a conductive film is formed once in a wide range by using a wet film formation method or a dry film formation method (once the conductive film is solid (entirely formed)), and then a resist is formed on the “solid conductive film”. A pattern is formed by photolithography or printing, and then etched;
Patterning the “solid conductive film” by laser ablation or the like;
A direct patterning method using a dry film formation method through a mask;
Direct patterning using printing methods;
Etc.

Examples of the dry film forming method include chemical vapor deposition (CVD) methods such as plasma CVD, thermal CVD, and laser CVD; physical vapor deposition (PVD) such as vacuum deposition, sputtering, and ion plating; The
Examples of the wet film forming method include an electrolytic plating method, an immersion plating method, an electroless plating method, a sol-gel method, an organometallic decomposition (MOD) method, a coating method, and a printing method.
In addition, as a method through the mask, a metal mask method, a lift-off method, and the like are used. As the coating method, an ESD (Electro Spray Deposition) method, an ESDUS (Evaporative Spray Deposition Ultra-dilution Solution) method, and an air draping method. Method, air knife coating method, edge casting method, impregnation coating method, kiss coating method, cast coating method, squeeze coating method, spin coating method, slit coating method, electrostatic coating method, electrostatic spray coating method, die coating method, ultrasonic spraying method Coating method, supercritical spray coating method, dispensing method, dip coating method, doctor blade coating method, transfer roll coating method, drop cast method, bar coating method, blade coating method , Reverse coat method, roll coat method, wire bar coat method, etc.
As the printing method, inkjet printing method, offset printing method, capillary pen printing method, gravure printing method, gravure offset printing method, screen printing method, dispensing method, letterpress printing method, letterpress reverse printing method, drop cast method, flexographic printing Method, lithographic printing method, microcontact printing method and the like.

Among these, from the viewpoint of reducing the manufacturing cost, a method using a wet film forming method that eliminates the need for a vacuum environment is preferable, and among the wet film forming methods, a method using a printing method with fewer steps is more preferable.

Next, a gate insulating layer which is a component of the transistor of the present invention will be described.
The gate insulating layer has a function of electrically insulating the gate electrode and the source electrode, the gate electrode and the drain electrode, and the gate electrode and the semiconductor layer. Therefore, the material of the gate insulating layer is not particularly limited as long as it is an electrically insulating material. For example, cyanoethyl pullulan, cellulose acetate propionate (CAP), cellulose triacetate (TAC), polyarylate (PAR) ), Polyimide, polyester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetherimide (PEI), polyetheretherketone (PEEK), polyethersulfone (PES), polyvinylidene chloride (PVDC), polychlorinated Vinyl (PVC), polycarbonate (PC), polycycloolefin, polystyrene and polystyrene derivatives, polytetrafluoroethylene (PTFE), polyparaxylylene derivatives (eg, Parylene series) Trade name)), polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polyphenylene sulfide (PPS), polymethyl methacrylate (PMMA), acrylic resin, amorphous fluororesin (for example, Cytop series (trade name, manufactured by Asahi Glass)) , Alkyd resin, urethane resin, epoxy resin, electron beam curable resin (for example, electron beam curable acrylic resin or electron beam curable methacrylic resin), phenol resin, polyimide resin, polyvinyl phenol resin, phenoxy resin, phenol resin , Polymer compounds such as fluorine resin, unsaturated polyester resin, melamine resin, UV curable resin (for example, UV curable acrylic resin and UV curable methacrylic resin);
Inorganic substances such as Al ₂ O ₃ , SiO ₂ , Ba _x Sr _(1-x) TiO ₃ , BaTi _x Zr _(1-x) O ₃ ;
And so on.

Note that the gate insulating layer may be made of one type of insulating material or may be made of two or more types of insulating material. Further, it may contain a reaction (polymerization) initiator, a crosslinking agent, a crosslinking auxiliary agent and the like.
When it consists of two or more types of insulating materials, each insulating material may be simply mixed and the covalent bond may be formed between insulating materials. Furthermore, when a reaction (polymerization) initiator, a crosslinking agent, and a crosslinking auxiliary agent are included, these materials and the insulating material may be simply mixed, and a covalent bond is formed between these materials. Also good.
The thickness of the gate insulating layer is appropriately determined within a range in which a desired insulating property can be achieved, depending on the type of insulating material used for forming the gate insulating layer, and is usually 10 nm to 5 μm. It is preferable that it is the range of these.

A method for forming the gate insulating layer is particularly limited as long as a film (layer) that can electrically insulate between the gate electrode and the source electrode, between the gate electrode and the drain electrode, and between the gate electrode and the semiconductor layer can be formed. Instead, for example, publicly known dry film forming methods and wet film forming methods can be mentioned.

Examples of the dry film forming method include chemical vapor deposition (CVD) methods such as a plasma CVD method, a thermal CVD method, and a laser CVD method;
Physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating;
Examples of the wet film forming method include an electrolytic plating method, an immersion plating method, an electroless plating method, a sol-gel method, an organometallic decomposition (MOD) method, a coating method, and a printing method.
Examples of the coating method include an ESD (Electro Spray Deposition) method, an ESDUS (Evaporative Spray Deposition ultra-dilute Solution) method, an air doctor coating method, an air knife coating method, an edge casting method, an impregnation coating method, Coating method, squeeze coating method, spin coating method, slit coating method, electrostatic coating method, electrostatic spray coating method, die coating method, ultrasonic spray coating method, supercritical spray coating method, dispensing method, dip coating method, doctor Blade coating method, transfer roll coating method, drop cast method, bar coating method, blade coating method, reverse coating method, roll coating method, wire bar coating method, etc.
As the printing method, inkjet printing method, offset printing method, capillary pen printing method, gravure printing method, gravure offset printing method, screen printing method, dispensing method, letterpress printing method, letterpress reverse printing method, drop cast method, flexographic printing Method, lithographic printing method, microcontact printing method and the like.

Among these, from the viewpoint of reducing manufacturing costs, a method using a wet film forming method that does not require a vacuum facility is preferable.
If patterning is required, patterning can be performed by the same method as described in the section “Electrodes”.

A semiconductor layer which is a component of the transistor of the present invention will be described.
A feature of the transistor of the present invention resides in that the compound of the present invention is contained in a semiconductor layer which is a constituent element thereof. Note that the semiconductor layer which is a constituent element of the transistor of the present invention may contain a material other than the compound of the present invention as long as desired semiconductor characteristics can be exhibited. Examples of such materials include other semiconductor materials, polymer compounds and resins, constitutional components, surfactants, release agents and the like described in the section “(Ink of the present invention)”.

The thickness of the semiconductor layer is appropriately determined within a range in which desired semiconductor characteristics can be achieved, depending on the type of semiconductor material used to form the semiconductor layer, and is usually in the range of 0.5 nm to 1 μm. Preferably, the range is from 5 nm to 500 nm, and more preferably from 10 nm to 300 nm.

The method for forming the semiconductor layer is not particularly limited as long as it can form the semiconductor layer so as to cover at least the channel region (the region sandwiched between the source electrode and the drain electrode). Conventional dry film forming methods and wet film forming methods can be exemplified.

As a dry film forming method, for example,
Chemical vapor deposition (CVD) methods such as plasma CVD, thermal CVD, and laser CVD;
Physical vapor deposition (PVD) methods such as vacuum deposition, sputtering and ion plating;
As a wet film formation method, for example,
ESD (Electro Spray Deposition) method, ESDUS (Evaporative Spray Deposition Ultra-dilution Solution) method, air doctor coat method, air knife coat method, edge cast method, impregnation coat method, spin coat method, spin coat method, spin coat method Coating method, slit coating method, electrostatic coating method, electrostatic spray coating method, die coating method, ultrasonic spray coating method, supercritical spray coating method, dispensing method, dip coating method, doctor blade coating method, transfer roll coating method Coating methods such as drop casting, bar coating, blade coating, reverse coating, roll coating, and wire bar coating;
Inkjet printing method, offset printing method, capillary pen printing method, gravure printing method, gravure offset printing method, screen printing method, dispensing method, letterpress printing method, letterpress reverse printing method, drop cast method, flexographic printing method, planographic printing method, Printing method such as micro contact printing method;
Etc.

Among these, a method using a wet film forming method is preferable from the viewpoint of reducing the manufacturing cost and lowering the manufacturing process.

In forming the semiconductor layer, annealing may be performed after the film is formed as described above for the purpose of increasing the crystallinity of the semiconductor material and improving the semiconductor characteristics. The annealing temperature is preferably in the range of 50 to 200 ° C, more preferably in the range of 70 to 200 ° C, and the annealing time is preferably in the range of 10 minutes to 12 hours, and is preferably in the range of 1 hour to 10 hours. A time range is more preferable, and a range of 30 minutes to 10 hours is more preferable.

Applications of the transistor of the present invention include a switching element of a pixel constituting a display device, a signal driver circuit of a pixel constituting the display device, a memory circuit, a sensor circuit, an inverter, a ring oscillator, an RFID, and the like.
Examples of the display device include a liquid crystal display device, a dispersion type liquid crystal display device, an electrophoretic display device, a particle rotation display device, an electrochromic display device, an organic EL display device, and electronic paper.

The invention is explained in more detail in the examples.

Example 1
<Method for Producing Compound (101)>
A method for producing compound (101) will be described. The compound (101) is a compound corresponding to the case where Ar is a phenyl group, R ¹ is a decyl group, and n is 0 in the compound represented by the general formula (1).

The production scheme is shown in (S101).

First, a synthesis method of the compound (101-1) will be described.
Under an argon atmosphere, 55 mL of dry tetrahydrofuran was added to 3.3 g (17 mmol) of TBT, and the mixture was cooled to −78 ° C. To the reaction solution, 12 mL (19 mmol) of a 1.6 mol / L hexane solution of n-butyllithium was slowly added dropwise. The reaction was warmed to room temperature and stirred for an additional hour. The reaction solution was cooled to -78 ° C, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.9 mL, 19 mmol) was slowly added, and the temperature was raised to room temperature. And stirred for 16 hours. Water was added to the reaction solution to stop the reaction, and then the solvent was distilled off. After adding ethyl acetate and washing with water, the organic phase was dried over magnesium sulfate and the solvent was distilled off. The obtained crude product was separated and purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 3.4 g (yield, 62%) of compound (101-1).

Next, a synthesis method of the compound (101-2) will be described.
Under an argon atmosphere, 1.04 g (3.3 mmol) of the compound (101-1), 0.18 g (0.16 mmol) of tetrakis (triphenylphosphine) palladium (0), 2.2 g (16 mmol) of potassium carbonate and 13 mL of dry toluene Then, 3 mL of dry N, N-dimethylformamide was added and stirred at room temperature. To the reaction solution, 0.75 g (4.7 mmol) of bromobenzene was added dropwise, followed by stirring at 100 ° C. for 1 hour. Chloroform was added to the reaction solution, washed with water, the organic phase was dried over magnesium sulfate, and the solvent was distilled off. The obtained crude product was dispersed in hexane and filtered to obtain 0.57 g (yield, 64%) of compound (101-2).

Finally, a method for synthesizing the compound (101) will be described.
Under an argon atmosphere, 19 mL of dry tetrahydrofuran was added to 0.23 g (0.86 mmol) of the compound (101-2), and the mixture was cooled to −78 ° C. To the reaction solution, 1.1 mL (1.9 mmol) of a 1.6 mol / L hexane solution of n-butyllithium was slowly added dropwise. The reaction was warmed to room temperature and stirred for an additional hour. The reaction solution was cooled to −78 ° C., 0.39 mL (1.9 mmol) of 1-bromodecane was slowly added, the temperature was raised to room temperature, and the mixture was stirred for 16 hours. After adding water to the reaction solution to stop the reaction, the solvent was distilled off. After adding chloroform and washing with water, the organic phase was dried over magnesium sulfate and the solvent was distilled off. The obtained crude product was separated and purified by silica gel column chromatography (cyclohexane) to obtain 76 mg (yield, 22%) of compound (101).

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.14 (s, 1H), δ 8.08 (s, 1H), δ 7.51 (d, J = 6.9 Hz, 2H), δ 7.47-7.41. (M, 3H), δ 7.01 (s, 1H), δ 2.92 (t, J = 7.5 Hz, 2H), δ 1.79-1.75 (m, 2H), δ 1.45-1.20 (M, 14H), δ 0.88 (t, J = 7.8 Hz, 3H).

<Method for Producing Transistor Using Compound (101)>
A heavy-doped p-type silicon wafer with thermal oxide film (thickness of thermal oxide film (SiO ₂ ): 300 nm) is neutral detergent, ultrapure water, isopropyl alcohol (hereinafter abbreviated as IPA), acetone, and IPA in this order. The sample was subjected to ultrasonic cleaning.
Next, after adding 0.4% by mass of compound (101) to p-xylene and stirring well at 80 ° C., this was spin-coated on the washed silicon wafer (spin coating condition: 3000 rpm). , 30 seconds).
Finally, gold is pattern deposited on the silicon wafer coated with the compound (101) as described above by a vacuum deposition method (2 × 10 ⁻⁶ Torr) through a metal mask. A drain electrode was formed (channel length: channel width = 75 μm: 3000 μm).

<Evaluation Method for Mobility of Transistor Using Compound (101)>
The mobility of the transistor manufactured as described above is that the source electrode is grounded and −80 V is applied to the drain electrode, and the voltage (V _g ) is swept (+40 V to −60 V) to the gate electrode. Measure the current (I _d ) flowing through the drain electrode,
From the slope of √I _d −V _g , it was determined using the equation (Eq. 101). The unit is cm ² / Vs.

(Wherein, W is the channel width, L is the channel length, μ is the mobility, C is the capacitance per unit area of the gate insulating layer, and V _T is the threshold voltage.)
The results are shown in Table 1.

(Example 2)
<Method for Producing Compound (102)>
A method for producing compound (102) will be described. The compound (102) is a compound corresponding to the compound represented by the general formula (1), in which Ar is a phenyl group, R ¹ is a hydrogen atom, and n is 1.

The production scheme is shown in (S102).

First, a method for synthesizing the compound (102-1) will be described.
Under argon atmosphere, 140 mL of tetrahydrofuran was added to 7.7 g (40 mmol) of TBT, and the mixture was cooled to −78 ° C. To the reaction solution, 30 mL (47 mmol) of a 1.6 mol / L hexane solution of n-butyllithium was slowly added dropwise. The reaction was warmed to room temperature and stirred for an additional hour. The reaction solution was cooled to −78 ° C., 12 g (47 mmol) of iodine was slowly added, the temperature was raised to room temperature, and the mixture was stirred for 16 hours. Water was added to the reaction solution to stop the reaction, and then the solvent was distilled off. The obtained crude product was washed with methanol and then dispersed in acetone. Insoluble matter was filtered off, and the filtrate was distilled off to obtain 6.6 g of compound (102-1) (yield, 52%).

Next, the synthesis method of a compound (102) is demonstrated.
Under an argon atmosphere, 1.0 g (3.2 mmol) of compound (102-1), 0.14 g (0.19 mmol) of dichlorobis (triphenylphosphine) palladium (II), 0.074 g (0. 39 mmol) was added 80 mL of dry tetrahydrofuran and stirred at room temperature. To the reaction solution, 0.70 mL (6.4 mmol) of ethynylbenzene was added dropwise, followed by stirring at room temperature for 2 hours. Chloroform was added to the reaction solution, washed with water, the organic phase was dried over magnesium sulfate, and the solvent was distilled off. The obtained crude product was dispersed in hexane and separated and purified by silica gel column chromatography (cyclohexane) to obtain 0.31 g (yield, 34%) of Compound (102).

^{_{1 H NMR (400MHz, CDCl 3}} ): δ8.26 (s, 1H), δ8.21 (s, 1H), δ7.58-7.54 (m, 3H), δ7.49 (d, J = 5 .2 Hz, 1H), δ 7.39-7.35 (m, 4H).

<Evaluation of Solubility of Compound (102)>
At room temperature (25 ° C.), p-xylene was added to the compound (102) obtained in Example 2 until it was completely dissolved visually to evaluate the solubility. The results are shown in Table 2.

<Method for Producing Transistor Using Compound (102)>
A transistor was produced in the same manner as in Example 1 except that the compound (102) was used instead of the compound (101).

<Evaluation Method for Mobility of Transistor Using Compound (102)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (102) was used instead of the transistor using the compound (101). The results are shown in Table 1.

(Example 3)
<Method for Producing Compound (103)>
A method for producing compound (103) will be described. The compound (103) is a compound corresponding to the compound represented by the general formula (1) when Ar is a 4-propylphenyl group, R ¹ is a hydrogen atom, and n is 1.

In Example 2, compound (103) was obtained in the same manner as in Example 2, except that 1-ethynyl-4-propylbenzene was used instead of ethynylbenzene.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.23 (s, 1H), δ 8.19 (s, 1H), δ 7.50-7.45 (m, 4H), δ 7.34 (d, J = 5 .2 Hz, 1 H), δ 7.17 (d, J = 8.0 Hz, 1 H), δ 2.59 (t, J = 7.6 Hz, 2 H), δ 1.67-1.60 (m, 2 H), δ 0 .93 (t, J = 7.4 Hz, 3H).

<Evaluation of Solubility of Compound (103)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (103) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (103)>
A transistor was manufactured in the same manner as in Example 1, except that the compound (103) was used instead of the compound (101).

<Evaluation Method of Mobility of Transistor Using Compound (103)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (103) was used instead of the transistor using the compound (101). The results are shown in Table 1.

(Example 4)
<Method for Producing Compound (104)>
A method for producing the compound (104) will be described. Note that the compound (104) is a compound corresponding to the compound represented by the general formula (1) when Ar is a 4-pentylphenyl group, R ¹ is a hydrogen atom, and n is 1.

In Example 2, compound (104) was obtained in the same manner as in Example 2, except that 1-ethynyl-4-pentylbenzene was used instead of ethynylbenzene.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.25 (s, 1H), δ 8.20 (s, 1H), δ 7.51-7.46 (m, 4H), δ 7.35 (d, J = 6 .3 Hz, 1 H), δ 7.18 (d, J = 8.1 Hz, 1 H), δ 2.64 (t, J = 6.6 Hz, 2 H), δ 1.67-1.57 (m, 2 H), δ 1 .35-1.30 (m, 4H), δ 0.90 (t, J = 7.0 Hz, 3H).

<Evaluation of Solubility of Compound (104)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (104) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (104)>
A transistor was produced in the same manner as in Example 1 except that the compound (104) was used instead of the compound (101).

<Evaluation Method for Mobility of Transistor Using Compound (104)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (104) was used instead of the transistor using the compound (101). The results are shown in Table 1.

(Example 5)
<Method for Producing Compound (105)>
A method for producing compound (105) will be described. The compound (105) is a compound corresponding to the compound represented by the general formula (1) in which Ar is a 4-octylphenyl group, R ¹ is a hydrogen atom, and n is 1.

In Example 2, compound (105) was obtained in the same manner as in Example 2, except that 1-ethynyl-4-octylbenzene was used instead of ethynylbenzene.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.25 (s, 1H), δ 8.20 (s, 1H), δ 7.51-7.47 (m, 4H), δ 7.35 (d, J = 5 .6 Hz, 1 H), δ 7.18 (d, J = 8.4 Hz, 1 H), δ 2.63 (t, J = 6.8 Hz, 2 H), δ 1.62-1.60 (m, 2 H), δ 1 .31-1.27 (m, 10H), δ 0.88 (t, J = 6.6 Hz, 3H).

<Evaluation of Solubility of Compound (105)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (105) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (105)>
A transistor was produced in the same manner as in Example 1 except that the compound (105) was used instead of the compound (101).

<Evaluation Method for Mobility of Transistor Using Compound (105)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (105) was used instead of the transistor using the compound (101). The results are shown in Table 1.

(Example 6)
<Method for Producing Compound (106)>
A method for producing compound (106) will be described. The compound (106) is a compound corresponding to the compound represented by the general formula (1) when Ar is a phenyl group, R ¹ is a hexyl group, and n is 1.

The production scheme is shown in (S103).

A method for synthesizing the compound (106) will be described.
Under an argon atmosphere, 20 mL of dry tetrahydrofuran was added to 0.20 g (0.69 mmol) of the compound (102), and the mixture was cooled to −78 ° C. To the reaction solution, 0.90 mL (1.4 mmol) of a 1.6 mol / L hexane solution of n-butyllithium was slowly added dropwise. The reaction was warmed to room temperature and stirred for an additional hour. The reaction solution was cooled to −78 ° C., 0.40 mL (2.8 mmol) of 1-bromohexane was slowly added, and then the mixture was warmed to room temperature and stirred for 10 hours. Water was added to the reaction solution to stop the reaction, and then the solvent was distilled off. After adding chloroform and washing with water, the organic phase was dried over magnesium sulfate and the solvent was distilled off. The obtained crude product was separated and purified by silica gel column chromatography (cyclohexane) to obtain 67 mg (yield, 26%) of compound (106).

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.13 (s, 1H), δ 8.03 (s, 1H), δ 7.57-7.55 (m, 2H), δ 7.51 (s, 1H), δ 7.38-7.36 (m, 3H), δ 7.01 (s, 1H), δ 2.92 (t, J = 7.2 Hz, 2H), δ 1.80-1.74 (m, 2H), δ1.44-1.39 (m, 2H), δ1.34-1.30 (m, 2H), δ0.90 (t, J = 7.0 Hz, 3H).

<Evaluation of Solubility of Compound (106)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (106) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (106)>
A transistor was manufactured in the same manner as in Example 1 except that the compound (106) was used instead of the compound (101).

<Evaluation Method for Mobility of Transistor Using Compound (106)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (106) was used instead of the transistor using the compound (101). The results are shown in Table 1.

(Example 7)
<Method for Producing Compound (107)>
A method for producing compound (107) will be described. The compound (107) is a compound corresponding to the compound represented by the general formula (1) when Ar is a phenyl group, R ¹ is a decyl group, and n is 1.

In Example 6, compound (107) was obtained in the same manner as in Example 6, except that 1-bromodecane was used instead of 1-bromohexane.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.13 (s, 1H), δ 8.03 (s, 1H), δ 7.57-7.55 (m, 2H), δ 7.50 (s, 1H), δ 7.39-7.36 (m, 3H), δ 7.01 (s, 1H), δ 2.91 (t, J = 7.2 Hz, 2H), δ 1.82-1.73 (m, 2H), δ1.41-1.27 (m, 14H), δ0.88 (t, J = 7.0 Hz, 3H).

<Evaluation of Solubility of Compound (107)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (107) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (107)>
A transistor was produced in the same manner as in Example 1 except that the compound (107) was used instead of the compound (101).

<Evaluation Method of Mobility of Transistor Using Compound (107)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (107) was used instead of the transistor using the compound (101). The results are shown in Table 1.

(Example 8)
<Method for Producing Compound (108)>
A method for producing compound (108) will be described. The compound (108) is a compound corresponding to the compound represented by the general formula (1) when Ar is a phenyl group, R ¹ is a heptyl group, and n is 1.

In Example 6, Compound (108) was obtained in the same manner as in Example 6, except that 1-iodoheptane was used instead of 1-bromohexane.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.13 (s, 1H), δ 8.04 (s, 1H), δ 7.57-7.55 (m, 2H), δ 7.51 (s, 1H), δ 7.40-7.36 (m, 3H), δ 7.01 (s, 1H), δ 2.92 (t, J = 7.4 Hz, 2H), δ 1.81-1.71 (m, 2H), δ1.45-1.26 (m, 8H), δ0.89 (t, J = 6.6 Hz, 3H).

<Evaluation of Solubility of Compound (108)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (108) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (108)>
A transistor was produced in the same manner as in Example 1 except that the compound (108) was used instead of the compound (101).

<Evaluation Method for Mobility of Transistor Using Compound (108)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (108) was used instead of the transistor using the compound (101). The results are shown in Table 1.

Example 9
<Method for Producing Compound (109)>
A method for producing compound (109) will be described. The compound (109) is a compound corresponding to the compound represented by the general formula (1) when Ar is a phenyl group, R ¹ is an octyl group, and n is 1.

In Example 6, compound (109) was obtained in the same manner as in Example 6, except that 1-iodooctane was used instead of 1-bromohexane.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.13 (s, 1H), δ 8.04 (s, 1H), δ 7.58-7.55 (m, 2H), δ 7.51 (s, 1H), δ 7.39-7.36 (m, 3H), δ 7.01 (s, 1H), δ 2.92 (t, J = 7.4 Hz, 2H), δ 1.81-1.72 (m, 2H), δ1.45-1.23 (m, 10H), δ0.88 (t, J = 6.8 Hz, 3H).

<Evaluation of Solubility of Compound (109)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (109) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (109)>
A transistor was manufactured in the same manner as in Example 1 except that the compound (109) was used instead of the compound (101).

<Evaluation Method for Mobility of Transistor Using Compound (109)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (109) was used instead of the transistor using the compound (101). The results are shown in Table 1.

(Example 10)
<Method for Producing Compound (110)>
A method for producing compound (110) will be described. The compound (110) is a compound corresponding to the case where Ar is a phenyl group, R ¹ is a nonyl group, and n is 1 in the compound represented by the general formula (1).

In Example 6, compound (110) was obtained in the same manner as in Example 6, except that 1-iodononane was used instead of 1-bromohexane.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.11 (s, 1H), δ 8.02 (s, 1H), δ 7.56-7.52 (m, 2H), δ 7.49 (s, 1H), δ 7.39-7.34 (m, 3H), δ 6.99 (s, 1H), δ 2.89 (t, J = 7.6 Hz, 2H), δ 1.78-1.71 (m, 2H), δ1.43-1.20 (m, 12H), δ0.87 (t, J = 7.0 Hz, 3H).

<Evaluation of Solubility of Compound (110)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (110) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (110)>
A transistor was produced in the same manner as in Example 1 except that the compound (110) was used instead of the compound (101).

<Evaluation Method for Mobility of Transistor Using Compound (110)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (110) was used instead of the transistor using the compound (101). The results are shown in Table 1.

(Comparative Example 1)
<Method for Producing Compound (C101)>
Compound (C101) was produced according to the synthesis method described in Non-Patent Document 1.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.13 (s, 2H), δ 7.50-7.47 (m, 6H), δ 7.19 (d, J = 8.4 Hz, 4H), δ 2.62. (T, J = 7.8 Hz, 4H), δ 1.67-1.65 (m, 4H), 0.95 (t, J = 7.0 Hz, 6H).

<Evaluation of Solubility of Compound (C101)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (C101) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (C101)>
A transistor was produced in the same manner as in Example 1 except that the compound (C101) was used instead of the compound (101).

<Evaluation Method of Mobility of Transistor Using Compound (C101)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (C101) was used instead of the transistor using the compound (101). The results are shown in Table 1.

(Comparative Example 2)
<Method for Producing Compound (C102)>
Compound (C102) was produced according to the synthesis method described in Non-Patent Document 1.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.14 (s, 2H), δ 7.50-7.47 (m, 6H), δ 7.19 (d, J = 8.0 Hz, 4H), δ 2.63 (T, J = 7.8 Hz, 4H), δ1.63 (m, 4H), δ1.34 (m, 8H), 0.90 (t, J = 6.6 Hz, 6H).

<Evaluation of Solubility of Compound (C102)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (C102) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (C102)>
A transistor was manufactured in the same manner as in Example 1 except that the compound (C102) was used instead of the compound (101).

<Evaluation Method of Mobility of Transistor Using Compound (C102)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (C102) was used instead of the transistor using the compound (101). The results are shown in Table 1.

(Comparative Example 3)
<Method for Producing Compound (C103)>
Compound (C103) was produced according to the synthesis method described in Patent Document 3.

<Evaluation of Solubility of Compound (C103)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (C103) was used instead of the compound (102). The results are shown in Table 2.

(Comparative Example 4)
<Method for Producing Compound (C104)>
Compound (C104) was produced according to the synthesis method described in Patent Document 3.

<Evaluation of Solubility of Compound (C104)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (C104) was used instead of the compound (102). The results are shown in Table 2.

(Comparative Example 5)
<Method for Producing Compound (C105)>
Compound (C105) was produced according to the synthesis method described in Patent Document 3.

<Evaluation of Solubility of Compound (C105)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (C105) was used instead of the compound (102). The results are shown in Table 2.

(Comparative Example 6)
<Method for Producing Compound (C106)>
Compound (C106) was produced according to the synthesis method described in Non-Patent Document 1.

<Evaluation of Solubility of Compound (C106)>
In Example 2, the solubility was evaluated in the same manner as in Example 2 except that the compound (C106) was used instead of the compound (102). The results are shown in Table 2.

<Method for Producing Transistor Using Compound (C106)>
A transistor was manufactured in the same manner as in Example 1 except that the compound (C106) was used instead of the compound (101).

<Evaluation Method of Mobility of Transistor Using Compound (C106)>
In Example 1, the mobility of the transistor was evaluated in the same manner as in Example 1 except that the transistor using the compound (C106) was used instead of the transistor using the compound (101). The results are shown in Table 1.

From Table 1, a transistor having a semiconductor layer formed by a wet film-forming method using the compound of the present invention exhibits a high mobility of 0.5 cm ² / Vs or more, and further, from compounds (102) to (110) Is used, a high mobility of 1 cm ² / Vs or higher is exhibited. On the other hand, the mobility of the transistor using the compound of the comparative example (a compound having a TBT skeleton similar to the compound of the present invention (Non-patent Document 1, etc.)) is low.

As is clear from Table 2, the compound of the present invention exhibits a high solvent solubility of 0.1 wt% or higher even at room temperature. Showing gender. In contrast, the compound of the comparative example (one having a bis (arylethynyl) group in the TBT skeleton (Non-patent Document 1) and the TBT in the compound of the present invention having other polycyclic aromatics (Patent Document 3) ) Is inferior in solvent solubility of less than 0.1 wt% (the higher the solubility, the higher the suitability for ink and the industrial advantage).

The compound of the present invention achieves both high semiconductor characteristics and high solubility by introducing an appropriate substituent at an appropriate substituent position with respect to the TBT skeleton. It can be used as a semiconductor that can be manufactured by the method, and can be used for a semiconductor element using the semiconductor as a semiconductor layer.

1. Substrate 2. 2. Gate electrode 3. Gate insulating layer 4. Semiconductor layer Source electrode 6. Drain electrode

Claims

The compound represented by General formula (1). However, Compound (1-1), Compound (1-2), Compound (1-3), Compound (1-4), Compound (1-5), Compound (1-6), Compound (1-7) , Compound (1-8), Compound (1-9), Compound (1-10), Compound (1-11), Compound (1-12), Compound (1-13), Compound (1-14), Compound (1-15), Compound (1-16), Compound (1-17), Compound (1-18), Compound (1-19), Compound (1-20), Compound (1-21), Compound (1-22), Compound (1-23), Compound (1-24), Compound (1-25), Compound (1-26), Compound (1-27), Compound (1-28), Compound ( 1-29), Compound (1-30), Compound (1-31), Compound (1-32), Compound (1-33), Compound (1-34) Compound (1-35), Compound (1-36), Compound (1-37), Compound (1-38), Compound (1-39), Compound (1-40), Compound (1-41), Compound (1-42), Compound (1-43), Compound (1-44), Compound (1-45), Compound (1-46), Compound (1-47), Compound (1-48), Compound (1-49), Compound (1-50), Compound (1-51), Compound (1-52), Compound (1-53), Compound (1-54), Compound (1-55), Compound ( 1-56), Compound (1-57), Compound (1-58), Compound (1-59), Compound (1-60), and Compound (1-61) are excluded.

(In the formula, Ar represents an heteroaromatic group optionally having a good aromatic hydrocarbon group or a substituent a substituent, R 1 is 1 carbon atom number of hydrogen atoms or acyclic ~ 20 alkyl groups (wherein —CH 2 — in the alkyl group is such that —O—, —R′C═CR′—, —CO—, —so that oxygen atoms, sulfur atoms and nitrogen atoms are not directly bonded to each other, OCO—, —COO—, —S—, —SO 2 —, —SO—, —NH—, —NR′— or —C≡C— may be substituted, and the hydrogen atom in the alkyl group may be halogeno A group, a nitrile group or an aromatic group (wherein R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms), and n is 0 or 1 is represented.)
A semiconductor material containing the compound according to claim 1.
An ink containing the compound according to claim 1.
A semiconductor film containing the compound according to claim 1.
A semiconductor element having a semiconductor layer containing the compound according to claim 1.
A transistor having a semiconductor layer containing the compound according to claim 1.