JP7091837B2 - New compounds and semiconductor materials containing them - Google Patents

Description

The present invention relates to novel compounds and semiconductor materials containing them.

Organic semiconductor materials can be wet-formed at low temperatures by converting them into ink by utilizing their solvent solubility. Therefore, flexible display devices and flexible displays that are expected to use plastic substrates with poor heat resistance. It is expected to be applied to electronics (electronic devices with lightweight and flexible electronic tags and sensors).

Semiconductors include p-type semiconductors in which holes play the role of transmitting current, and n-type semiconductors in which electrons play the role. When constructing digital circuits and analog circuits, both p-type and n-type semiconductors should be used. If this is possible, the configuration of basic units such as inverters will be simpler, and the degree of freedom in circuit design will increase. However, regarding organic semiconductors, there are few reports of n-type semiconductors compared to p-type semiconductors, and in particular, reports of n-type semiconductors that have semiconductor characteristics, stability in air, and solvent solubility have been reported. There was almost no. Under such circumstances, a compound having a benzo [1,2-c: 4,5-c'] bis [1,2,5] thiadiazole (hereinafter, may be abbreviated as benzobisthiadiazole or B2T) skeleton. (Hereinafter referred to as a B2T derivative) is attracting attention as an n-type semiconductor material having stability in air.

Patent Documents 1 to 16 and Non-Patent Documents 1 and 2 disclose B2T derivatives having an aryl group (including an aryl group substituted with an aryl group) at positions 4 and 8, and most of them are transistors. Shows n-type semiconductor characteristics in the atmosphere. On the other hand, as described in Patent Document 5, these B2T derivatives have a problem of low solvent solubility (in the comparative example described later, B2T derivatives having aryl groups at the 4- and 8-positions are actually synthesized. However, the problem has been confirmed.) Patent Document 5 discloses B2T derivatives (compounds C13, C19, C22, C26 and C31 in the document) exhibiting solvent solubility of 0.2 to 0.3% by mass at room temperature as a means for solving the problem. However, these compounds (for example, the compound (R1) described later, which is the compound (C19) disclosed in Patent Document 5) have two aryl groups (phenyl group in the compound (R1)). It has two different substituents (nitrile group and hexadecyl group in compound (R1)) (hereinafter, the means in Patent Document 5 is referred to as "a method of introducing two substituents into one aryl group"". In the process of introducing two substituents into the aryl group in the production thereof, the position isomers involved in the substituents and compounds having different numbers of substituents are by-produced, which is essential for semiconductor applications. Removal of these by-products (purification process) is an issue (for example, high cost related to production) in purifying.

（Ｒ１）

(R1)

Patent Documents 17 and 18 and Non-Patent Document 3 disclose B2T derivatives having an alkynylene group at positions 4 and 8 (in Non-Patent Document 3, only compound 3 in the document is applicable). However, in Patent Document 17 and Non-Patent Document 3, the corresponding compound is not provided for the transistor, and in Patent Document 18, although the structural formula is described in the 0026 stage, synthesis and structure identification are performed in the examples. There is no description related to. Further, in any of the documents, there is no description regarding the characteristics of the n-type semiconductor, the stability in air, and the solvent solubility. In the comparative example described later, the compound 58 described in Patent Document 18 (however, in the examples of the patent document, there is no description related to the method for synthesizing the compound and the structure identification) is actually synthesized and the solvent is used. It has been confirmed that the solubility is low.

Japanese Unexamined Patent Publication No. 2015-196659 Japanese Unexamined Patent Publication No. 2016-05017 Japanese Unexamined Patent Publication No. 2017-025047 International Publication No. 2013/141182 International Publication No. 2015/041026 Japanese Unexamined Patent Publication No. 2016-096242 International Publication No. 2016/024567 Japanese Unexamined Patent Publication No. 2013-124231 Special Table 2016-509621 JP-A-2015-207759 Japanese Unexamined Patent Publication No. 2014-055804 Special Table 2003-513100 Gazette Japanese Unexamined Patent Publication No. 2016-134570 US Publication No. 2016/0244614 Japanese Unexamined Patent Publication No. 2017-07319 International Publication No. 2018/015320 International Publication No. 2007/089911 Japanese Unexamined Patent Publication No. 2017-193521

Chemical Communications, 2010, Vol. 46, p. 3265 Chemistry of Materials, 2015, Vol. 27, p. 141 Journal of Materials Chemistry C, 2014, Volume 2, pp. 9609

As described above, the B2T derivative has both stability in air and n-type semiconductor characteristics, but has a problem in solvent solubility. Therefore, an object of the present invention is to provide a B2T derivative exhibiting n-type semiconductor properties having both stability in air and solvent solubility. In particular, stability in air and a solvent without means of the method of "introducing two substituents into one aryl group" relating to the B2T derivative (for example, compound (R1)) described in Patent Document 5. It is an object of the present invention to provide a B2T derivative exhibiting n-type semiconductor characteristics having both solubility. Furthermore, it is an object of the present invention to provide a semiconductor device exhibiting stability in air and n-type semiconductor characteristics by using the B2T derivative.

In order to overcome the above problems, the inventors have made extensive studies to provide a semiconductor material in which a B2T derivative having a substituent having a specific structure has stability in air, n-type semiconductor properties, and solvent solubility. We found it and came to complete the present invention.

That is, the present invention is composed of the following items.
1. 1. A compound represented by the general formula (1).

（１）

(1)

(In the general formula (1), R ¹ and R ² represent monovalent substituents represented by the general formula (2), n is the number of substituents of R ¹ , and an integer of 1 to 5 is used. Represented, m is the number of substituents of ^R2 and represents an integer from 1 to 5).

（２）

(2)

(In the general formula (2), * represents a binding site as a monovalent substituent, R ³ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and X represents a halogen atom. .)
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 device having a semiconductor layer containing the compound described in 1.
6.1. A transistor having a semiconductor layer containing the compound described in 1.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a semiconductor device exhibiting stable n-type semiconductor characteristics in air by a wet film forming method.

It is a conceptual cross-sectional view of a top gate bottom contact (TGBC) type transistor. It is a figure which shows the transmission characteristic of the transistor manufactured in Example 1. FIG. It is a figure which shows the transmission characteristic of the transistor manufactured in Example 2. FIG. It is a figure which shows the transmission characteristic of the transistor manufactured in Example 3. FIG.

(Compound of the present invention)
Hereinafter, the compound of the present invention will be described.

The compound of the present invention is a B2T derivative represented by the general formula (1).

（１）

(1)

(In the general formula (1), R ¹ and R ² represent monovalent substituents represented by the general formula (2), n is the number of substituents of R ¹ , and an integer of 1 to 5 is used. Represented, m is the number of substituents of ^R2 and represents an integer from 1 to 5).

（２）

(2)

(In the general formula (2), * represents a binding site as a monovalent substituent, R ³ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and X represents a halogen atom. .)

In the general formula (1), R ¹ and R ² may be the same or different from each other, but are preferably the same from the viewpoint of ease of synthesis. Further, n and m are preferably 2 to 5 from the viewpoint of solvent solubility, and preferably 1 from the viewpoint of ease of synthesis. When 1, the binding site in the phenyl group of R ¹ and R ² is synthetic with respect to the ethynyl group (...- B2T-C≡C- group (... is the other substituent of B2T)). From the viewpoint of convenience, the p-position and the m-position are preferable, and the p-position is more preferable. From the viewpoint of solubility, the o-position is preferable.

In the general formula (2), X represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of n-type semiconductor characteristics, fluorine atom and chlorine atom are preferable, and n-type semiconductor characteristics and synthesis are used. From the viewpoint of convenience, a fluorine atom is preferable.

In the general formula (2), R ³ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and specifically, an alkyl group having 1 to 20 carbon atoms, said alkyl group. In -CH _2- , -O-, -R'C = CR'-, -CO-, -OCO-, -COO-,-so that oxygen atom, sulfur atom and nitrogen atom are not directly bonded to each other. It may be substituted with S-, -SO _2- , -SO-, -NH-, -NR'-or -C≡C-, 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 (where R'represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms).

More specifically, regarding R ³ , a monovalent group (alkyl group, cycloalkyl group, alkylcycloalkyl group) derived from a saturated hydrocarbon having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. , Alkinyl group with 2 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, alkoxyalkyl group with 2 to 20 carbon atoms, alkanoyl group with 1 to 20 carbon atoms, alkanoyl with 2 to 20 carbon atoms Alkyl group, alkoxycarbonyl group with 2 to 20 carbon atoms (alkyl-OCO-), alkanoyloxy group with 1 to 20 carbon atoms (alkyl-COO- or HCOO-), alkylsulfanyl group with 1 to 20 carbon atoms , Alkyl sulfanyl alkyl group with 2 to 20 carbon atoms, Alkyl sulphinyl group with 1 to 20 carbon atoms, Alkyl sulfinyl alkyl group with 2 to 20 carbon atoms, Alkyl sulfonyl group with 1 to 20 carbon atoms, Number of carbon atoms An alkylsulfonylalkyl group having 2 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an alkylaminoalkyl group having 2 to 20 carbon atoms, and the like.

Regarding R3 ^, from the viewpoint of improving solvent solubility and semiconductor properties, monovalent groups (alkyl group, cycloalkyl group, alkylcycloalkyl group) and carbon atoms derived from saturated hydrocarbons having 1 to 20 carbon atoms. An alkenyl group having 2 to 20, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkylsulfanyl group having 1 to 20 carbon atoms, Alkyl sulfanyl alkyl groups having 2 to 20 carbon atoms are preferable, and monovalent groups (alkyl groups, cycloalkyl groups, etc.) derived from saturated hydrocarbons having 1 to 20 carbon atoms are preferable from the viewpoint of further improving semiconductor properties. Alkylcycloalkyl groups) are more preferred.

Examples of the monovalent group (alkyl group, cycloalkyl group, alkylcycloalkyl group) derived from a saturated hydrocarbon having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and n. -Butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group , N-Heptyl group, 1-methylhexyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2, 2-Dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group Examples include a group, a 1-hexylheptyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group and the like (these are examples). Is an example and is not limited thereto.) From the viewpoint of combining solvent solubility and mobility, a monovalent group derived from a saturated hydrocarbon having 3 to 20 carbon atoms is preferable, and carbon is preferable. More preferably, a monovalent group derived from a saturated hydrocarbon having 5 to 20 atoms.

Specific examples of the compound of the present invention include the following compounds, but the compound of the present invention is not limited thereto.

(Method for producing the compound of the present invention)
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 conventional synthetic reactions.

The method for producing the compound of the present invention will be described using the production scheme (S1).

（Ｓ１）

(S1)

(In the formula (S1), R ¹ , R ² , n, m have the same meanings as described above. R ″ represents an arbitrary alkyl group.)

First, potassium nitrate is allowed to act on 1,3-dichlorobenzene for dinitrification (first step), and then ammonia is allowed to act for diamination (second step). Next, it is reduced with tin (II) chloride to be tetraaminated (third step), and then thionyl bromide is allowed to act to obtain 4,8-dibromo B2T (fourth step). Finally, the organotin compound (Ar ¹ -≡-SnR ″ ₃ and Ar ² -≡-SnR ″ ₃ ) is subjected to a Stille coupling reaction to obtain the desired compound Ar ¹ -≡-B2T-≡-Ar ² . (5th stage). In the fifth stage, Ar ¹ -≡-SnR ″ ₃ and Ar ² -≡-SnR ″ ₃ may be the same or different, and if they are different, they may act at the same time. It may act sequentially.

Next, a method for producing the organotin compound used for producing the compound of the present invention will be described using the production scheme (S2).

（Ｓ２）

(S2)

(In the equation (S2), R ¹ , R ³ , R ″, and n have the same meanings as described above.)
First, in the Friedel-Crafts reaction, an aliphatic carboxylated product (R3 ^- CO-Cl) was allowed to act on bromobenzene for acylation (first step), and then a halogenating agent (bis (2-methoxyethyl)). A nucleophilic fluorinating agent such as aminosulfatrifluoride or a chlorinating agent such as phosphorus pentoxide) is allowed to act to dihalogenate the benzyl position (second step). Next, trimethylsilylacetylene is reacted with Sonogashira coupling (third step), and then potassium carbonate is allowed to act to obtain an ethynylbenzene derivative (fourth step). Finally, after the action of butyl lithium, the desired organic tin compound is obtained by reacting with trialkyl tin chloride (Cl-SnR ″ ₃ ) (fifth step).

Further, the organotin compound used for producing the compound of the present invention can also be produced according to the production scheme (S3).

（Ｓ３）

(S3)

(In Eq. (S3), R ¹ , R ³ , R ″, n are synonymous with the above.)
First, benzene is acylated, and then a brominating agent is allowed to act on it to obtain acylated bromobenzene. After that, the desired organic tin compound can be obtained in the same manner as in the second and subsequent steps of the production scheme (S2). In the case of n = 1, when the p-substituted product is the target product, the production scheme (S2) is used, and when the m-substituted product is the target product, the production scheme (S3) is used. It is preferable to do this.

(Semiconductor material of the present invention)
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 can be used for manufacturing a semiconductor element, and is a single crystal, a polycrystal, a powder, an amorphous film, a polycrystal film, a single crystal film, or a thin film. Solid forms such as; liquid forms such as solutions, dispersions, coatings, inks; and the like. Above all, considering that the characteristic of the organic semiconductor material is that a semiconductor element can be provided by a wet film forming method, a solution, a coating liquid, and an ink are 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 is a material for forming a semiconductor film containing the compound of the present invention by a wet film forming method, and is a semiconductor layer containing the compound of the present invention, and is a semiconductor of the present invention. It is a material for forming a semiconductor layer of an element by a wet film forming 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, for example.
Ethyl acetate, normal propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-butyl acetate, ethoxyethyl propionate, propylene Ester solvent such as 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- Alcoholic solvents such as methyl-2-pentanol, 1-hexanol, cyclohexanol;

Hydrocarbon solvents such as pentane, hexane, n-hexane, heptane, octane, n-octane, isooctane, nonane, decane, n-decane, dodecane, octadecane, cyclohexane, methylcyclohexane, decalin;
Halogen solvents such as dichloromethane, chloroform, dibromomethane, dichloroethane, dibromoethane, 1,1,2-trichloroethane, dichloropropane, dibromopropane;

Benzene, toluene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, n-pentylbenzene, n-hexylbenzene, o-xylene, m-xylene, p-xylene, p-simene, 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, phenetol, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, chlorobenzene, o-dichlorobenzene, trichlorobenzene, tetraline, 1,5-dimethyltetraline, 1-methylnaphthalene, 1, Aromatic solvents such as 2,4-trichlorobenzene, bromobenzene and bromonaphthalene;

Tetrahydrofuran, 2-methyltetratetra, dioxane, ethylene glycol diethyl ether (monoglyme), diglyme, triglime, 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 benzoditril propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether. , Ethylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, diethylene glycol butyl ether, diethylene glycol ethyl ether and other ether-based solvents;

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;
And so on.

The solvent used in the ink of the present invention may be one kind or a mixture of two or more kinds.

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 intended use. Examples of such semiconductor materials include electron donating materials, electron accepting materials, electron transporting materials, hole transporting materials, light emitting materials, and light absorbing materials.

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

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 has desired semiconductor characteristics, and is usually 0.01 to 20.00. It is preferably in the range of% by mass, more preferably in the range of 0.05 to 10.00% by mass, and even more preferably in the range of 0.30 to 10.00% by mass.

(Semiconductor device of the present invention)
The semiconductor device of the present invention is not particularly limited as long as it is a semiconductor device having a semiconductor film made of the compound of the present invention as a semiconductor layer. Photoelectric conversion elements such as; electric field effect type transistors, electrostatic induction type transistors, bipolar transistors, thin film transistors and the like; light emitting elements such as organic EL elements and light emitting transistors; memory; temperature sensors, chemical sensors, gas sensors, humidity sensors, radiation Sensors such as sensors, biosensors, blood sensors, immune sensors, artificial retinas, taste sensors, and pressure sensors; logic circuits such as inverters, ring oscillators, and RFIDs; and the like can be mentioned.

(Transistor of the present invention)

The structure of the transistor of the present invention is not particularly limited as long as the film of the present invention is contained as a semiconductor layer. For example, a bottom gate bottom contact (hereinafter abbreviated as BGBC) electric field effect transistor, bottom gate Top contact (hereinafter abbreviated as BGTC) electric field effect transistor, top gate bottom contact (hereinafter abbreviated as TGBC) electric field effect transistor, top gate top contact (hereinafter abbreviated as TGTC) electric field effect type Examples thereof include a transistor, a metal-based organic transistor (hereinafter abbreviated as MBOT), an electrostatic induction transistor (hereinafter abbreviated as SIT), and the like.

The semiconductor layer which is a component of the transistor of this invention will be described.

A feature of the transistor of the present invention is that the film of the present invention containing the compound of the present invention is used for the semiconductor layer which is a component thereof. The semiconductor layer, which is a component of the transistor of the present invention, may contain a material other than the compound of the present invention as long as it can exhibit desired semiconductor characteristics. Examples of such a material include other semiconductor materials, polymer compounds and resins, constitutional components, surfactants, mold release agents and the like described in the section of "(Ink of the present invention)".

The thickness of the semiconductor layer is not particularly limited as long as the desired semiconductor characteristics can be achieved, depending on the type of semiconductor material used to form the semiconductor layer, and is usually from 0.5. It is preferably in the range of 1000 nm, more preferably in the range of 5 to 500 nm, and even more preferably in the range of 10 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), and is, for example, known. Examples include conventional dry film forming methods and wet film forming methods.

As a dry film forming method, for example,
CVD methods such as plasma chemical vapor deposition (CVD), thermal CVD, and laser CVD;
Physical vapor deposition (PVD) methods such as vacuum vapor deposition, sputtering, and ion plating;

As a wet film forming method, for example,
ESD (Electro Spray Deposition) method, ESDUS (Evaporative Spray Deposition) method, Ultra-dilute Solution) method, air doctor coat method, air knife coat method, edge cast method, impregnation coat method, kiss coat method, cast Coat method, slit coat method, electrostatic coat method, electrostatic spray coat method, die coat method, ultrasonic spray coat method, supercritical spray coat method, dispense method, dip coat method, doctor blade coat method, transfer roll coat method, Application method such as drop cast method, bar coat method, blade coat method, reverse coat method, roll coat method, wire bar coat method;
Inkjet printing method, offset printing method, capillary pen printing method, gravure printing method, gravure offset printing method, screen printing method, dispense method, letterpress printing method, letterpress reversal printing method, drop cast method, flexo printing method, flat plate printing method, Printing methods such as the microcontact printing method; etc. can be mentioned.

Above all, the wet film forming method is preferable from the viewpoint of reducing the manufacturing cost and lowering the temperature of the manufacturing process.

Further, in forming the semiconductor layer, if necessary, annealing may be performed after forming a film as described above for the purpose of enhancing the crystallinity of the semiconductor material and improving the semiconductor characteristics. Annealing methods include, for example, applying heat, exposing to solvent vapor, and the like.

Applications of the transistor of the present invention include switching elements of the pixels constituting the display device, signal driver circuits of the pixels constituting the display device, memory circuits, sensor circuits, inverters, ring oscillators, RFIDs and the like.

Examples of the display device include a liquid crystal display device, a distributed liquid crystal display device, an electrophoresis display device, a particle rotation display device, an electrochromic display device, an organic EL display device, an electronic paper, and the like.

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

(Example 1)
<Manufacturing method of compound (101)>

（１０１）
化合物（１０１）の製造方法について説明する。

(101)
A method for producing compound (101) will be described.

Under an argon atmosphere, 10 g (64 mmol) of bromobenzene, 5.1 g (38 mmol) of anhydrous aluminum chloride, and 4.4 mL (32 mmol) of hexanoyl chloride were mixed and stirred at 50 ° C. for 2 hours. After adding water to the reaction solution, the precipitated solid was filtered. The obtained solid was washed with water and ethanol to obtain 5.7 g (yield 47%) of a white solid of 1- (4-bromophenyl) -1-hexanone.

Under an argon atmosphere, 1.0 g (3.9 mmol) of 1- (4-bromophenyl) -1-hexanone and 2.9 mL (16 mmol) of bis (2-methoxyethyl) aminosulfatrifluoride were mixed and 17 at 80 ° C. Stir for hours. After adding water and chloroform to the reaction solution 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 0.66 g (yield 61%) of 1-bromo-4- (1,1-difluorohexyl) benzene.

Dichloromethane addition of 1-bromo-4- (1,1-difluorohexyl) benzene 0.60 g (2.2 mmol), [1,1'-bis (diphenylphosphine) ferrocene] palladium (II) dichloride under an argon atmosphere. (Pd (dppf) Cl ₂ · CH ₂ Cl ₂ ) 0.029 g (0.036 mmol), copper (I) iodide 0.021 g (0.11 mmol), triphenylphosphine 0.0095 g (0.036 mmol), 4.4 mL of diisopropylamine was added to 0.50 mL (3.6 mmol) of trimethylsilylacetylene, and the mixture was stirred at 80 ° C. for 10 hours. The reaction mixture was concentrated, hexane was added, the mixture was washed with water, the organic phase was dried over magnesium sulfate, and the solvent was distilled off to obtain a brown solid. Under an argon atmosphere, the obtained brown solid, 0.75 g (5.4 mmol) of potassium carbonate and 2.7 mL of methanol were mixed and stirred at room temperature for 2 hours. Hexane 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 separated and purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 0.43 g (yield 89%) of 1- (1,1-difluorohexyl) -4-ethynylbenzene.

Under an argon atmosphere, 3.8 mL of dry tetrahydrofuran was added to 0.43 g (1.9 mmol) of 1- (1,1-difluorohexyl) -4-ethynylbenzene, and the mixture was cooled to −78 ° C. 1.2 mL of a 1.6 mol / L hexane solution of n-butyllithium (1.9 mmol for n-butyllithium) was slowly added dropwise to the reaction solution. The reaction solution was heated to room temperature and stirred for another 1 hour. The reaction mixture was cooled to −78 ° C., 0.38 g (1.9 mmol) of trimethyltin (IV) chloride was slowly added, the temperature was raised to room temperature, and the mixture was stirred for 6 hours. Water was added to the reaction solution to stop the reaction, and then the solvent was distilled off. Hexane was added to the concentrate, washed with water, the organic phase was dried over magnesium sulfate, and the solvent was distilled off. The obtained crude product of trimethyl {[4- (1,1-difluorohexyl) phenyl] ethynyl} tin (IV) was used in the next reaction without further purification.

Advanced Materials Research, 2012, 482-484, p. 1221. 4,8-Dibromo B2T 0.10 g (0.28 mmol) obtained according to the synthetic method, trimethyl {[4- (1) obtained as described above. , 1-difluorohexyl) phenyl] ethynyl} tin (IV) crude product 0.33 g, and tetrakis (triphenylphosphine) palladium (0) 0.040 g (0.034 mmol) with 20 mL of toluene added at 100 ° C. for 5 hours. Stirred. The reaction solution was concentrated and the obtained crude product was separated and purified by silica gel column chromatography (hexane / chloroform) to obtain 0.032 g (yield 18%) of compound (101).
^{1 1} H NMR (400 MHz, CDCl ₃ ): δ7.87 (d, J = 8.2 Hz, 4H), δ7.55 (d, J = 8.2 Hz, 4H), δ2.25-2.03 (m, 4H), δ1.47-1.22 (m, 12H), δ0.88 (t, J = 6.8Hz, 6H).

<Method for evaluating solubility of compound (101)>
The solubility evaluation was carried out in two stages as follows.

The first step was carried out to roughly grasp the solubility, p-xylene was added to the compound (101) so as to be 0.1% by mass at room temperature (25 ° C.), and the undissolved residue was visually observed. Confirmed the presence or absence. Regarding the judgment, no undissolved residue: 0.1% by mass dissolved "possible"; with undissolved residue: 0.1% by mass dissolved "no".

In the second stage, it was confirmed whether or not 0.4% by mass of p-xylene could be dissolved at room temperature (25 ° C.) (as described later, a 0.4% by mass solution of p-xylene was used for forming the semiconductor layer. For.). Since the compound of the present invention has a large molar extinction coefficient and the solution is strongly colored when the concentration is high, it is difficult to visually judge the solubility. Therefore, the evaluation was carried out as follows. At room temperature (25 ° C.), p-xylene was added to the compound (101) so as to be 0.4% by mass, and the mixture was filtered using a hydrophobic PTFE type syringe filter (pore size: 0.10 um) manufactured by Whatman (insoluble). Filtration is carried out for the purpose of removing the insoluble matter when there is a minute.) The filtrate was accurately diluted with p-xylene, and the absorbance at the maximum absorption wavelength was measured using an ultraviolet-visible near-infrared spectrophotometer (UV-3600 (trade name)) manufactured by Shimadzu Corporation. From the absorbance of the diluted filtrate measured in this way and the calibration curve prepared in advance, the concentration of the diluted filtrate was obtained using Lambert-Beer's law, and the concentration of the filtrate was calculated from the diluted amount. did. Regarding the judgment, the calculated value was 0.4% by mass: 0.4% by mass dissolved “possible”; the calculated value was less than 0.4% by mass: 0.4% by mass dissolved “no”.

The results of the first stage are shown in the "0.1% by mass dissolution possibility (visual)" column of Table 1, and the results of the second stage are shown in the "0.4% by mass dissolution possibility" column of Table 1.

<Method for manufacturing a transistor using compound (101)>
A parylene (registered trademark) vapor deposition device (registered trademark) was deposited on a glass substrate (FIG. 1, reference numeral 1) that was ultrasonically washed (30 minutes x 3 times each) in this order using a water-diluted neutral detergent, distilled water, acetone, and ethanol. Using Labcoater PDS2010 (trade name, manufactured by Japan Parylene GK), using dichlorodi-p-xylylene (DPX-C (trade name, manufactured by Japan Parylene GK)) as a raw material, polyparachloroxylylene (parylene C) ) (Fig. 1, reference numeral 2) was formed to a thickness of 100 nm. Next, a source / drain electrode (reference numeral 3 in FIG. 1) is formed by pattern-depositing gold on the insulating film by a vacuum vapor deposition method (2 × ^10-6 Torr) via a metal mask. (Thickness: 20 nm, channel length: channel width = 100 μm: 500 μm), this was immersed in an ethanol solution of 4-methylbenzenethiol (concentration: 0.08% by mass) for 1 hour, and then rinsed with ethanol. Then, 0.05 μL of a p-xylene solution (0.4 mass%) of the compound (101) was drop-cast so as to cover the source / drain electrode, and dried at room temperature to obtain a semiconductor layer (FIG. 1, reference numeral 4). ) Is formed, and a gate insulating layer (FIG. 1, reference numeral 5) made of an amorphous fluororesin (Cytop®) is provided so as to cover the source / drain electrode and the semiconductor layer. Spin coating method (coating conditions: 1000 rpm, 30) from a resin solution in which (trade name, manufactured by AGC Asahi Glass Co., Ltd.) and Cytop CT-SOLV180 (trade name, manufactured by AGC Asahi Glass Co., Ltd.) are mixed at a mass ratio of 5: 2. Seconds, firing conditions after spin coating: Pre-dried at 80 ° C. for 30 minutes, and then formed at 100 ° C. for 30 minutes). Finally, a gate electrode (reference numeral 6 in FIG. 1) is formed by pattern-depositing gold on the gate insulating layer made of the amorphous fluororesin by a vacuum vapor deposition method (2 × ^10-6 Torr) via a metal mask. ) (Thickness: 20 nm) to manufacture a TGBC type transistor.

<Method of evaluating the mobility of a transistor using compound (101)>
The mobility of the transistor manufactured as described above is such that the source electrode is grounded, 100 V is applied to the drain electrode, and a voltage (V _g ) is sweeped to the gate electrode (20 V to 60 V) while the drain electrode is applied. The current (Id ₎ flowing through the wire was measured in a light-shielded atmosphere, and was calculated from the gradient of _√Id −V _g using the following formula. The unit is cm ² / Vs.

I _d = (W / 2L) · _C · μ · (V _g −VT) ²
(In the equation, W is the channel width, L is the channel length, μ is the mobility, _C is the electric capacity per unit area of the gate insulating layer, and VT is the threshold voltage.)
The results are shown in Table 2 and FIG.

(Example 2)
<Method for producing compound (102)>

（１０２）
化合物（１０２）の製造方法について説明する。

(102)
A method for producing the compound (102) will be described.

The same operation as in Example 1 was carried out except that octanoyl chloride was used instead of hexanoyl chloride in Example 1 to obtain compound (102).
^{1 1} H NMR (400 MHz, CDCl ₃ ): δ7.87 (d, J = 8.2 Hz, 4H), δ7.55 (d, J = 8.2 Hz, 4H), δ2.25-2.03 (m, 4H), δ1.51-1.17 (m, 20H), δ0.88 (t, J = 6.8Hz, 6H).
<Evaluation method of compound (102)>
The solubility and mobility were evaluated in the same manner as in Example 1 except that compound (102) was used instead of compound (101) in Example 1. The results are shown in Tables 1 and 2 and FIG.
(Example 3)
<Manufacturing method of compound (103)>

（１０３）

化合物（１０３）の製造方法について説明する。

(103)

A method for producing the compound (103) will be described.

The same operation as in Example 1 was carried out except that undecanoyl chloride was used instead of hexanoyl chloride in Example 1 to obtain compound (103).
^{1 1} H NMR (400 MHz, CDCl ₃ ): δ7.87 (d, J = 8.2 Hz, 4H), δ7.55 (d, J = 8.2 Hz, 4H), δ2.25-2.03 (m, 4H), δ1.52-1.15 (m, 32H), δ0.88 (t, J = 6.8Hz, 6H).
<Evaluation method of compound (103)>
The solubility and mobility were evaluated in the same manner as in Example 1 except that compound (103) was used instead of compound (101) in Example 1. The results are shown in Tables 1 and 2 and FIG.

(Comparative Example 1)
<Manufacturing method of compound (C101)>

（Ｃ１０１）

(C101)

Compound (C101) was produced according to the synthesis method described in Example 1-4 (stage 0168) of Patent Document 4.
<Evaluation method of compound (C101)>
The solubility and mobility were evaluated in the same manner as in Example 1 except that compound (C101) was used instead of compound (101) in Example 1. The results are shown in Tables 1 and 2.

(Comparative Example 2)
<Method for producing compound (C102)>

（Ｃ１０２）

(C102)

Compound (C102) was produced according to the synthesis method described in Example S-1 (0300 steps) of Patent Document 3.

<Evaluation method of compound (C102)>
The solubility and mobility were evaluated in the same manner as in Example 1 except that compound (C102) was used instead of compound (101) in Example 1. The results are shown in Tables 1 and 2.

(Comparative Example 3)
<Manufacturing method of compound (C103)>

（Ｃ１０３）

(C103)

Compound (C103) was produced according to the synthetic method described in Non-Patent Document 1.

<Evaluation method of compound (C103)>
The solubility and mobility were evaluated in the same manner as in Example 1 except that compound (C103) was used instead of compound (101) in Example 1. The results are shown in Tables 1 and 2.

(Comparative Example 4)
<Method for producing compound (C104)>

（Ｃ１０４）

(C104)

A method for producing the compound (C104) will be described.

Under an argon atmosphere, 12 mL of dry tetrahydrofuran was added to 1.0 g (5.9 mmol) of 1-ethynyl-4- (trifluoromethyl) benzene, and the mixture was cooled to −78 ° C. 3.7 mL (5.9 mmol) of a 1.6 mol / L hexane solution of n-butyllithium was slowly added dropwise to the reaction solution. The reaction solution was heated to room temperature and stirred for another 1 hour. The reaction mixture was cooled to −78 ° C., 1.2 g (5.9 mmol) of trimethyltin (IV) chloride was slowly added, the temperature was raised to room temperature, and the mixture was stirred for 6 hours. Water was added to the reaction solution to stop the reaction, and then the solvent was distilled off. Hexane was added to the concentrate, washed with water, the organic phase was dried over magnesium sulfate, and the solvent was distilled off. 1.7 g of the obtained crude product of trimethyl {[4- (trifluoromethyl) phenyl] ethynyl} tin (IV) was used for the next reaction without further purification.

Under an argon atmosphere, 0.25 g (0.71 mmol) of 4,8-dibromoB2T, 0.95 g of crude trimethyl {[4- (trifluoromethyl) phenyl] ethynyl} tin (IV), tetrakis (triphenylphosphine) palladium. (0) 50 mL of toluene was added to 0.099 g (0.086 mmol), and the mixture was stirred at 100 ° C. for 3 hours. The reaction solution was concentrated and the obtained crude product was separated and purified by silica gel column chromatography (hexane / chloroform) to obtain 0.024 g (yield 6.4%) of the compound (C104).
^{1 1} H NMR (400 MHz, CDCl ₃ ): δ7.93 (d, J = 8.0 Hz, 4H), δ7.72 (d, J = 8.0 Hz, 4H).
<Evaluation method of compound (C104)>
The solubility and mobility were evaluated in the same manner as in Example 1 except that compound (C104) was used instead of compound (101) in Example 1. The results are shown in Tables 1 and 2.

(Comparative Example 5)
<Method for producing compound (C105)>

（Ｃ１０５）

(C105)

Compound (C105) was produced according to the method described in Example 1-5 of Patent Document 4.
<Evaluation method of compound (C105)>
The solubility and mobility were evaluated in the same manner as in Example 1 except that compound (C105) was used instead of compound (101) in Example 1. The results are shown in Tables 1 and 2.

As is clear from Table 1, the compound of the present invention does not use the method of "introducing two substituents into one aryl group" found in the compound (R1) and the like described in Patent Document 5, 0. It has a high solubility of 4% by mass. The maximum solubility of the compound disclosed in Patent Document 5 is 0.3% by mass, which is lower than the solubility of the compound of the present invention, and the B2T derivative having an aryl group at the 4- and 8-positions of Comparative Example ( (C101), (C102), (C103), (C105)) ”has a solubility of less than 0.1% by mass.

Comparing the compound of the present invention with the compound (C104), it is common that the B2T ring and the phenyl group are connected by -C≡C-, but the compound of the present invention exhibits high solubility, whereas the compound of the present invention exhibits high solubility. The solubility of compound (C104) is low. Further, comparing the compound of the present invention with the compounds (C101) and (C105), it is common that the R ³ -CF ₂ -group is present in the side chain of the phenyl group, but the compound of the present invention is highly soluble. While exhibiting sex, the solubility of the compounds (C101) and (C105) is low. These facts indicate that the high solubility of the compound of the present invention is not a combination of the prior art.

As mentioned above, the compound of the present invention exhibits high solubility. Due to this effect, the compound of the present invention imparts a semiconductor layer and a transistor by a wet film forming method at room temperature, and thus exhibits semiconductor characteristics (mobility is as shown in Table 2. n-type characteristics are shown in FIG. 2 to 4). On the other hand, the semiconductor layer could not be formed from the compound of the comparative example at room temperature, and therefore the transistor could not be manufactured.

If the solubility is high, a known and commonly used purification method such as a solvent extraction method or a column chromatography method can be applied in the process of producing the compound, which is suitable for industrial production. This is extremely important for achieving high purity, which is essential for organic semiconductors.

As is clear from Table 2 and FIGS. 2, 3 and 4, the transistor using the compound of the present invention exhibited n-type semiconductor characteristics in the atmosphere. Therefore, the present invention introduces the above-mentioned problematic material "combining solvent solubility, air stability and n-type semiconductor properties" into one aryl substituent described in Patent Document 5. It can be provided without using the method.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an organic semiconductor material having solvent solubility, atmospheric stability and n-type semiconductor characteristics. This makes it possible to more easily provide an analog circuit or a digital circuit by combining with a known and commonly used p-type semiconductor.

1. 1. Substrate 2. Base (primary) layer (may not be present)
3. 3. Source / drain electrodes 4. Semiconductor layer 5. Gate insulating layer 6. Gate electrode

Claims (6)

A compound represented by the general formula (1).

(1)

(In the general formula (1), R ¹ and R ² represent monovalent substituents represented by the general formula (2), n is the number of substituents of R ¹ , and an integer of 1 to 5 is used. Represented, m is the number of substituents of ^R2 and represents an integer from 1 to 5).

(2)
(In the general formula (2), * represents a binding site as a monovalent substituent, R ³ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and X represents a halogen atom. .) 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 device having a semiconductor layer containing the compound according to claim 1. A transistor having a semiconductor layer containing the compound according to claim 1.

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