JP6656508B2 - Benzothienobenzothiophene derivative, organic semiconductor material, and organic transistor - Google Patents

Description

The present invention relates to a benzothienobenzothiophene derivative, an organic semiconductor material using the same, an organic semiconductor ink containing the same, and an organic transistor using the same.

Conventionally, thin film transistors (TFTs) using amorphous silicon or polycrystalline silicon have been widely used as switching elements in liquid crystal display devices, organic EL display devices, and the like. However, since a CVD apparatus used for manufacturing a TFT using silicon is expensive, manufacturing a large-sized TFT element causes an increase in manufacturing cost. Further, since a silicon material is formed at a high temperature, it cannot be applied to a plastic substrate which is a substrate candidate of a flexible display in the future due to a problem of heat resistance. To solve this, an organic TFT using an organic semiconductor for the channel semiconductor layer instead of the silicon semiconductor has been proposed.

  Since organic semiconductors can be formed into a solution by printing at a low temperature, they do not require large-scale manufacturing equipment, and can be applied to plastics having poor heat resistance, and are expected to lead flexible displays. On the other hand, organic semiconductors have a lower carrier mobility than silicon semiconductors, and as a result, the response speed of TFTs has been a problem for practical use. However, in recent years, organic semiconductors having mobility equivalent to amorphous silicon have been developed. It has been.

For example, Patent Document 1 discloses a 2,7-substituted [1] benzothieno [3,2-b] [1] benzothiophene skeleton (hereinafter referred to as [1] benzothieno [3,2-b] [1] benzothiophene. (Abbreviated as BTBT) are described, as the substituents of which are halogen, C ₁ -C ₁₈ alkyl, halogen-containing C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkyloxy, C ₁ -C _{18 18} alkylthio or aryl, or aryl having at least one of halogen, C ₁ -C ₁₈ alkyl, halogen-containing C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkyloxy, and C ₁ -C ₁₈ alkylthio. Things are listed. That the mobility of these compounds ^(cm 2 / Vs) is 0.17~0.31cm ² / Vs.

Patent Document 2 describes a compound having a 2,7-substituted BTBT skeleton, and describes, as a substituent thereof, a hydrogen atom or a halogeno-substituted C ₁ -C ₃₆ fatty fast hydrocarbon group. ing. The mobility of these compounds ^(cm 2 / Vs) has been described to be 0.12~4.5cm ² / Vs.

On the other hand, Patent Literature 3 discloses a 2-alkyl-7-aryl BTBT. This compound can be easily formed into a film having high molecular order by crystallizing through a higher-order liquid crystal phase, and a film having a high mobility of 5 cm ² / Vs can be obtained. It can be given easily. However, this compound has a problem that the aryl group is directly bonded to BTBT and the solubility in an organic solvent is low.

WO2006-077888 WO2008-47896 WO2012-121393

However, many of the conventional materials still have a mobility of less than 1 cm ² / Vs, which is insufficient for driving a liquid crystal display device or an organic EL. In addition, although the compound of Patent Document 2 reported to have high mobility can be formed by spin coating, heat treatment must be performed in order to exhibit high mobility, and the treatment temperature and the treatment time may vary. In addition, even in a TFT manufactured under the same conditions, there is a large variation in mobility.

  Accordingly, there is a demand for an organic semiconductor material to easily form a high-mobility film without deteriorating its performance even when printing and forming a film, in addition to improving the carrier mobility of the molecule itself.

  Therefore, an object of the present invention is to provide a compound having high solvent solubility and capable of obtaining a film having high carrier mobility without obtaining a complicated process.

  In the present invention, after intensive studies, the introduction of a soluble functional group having a specific structure into the alkyl substituent of the BTBT derivative shows high solubility in an organic solvent and facilitates formation of a high mobility film. This led to the completion of the present invention.

  According to the present invention, an organic semiconductor having both high solubility and high mobility can be provided.

FIG. 3 is a schematic cross-sectional view of a bottom-gate bottom-contact transistor.

That is, the present invention includes the following items.
1. General formula (1)

(In the formula, Ar represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, and R ₁ and R ₂ are each independently an alkylene group having 1 to 20 carbon atoms, or -valent alicyclic _group, X 1, _{X 2} are each independently in Table O, S, and NH, n is 0 or 1, _{R 3} in the case of n = 0, as a substituent An alkyl group having 1 to 20 carbon atoms having an aromatic hydrocarbon group, a heteroaromatic group or an alicyclic hydrocarbon group, or a general formula (A) to (C)

(Ar ′ represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, and m represents an integer of 1 to 20.)
Represents a group selected from
In the case of n = 1, an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, a carbon number of 1 to 20 which may have an aromatic hydrocarbon group or a heteroaromatic group as a substituent. Alkyl group, or general formulas (A) to (C)

(Ar ′ represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, and m represents an integer of 1 to ○.)
Represents a group selected from )
A compound represented by
2.1. Organic semiconductor material containing the compound described in 3.2. Organic semiconductor ink containing the organic semiconductor material according to,
4.2. Organic semiconductor film containing the organic semiconductor material according to,
5.2. An organic semiconductor device using the organic semiconductor material according to the above,
6.2. An organic transistor using the organic semiconductor material described in 1 above as an organic semiconductor layer.

(Compound represented by the general formula (1))
Ar of the substituent represented by the general formula (1) of the present invention is particularly limited as long as it is an aromatic hydrocarbon group which may have a substituent or a heteroaromatic group which may have a substituent. However, for example, the following can be mentioned.
Examples of the aromatic hydrocarbon group which may have a substituent include phenyl, naphthyl, azulenyl, acenaphthenyl, anthranyl, phenanthryl, naphthacenyl, fluorenyl, pyrenyl, chrysenyl, perylenyl, biphenyl An unsubstituted monocyclic or polycyclic aromatic hydrocarbon group having 6 to 24 carbon atoms, such as a group, a p-terphenyl group, or a quarterphenyl group;
o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, 2,6-xylyl group, mesityl group, juryl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4 -Isopropylphenyl group, 4-n-butylphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4-n-decaphenyl group, 4-stearylphenyl group, 9,9'-dihexylfur An alkyl-substituted aromatic hydrocarbon group in which the aromatic hydrocarbon group is substituted with an alkyl group having 1 to 18 carbon atoms, such as an olenyl group;
An alkenyl-substituted aromatic hydrocarbon group in which the aromatic hydrocarbon group is substituted with an alkenyl group having 2 to 20 carbon atoms, such as a styryl group, a 4-butenylphenyl group, and a 4-octadecenylphenyl group;

When the aromatic hydrocarbon group such as a 4-fluorophenyl group, a 2,6-fluorophenyl group, a 4-chlorophenyl group, a 2,3,4,5,6-perfluorophenyl group is a fluorine atom, a chlorine atom, or a bromine A halogenated aromatic hydrocarbon group substituted with a halogen such as an atom,
4- (2-ethoxyethyl) phenyl group, 4- (2-n-hexyloxyethyl) phenyl group, 4- (2-n-heptyloxyethyl) phenyl group, 4- (2-n-tetradecyloxyethyl) ) Phenyl group, 4- (2-cyclohexyloxyethyl) phenyl group, 4- (12-ethoxydodecyl) phenyl group, 4- (cyclohexyloxyethyl) phenyl group and the like, the aromatic hydrocarbon group has 3 to 20 carbon atoms. An alkoxyalkyl-substituted aromatic hydrocarbon group substituted with an alkoxyalkyl group of
A 4- (methylsulfanylpropyl) phenyl group, a 4- (2-n-hexylsulfanylethyl) phenyl group, a 4- (3-n-decylsulfanylpropyl) phenyl group, a 4- (cyclohexylsulfanylpropyl) phenyl group, etc. An alkylsulfanylalkyl-substituted aromatic hydrocarbon group in which the aromatic hydrocarbon group is substituted with an alkylsulfanylalkyl group having 3 to 20 carbon atoms,
When the aromatic hydrocarbon group is an alkylamino having 3 to 20 carbon atoms, such as a 4- (3-octylaminopropyl) phenyl group, a 4- (3-dodecylaminopropyl) phenyl group, and a 4- (diethylaminoethyl) phenyl group. And an alkylaminoalkyl-substituted aromatic hydrocarbon group substituted with an alkyl group.

Examples of the heteroaromatic group which may have a substituent include a pyrrolyl group, an indolyl group, a furyl group, a thienyl group, an imidazolyl group, a benzofuryl group, a triazolyl group, a benzotriazolyl group, a benzothienyl group, and a pyrazolyl group. , Indolizinyl group, quinolinyl group, isoquinolinyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, indolinyl group, thiazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, thiadiazinyl group, oxadiazolyl group, benzoquinolinyl group, 5- or 6-membered heteroaromatic groups such as thiadiazolyl, pyrrolothiazolyl, pyrrolopyridazinyl, tetrazolyl, and oxazolyl groups, and polycyclic heteroaromatics in which benzene is fused to the heteroaromatic group Group,
An alkyl-substituted heteroaromatic group in which the heteroaromatic group such as a 5-methylthienyl group, a 5-hexylthienyl group, a 5-decathienyl group, or a 5-stearylthienyl group is substituted with an alkyl group having 1 to 20 carbon atoms;

Such as a fluoropyridinyl group and a fluoroindolyl group, a halogenated heteroaromatic group in which the heteroaromatic group is substituted with a halogen such as a fluorine atom, a chlorine atom, and a bromine atom;
5- (2-ethoxyethyl) thienyl group, 5- (2-n-tetradecyloxyethyl) thienyl group, 5- (2-cyclohexyloxyethyl) thienyl group, 5- (12-ethoxydodecyl) thienyl group, etc. An alkoxyalkyl-substituted heteroaromatic group in which the aromatic hydrocarbon group is substituted with an alkoxyalkyl group having 3 to 20 carbon atoms,

A 5- (methylsulfanylpropyl) thienyl group, a 5- (2-n-hexylsulfanylethyl) thienyl group, a 5- (3-n-decylsulfanylpropyl) thienyl group, a 5- (cyclohexylsulfanylpropyl) thienyl group, etc. An alkylsulfanylalkyl-substituted heteroaromatic group in which an aromatic hydrocarbon group is substituted with an alkylsulfanylalkyl group having 3 to 20 carbon atoms,
The heteroaromatic group is an alkylaminoalkyl having 3 to 20 carbon atoms, such as a 5- (3-octylaminopropyl) thienyl group, a 5- (3-dodecylaminopropyl) thienyl group, or a 5- (diethylaminoethyl) thienyl group; And an alkylaminoalkyl-substituted heteroaromatic group substituted with a group.

  Among them, Ar is preferably a monocyclic aromatic hydrocarbon group or a monocyclic heteroaromatic group in order to maintain high solubility and mobility. When the compound has a substituent, an aromatic hydrocarbon group or a heteroaromatic group having a substituent having 1 to 12 carbon atoms is particularly preferable.

In the general formula (1), R ₁ and R ₂ of the substituent represented by —R ₁ —X ₁ — (R ₂ —X ₂ ) n—R ₃ are each independently an alkylene having 1 to 20 carbon atoms. There is no particular limitation as long as it is a group or an alicyclic group, but R ₁ preferably has 8 to 15 carbon atoms from the viewpoint of solubility and mobility. R ₂ preferably has 5 or less carbon atoms, particularly preferably 3 or less carbon atoms, from the viewpoint of solubility.

X _{1 and} X ₂ represented by the general formula (1) are not particularly limited as long as they are independently O, S, and NH, but O is preferable from the viewpoint of solubility and mobility.

When n = 0, R ₃ represented by the general formula (1) is an alkyl group having 1 to 20 carbon atoms having an aromatic hydrocarbon group, a heteroaromatic group, or an alicyclic hydrocarbon group as a substituent; Or the general formulas (A) to (C)

(Ar ′ represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, and m represents an integer of 1 to 20.)
There is no problem as long as it is a group selected from the group consisting of, but R ₃ is preferably an alkyl group having 5 or less, particularly preferably an alkyl group having 3 or less carbon atoms, from the viewpoint of solubility and mobility.

  Further, an aromatic hydrocarbon group as a substituent includes a phenyl group, a naphthyl group, an azulenyl group, an acenaphthenyl group, an anthranyl group, a phenanthryl group, a naphthacenyl group, a fluorenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a biphenyl group, a p-phenyl group. An unsubstituted monocyclic or polycyclic aromatic hydrocarbon group having 6 to 24 carbon atoms, such as a terphenyl group or a quarterphenyl group;

o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, 2,6-xylyl group, mesityl group, juryl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4 -Isopropylphenyl group, 4-n-butylphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4-n-decaphenyl group, 4-stearylphenyl group, 9,9'-dihexylfur An alkyl-substituted aromatic hydrocarbon group in which the aromatic hydrocarbon group is substituted with an alkyl group having 1 to 18 carbon atoms, such as an olenyl group;
An alkenyl-substituted aromatic hydrocarbon group in which the aromatic hydrocarbon group is substituted with an alkenyl group having 2 to 20 carbon atoms, such as a styryl group, a 4-butenylphenyl group, and a 4-octadecenylphenyl group;

When the aromatic hydrocarbon group such as a 4-fluorophenyl group, a 2,6-fluorophenyl group, a 4-chlorophenyl group, a 2,3,4,5,6-perfluorophenyl group is a fluorine atom, a chlorine atom, or a bromine A halogenated aromatic hydrocarbon group substituted with a halogen such as an atom,
4- (2-ethoxyethyl) phenyl group, 4- (2-n-hexyloxyethyl) phenyl group, 4- (2-n-heptyloxyethyl) phenyl group, 4- (2-n-tetradecyloxyethyl) ) Phenyl group, 4- (2-cyclohexyloxyethyl) phenyl group, 4- (12-ethoxydodecyl) phenyl group, 4- (cyclohexyloxyethyl) phenyl group and the like, the aromatic hydrocarbon group has 3 to 20 carbon atoms. An alkoxyalkyl-substituted aromatic hydrocarbon group substituted with an alkoxyalkyl group of

A 4- (methylsulfanylpropyl) phenyl group, a 4- (2-n-hexylsulfanylethyl) phenyl group, a 4- (3-n-decylsulfanylpropyl) phenyl group, a 4- (cyclohexylsulfanylpropyl) phenyl group, etc. An alkylsulfanylalkyl-substituted aromatic hydrocarbon group in which the aromatic hydrocarbon group is substituted with an alkylsulfanylalkyl group having 3 to 20 carbon atoms,
When the aromatic hydrocarbon group is an alkylamino having 3 to 20 carbon atoms, such as a 4- (3-octylaminopropyl) phenyl group, a 4- (3-dodecylaminopropyl) phenyl group, and a 4- (diethylaminoethyl) phenyl group. And an alkylaminoalkyl-substituted aromatic hydrocarbon group substituted with an alkyl group.

Further, a heteroaromatic group as a substituent includes a pyrrolyl group, an indolyl group, a furyl group, a thienyl group, an imidazolyl group, a benzofuryl group, a triazolyl group, a benzotriazolyl group, a benzothienyl group, a pyrazolyl group, an indolizinyl group, and a quinolinyl group. , Isoquinolinyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, indolinyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, thiadiazinyl, oxadiazolyl, benzoquinolinyl, thiadiazolyl, pyrrolothiazolyl, A 5- or 6-membered heteroaromatic group such as a pyrrolopyridazinyl group, a tetrazolyl group or an oxazolyl group, or a polycyclic heteroaromatic group in which benzene is fused to the heteroaromatic group;
An alkyl-substituted heteroaromatic group in which the heteroaromatic group such as a 5-methylthienyl group, a 5-hexylthienyl group, a 5-decathienyl group, or a 5-stearylthienyl group is substituted with an alkyl group having 1 to 20 carbon atoms;

  5- (2-ethoxyethyl) thienyl, a halogenated heteroaromatic group in which the aforementioned heteroaromatic group such as a fluoropyridinyl group and a fluoroindolyl group is substituted with a halogen such as a fluorine atom, a chlorine atom, and a bromine atom Group, 5- (2-n-tetradecyloxyethyl) thienyl group, 5- (2-cyclohexyloxyethyl) thienyl group, 5- (12-ethoxydodecyl) thienyl group, and the like, the aromatic hydrocarbon group has carbon atoms. An alkoxyalkyl-substituted heteroaromatic group substituted with 3 to 20 alkoxyalkyl groups,

A 5- (methylsulfanylpropyl) thienyl group, a 5- (2-n-hexylsulfanylethyl) thienyl group, a 5- (3-n-decylsulfanylpropyl) thienyl group, a 5- (cyclohexylsulfanylpropyl) thienyl group, etc. An alkylsulfanylalkyl-substituted heteroaromatic group in which an aromatic hydrocarbon group is substituted with an alkylsulfanylalkyl group having 3 to 20 carbon atoms,
The heteroaromatic group is an alkylaminoalkyl having 3 to 20 carbon atoms, such as a 5- (3-octylaminopropyl) thienyl group, a 5- (3-dodecylaminopropyl) thienyl group, or a 5- (diethylaminoethyl) thienyl group; And an alkylaminoalkyl-substituted heteroaromatic group substituted with a group.

  Further, as the alicyclic hydrocarbon group as a substituent, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclopropene group, cyclobutene group, cyclopentene group, cyclohexene Group, cycloheptene group, cyclooctene group and the like.

  Among these, a monocyclic aromatic hydrocarbon group and a monocyclic heteroaromatic group are preferable as the substituent in order to maintain high solubility.

When n = 1, R ₃ represented by the general formula (1) represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, and an aromatic hydrocarbon group or a heteroaromatic group as a substituent. An alkyl group having 1 to 20 carbon atoms which may have a group, or a general formula (A) to (C)

(Ar ′ represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, and m represents an integer of 1 to ○.)
The group is not particularly limited as long as it is selected from the group consisting of, but from the viewpoint of solubility, an alkyl group having 5 or less carbon atoms is preferable, and an alkyl group having 3 or less carbon atoms is particularly preferable.

  Ar ′ is an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, and the Ar ′ is an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent. The same groups as the group groups can be mentioned.

Further, specifically, when n = 0, the substitution represented by -R ₁ -X _1- (R ₂ -X ₂ ) n-R ₃ in the general formula (1) is (I) an aralkoxyalkyl When n = 1, the group is (II) an alkoxyalkoxyalkyl group and (III) an aryloxyalkoxyalkyl group, each of which can be exemplified as follows.

(I) Examples of the aralkoxyalkyl group include benzyloxymethyl, 2- (benzyloxy) ethyl, 3- (benzyloxy) propyl, 4- (benzyloxy) butyl, and 5- (benzyloxy) ) Pentyl, 6- (benzyloxy) hexyl, 7- (benzyloxy) heptyl, 8- (benzyloxy) octyl, 9- (benzyloxy) nonyl, 10- (benzyloxy) decyl, 11 -(Benzyloxy) undecyl group, 12- (benzyloxy) dodecyl group, 13- (benzyloxy) tridecyl group, 14- (benzyloxy) tetradecyl group, 15- (benzyloxy) pentadecyl group, 16- (benzyloxy) Hexadecyl group, 17- (benzyloxy) heptadecyl group, 18- (benzyloxy) Octadecyl group, 19- (benzyloxy) nonadecyl, 20- (benzyloxy) icosyl group,

Phenethoxymethyl group, 2-phenethoxyethyl group, 3-phenethoxypropyl group, 4-phenethoxybutyl group, 5-phenethoxypentyl group, 6-phenethoxyhexyl group, 7-phenethoxyheptyl group, 8-phenene Toxioctyl, 9-phenethoxynonyl, 10-phenethoxydecyl, 11-phenethoxyundecyl, 12-phenethoxydodecyl, 13-phenethoxytridecyl, 14-phenethoxytetradecyl, 15 -Phenethoxypentadecyl group, 16-phenethoxyhexadecyl group, 17-phenethoxyheptadecyl group, 18-phenethoxyoctadecyl group, 19-phenethoxynononadecyl group, 20-phenethoxyicosyl group,
And the like.

(II) Examples of the alkoxyalkoxyalkyl group include a (methoxymethoxy) methyl group, a 2- (methoxymethoxy) ethyl group, a 3- (methoxymethoxy) propyl group, a 4- (methoxymethoxy) butyl group, and a 5- (methoxymethoxy) group. ) Pentyl, 6- (methoxymethoxy) hexyl, 7- (methoxymethoxy) heptyl, 8- (methoxymethoxy) octyl, 9- (methoxymethoxy) nonyl, 10- (methoxymethoxy) decyl, 11 -(Methoxymethoxy) undecyl group, 12- (methoxymethoxy) dodecyl group, 13- (methoxymethoxy) tridecyl group, 14- (methoxymethoxy) tetradecyl group, 15- (methoxymethoxy) pentadecyl group, 16- (methoxymethoxy) Hexadecyl group, 17- (methoxymeth Shi) heptadecyl, 18- (methoxymethoxy) octadecyl, 19- (methoxymethoxy) nonadecyl, 20- (methoxymethoxy) icosyl group,

(Methoxyethoxy) methyl group, 2- (methoxyethoxy) ethyl group, 3- (methoxyethoxy) propyl group, 4- (methoxyethoxy) butyl group, 5- (methoxyethoxy) pentyl group, 6- (methoxyethoxy) hexyl Group, 7- (methoxyethoxy) heptyl group, 8- (methoxyethoxy) octyl group, 9- (methoxyethoxy) nonyl group, 10- (methoxyethoxy) decyl group, 11- (methoxyethoxy) undecyl group, 12- ( Methoxyethoxy) dodecyl group, 13- (methoxyethoxy) tridecyl group, 14- (methoxyethoxy) tetradecyl group, 15- (methoxyethoxy) pentadecyl group, 16- (methoxyethoxy) hexadecyl group, 17- (methoxyethoxy) heptadecyl group , 18- (methoxyethoxy) octa Sill group, 19- (methoxyethoxy) nonadecyl, 20- (methoxyethoxy) icosyl group,

(Methoxypropoxy) methyl group, 2- (methoxypropoxy) ethyl group, 3- (methoxypropoxy) propyl group, 4- (methoxypropoxy) butyl group, 5- (methoxypropoxy) pentyl group, 6- (methoxypropoxy) hexyl Group, 7- (methoxypropoxy) heptyl group, 8- (methoxypropoxy) octyl group, 9- (methoxypropoxy) nonyl group, 10- (methoxypropoxy) decyl group, 11- (methoxypropoxy) undecyl group, 12- ( (Methoxypropoxy) dodecyl group, 13- (methoxypropoxy) tridecyl group, 14- (methoxypropoxy) tetradecyl group, 15- (methoxypropoxy) pentadecyl group, 16- (methoxypropoxy) hexadecyl group, 17- (methoxypropoxy) heptadecyl group 18- (methoxypropoxy) octadecyl, 19- (methoxypropoxy) nonadecyl, 20- (methoxypropoxy) icosyl group,

(Benzyloxymethoxy) methyl group, 2-((benzyloxy) methoxy) ethyl group, 3-((benzyloxy) methoxy) propyl group, 4-((benzyloxy) methoxy) butyl group, 5-((benzyloxy )) Methoxy) pentyl group, 6-((benzyloxy) methoxy) hexyl group, 7-((benzyloxy) methoxy) heptyl group, 8-((benzyloxy) methoxy) octyl group, 9-((benzyloxy) methoxy )) Nonyl group, 10-((benzyloxy) methoxy) decyl group, 11-((benzyloxy) methoxy) undecyl group, 12-((benzyloxy) methoxy) dodecyl group, 13-((benzyloxy) methoxy) Tridecyl group, 14-((benzyloxy) methoxy) tetradecyl group, 15-((benzylo C) methoxy) pentadecyl group, 16-((benzyloxy) methoxy) hexadecyl group, 17-((benzyloxy) methoxy) heptadecyl group, 18-((benzyloxy) methoxy) octadecyl group, 19-((benzyloxy) A methoxy) nonadecyl group, a 20-((benzyloxy) methoxy) icosyl group,

(Phenethoxymethoxy) methyl group, 2-((phenethoxy) methoxy) ethyl group, 3-((phenethoxy) methoxy) propyl group, 4-((phenethoxy) methoxy) butyl group, 5-((phenethoxy) methoxy) pentyl Group, 6-((phenethoxy) methoxy) hexyl group, 7-((phenethoxy) methoxy) heptyl group, 8-((phenethoxy) methoxy) octyl group, 9-((phenethoxy) methoxy)) nonyl group, 10- ( (Phenethoxy) methoxy) decyl group, 11-((phenethoxy) methoxy) undecyl group, 12-((phenethoxy) methoxy) dodecyl group, 13-((phenethoxy) methoxy) tridecyl group, 14-((phenethoxy) methoxy) tetradecyl Group, 15-((phenethoxy) methoxy) pentadecyl group 16-((phenethoxy) methoxy) hexadecyl group, 17-((phenethoxy) methoxy) heptadecyl group, 18-((phenethoxy) methoxy) octadecyl group, 19-((phenethoxy) methoxy) nonadecyl group, 20-((phenethoxy) Methoxy) icosyl group,

(Benzyloxyethoxy) methyl group, 2-((benzyloxy) ethoxy) ethyl group, 3-((benzyloxy) ethoxy) propyl group, 4-((benzyloxy) ethoxy) butyl group, 5-((benzyloxy ) Ethoxy) pentyl group, 6-((benzyloxy) ethoxy) hexyl group, 7-((benzyloxy) ethoxy) heptyl group, 8-((benzyloxy) ethoxy) octyl group, 9-((benzyloxy) ethoxy )) Nonyl group, 10-((benzyloxy) ethoxy) decyl group, 11-((benzyloxy) ethoxy) undecyl group, 12-((benzyloxy) ethoxy) dodecyl group, 13-((benzyloxy) ethoxy) Tridecyl group, 14-((benzyloxy) ethoxy) tetradecyl group, 15-((benzylo B) ethoxy) pentadecyl group, 16-((benzyloxy) ethoxy) hexadecyl group, 17-((benzyloxy) ethoxy) heptadecyl group, 18-((benzyloxy) ethoxy) octadecyl group, 19-((benzyloxy) An ethoxy) nonadecyl group, a 20-((benzyloxy) ethoxy) icosyl group,

(Phenethoxyethoxy) methyl group, 2-((phenethoxy) ethoxy) ethyl group, 3-((phenethoxy) ethoxy) propyl group, 4-((phenethoxy) ethoxy) butyl group, 5-((phenethoxy) ethoxy) pentyl Group, 6-((phenethoxy) ethoxy) hexyl group, 7-((phenethoxy) ethoxy) heptyl group, 8-((phenethoxy) ethoxy) octyl group, 9-((phenethoxy) ethoxy)) nonyl group, 10- ( (Phenethoxy) ethoxy) decyl group, 11-((phenethoxy) ethoxy) undecyl group, 12-((phenethoxy) methoxy) dodecyl group, 13-((phenethoxy) ethoxy) tridecyl group, 14-((phenethoxy) ethoxy) tetradecyl Group, 15-((phenethoxy) ethoxy) pentadecyl group 16-((phenethoxy) ethoxy) hexadecyl group, 17-((phenethoxy) ethoxy) heptadecyl group, 18-((phenethoxy) ethoxy) octadecyl group, 19-((phenethoxy) ethoxy) nonadecyl group, 20-((phenethoxy) Ethoxy) icosyl group,

(Benzyloxypropoxy) methyl group, 2-((benzyloxy) propoxy) ethyl group, 3-((benzyloxy) propoxy) propyl group, 4-((benzyloxy) propo) butyl group, 5-((benzyloxy ) Propoxy) pentyl, 6-((benzyloxy) propoxy) hexyl, 7-((benzyloxy) propoxy) heptyl, 8-((benzyloxy) propoxy) octyl, 9-((benzyloxy) propoxy )) Nonyl group, 10-((benzyloxy) propoxy) decyl group, 11-((benzyloxy) propoxy) undecyl group, 12-((benzyloxy) propoxy) dodecyl group, 13-((benzyloxy) propoxy) Tridecyl group, 14-((benzyloxy) propoxy) tetradecyl group, 5-((benzyloxy) propoxy) pentadecyl group, 16-((benzyloxy) propoxy) hexadecyl group, 17-((benzyloxy) propoxy) heptadecyl group, 18-((benzyloxy) propoxy) octadecyl group, 19- ((Benzyloxy) propoxy) nonadecyl group, 20-((benzyloxy) propoxy) icosyl group,

(Phenethoxypropoxy) methyl group, 2-((phenethoxy) propoxy) ethyl group, 3-((phenethoxy) propoxy) propyl group, 4-((phenethoxy) propoxy) butyl group, 5-((phenethoxy) propoxy) pentyl Groups, 6-((phenethoxy) propoxy) hexyl group, 7-((phenethoxy) propoxy) heptyl group, 8-((phenethoxy) propoxy) octyl group, 9-((phenethoxy) propoxy)) nonyl group, 10- ( (Phenethoxy) propoxy) decyl group, 11-((phenethoxy) propoxy) undecyl group, 12-((phenethoxy) propoxy) dodecyl group, 13-((phenethoxy) propoxy) tridecyl group, 14-((phenethoxy) propoxy) tetradecyl Group, 15-((phenetoki ) Propoxy) pentadecyl group, 16-((phenethoxy) propoxy) hexadecyl group, 17-((phenethoxy) propoxy) heptadecyl group, 18-((phenethoxy) propoxy) octadecyl group, 19-((phenethoxy) propoxy) nonadecyl group, 20-((phenethoxy) propoxy) icosyl group, and the like.

(III) As the aryloxyalkoxyalkyl group, for example, a (phenoxymethoxy) methyl group, a 2- (phenoxymethoxy) ethyl group, a 3-((phenoxymethoxy) propyl group, a 4- (phenoxymethoxy) butyl group, a 5- ( Phenoxymethoxy) pentyl group, 6- (phenoxymethoxy) hexyl group, 7- (phenoxymethoxy) heptyl group, 8- (phenoxymethoxy) octyl group, 9- (phenoxymethoxy) nonyl group, 10- (phenoxymethoxy) decyl group , 11- (phenoxymethoxy) undecyl group, 12- (phenoxymethoxy) dodecyl group, 13- (phenoxymethoxy) tridecyl group, 14- (phenoxymethoxy) tetradecyl group, 15- (phenoxymethoxy) pentadecyl group, 16- (phenoxy group) Methoki ) Hexadecyl group, 17- (phenoxy methoxy) heptadecyl, 18- (phenoxy methoxy) octadecyl, 19- (phenoxy methoxy) nonadecyl, 20- (phenoxy methoxy) icosyl group,

(Phenoxyethoxy) methyl group, 2- (2-phenoxyethoxy) ethyl group, 3-((2-phenoxyethoxy) propyl group, 4- (2-phenoxyethoxy) butyl group, 5- (2-phenoxyethoxy) pentyl Group, 6- (2-phenoxyethoxy) hexyl group, 7- (2-phenoxyethoxy) heptyl group, 8- (2-phenoxyethoxy) octyl group, 9- (2-phenoxyethoxy) nonyl group, 10- (2 -Phenoxyethoxy) decyl group, 11- (2-phenoxyethoxy) undecyl group, 12- (2-phenoxyethoxy) dodecyl group, 13- (2-phenoxyethoxy) tridecyl group, 14- (2-phenoxyethoxy) tetradecyl group , 15- (2-phenoxyethoxy) pentadecyl group, 16- (2-phenoxyethoxy) ) Hexadecyl group, 17- (2-phenoxy-ethoxy) heptadecyl, 18- (2-phenoxy-ethoxy) octadecyl, 19- (2-phenoxy-ethoxy) nonadecyl, 20- (2-phenoxy-ethoxy) icosyl group,

(3-phenoxypropoxy) methyl group, 2- (3-phenoxypropoxy) ethyl group, 3- (3-phenoxypropoxy) propyl group, 4- (3-phenoxypropoxy) butyl group, 5- (3-phenoxypropoxy) ) Pentyl group, 6- (3-phenoxypropoxy) hexyl group, 7- (3-phenoxypropoxy) heptyl group, 8- (3-phenoxypropoxy) octyl group, 9- (3-phenoxypropoxy) nonyl group, 10- (3-phenoxypropoxy) decyl group, 11- (3-phenoxypropoxy) undecyl group, 12- (3-phenoxypropoxy) dodecyl group, 13- (3-phenoxypropoxy) tridecyl group, 14- (3-phenoxypropoxy) Tetradecyl group, 15- (3-phenoxypropoxy) pentadecyl group, 6- (3-phenoxypropoxy) hexadecyl group, 17- (3-phenoxypropoxy) heptadecyl group, 18- (3-phenoxypropoxy) octadecyl group, 19- (3-phenoxypropoxy) nonadecyl group, 20- (3-phenoxy A propoxy) icosyl group.

Among the above,
(I) an aralkoxyalkyl group consisting of an aliphatic hydrocarbon having 8 to 20 carbon atoms,
(II) an alkoxyalkoxyalkyl group consisting of an aliphatic hydrocarbon having 8 to 20 carbon atoms,
(III) An aryloxyalkoxyalkyl group composed of an aliphatic hydrocarbon having 8 to 20 carbon atoms is preferable from the viewpoint of solubility in organic solvents and mobility.

In addition, among the above, the number of carbon atoms in the aliphatic hydrocarbon is more preferably R ₁ > (R ₂ + R ₃ ) from the viewpoint of solubility in organic solvents and mobility.

Specific compounds of the present invention having the substituents described above include the following.
However, it is not limited to these.

(Synthesis of the compound of the present invention)
The compound of the present invention can be synthesized by a combination of known and commonly used methods.
An example of the synthesis route is as follows.
(Example of synthesis route)

  First, after BTBT is brominated, a Suzuki-Miyaura coupling reaction with an aryl derivative is performed. Next, a halogen-substituted aliphatic carboxylic acid chloride is subjected to Friedel-Crafts acylation reaction, followed by Wolff-Kishner reduction to obtain an alkylated compound having a halogen group at a terminal. Next, the desired compound can be obtained by performing an etherification reaction with the compound having a hydroxyl group.

  The reaction is not particularly limited, and a known and commonly used reagent can be used, and the reaction temperature can be applied at any known and commonly used temperature.

  The organic semiconductor material of the present invention obtained as described above has high solvent solubility and exhibits high charge mobility because the arrangement of molecules is controlled after film formation. Since the variation in mobility between elements is smaller than that of conventional compounds, it is useful for various organic semiconductor devices.

  From the viewpoint of applying the organic semiconductor material according to the present invention to a device, the energy levels of HOMO and LUMO in the core are also important. Generally, the HOMO level of an organic semiconductor is determined by dissolving a test substance in an organic solvent such as dehydrated dichloromethane so as to have a concentration of, for example, 1 mmol / L to 10 mmol / L, and dissolving a supporting electrolyte such as a tetrabutylammonium salt. After adding about 0.2 mol / L, a working electrode such as Pt and a counter electrode such as Pt, and a reference electrode such as Ag / AgCl were inserted into the solution, and the solution was swept with a potentiostat at a speed of about 50 mV / sec to obtain a CV curve. And the HOMO level and LUMO level can be estimated from the difference between the peak potential and a reference potential, for example, a known substance such as ferrocene. When the HOMO level and the LUMO level are out of the potential window of the organic solvent used, the HOMO-LUMO level is calculated from the absorption edge of the ultraviolet-visible absorption spectrum, and the HOMO level and the LUMO level are subtracted from the measured level. Can be estimated. This method is described in Pommerehne, H .; Westweber, W.C. Guss, R.A. F. Mahhrt, H .; Bassler, M .; Porsch, and J.M. Daub, Adv. Mater. , 7, 551 (1995).

Generally, the HOMO and LUMO levels of an organic semiconductor material provide a measure of electrical contact with the anode and cathode, respectively, and charge injection is limited by the size of the energy barrier determined by the difference between the work function of the electrode material. Be careful. The work function of a metal is often 4.0 eV for silver (Ag), 4.28 eV for aluminum (Al), 5.1 eV for gold (Au), and 2.87 eV for calcium (Ca), as examples of materials used as electrodes. Chromium (Cr) 4.5 eV, copper (Cu) 4.65 eV, magnesium (Mg) 3.66 eV, molybdenum (Mo) 4.6 eV, platinum (Pt) 5.65 eV, indium tin oxide (ITO) 4. From 35 to 4.75 eV and 4.68 eV of zinc oxide (ZnO), the work function difference between the organic semiconductor material and the electrode material is preferably 1 eV or less, more preferably 0.8 eV or less, from the viewpoint described above. More preferably, it is 0.6 eV or less. For the work function of the metal, the following literature can be referred to as needed.
Reference D: Chemical Handbook Basic Edition, Revised 5th Edition II-608-610 14.1 b work function (Maruzen Publishing Co., Ltd.) (2004)

  Since the HOMO and LUMO energy levels are affected by the size of the conjugated π-electron system in the core portion, the size of the conjugate system is helpful when selecting a material. As a method of changing the HOMO and LUMO energy levels, it is effective to introduce a hetero element into the core.

Applicable organic semiconductor devices include diodes, organic transistors, memories, photodiodes, light-emitting diodes, light-emitting transistors, sensors such as gas sensors, biosensors, blood sensors, immune sensors, artificial retinas, taste sensors, RFID, and the like. Is mentioned.

Among them, the organic semiconductor material of the present invention has a high charge mobility of 0.1 cm ² / Vs or more, and thus is particularly useful for application to an organic transistor or a light emitting device. The organic transistor can be suitably used as a switching transistor of a pixel constituting a display, a signal driver circuit element, a memory circuit element, a signal processing circuit element, or the like. Examples of the display include a liquid crystal display, a dispersion liquid crystal display, an electrophoretic display, a particle rotating display device, an electrochromic display, an organic electroluminescent display, and electronic paper.

Note that an organic transistor usually includes a source electrode, a drain electrode and a gate electrode, and a gate insulating layer and an organic semiconductor layer, and there are various types of transistors depending on the arrangement of each electrode and each layer. The organic semiconductor material of the present invention can be used for any transistor without being limited to the type of transistor. For the type of transistor, reference can be made to Aldrich's Material Science Fundamentals No. 6, "Basics of Organic Transistors".

(About mobility)
The mobility in the present invention is the mobility of carriers such as holes and electrons, and is an index indicating the performance of an organic semiconductor material. The mobility includes a mobility (μ ^TOF : unit cm ² / V · s) by a TOF (Time-of-Flight) method and a mobility (μ ^FET : unit cm ² / V · s) obtained by an organic transistor. There are, as μ ^TOF and ^{μ FET} is high, will be easy carriers flow.

The mobility (μ ^TOF ) is determined by the following equation (i), where V is the voltage between the electrodes of the TOF measurement cell, d is the distance between the electrodes, and Tr is the time traversing the film thickness calculated from the photocurrent waveform. Can be Moreover, the mobility (mu ^FET) is a drain voltage V _D is fixed, with the curve of the transmission characteristics obtained by varying the gate voltage V _G, is obtained by the following formula (ii).

(In the formula (ii), C _in is an electric capacity per unit area of the gate insulating film, _ID is a drain current, L is a channel length, W is a channel width, and V _TH is a threshold voltage.)
The usefulness of applying an organic semiconductor to a device is based on the mobility of the substance. This is because the characteristics of the device are limited by the mobility. Conventionally, in an amorphous organic semiconductor, the mobility is about 10 ⁻² cm ² / Vs even at a high mobility, and generally 10 ⁻¹⁰ to 10 ⁻³ cm ² / Vs.

Since a liquid crystal substance shows a crystal phase similarly to a non-liquid crystal substance, it goes without saying that when a liquid crystal substance is used as an organic semiconductor, it can be used as an organic semiconductor not only in the liquid crystal phase but also in the crystal phase. In general, the mobility in the crystal phase is often about half to one digit higher than the mobility in the liquid crystal phase. Particularly, transistor applications requiring high mobility and large diffusion lengths of charges and excitons are particularly difficult. Crystals are required for applications such as solar cells
Use of phases is effective.

(Confirmation of semiconductor device operation)
As shown in the examples, it is possible to confirm that the organic semiconductor material of the present invention can be used as an organic transistor by manufacturing a FET and evaluating its characteristics.
For details of the semiconductor device operation confirmation by such a method, see, for example, Reference S. F. Nelsona, Y .; -Y. Lin, D.A. J. Gundlach, and T.W. N. Jackson, Temperature-independent transport in high-mobility pentacene transistors, Appl. Phys. Lett. , 72, No. 15 1854-1856 (1998).

(Organic semiconductor ink)
The organic semiconductor material of the present invention may be formed by vapor deposition to form a semiconductor film, but is preferably used as a printing ink which can be formed at a low temperature and has excellent productivity. In order to prepare ink, the organic semiconductor material of the present invention is dissolved in a solvent, and a fluorine-based or silicon-based leveling agent, and polystyrene or acryl are used in order to impart ink properties within a range that does not impair the semiconductor performance. A polymer compound such as a resin can be added as a viscosity modifier.

Any organic solvent may be used, or two or more organic solvents may be used as a mixture. Specifically, aliphatic solvents such as n-hexane, n-octane, n-decane and n-dodecane; alicyclic solvents such as cyclohexane; benzene, toluene, cumene, o-xylene, m-xylene, p-xylene, p-cymene, mesitylene, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, 2,5-dimethylanisole, 3,5-dimethoxytoluene, 2,4-dimethylanisole, phenetole, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, 1,5-dimethyltetralin, n-propylbenzene, n-butylbenzene, n-pentylbenzene, 1,3,5-triethylbenzene, 1,3 -Dimethoxybenzene, chlorobenzene, o-dichlorobenzene, trichlorobenzene, etc. Aromatic solvents; ether solvents such as tetrahydrofuran, dioxane, ethylene glycol diethyl ether, anisole, benzyl ethyl ether, ethyl phenyl ether, diphenyl ether, methyl-t-butyl ether; methyl acetate, ethyl acetate, ethyl cellosolve, propylene glycol methyl ether Ester solvents such as acetate; alcohol solvents such as methanol, ethanol, and isopropanol; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, 2-hexanone, 2-heptanone, and 3-heptanone; and other dimethylformamide, dimethylsulfoxide, and diethylformamide And the like, but are not limited thereto.
The concentration of the organic semiconductor material of the present invention in the prepared liquid composition is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 10% by weight.
One type of organic solvent may be used, but a plurality of types of solvents may be mixed and used in order to obtain a desired highly uniform thin film.

(Organic transistor)
Next, an organic transistor containing the organic semiconductor material of the present invention will be described.
An organic transistor generally has a source electrode, a drain electrode and a gate electrode, and a gate insulating layer and an organic semiconductor layer. There are various types of transistors depending on the arrangement of each electrode and each layer. The organic semiconductor material described above can be used for any transistor without being limited to the type of transistor. For the type of transistor, reference can be made to Aldrich's Material Science Fundamentals No. 6, "Basics of Organic Transistors".
The bottom contact type shown in FIG. 1 will be described in detail as an example. 1 is a substrate, 2 is a gate electrode, 3 is a gate insulating layer, 4 is an organic semiconductor, 5 is a source electrode, and 6 is a drain electrode.

  The substrate is made of glass or a flexible resin sheet. For example, a plastic film can be used as the sheet. Examples of the plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), polyether imide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, and polycarbonate (PC). , Cellulose triacetate (TAC), cellulose acetate propionate (CAP) and the like. As described above, by using a plastic film, the weight can be reduced as compared with the case of using a glass substrate, portability can be improved, and resistance to impact can be improved.

The electrode material of the gate electrode, the source electrode, or the drain electrode is not particularly limited as long as it is a conductive material. Platinum, gold, silver, nickel, chromium, copper, iron, tin, tin oxide / antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, carbon, graphite, glassy carbon, silver paste and carbon paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium- Potassium alloy, magnesium, lithium, aluminum, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, lithium / aluminum A metal electrode such as a compound is used, but a known conductive polymer having improved conductivity by doping or the like, for example, a conductive polyaniline, a conductive polypyrrole, a conductive polythiophene, a complex of polyethylene dioxythiophene and polystyrene sulfonic acid. Are also preferably used.

  As a method for forming an electrode, a method for forming an electrode using a known photolithographic method or a lift-off method on a conductive thin film formed by using a method such as evaporation or sputtering using the above as a raw material, or a metal foil such as aluminum or copper There is a method of etching using a resist by thermal transfer, ink jet or the like. In addition, a conductive polymer solution or dispersion liquid, or a conductive fine particle dispersion liquid may be directly patterned by ink jet, or may be formed from a coating film by lithography or laser ablation. Further, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as letterpress, intaglio, lithographic, or screen printing can also be used.

  The gate insulating layer is made of a thermoplastic resin such as parylene, polystyrene, acrylic resin, or polyester resin; a thermosetting resin such as epoxy resin, urethane resin, phenol resin, unsaturated polyester resin, alkyd resin, or melamine resin; a UV-curable resin Although an organic thin film such as a silicon oxide film can be suitably used, an inorganic material such as a silicon oxide film can also be used.

The gate insulating layer is formed by spin coating, casting, dipping, inkjet, doctor blade, screen printing, offset printing, letterpress printing, reverse printing, microcontact printing, wire bar coating, spray coating. A thin film can be formed by a known wet film forming method such as a dispensing method, and may be patterned into a required shape by a photolithographic method as needed.
The organic semiconductor layer can be manufactured by a known and commonly used manufacturing method such as a vacuum evaporation method. The organic semiconductor layer can be easily formed by a printing method using the composition as an ink for an organic semiconductor material.

Examples of the printing method include a spin coating method, a casting method, a dip method, an ink jet method, a doctor blade method, a gravure printing method, a screen printing method, an offset printing method, a letterpress printing method, a reverse printing method, a micro contact printing method, A thin film can be prepared by a known wet film forming method such as a wire bar coating method, a spray coating method, and a dispensing method. Further, depending on the casting method or the like, it is also possible to take the form of a flat crystal or a thick film.
The organic transistor of the present invention can be suitably used as a switching transistor of a pixel constituting a display, a signal driver circuit element, a memory circuit element, a signal processing circuit element, and the like. Examples of the display include a liquid crystal display, a dispersion liquid crystal display, an electrophoretic display, a particle rotating display device, an electrochromic display, an organic electroluminescent display, and electronic paper.

(Organic semiconductor device)
Applicable organic semiconductor devices include diodes, organic transistors, memories, photodiodes, light-emitting diodes, light-emitting transistors, sensors such as gas sensors, biosensors, blood sensors, immune sensors, artificial retinas, taste sensors, RFID, and the like. Is mentioned.

The present invention will be described in more detail with reference to examples.
<Production of transistor>
A silicon wafer with a thermal oxide film (heavy-doped p-type silicon (P + -Si), thermal oxide film (SiO ₂ ) thickness: 300 nm) is cut into 20 × 25 mm, and the cut silicon wafer (hereinafter abbreviated as a substrate) is cut. Ultrasonic cleaning was performed in the order of a neutral detergent, ultrapure water, isopropyl alcohol (IPA), acetone, and IPA.
Next, the compounds synthesized in the following Examples and Comparative Examples were dissolved in p-xylene to prepare solutions. The concentration of the solution was from 0.4 wt% to 0.1 wt%. This solution and a glass pipette for applying the solution to the substrate are previously heated to a predetermined temperature on a hot stage, and the substrate is placed on a spin coater placed in an oven. After the temperature was raised to ° C., the solution was applied on a substrate, and the substrate was rotated (about 3000 rpm, 30 seconds). After stopping the rotation, the substrate was quickly taken out and cooled to room temperature.
Further, a source / drain electrode was formed on the substrate coated with the organic semiconductor layer by pattern deposition of gold through a metal mask using a vacuum deposition method (2 × 10 ⁻⁶ Torr) (channel length: Channel width = 75 μm: 3000 μm).

In the evaluation of the manufactured organic transistor, a current flowing between a source electrode and a drain electrode and a voltage were applied to a gate electrode (P + -Si) by sweeping a current flowing between a source electrode and a drain electrode using a source measurement unit with two power supplies in a normal atmosphere. (Transmission characteristics) while measuring (Vsg: +40 to -60 V) (voltage Vsd between the source electrode and the drain electrode: -80 V). The mobility was calculated from the slope of √Id−Vg in the transfer characteristic by a well-known method using a formula of a saturation characteristic. Note that the mobility and the on / off ratio were measured for five transistors, and the average value was described.

(Solubility test)
In a constant temperature water bath at 25 ± 1 ° C., 0.1 g of the compounds synthesized in the following Examples and Comparative Examples were charged into a screw tube, and an arbitrary amount of p-xylene was adjusted to 1 wt% with respect to the total content. In addition, a solubility test was performed. The dissolution was confirmed by visual observation, left for 30 minutes in a constant temperature water bath, and the case where there was no precipitation was defined as the amount of dissolution. When it did not dissolve at 1 wt%, p-xylene was added, the amount of the synthesized compound was reduced so as to be in increments of 0.05 wt%, and the test was carried out until dissolution.
(Example 1)

A solution obtained by dissolving 4.45 g (18.5 mmol) of BTBT, 400 mL of chloroform, and 3.58 g (22.4 mmol) of bromine in 20 mL of chloroform obtained by the method described in JP 2010-275192 A is added at room temperature for 3 days. Reacted. Next, 50 mL of a 1% aqueous sodium hypochlorite solution was added to the reaction solution, and the mixture was stirred, and the organic phase was separated. The organic phase was washed with a saturated sodium chloride aqueous solution (50 mL), the organic phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a mixture of 2-bromoBTBT.

Next, 3.4 g (27.9 mmol) of phenylboric acid, 6.3 g (46 mmol) of potassium carbonate, 400 mL of dioxane, and 50 mL of distilled water were added to the mixture of the above 2-bromoBTBT, and the inside of the flask was replaced with argon for 20 minutes. Thereafter, 1.0 g (0.9 mmol) of tetrakis (triphenylphosphine) palladium (4.3 mL, 4.3 mmol) of tri-t-butylphosphine was added, and the mixture was heated under reflux for 3 hours. After cooling, 400 mL of distilled water was added, insolubles were collected by filtration, washed with water, and further washed with methanol. The starting component was removed from the reaction product by silica gel column chromatography (eluent: cyclohexane) to obtain 4.04 g of a mixture of 2-phenyl BTBT, which was further recrystallized from 60 mL of toluene and 3.23 g of 2-phenyl BTBT. (56% yield from BTBT).
¹ H-NMR (CDCl ₃ ): 8.14 ppm (d, J = 1.6 Hz, 1H), 7.95 ppm (d, J = 7.0 Hz, 1H), 7.94 ppm (d, J = 8.2 Hz) , 1H), 7.90 ppm (d, J = 8.2 Hz, 1H), 7.71 ppm (dd, J = 7.0 and 1.6 Hz, 1H), 7.70 ppm (dd, J = 7.2 and 1.4 Hz. 7.2 ppm), 7.49 ppm (t, J = 7.2 Hz, 2H), 7.47 ppm (t, J = 8.2 Hz, 1H), 7.42 ppm (t, J = 8.2 Hz, 1H), 35 ppm (tt, J = 7.2 and 1.4 Hz, 1H)

  2.80 g (10.1 mmol) of 12-bromododecanoic acid is dissolved in dehydrated chloroform (20 mL, manufactured by Kanto Kagaku), and 2.67 g (21 mmol) of oxalyl chloride and 0.1 mL of dehydrated DMF are added dropwise in an ice bath. After further reacting at 45 ° C. (bath temperature) for 2 hours, the reaction solution is distilled off, benzene is further added and concentrated. The residue (oil containing a small amount of gummy solid) was extracted with petroleum benzine (（30 mL), washed with ice water, dried over anhydrous sodium sulfate, concentrated to dryness, and dried to give 2.93 g of 12-bromododecanoyl chloride (98%). %).

2.39 g (18.1 mmol) of anhydrous aluminum chloride was added to 180 mL of a dichloromethane solution of 1.59 g (5.03 mmol) of 2-phenylBTBT under cooling at 6 ° C. (internal temperature). After cooling to 60 ° C., 8 mL of a dichloromethane solution of 2.93 g (9.9 mmol) of 2-bromododecanoyl chloride is added dropwise. After reacting at that temperature for 2 hours, 100 mL of water is added dropwise to stop the reaction, and the mixture is stirred at room temperature overnight. Approximately 400 mL of chloroform was added, and the lower layer (containing the solid) was taken. After washing with 10% saline, the lower layer was concentrated, methanol was added, and the mixture was stirred. The solid was collected by filtration and recrystallized from toluene. And purified to give 2.39 g (81%) of 2- (12-bromododecyl-1-one) -7-phenylBTBT.

A suspension of 2.33 g (4.04 mmol) of 2- (12-bromododecyl-1-one) -7-phenylBTBT in 300 mL of dichloromethane was mixed with 2.3 g of BH ₃ -tBuNH ₂ prepared in advance and 1.69 g of AlCl ₃ . Is added dropwise to a dichloromethane solution (35 mL) under an ice bath. After reacting at 15 ° C. overnight, the reaction was stopped by adding 0.5 M hydrochloric acid (60 mL), followed by usual treatment with chloroform, followed by concentration to dryness and 2.2-g of 2- (12-bromodecyl) -7-phenylBTBT ( (3.93 mmol, 97%).

Dissolve 200 mg (0.354 mmol) of 2- (12-bromodecyl) -7-phenyl BTBT in a mixture of 10 mL of dehydrated THF, 2 mL of dehydrated DMF, and 2 mL of benzyl alcohol, and add 100 mg of 55% sodium hydride while cooling in an ice bath. After stirring at room temperature for 20 minutes, the reaction is performed at 80 ° C. (bath temperature) for another 2 hours. The reaction is stopped by adding 1 M hydrochloric acid (2.5 mL) in an ice bath, and extracted with chloroform. The lower layer is further washed with water five times, dehydrated with anhydrous sodium sulfate, most of the solvent is distilled off, 10 mL of methanol is added to the resulting solid, the mixture is stirred for 1 hour, and filtered. This solid was purified by silica gel column chromatography (eluent; cyclohexane-chloroform, 2: 1 to 1: 1) to give 142 mg of the desired product, 2- (11- (benzyloxy) dodecyl) -7-phenylBTBT (yield). 68%). This was further recrystallized from toluene-ligroin to obtain 123 mg.
With respect to the obtained compound, the above transistor was prepared, and the mobility, the on / off ratio, and the solubility were evaluated. The results are shown in Table 1.
¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.12 (d, 1H, J 1.8 Hz), 7.92 (d, 1 H, J 8.2 Hz), 7.79 (d, 1 H, J to 8 Hz). , 7.73 (br.s, 1H), 7.69 (dx2, 3H, J-8 Hz), 7.49 (t, 2H, J-8 Hz), 7.38 (tt, 1H, J-1, ８8 Hz), 7.34 to 7.2 (m, 6Overlappd), 4.50 (s, 2H, CH ₂ -Ph), 3.46 (t, 2H, J6.7 Hz), 2.77 (t, 2H, J 7.7 Hz), 1.70 (quint. 2H, J-7 Hz) 1.61 (quint. 2H, J-7 Hz), -1.2-1.4 (m, 16H)
(Example 2)

2- (12-bromodecyl) -7-phenyl BTBT (200 mg) was reacted in the same manner as in Example 1 using 2 mL of 2-methoxyethanol instead of benzyl alcohol, and purified by a silica gel column to give 2- (12-bromodecyl) -7-phenyl BTBT. 135 mg (68%) of (11- (2-methoxyethoxy) dodecyl) -7-phenylBTBT were obtained and recrystallized from toluene-ligroin to obtain 110 mg. Table 1 shows the solubility of the obtained compounds and the evaluation results of the transistors manufactured in the same manner as in Example 1.
¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.12 (d, 1H, J 1.8 Hz), 7.92 (d, 1 H, J 8.2 Hz), 7.79 (d, 1 H, J to 8 Hz). , 7.73 (br.s, 1H), 7.69 (dx2, 3H, J-8 Hz), 7.49 (t, 2H, J-8 Hz), 7.38 (tt, 1H, J-1, ８8 Hz), 7.29 (dd, 1H, J> 1, 7.8 Hz), 3.55 (m, 4H, OC ₂ H ₄ O), 3.45 (t, 2H, J 6.8 Hz), 3 .38 (s, 3H, OCH ₃ ), 2.77 (t, 2H, J 7.7 Hz), 1.70 (quint. 2H, J-7 Hz), 1.59 (quint. 2H, J-7 Hz), -1.2-1.4 (m, 16H)
(Example 3)

2- (12-bromodecyl) -7-phenyl BTBT (200 mg) was reacted in the same manner as in Example 1 using 2-phenoxyethanol (2 mL) instead of benzyl alcohol, and purified by a silica gel column to give 2- (12- (2-Phenoxyethoxy) dodecyl) -7-phenylBTBT (143 mg, 65% yield) was obtained and recrystallized from toluene to give 103 mg. Table 1 shows the solubility of the obtained compounds and the evaluation results of the transistors manufactured in the same manner as in Example 1.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.12 (dd, 1H, J0.5, 1.8 Hz), 7.92 (dd, 1H, J0.5, 8.2 Hz), 7.79 ( d, 1H, J-8 Hz), 7.73 (br.s, 1H), 7.69 (dx2, 3H, J-8 Hz), 7.49 (t, 2H, J-8 Hz), 7.38 ( tt, 1H, J〜1, ８8 Hz), 7.25 to 7.30 (m, 3H, H-3 and 2HofOPh), 6.93 (m, 3H, OPh), 4.11 (t-likem, 2H, OCH ₂ CH ₂ O), 3.775 (t-like, 2H, OCH ₂ CH ₂ O), 3.52 (t, 2H, J 6.8 Hz), 2.77 (t, 2H, J 7.7 Hz), 1.70 (quint. 2H, J-7 Hz), 1.60 (quint. 2H, J-7H) ), ~1.2~1.4 (m, 16H),
(Example 4)

2- (12-bromodecyl) -7-phenyl BTBT (200 mg) was reacted in the same manner as in Example 1 except that 2-mL of 2- (benzyloxy) ethanol was used instead of benzyl alcohol. Certain 2- (12- (2- (benzyloxy) ethoxy) dodecyl) -7-phenylBTBT (133 mg, 59% yield) was obtained and recrystallized from toluene-petroleum benzine to give 103 mg. Table 1 shows the solubility of the obtained compounds and the evaluation results of the transistors manufactured in the same manner as in Example 1.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.12 (dd, 1H, J0.5, 1.8 Hz), 7.92 (dd, 1H, J0.5, 8.2 Hz), 7.79 ( d, 1H, J-8 Hz), 7.73 (br.s, 1H), 7.69 (dx2, 3H, J-8 Hz), 7.49 (t, 2H, J-8 Hz), 7.38 ( tt, 1H, J〜1, Ｈｚ8 Hz), 7.25 to 7.36 (m, 6H, H-3 and 5HofCH ₂ Ph), 4.57 (s, 2H, CH ₂ Ph), 3.61 (m, _{4H, OC 2 H 4 O)} , 3.45 (t, 2H, J6.8Hz), 2.77 (t, 2H, J7.7Hz), 1.70 (quint.2H, J~7Hz), 1. 58 (quint. 2H, J-7 Hz), -1.2-1.4 (m, 16H).

(Comparative Example 1)
The following compounds were synthesized by the method described in JP-A-2015-129098. Table 1 shows the solubility of the obtained compounds and the evaluation results of the transistors manufactured in the same manner as in the examples.

(Comparative Example 2)
I would like to change 2- (4-bromobutyl) -7-phenylBTBT obtained by the same method and methoxyethanol of Example 2 to butanol except that 12-bromodecanoic acid of Example 1 was changed to 4-bromobutanoic acid. Except for the above, 2-((4-pentyloxy) butyl) -7-phenylBTBT was synthesized in the same manner. Table 1 shows the solubility of the obtained compounds and the evaluation results of the transistors manufactured in the same manner as in Example 1.

  As shown in Table 1, the organic semiconductor material of the present invention has high solubility, gives a transistor element having practical mobility, and is excellent in handling during manufacture. On the other hand, the compound of the comparative example has a low mobility of the obtained transistor characteristics and cannot obtain a transistor element having practical mobility. Alternatively, due to low solubility, handling during production becomes difficult.

  The compound of the present invention can be used as an organic semiconductor, and can be used in an organic transistor using the organic semiconductor material as an organic semiconductor layer.

1. Substrate 2. Gate electrode3. 3. gate insulating film Organic semiconductor5. Source electrode 6. Drain electrode

Claims (1)

General formula (1)

(In the formula, Ar represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, and R ₁ and R ₂ each independently represent an alkylene group having 1 to 20 carbon atoms, or -valent alicyclic _group, X 1, _{X 2} are each independently in Table O, S, and NH, n is 0 or 1, _{R 3} in the case of n = 0, as a substituent An alkyl group having 1 to 20 carbon atoms having an aromatic hydrocarbon group, a heteroaromatic group or an alicyclic hydrocarbon group, or a general formula (A) to (C)

(Ar ′ represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, and m represents an integer of 1 to 20.)
Represents a group selected from
In the case of n = 1, an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, a carbon number of 1 to 20 which may have an aromatic hydrocarbon group or a heteroaromatic group as a substituent. Alkyl group, or general formulas (A) to (C)

(Ar ′ represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, and m represents an integer of 1 to 20.)
Represents a group selected from )
A compound represented by the formula:

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