JP2021125476A - Perylene derivative compound, organic semiconductor composition using the compound, and organic thin film transistor using the organic semiconductor composition - Google Patents

Abstract

To provide an n-type organic semiconductor material having high solubility corresponding to a solution process, and further to provide an organic semiconductor device with high electron mobility and an organic thin-film transistor using the n-type organic semiconductor material as an organic semiconductor composition.SOLUTION: A perylene derivative compound represented by the following formula (1). In the formula, R1 and R4 are the same, R2 and R3 may be the same or different, R5 and R6 may be the same or different, and R2 and R3, R5 and R6 may be bonded to each other to form a ring.SELECTED DRAWING: None

Description

The present invention relates to a perylene derivative compound, a composition for an organic semiconductor using the compound, an organic semiconductor device using the organic semiconductor composition, and an organic thin film.

Conventionally, thin film transistors using a silicon-based inorganic material as an inorganic semiconductor material have been widely used, but since these films are formed at a high temperature, they are lightweight and flexible as a substrate compatible with a thin display. Plastic materials and the like have a drawback that they have poor heat resistance and cannot be used. Therefore, in recent years, there has been active development of organic thin film transistors using an organic compound exhibiting properties as a semiconductor as an organic semiconductor material instead of a silicon-based inorganic material.

In the formation of an organic semiconductor layer containing an organic semiconductor material in an organic thin film transistor, a solution process produced in the air is used as compared with a vacuum vapor deposition process produced in a vacuum at a high temperature to reduce the production cost of the organic thin film transistor element. It becomes easy to increase the size. Further, the temperature required for film formation can be lowered, and a plastic material or the like can be used for the substrate. For this reason, there is a demand for organic semiconductor materials that are compatible with solution processes that can be applied to flexible devices.

Organic semiconductors that form an organic semiconductor layer are classified into p-type organic semiconductor materials in which holes flow as carriers and n-type organic semiconductor materials in which electrons flow as carriers. Many p-type organic semiconductor materials have been reported so far.

On the other hand, as n-type organic semiconductor materials, materials such as perylene derivatives and fullerenes are being developed, but their solubility in solvents is low and their compatibility with solution processes is low.

In addition, high-performance n-type organic semiconductor materials are necessary for pn junctions and integrated circuit construction, but electron currents are more susceptible to external factors such as the atmosphere and impurities than hole currents. Its electron mobility is still low compared to p-type organic semiconductor materials.

As described above, it is desired to develop an organic semiconductor material having both high solubility in a solvent suitable for a solution process and high carrier mobility.

Special table 2007-527114 Special table 2008-524846 JP 2015-115490

Angew. Chem. Int. Ed. 2004, 43, P.M. 6363-6366 J. Org. Chem. , 2004,69, P.M. 7933-7939

The problem to be solved by the present invention is to provide an n-type organic semiconductor material having high solubility corresponding to a solution process, and further to use the n-type organic semiconductor material as a composition for an organic semiconductor for high electron mobility. It is to provide an organic semiconductor element and an organic thin film.

In order to solve the above problems, the inventors have diligently studied an n-type organic semiconductor material having solubility corresponding to a solution process and an organic thin film having excellent electron mobility, and as a result, they are dissolved by having a specific structure. It has been found that an organic thin film having high mobility can be obtained by using a compound having improved properties as an n-type organic semiconductor material and further incorporating the compound in an organic semiconductor layer. That is, the gist of the present invention is as follows.

1. 1. A perylene derivative compound represented by the following general formula (1).

[In the formula, R ¹ and R ⁴ are the same,
Hydrogen atom, halogen atom,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have a substituent,
Alternatively, it represents a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent.
R ² and R ³ may be the same or different
Hydrogen atom, hydroxyl group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms, which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkoxy group having 5 to 10 carbon atoms, which may have a substituent,
A thio group having 0 to 18 carbon atoms which may have a substituent,
An amino group having 0 to 20 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have a substituent,
Alternatively, it represents a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent.
R ⁵ and R ⁶ may be the same or different.
Hydrogen atom, halogen atom, cyano group, nitro group, nitroso group,
A linear or branched alkyl fluoride group having 1 to 20 carbon atoms, which may have a substituent,
Aryl fluoride group having 6 to 36 carbon atoms, which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
Alternatively, it represents a sulfonyl group having 0 to 20 carbon atoms which may have a substituent.
R ² and R ³ and R ⁵ and R ⁶ may be coupled to each other to form a ring. ]

2. The above-mentioned perylene derivative compound represented by the following general formula (2).

[In the formula, R ¹ and R ⁴ are the same,
Hydrogen atom, halogen atom,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have a substituent,
Alternatively, it represents a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent.
R ² is a hydroxyl group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms, which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkoxy group having 5 to 10 carbon atoms, which may have a substituent,
A thio group having 0 to 18 carbon atoms which may have a substituent,
An amino group having 0 to 20 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have a substituent,
Alternatively, it represents a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent.
R ⁵ is a halogen atom, a cyano group, a nitro group, a nitroso group,
A linear or branched alkyl fluoride group having 1 to 20 carbon atoms, which may have a substituent,
Aryl fluoride group having 6 to 36 carbon atoms, which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
Alternatively, it represents a sulfonyl group having 0 to 20 carbon atoms which may have a substituent. ]

3. 3. In the general formula (1), a perylene derivative compound in which at least one of the substituents of ^{R 1} and R ^{4 is a fluorine atom.}

4. In the general formula (1), ^{at least one of R 2} and R ³ may have a hydroxyl group or a substituent as a linear or branched alkoxy group having 1 to 20 carbon atoms, or a substituent. A perylene derivative compound which is a thio group having 0 to 18 carbon atoms which may have.

5. In the general formula (1), ^{at least one of R 5} and R ^{6 is} a linear or branched alkyl fluoride group having 1 to 20 carbon atoms which may have a cyano group or a substituent. A perylene derivative compound.

The perylene derivative compound according to the above, which has a solubility in an aromatic organic solvent or a halogen-based organic solvent at 6.25 ± 2 ° C. at a concentration of 0.02 to 5% by mass.

7. A composition for an organic semiconductor containing the above-mentioned perylene derivative compound.

8. An organic semiconductor device using the above-described composition for an organic semiconductor.

9. An organic thin film transistor using the organic semiconductor device described above.

The perylene derivative compound according to the present invention can provide an n-type organic semiconductor material having solubility in an organic solvent corresponding to the solution process, and further, an organic semiconductor composition containing the organic semiconductor material shall be used. Therefore, an organic thin film having excellent electron mobility can be obtained.

It is schematic cross-sectional view which shows the structure of the bottom gate bottom contact type organic thin film transistor which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail. The compound represented by the general formula (1) of the present invention is dissolved in a solvent, an organic semiconductor layer is formed by using a composition for an organic semiconductor containing the compound, and the compound is further used as an organic semiconductor device. In the specification of the present application, the composition for an organic semiconductor and the organic semiconductor layer contain at least one compound represented by the general formula (1), and optionally other materials for semiconductors that do not belong to the present invention. And the like.

Hereinafter, the compound represented by the general formula (1) will be specifically described, but the present invention is not limited thereto. In the specification of the present application, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

In the present invention, examples of the "halogen atom" include fluorine, chlorine, bromine and iodine.

In the general formula (1), the "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 1} and R ^{4 has "1 to 1 carbon atoms".} Specific examples of the "20 linear or branched alkyl groups" include methyl group, ethyl group, n-propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. , Isobutyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group, t-octyl group and the like.

In the general formula (1), the "linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent" represented by ^{R 1} and R ^{4 has "2 to 2 carbon atoms".} Specific examples of the "20 linear or branched alkenyl groups" include a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group and a 1-hexenyl group. Examples thereof include an isopropenyl group, an isobutenyl group, and a linear or branched alkenyl group having 2 to 18 carbon atoms to which a plurality of these alkenyl groups are bonded.

In the general formula (1), "cycloalkyl group having 5 to 10 carbon atoms" in the "cycloalkyl group substituent may having 5 to 10 carbon atoms which may have a" R ¹ and R ⁴ in the formula Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group and the like.

In the general formula (1), the "aromatic hydrocarbon group having 6 to 36 carbon atoms" in the "aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent" represented by ^{R 1} and R ^{4 is used.} Specific examples of the "hydrocarbon group" include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a biphenyl group, an anthracenyl group (anthryl group), a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylenel group, and a fluorane group. Examples include a tenyl group and a triphenylenyl group. In the present invention, the aromatic hydrocarbon group includes a "condensed polycyclic aromatic group".

In the general formula (1), the "heterocycle having 5 to 36 ring-forming atoms" in the "heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" represented by ^{R 1} and R ^{4 is used.} Specific examples of the "group" include pyridyl group, pyrimidilinyl group, triazinyl group, thienyl group, furyl group (furanyl group), pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyldinyl group and acridinyl group. , Phenanthrolinyl group, benzofuranyl group, benzothienyl group, oxazolyl group, indolyl group, carbazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, quinoxalinyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzo Examples include a thienyl group and a carbonylyl group.

In the general formula (1), "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" and "having a substituent" represented by ^{R 1} and R ⁴ It may have a linear or branched alkenyl group having 2 to 20 carbon atoms, "a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent", and "having a substituent". The "substituent" in "an aromatic hydrocarbon group having 6 to 36 carbon atoms which may be present" or "a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" is specific. Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; cyano group; hydroxyl group; nitro group; nitroso group; carboxyl group;
Carboxylate ester groups such as methyl ester groups and ethyl ester groups;
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, 2-ethylhexyl group, A linear or branched alkyl group having 1 to 18 carbon atoms such as a heptyl group, an octyl group, an isooctyl group, a nonyl group, and a decyl group;
Linear or branched with 2 to 20 carbon atoms such as vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group Alkenyl group;
A linear or branched alkoxy group having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, a pentyloxy group, and a hexyloxy group;
Aromatic hydrocarbon groups with 6 to 30 carbon atoms such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group;
Pyridyl group, pyrimidilinyl group, triazinyl group, thienyl group, frill group (furanyl group), pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyldinyl group, acridinyl group, phenanthrolinyl group, benzofuranyl Rings of groups, benzothienyl groups, oxazolyl groups, indolyl groups, carbazolyl groups, benzoxazolyl groups, thiazolyl groups, benzothiazolyl groups, quinoxalinyl groups, benzoimidazolyl groups, pyrazolyl groups, dibenzofuranyl groups, dibenzothienyl groups, carbonylyl groups, etc. Heterocyclic group with 2 to 30 atoms formed;
Carbon, which is a monosubstituted amino group such as an unsubstituted amino group (-NH ₂ ), an ethylamino group, an acetylamino group, or a phenylamino group, or a disubstituted amino group such as a diethylamino group, a diphenylamino group, or an acetylphenylamino group. Amino group with 0 to 18 atoms;
Number of carbon atoms such as unsubstituted thio group (thiol group: -SH), methyl thio group, ethane thio group, propyl thio group, di-t-butyl thio group, hexa-5-en-3-thio group, phenyl thio group, biphenyl thio group, etc. 0-18 thio groups;
And so on. Only one of these "substituents" may be contained, a plurality of these "substituents" may be contained, and when a plurality of these "substituents" are contained, they may be the same or different from each other. In addition, these "substituents" may further have the above-exemplified substituents.

In the general formula (1), R ¹ and R ⁴ may be the same or different, but are preferably the same. Further, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent may be used. It is preferable that it is present, and it is preferable that it further contains at least one fluorine atom.

In the general formula (1), R ² and R ³ may be the same or different, but preferably contain an electron-donating substituent. R ² and R ³ are not limited, but
Hydrogen atom, hydroxyl group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms, which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkoxy group having 5 to 10 carbon atoms, which may have a substituent,
A thio group having 0 to 18 carbon atoms which may have a substituent,
An amino group having 0 to 20 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have a substituent,
Alternatively, a heterocyclic group having 5 to 36 ring-forming atoms, which may have a substituent, and the like can be mentioned.

In the general formula (1), the "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 2} and R ^{3 has "1 to 1 carbon atoms".} As the "20 linear or branched alkyl group", in the general formula (1), "a straight chain having 1 to 20 carbon atoms which may have a substituent may have a substituent" represented by ^{R 1} and R ^4. The same as the "formal or branched alkyl group" can be mentioned.

In the general formula (1), the "linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 2} and R ^{3 has "1 to 1 carbon atoms".} As the "20 linear or branched alkenyl group", in the general formula (1), the "linear group having 1 to 20 carbon atoms which may have a substituent may be represented by ^{R 1} and R ^4". The same as the "formal or branched alkenyl group" can be mentioned.

In the general formula (1), the "cycloalkyl group having 5 to 10 carbon atoms" in the "cycloalkyl group having 5 to 10 carbon atoms which may have a substituent" represented by ^{R 2} and R ^3. As the general formula (1), the same group as the “cycloalkyl group having 5 to 10 carbon atoms which may have a substituent” represented by ^{R 1} and R ^{4 can be mentioned.}

In the general formula (1), the "linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 2} and R ^{3 has "1 to 1 carbon atoms".} Specific examples of the "20 linear or branched alkoxy groups" include methoxy group, ethoxy group, propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, heptyloxy group and octyl. Oxy group, nonyloxy group, decyloxy group, isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group, t-octyloxy group, phenoxy group, tolyloxy group, biphenylyloxy group, terpheni Examples thereof include a lyloxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, a fluorenyloxy group, an indenyloxy group and the like.

In the general formula (1), "a linear or linear group having 1 to 20 carbon atoms" in "a cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent" represented by ^{R 2} and R ^3. Specific examples of the "branched alkoxy group" include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

In the general formula (1), _{the "thio group" (-SR 7} ) in the "thio group having 0 to 18 carbon atoms which may have a substituent" represented by ^{R 2} and R ³ is unsubstituted. Alternatively, it is a monosubstituted product, and R ₇ represents a linear or branched alkyl group having 0 to 18 carbon atoms or an aromatic hydrocarbon group having 0 to 18 carbon atoms. Specific examples of the "thio group" include an unsubstituted thio group (thiol group: -SH), a methyl thio group, an ethane thio group, a propyl thio group, a di-t-butyl thio group, and a hexa-5-ene-3-thio group. , Phenylthio group, biphenylthio group and the like can be mentioned. R ₇ is a linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent, methyl group, ethyl group, n-propyl group, butyl group, pentyl group, hexyl group and heptyl. Examples thereof include a group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, an isooctyl group and a t-octyl group.

In the general formula (1), the "amino group having 0 to 20 carbon atoms" in the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by ^{R 2} and R ^{3 is used.} , Specifically, an unsubstituted amino group (-NH ₂ ), an ethylamino group, an acetylamino group, a phenylamino group, etc. as a monosubstituted amino group, and a diethylamino group, a diphenylamino group, an acetylphenylamino as a disubstituted amino group. You can give a base.

In the general formula (1), the "aromatic hydrocarbon group having 6 to 36 carbon atoms" in the "aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent" represented by ^{R 2} and R ^{3 is used.} The "hydrocarbon group" is the same as the "aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent" represented by ^{R 1} and R ⁴ in the general formula (1). I can give it.

In the general formula (1), the "heterocycle having 5 to 36 ring-forming atoms" in the "heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" represented by ^{R 2} and R ^{3 is used.} As the "group", the same group as the "heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" represented by ^{R 1} and R ⁴ can be mentioned in the general formula (1). ..

In the general formula (1), "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" and "having a substituent" represented by ^{R 2} and R ³ It may have a linear or branched alkenyl group having 2 to 20 carbon atoms, "a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent", and "having a substituent". It may have a linear or branched alkoxy group having 1 to 20 carbon atoms, "a cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent", and "having a substituent". A thio group having 0 to 18 carbon atoms which may be present, an amino group having 0 to 20 carbon atoms which may have a substituent, and 6 carbon atoms which may have a substituent. The "substituent" of the "aromatic hydrocarbon group of ~ 36" or the "heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" is R in the above general formula (1). "A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" and " ^{2 which may have a substituent" represented by 1} and R4. ~ 20 linear or branched alkenyl groups ”,“ cycloalkyl groups having 5 to 10 carbon atoms which may have substituents ”,“ 6 carbon atoms which may have substituents ” The same as the "substituent" in "the aromatic hydrocarbon group of ~ 36" or "the heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" can be mentioned.

In the general formula (1), R ² and R ³ may be the same or different, and may have a hydroxyl group or a substituent, and may have a linear or branched alkoxy group having 1 to 20 carbon atoms. It is preferably a cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent.

In the general formula (1), R ⁵ and R ⁶ may be the same or different, but are preferably electron-attracting substituents. R ⁵ and R ⁶ are not limited, but
Hydrogen atom, halogen atom, cyano group, nitro group, nitroso group,
A linear or branched alkyl fluoride group having 1 to 20 carbon atoms, which may have a substituent,
Aryl fluoride group having 6 to 36 carbon atoms, which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
Alternatively, a sulfonyl group having 0 to 20 carbon atoms which may have a substituent may be mentioned.

In the general formula (1), "number of carbon atoms in the" linear or branched fluorinated alkyl group which may having 1 to 20 carbon atoms optionally having a substituent "represented by R ⁵ and R ⁶ Specific examples of the "1 to 20 linear or branched alkyl fluorinated groups" include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, and 1,1. , 2,2-Tetrafluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octa Fluorobutyl group, perfluoropentyl group and the like can be mentioned. The "fluorinated alkyl group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a fluorine atom, and is a perfluoroalkyl group (or perfluoroalkyl group). Alkyl group) shall be included.

In the general formula (1), fluorinated aryl R ⁵ and the number "carbon atoms in the" fluoroaryl group which may carbon atoms 6 to 36 which may have a substituent "represented by R ⁶ 6-36 Specific examples of the "group" include a pentafluorophenyl group and a heptafluoro-2-naphthyl group. The "arylfluoride group" is a fluorine atom or a whole of hydrogen atoms of an aryl group. It also includes those in which one or more of the above-mentioned "linear or branched alkyl fluoride groups having 1 to 20 carbon atoms which may have a substituent" are substituted. The "arylfluoride group" is assumed to include a perfluoroaryl group (or a perfluoroaryl group) in which all the hydrogen atoms contained in the aryl group (aromatic hydrocarbon group) are substituted with fluorine atoms.

In the general formula (1), the "acyl group having 1 to 20 carbon atoms" in the "acyl group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 5} and R ^{6 is used as the "acyl group having 1 to 20 carbon atoms".} Specifically, a formyl group, an acetyl group, a propionyl group, an acryryl group, a benzoyl group and the like can be mentioned.

In the general formula (1), the "sulfonyl group having 0 to 20 carbon atoms" in the "sulfonyl group having 0 to 20 carbon atoms which may have a substituent" represented by ^{R 5} and R ^{6 is} Specifically, a sulfonamide group (-S (= O) _2- NH ₂ ), a mesyl group, a tosyl group, and the like can be mentioned.

In the general formula (1), "a linear or branched alkyl fluoride group having 1 to 20 carbon atoms which may have a substituent" and "a substituent may be represented by ^{R 5} and R ^6". It may have an aryl fluoride group having 6 to 36 carbon atoms, an acyl group having 1 to 20 carbon atoms which may have a substituent, or an acyl group having a substituent. As the "substituent" of the "sulfonyl group having a good number of carbon atoms 0 to 20," the "substituted group may have a substituent" represented by ^{R 1} and R ^{4 in the general formula (1).} ~ 20 linear or branched alkyl group ”,“ linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent ”,“ having a substituent It may have a cycloalkyl group having 5 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, or a ring formation which may have a substituent. The same as the "substituent" in the "heterocyclic group having 5 to 36 atoms" can be mentioned.

In the general formula (1), R ⁵ and R ⁶ may be the same or different, and may have a hydrogen atom, a cyano group, and a substituent, and may have 1 to 20 carbon atoms in a linear or branched form. It is preferably an alkyl fluoride group or an aryl fluoride group having 6 to 36 carbon atoms which may have a substituent.

In the general formula (1), R ² , R ³ , R ⁵ , and R ⁶ represent the substituents as described above, whereas R ² and R ³ , R ⁵ and R ⁶ are single bonds and sulfur atoms. The rings may be formed by bonding with each other by a bond via a bond or a bond via a nitrogen atom.

The general formula (1) is preferably represented by the general formula (2).

In the general formula (2), "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" and "having a substituent" represented by ^{R 1} and R ⁴ It may have a linear or branched alkenyl group having 2 to 20 carbon atoms, "a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent", and "having a substituent". The "aromatic hydrocarbon group having 6 to 36 carbon atoms which may be present" or the "heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" is given in the general formula (1). , R ¹ and R ⁴ "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent", "a carbon atom which may have a substituent". "Linear or branched alkenyl group of number 2 to 20,""cycloalkyl group having 5 to 10 carbon atoms which may have a substituent", "carbon atom which may have a substituent" The same as "aromatic hydrocarbon group of number 6 to 36" or "heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" can be mentioned.

In the general formula (2), "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" and "having a substituent" represented by ^{R 1} and R ⁴ It may have a linear or branched alkenyl group having 2 to 20 carbon atoms, "a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent", and "having a substituent". The "substituent" in "an aromatic hydrocarbon group having 6 to 36 carbon atoms which may be present" or "a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" is generally used. In the formula (1), it has "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" and "a substituent" represented by ^{R 1} and R ^4. It may have a linear or branched alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a substituent. The same as the "substituent" in the "aromatic hydrocarbon group having 6 to 36 carbon atoms" or the "heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" is given. Can be done.

In the general formula (2), R ¹ and R ⁴ may be the same or different, but are preferably the same, and may have a substituent and are linear or linear with 1 to 20 carbon atoms. It is preferably an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a branched alkyl group or substituent, and more preferably contains at least one fluorine atom.

In the general formula (2), R ² is preferably an electron-donating substituent. The electron-donating substituent is not limited, but is limited.
Hydroxy group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms, which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkoxy group having 5 to 10 carbon atoms, which may have a substituent,
A thio group having 0 to 18 carbon atoms which may have a substituent,
An amino group having 0 to 20 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have a substituent,
Alternatively, a heterocyclic group having 5 to 36 ring-forming atoms, which may have a substituent, and the like can be mentioned.

In the general formula (2), the "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 2 is "directly having 1 to 20 carbon atoms".} The chain or branched alkyl group is a linear or branched group having 1 to 20 carbon atoms which may have a substituent and is represented by ^{R 1} and R ^{4 in the general formula (1).} The same as the "alkane group" can be mentioned.

In the general formula (2), the "linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 2 is "directly having 1 to 20 carbon atoms".} The chain or branched alkenyl group is a linear or branched group having 1 to 20 carbon atoms which may have a substituent and is represented by ^{R 1} and R ^{4 in the general formula (1).} The same as the "alkenyl group in the form" can be mentioned.

In the general formula (2), the "cycloalkyl group having 5 to 10 carbon atoms" in the "cycloalkyl group having 5 to 10 carbon atoms which may have a substituent" represented by ^{R 2 is defined as.} In the general formula (1), the same group as the "cycloalkyl group having 5 to 10 carbon atoms which may have a substituent" represented by ^{R 1} and R ^{4 can be mentioned.}

In the general formula (2), the "linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 2 is "directly having 1 to 20 carbon atoms".} The chain or branched alkoxy group is a linear or branched group having 1 to 20 carbon atoms which may have a substituent and is represented by ^{R 2} and R ^{3 in the general formula (1).} The same as the "alkoxy group in the form" can be mentioned.

In the general formula (2), represented by R ² of "1 to 20 carbon atoms in the" cycloalkoxy group which may having 5 to 10 carbon atoms which may have a substituent "linear or branched The "alkoxy group" may be the same as the “cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent” represented by ^{R 2} and R ³ in the general formula (1). can.

In the general formula (2), the "thio group having 0 to 18 carbon atoms" in the "thio group having 0 to 18 carbon atoms which may have a substituent" represented by ^{R 2 is a general formula.} In (1), the same group as the “thio group having 0 to 18 carbon atoms which may have a substituent” represented by ^{R 2} and R ^{3 can be mentioned.}

In the general formula (2), the "amino group having 0 to 20 carbon atoms" in the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by ^{R 2 is a general formula.} In (1), the same as "amino group having 0 to 20 carbon atoms which may have a substituent" represented by ^{R 2} and R ^{3 can be mentioned.}

In the general formula (2), an aromatic hydrocarbon group of the "6-36 carbon atoms in the" aromatic hydrocarbon group with carbon atoms which may 6-36 have a substituent "represented by R ² Is the same as the "aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent" represented by ^{R 1} and R ⁴ in the general formula (1). can.

In the general formula (2), as the "heterocyclic group ring atoms 5 to 36" in "heterocyclic group which may have a substituent ring atoms 5 to 36" represented by R ² Can be the same as the "heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" represented by ^{R 1} and R ⁴ in the general formula (1).

In the general formula (2), "linear or branched alkyl group substituents carbon atoms which may have from 1 to 20" where R ² represented by, have a "substituent A good linear or branched alkenyl group having 2 to 20 carbon atoms "," a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent "," even if it has a substituent " A good linear or branched alkoxy group having 1 to 20 carbon atoms "," a cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent "," even if it has a substituent " A good thio group having 0 to 18 carbon atoms, an amino group having 0 to 20 carbon atoms which may have a substituent, and a 6 to 36 carbon atoms which may have a substituent. As the "substituent" of the "aromatic hydrocarbon group" or the "heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent", in the above general formula (1), R ¹ and R "A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" and "2 to 20 carbon atoms which may have a substituent" represented by ^4. A linear or branched alkenyl group, "a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent", and "a cycloalkyl group having 6 to 36 carbon atoms which may have a substituent". The same as the "substituent" in the "aromatic hydrocarbon group" or the "heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent" can be mentioned.

^{R 2} in the general formula (2) has a hydroxyl group and a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent and may have a substituent. It is preferably a heterocycle having 5 to 10 cycloalkoxy groups or a ring-forming atom number of 5 to 36 which may have a substituent.

^{R 5} in the general formula (2) is preferably an electron-attracting substituent. The electron-attracting substituent is not limited, but
Halogen atom, cyano group, nitro group, nitroso group,
A linear or branched alkyl fluoride group having 1 to 20 carbon atoms, which may have a substituent,
Aryl fluoride group having 6 to 36 carbon atoms, which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
Alternatively, a sulfonyl group having 0 to 20 carbon atoms, which may have a substituent,
And so on.

In the general formula (2), the number "carbon atoms in the represented" linear or branched fluoroalkyl group optionally carbon atoms which may 20 have a substituent "in R ⁵ to 20 The linear or branched alkyl group of the above is a linear alkyl group having 1 to 20 carbon atoms which may have a substituent and is represented by ^{R 5} and R ^{6 in the general formula (1).} Alternatively, the same group as the "branched alkyl fluoride group" can be mentioned.

In the general formula (2), as "fluoroaryl group having a carbon number of 6 to 36," in the "optionally substituted fluoroaryl group having a carbon number of 6 to 36" represented by R ⁵ Can be the same as the "aryl fluoride group having 6 to 36 carbon atoms which may have a substituent" represented by ^{R 5} and R ⁶ in the general formula (1).

In the general formula (2), "acyl group having 1 to 20 carbon atoms" in the "acyl group which has carbon atoms which may 20 have a substituent" represented by R ⁵ has the general formula In (1), the same “acyl groups having 1 to 20 carbon atoms which may have a substituent” represented by ^{R 5} and R ^{6 can be mentioned.}

In the general formula (2), as "sulfonyl group having a carbon number of 0 to 20" in the "sulfonyl group which may carbon atoms 0 to 20 which may have a substituent" represented by R ⁵ has the general formula In (1), the same group as the “sulfonyl group having 0 to 20 carbon atoms which may have a substituent” represented by ^{R 5} and R ^{6 can be mentioned.}

In the general formula (2), "linear or branched fluoroalkyl group optionally having 1 to 10 carbon atoms which may have a substituent" represented by R ^5, have a "substituent It may have an aryl fluoride group having 6 to 36 carbon atoms, an acyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom which may have a substituent. As the "substituent" of the "sulfonyl group of several to 20", in the above general formula (1), the "substituted group may have a substituent having 1 to 20 carbon atoms represented by ^{R 1} and R ^4". "Linear or branched alkyl group", "Linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent", "Carbon which may have a substituent" A cycloalkyl group having 5 to 10 atoms, an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, or a ring-forming atomic group which may have a substituent 5 The same as the "substituent" in "~ 36 heterocyclic groups" can be mentioned.

In the general formula (2), R ⁵ has a cyano group, a linear or branched alkyl fluoride group having 1 to 20 carbon atoms which may have a substituent, or a substituent. It is preferably an aryl fluoride group having 6 to 36 carbon atoms.

Specific examples of the compound of the present invention represented by the general formula (1) are shown below, but the present invention is not limited thereto. In addition, the following exemplified compounds are described by omitting some hydrogen atoms, carbon atoms, etc., and show an example of possible isomers, and include all other isomers. do. Further, it may be a mixture of two or more kinds of isomers.

The perylene derivative compound of the present invention represented by the general formula (1) is J.I. Org. Chem. , 2004,69, P.M. It can be synthesized by a known method such as 7933-7939 (Non-Patent Document 2). The 3,4,9,10-tetracarboxylic acid dianhydride is brominated, reacted with the relevant amines, further substituted with an electron-attracting group at the bromine moiety, and electron-donating to the other bromine moiety. By substituting the group, the perylene derivative represented by the general formula (1) can be obtained. The order of introduction of the substituents of the electron attracting group and the electron donating group is not particularly limited.

The method for purifying the perylene derivative compound represented by the general formula (1) can be carried out by purification by column chromatography, adsorption purification with silica gel, activated charcoal, active white clay or the like, recrystallization or crystallization with a solvent. Alternatively, it is effective to use a compound having an increased purity by using these methods in combination.
In addition, these compounds can be identified by nuclear magnetic resonance spectroscopy (NMR).

In the present invention, the compound represented by the general formula (1) in which ^{at least one of R 2} or R ³ is an electron donating group and at least one of R ⁵ or R ^{6 is an electron attracting group is used as a solvent.} Tends to improve the solubility of. The solubility of the compound represented by the general formula (1) according to the present invention is such that the compound represented by the general formula (1) is weighed in a transparent sample tube, an organic solvent is added, and the temperature is 20 to 60 ° C. After shaking underneath, the mixture is left at room temperature for several hours, and then the solubility (or saturated solubility) is visually evaluated at room temperature (20 to 27 ° C.). The solubility of the examples of the present application was measured in a toluene solvent having a concentration of 0.2% by mass, a chloroform solvent having a concentration of 0.5% by mass, a monochlorobenzene solvent having a concentration of 0.3% by mass, and a 1,2-dichlorobenzene solvent having a concentration of 0. The solubility at 3% by mass is evaluated. The solubility is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass.

The perylene derivative compound of the present invention can be used as an organic semiconductor material. In the present invention, the composition containing the organic semiconductor material and the solvent is referred to as a composition for an organic semiconductor. The composition for an organic semiconductor contains one or more of the compounds represented by the general formula (1), and may optionally contain other compounds not belonging to the present invention. Further, it may be a solution dissolved in a solvent or a dispersion liquid in which the organic semiconductor material is dispersed, and includes a state in which the organic semiconductor material partially remains in the dispersion liquid. The composition for organic semiconductors of the present invention is preferably a solution.

The perylene derivative compound of the present invention described above can be thinned, for example, to form an organic semiconductor layer of an electric field effect transistor, a diode such as a light emitting diode, a photoelectric conversion element, or an organic semiconductor element such as an organic thin-film solar cell. It can be suitably used as a semiconductor material. In the present invention, it is preferable to use it as an organic thin film transistor.

The thin film containing the organic semiconductor material based on the perylene derivative compound of the present invention can be formed by a dry process such as a vacuum vapor deposition method, but a stable and uniform thin film can also be formed by a solution process. The film forming by the solution process in the present invention refers to a method of forming a film using the composition for an organic semiconductor composed of the above organic semiconductor and a solvent. Specifically, coating methods such as drop casting method, dip coating method, die coater method, roll coater method, bar coater method, spin coating method, inkjet method, screen printing method, gravure printing method, flexography printing method, offset Various printing methods such as a printing method and a microcontact printing method, and a method such as the Langmuir-Blodgett (LB) method. A thin film can also be formed by removing the solvent by heating after forming the film as described above. The organic semiconductor thin film of the present invention is preferably formed by a drop casting method, a spin coating method, or an ink jet method.

In the present invention, the solvents used in the composition for organic semiconductors include benzene, toluene, xylene, mesitylene, tetralin (1,2,3,4-tetrahydronaphthalene), monochlorobenzene, o-dichlorobenzene, and m-dichlorobenzene. , P-Dichlorobenzene, nitrobenzene and other aromatic organic solvents; dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, dichloromethane and other halogen-based organic solvents; benzonitrile, acetonitrile and other nitrile-based solvents Ketone solvents such as 2-butanone; ether solvents such as tetrahydrofuran, dioxane, diisopropyl ether, c-propylmethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether; ethyl acetate, propylene glycol monomethyl ether acetate Ester solvents such as: Methanol, isopropanol, n-butanol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, cyclohexanol, 2-n-butoxyethanol and other alcohols. System solvent: Aprotonic polar solvents such as dimethylformamide, dimethylacetamide, and dimethylsulfoxide can be mentioned, but the solvent is not limited thereto. Further, the solvent may be used alone or in combination of two or more, and the solvent to be used can be selected depending on the structure. In particular, it is preferable to use an aromatic organic solvent and a halogen-based organic solvent.

In the present invention, the content of the compound represented by the general formula (1) in the composition for organic semiconductor is not particularly limited, but is preferably 0.01 to 20% by mass, and 0. The concentration is more preferably 02 to 10% by mass.

An organic thin film transistor will be described as an example of the organic semiconductor device of the present invention.
The organic thin film transistor generally includes a substrate, an organic semiconductor layer, a gate electrode laminated on the organic semiconductor layer via a gate insulating layer, and a source electrode and a drain electrode arranged to face each other via the organic semiconductor layer. It is configured with. In the present invention, as the organic semiconductor layer, an organic semiconductor thin film containing the perylene derivative compound represented by the general formula (1) is used. The form of the organic thin film transistor is not particularly limited, and any form of bottom gate / bottom contact type, bottom gate / top contact type, top gate / bottom contact type, and top gate / top contact type may be used. The gate electrode, the gate insulating layer, the source electrode, the drain electrode, and the organic semiconductor layer may be appropriately arranged according to each form.

Drawings will be described for the form of the organic thin film transistor of the present invention.
FIG. 1 is a schematic cross-sectional view showing one form of an organic thin film transistor, which has a bottom gate / bottom contact structure. In the form of this organic thin film transistor, a gate electrode 2 is provided on a substrate 1, a gate insulating film 3 is laminated on the gate electrode, and a source electrode 6 and a drain electrode are formed on the gate electrode 6 at predetermined intervals. 4 is formed, and an organic semiconductor layer 5 is laminated on the organic semiconductor layer 5.

In the element of the organic thin film transistor having the above configuration, the organic semiconductor layer forms a channel region, and the current flowing between the source electrode and the drain electrode is controlled by the voltage of the gate electrode to perform on / off operation.

The mobility is a quantity indicating the ease of movement of electron or hole carriers in the element of the present invention, and the electron mobility is a quantity indicating the ease of movement of electrons in a solid substance. The carrier velocity v in the electric field E is expressed by the following equation (a-1).
v = μE (a-1)
The proportional coefficient μ is the mobility (cm ² / V · s). Since mobility is inversely proportional to resistivity in semiconductors, mobility is an important parameter that determines the electrical properties of a substance.

The organic semiconductor device or the organic thin film transistor of the present invention can evaluate the transfer characteristics by the electron mobility. It is important that the electron mobility is a large value such that a large current can be obtained in an organic thin film transistor. The electron mobility is preferably 0.0001 cm ² / V · s or more.

When the organic semiconductor layer is formed by a solution process in the present invention, the above composition for organic semiconductor is used. After forming the organic semiconductor layer by a solution process, it may be preferable to perform heat treatment on a hot plate, an oven, or the like. The heat treatment temperature is not particularly limited, but is carried out at room temperature (20 to 27 ° C.) to about 200 ° C.

<substrate>
The substrate used for the organic semiconductor element such as the organic thin film of the present invention is not particularly limited, but generally, a plastic substrate such as glass, quartz, silicon, polyimide, polyester, polyethylene, polystyrene, polypropylene and polycarbonate is used. Can be used.

<electrode>
As the material used for the electrode of the organic thin film transistor, any conductive material can be used. A material having a small electron injection barrier into the organic semiconductor material is preferable.

The method for forming each electrode is not particularly limited, but it can be formed by using a dry film forming method such as thin film deposition or sputtering, or a printing method. In the case of dry film forming, photolithography or etching treatment is performed. It can be patterned into a desired shape, and can also be patterned using a metal mask.

The film thicknesses of the source and drain electrodes are not particularly limited, but are preferably set in the range of several nm to several μm. The distance between the source and drain electrodes is preferably set in the range of several hundred nm to several hundred μm.

<Gate electrode>
Materials constituting the gate electrode include, for example, p-doped silicon, n-doped silicon, indium tin oxide (ITO), doped conductive polymers such as polythiophene and polyaniline, gold, silver, platinum, aluminum, and chromium. In the present invention, it is preferable to use aluminum.

<Insulation layer>
Examples of the material constituting the gate insulating layer include inorganic compounds such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, and tantalum oxide, polyvinyl alcohol, polyvinylphenol, polymethylmethacrylate, cyanoethylpurrane, and parylene (Japan Parylene LLC). Organic polymer compounds such as (registered trademark) can be used.

The film thickness of the gate insulating film is not particularly limited, but is preferably set in the range of several nm to several μm.

<Source electrode, drain electrode>
Materials constituting the source electrode and the drain electrode include, for example, gold, silver, platinum, chromium, aluminum, indium, alkali metals (Li, Na, K, Rb, Cs), alkaline earth metals (Mg, Ca, Sr, Ba) and the like. It is preferable to use gold in the present invention.

<Organic semiconductor layer>
The organic thin film transistor of the present invention is formed by containing the compound represented by the general formula (1) in the organic semiconductor layer.
In addition to the perylene derivative compound of the present invention, the organic semiconductor layer contains, for example, fullerene and its derivatives, naphthalene, naphthalenediimide, anthracene, tetracene, perylene, pentacene, and pyrene substituted with electron-withdrawing groups such as fluorine and nitrile. , Coronen, chrysene, decacyclene, biolanthrene and other polycyclic aromatic molecules and their derivatives, triphenylene, thiophene oligomers, polythiophene and other aromatic ring oligomers, polymers and their derivatives, phthalocyanine, tetrathiafluvalene, tetrathiotetracene and their derivatives. An electron-deficient organic semiconductor material such as a derivative may be used in combination in an appropriate amount. Further, an appropriate amount of a polymer material such as polystyrene or polyvinylphenol may be added.

<Sealing>
In the organic thin film transistor of the present invention, a gas barrier layer can be provided on the entire surface or a part of the outer peripheral surface of the organic thin film transistor for the purpose of reducing the influence of oxygen, moisture, etc. in the atmosphere. Examples of the material forming the gas barrier layer include polyvinyl alcohol, ethylene-vinyl alcohol, copolymers, polyvinyl chloride, and polytetrafluoroethylene.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples. The compound obtained in the synthesis example was identified by ¹ H-NMR (1 H-NMR (Nuclear Magnetic Resonance Device manufactured by JEOL Ltd., JNM-ECZ400S / L1 type)).

[Synthesis Example 1] Synthesis of compound (A-2) Synthesis of 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dianhydride was carried out by J. Mol. Org. Chem. , 2004,69, P.M. By the method described in 7933-7939, 20 g of 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dianhydride represented by the following formula (3) was obtained. (Step 1)

1,7-Dibromoperylene-3,4,9,10-tetracarboxylic dianhydride (13.8 g) and heptafluorobutylamine (15.0 g) represented by the above formula (3) are placed in a nitrogen-substituted reaction vessel. , N-Methyl-2-pyrrolidone solution (345 mL) of acetic acid (7.5 g) was stirred at 65 ° C. for 77 hours under a nitrogen stream. The reaction mixture was allowed to cool to room temperature, poured into water (1 L), stirred for 30 minutes, and filtered to obtain a crude product. The crude product is purified by column chromatography (carrier: silica gel, developing solution: toluene), dried under reduced pressure, and represented by the following formula (4): 1,7-dibromoperylene-3,4,9,10- Diimide tetracarboxylic acid (yield: 16.9 g, yield: 74%) was obtained. (Step 2)

The obtained red-purple solid was subjected to NMR analysis, and the following 10 hydrogen signals were detected and identified as a structure represented by the following formula (4).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 4.99-5.06 (4H), 8.76-8.78 (2H), 8.98 (2H), 9.52-9 .54 (2H).

N, N-dimethyl of 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid diimide (1000 mg) and copper cyanide (97 mg) represented by the above formula (4) in an argon-substituted reaction vessel. Formaldehyde solution (50 mL) was stirred at 90 ° C. for 5 hours under an argon stream. The reaction mixture was cooled to room temperature, poured into water (200 mL), stirred for 30 minutes, and filtered to obtain a crude product. The dissolved chloroform is purified by column chromatography (carrier: silica gel, developing solution: chloroform), dried under reduced pressure, and 1-cyano-7-bromoperylene-3,4,9, represented by the following formula (5). Diimide 10-tetracarboxylic acid (yield: 164 mg, yield: 18%) was obtained. (Step 3)

The obtained red-purple solid was subjected to NMR analysis, and the following 10 hydrogen signals were detected and identified as a structure represented by the following formula (5).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 4.99-5.07 (4H), 8.87-8.91 (2H), 8.99 (1H), 9.05 (1H) ), 9.49-9.51 (1H), 9.72-9.75 (1H).

28% in a methanol solution (100 mL) of 1-cyano-7-bromoperylene-3,4,9,10-tetracarboxylic acid diimide (137 mg) represented by the above formula (5) in an argon-substituted reaction vessel. After dropping the NaOMe / MeOH solution (1000 mg), the mixture was stirred at room temperature for 6 hours. 1N Hydrochloric acid (50 mL) was added to the reaction mixture, the mixture was stirred for 30 minutes, and then filtered to obtain a crude product. The crude product is dissolved in chloroform, purified by column chromatography (carrier: silica gel, developing solution: toluene), dried under reduced pressure, and the target compound, 1-cyano-7-methoxy-3,4,9,10. -Tetracarboxylic acid diimide (yield: 53 mg, yield: 41%) was obtained as a magenta solid. (Step 4)

The obtained red-purple solid was subjected to NMR analysis to detect the following 13 hydrogen signals, and identified as a structure represented by the following formula (A-2).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 4.40 (3H), 4.99-5.07 (4H), 8.62 (1H), 8.75-8.77 (1H) ), 8.85-8.87 (1H), 8.96 (1H), 9.60-9.66 (2H).

[Synthesis Example 2] Synthesis of compound (A-3) 1-cyano-7-bromoperylene-3,4,9,10-tetracarboxylic acid represented by the above formula (5) is placed in an argon-substituted reaction vessel. A toluene solution (60 mL) of diimide (300 mL), phenol (50 mg), 18-Crown-6-Ether (555 mg) and potassium carbonate (145 mg) was stirred at room temperature for 2 hours under an argon stream. The reaction solution was concentrated to obtain a crude product. The crude product was washed with water (20 mL) and then with methanol (20 mL). The crude product after washing was dissolved in chloroform, purified by column chromatography (carrier: silica gel, developing solution: chloroform), and dried under reduced pressure. Toluene (20 mL) was added to the obtained purified product, and heating / reflux stirring was carried out for 1 hour. After dissolution, the mixture was cooled to room temperature, stirred for 1 hour, and the precipitated solid was filtered. The sample was dried under reduced pressure to obtain the target compound 1-cyano-7-phenoxy-3,4,9,10-tetracarboxylic dianimide (yield: 67 mg, yield: 21%) as a purplish red solid. rice field.

The obtained red-purple solid was subjected to NMR analysis to detect the following 15 hydrogen signals and identified as a structure represented by the following formula (A-3).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 4.93-5.06 (4H), 7.20-7.25 (2H), 7.35-7.38 (1H), 7 .51-7.55 (2H), 8.36 (1H), 8.77-8.89 (2H), 8.99 (1H), 9.65-9.70 (2H).

[Synthesis Example 3] Synthesis of compound (6) Diimide 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid diimide (912 mg) represented by the above formula (5) was placed in an argon-substituted reaction vessel. , Copper iodide (38 mg), 1,10-phenanthroline hydrate (39 mg), potassium trimethoxy (trifluoromethyl) borate (222 mg) in a dimethylsulfoxide solution (10 mL) was stirred at 60 ° C. for 7 hours under an argon stream. bottom. The reaction mixture was cooled to room temperature, poured into ethyl acetate (200 mL), stirred for 30 minutes, and filtered to remove insoluble matter. The obtained filtrate was washed twice with water (150 mL) and once with saturated brine (150 mL), and the organic layer was concentrated to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, developing solution: hexane / ethyl acetate), dried under reduced pressure, and 1-bromo-7-trifluoromethyl-3, represented by the following formula (6). Diimide 4,9,10-tetracarboxylic acid (yield: 450 mg, yield: 50%) was obtained.

The obtained red-purple solid was subjected to NMR analysis, and the following 10 hydrogen signals were detected and identified as a structure represented by the following formula (6).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 5.04-5.09 (4H), 8.61-8.63 (2H), 8.87-8.88 (2H), 8 .99 (1H), 9.15 (1H).

[Synthesis Example 4] Synthesis of compound (A-9) 1-trifluoromethyl-7-bromoperylene-3,4,9,10-tetra represented by the above formula (6) is placed in an argon-substituted reaction vessel. A 28% NaOMe / MeOH solution (2000 mg) was added dropwise to a methanol solution (100 mL) of diimide carboxylate (450 mg), and the mixture was stirred at room temperature for 6 hours. 1N Hydrochloric acid (50 mL) was added to the reaction mixture, the mixture was stirred for 30 minutes, and then filtered to obtain a crude product. The crude product is dissolved in chloroform, purified by column chromatography (carrier: silica gel, developing solution: toluene), dried under reduced pressure, and the target compound, 1-cyano-7-methoxy-3,4,9,10. -Diimide tetracarboxylic acid (yield: 170 mg, yield: 40%) was obtained as a magenta solid.

The obtained red-purple solid was subjected to NMR analysis to detect the following 13 hydrogen signals, and identified as a structure represented by the following formula (A-9).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 4.40 (3H), 5.04-5.09 (4H), 8.61-8.63 (2H), 8.87-8 .88 (2H), 8.50 (1H), 9.15 (1H).

[Comparative Compound] Synthesis of Compound (B-1) Angew. Chem. Int. Ed. By the method described in 2004,43,6363-6366, 1,7-dicyanoperylene-3,4,9,10-tetracarboxylic dianimide represented by the following formula (B-1) was obtained.

Experiment number EC234
[Comparative Compound] Synthesis of Compound (B-2) In an argon-substituted reaction vessel, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid diimide (912 mg) represented by the above formula (4), A dimethylsulfoxide solution (10 mL) of copper iodide (76 mg), 1,10-phenanthroline hydrate (79 mg) and potassium trimethoxy (trifluoromethyl) borate (1270 mg) was stirred at 60 ° C. for 7 hours under an argon stream. .. The reaction mixture was cooled to room temperature, poured into ethyl acetate (200 mL), stirred for 30 minutes, and filtered to remove insoluble matter. The obtained filtrate was washed twice with water (150 mL) and once with saturated brine (150 mL), and the organic layer was concentrated to obtain a crude product. The crude product is purified by column chromatography (carrier: silica gel, developing solution: hexane / ethyl acetate), then column chromatography (carrier: silica gel, developing solution: toluene) is performed again to purify, and then dried under reduced pressure. Diimide 1,7-ditrifluoromethylperylene-3,4,9,10-tetracarboxylic acid represented by (5) (yield: 180 mg, yield: 20%) was obtained.

The obtained red-purple solid was subjected to NMR analysis, and the following 10 hydrogen signals were detected and identified as a structure represented by the following formula (B-2).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 5.04-5.09 (4H), 8.61-8.63 (2H), 8.87-8.88 (2H), 9 .13 (2H).

[Example 1] Solubility measurement of (A-2) Compound (A-2) was weighed in a transparent sample tube, added to toluene so that the concentration was 0.2% by mass, and heated to 50 ° C. under heating. After shaking, the mixture was cooled to room temperature (25 ± 2 ° C.), and after several hours, the solubility was visually evaluated. Similarly, evaluation was made with 0.5% by mass of chloroform, 0.3% by mass of monochlorobenzene, and 0.3% by mass of 1,2-dichlorobenzene. The results are shown in Table 1. As the judgment conditions, complete dissolution (25 ± 2 ° C.) was indicated by ◯, precipitation (25 ± 2 ° C.) to the extent of turbidity was indicated by Δ, and insoluble or all precipitation after cooling to room temperature (25 ± 2 ° C.) was indicated by ×.

[Example 2] Measurement of solubility of (A-3) Solubility was measured in the same manner as in Example 1 using (A-3) instead of compound (A-2). The results are shown in Table 1.

[Comparative Example 1]
The solubility was measured in the same manner as in Example 1 using the comparative compound (B-1) instead of the compound (A-2). The results are shown in Table 1.

From Table 1, it is clear that the compounds represented by Examples have more solubility than Comparative Examples with respect to the solvent used in the organic semiconductor composition.

[Example 3] Measurement of transfer characteristics of organic thin film The glass substrate is ultrasonically washed with a neutral detergent for 10 minutes, water for 10 minutes, acetone for 10 minutes, and isopropyl alcohol for 10 minutes, and then in an oven at 100 ° C. Was dried for 1 hour. Aluminum to be a gate electrode was deposited on the surface of the substrate to a thickness of 50 nm using a metal mask. Then, a mixed solution of polyvinylphenol and melamine was applied by a spin coating method, and heated on a hot plate at 100 ° C. for 10 minutes and at 150 ° C. for 1 hour to form an insulating layer to a thickness of 400 nm. Subsequently, gold to be a source and drain electrodes was deposited on the insulating layer to a thickness of 50 nm, and a source and drain electrodes having a channel width of 500 μm and a channel length of 5 μm were formed by a photolithography method.

Tetralin was added to compound (A-2) so as to have a concentration of 0.1% by mass to prepare an organic semiconductor solution. After UV ozone treatment was performed on the substrate for 7 minutes, an organic semiconductor solution was applied onto the channel by a drop casting method and heated on a hot plate at 150 ° C. for 10 minutes to form an organic semiconductor layer.

The prepared organic thin film transistor was measured for transmission characteristics of the organic thin film transistor using a semiconductor analyzer (manufactured by Keithley, 4200-SCS type) in a gate voltage range of -40V to 80V under light shielding in the atmosphere.

From the measured values, the mobility μ (cm ² / Vs) was calculated using the following formulas (a-2) and (a-3). Table 2 shows the results of mobility obtained from this measurement.

ｄ_ｏｘ＝絶縁膜の厚さ
ε_ｏｘ＝真空の誘電率、ε_０＝絶縁膜の誘電率
Ｗ＝チャネル幅、Ｌ＝チャネル長
Ｉｄ＝ドレイン電流、Ｖｇ＝ゲート電圧

d _ox = Insulating film thickness ε _ox = Vacuum permittivity, ε ₀ = Insulating film permittivity W = Channel width, L = Channel length Id = Drain current, Vg = Gate voltage

[Example 4] Measurement of transfer characteristics of organic thin film transistor Example 3 except that compound (A-3) was used instead of compound (A-2) and dissolved in chloroform so as to have a concentration of 0.1% by mass. The transfer characteristics of the organic thin film transistor prepared in the same manner as above were measured. Table 2 shows the results of mobility obtained from this measurement.

[Comparative Example 2]
As the compound, (B-2) which does not belong to the present invention was used instead of (A-2), and the organic compound was prepared in the same manner as in Example 10 except that it was dissolved in toluene so as to have a concentration of 0.1% by mass. The transfer characteristics of the thin film transistor were measured. Table 2 shows the results of mobility obtained from this measurement.

From Table 2, it is clear that the organic thin film transistor using the compound represented by the examples in the organic semiconductor layer has higher electron mobility than that of the comparative example.

The perylene derivative compound according to the present invention can provide an n-type organic semiconductor material having solubility corresponding to a solution process. Further, by using a composition for an organic semiconductor containing the organic semiconductor material, it is possible to provide an organic thin film transistor having excellent electron transportability.

1: Substrate 2: Gate electrode 3: Gate insulating layer 4: Drain electrode 5: Organic semiconductor layer 6: Source electrode

Claims (9)

A perylene derivative compound represented by the following general formula (1).

[In the formula, R ¹ and R ⁴ are the same,
Hydrogen atom, halogen atom,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have a substituent,
Alternatively, it represents a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent.
R ² and R ³ may be the same or different
Hydrogen atom, hydroxyl group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms, which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkoxy group having 5 to 10 carbon atoms, which may have a substituent,
A thio group having 0 to 18 carbon atoms which may have a substituent,
An amino group having 0 to 20 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have a substituent,
Alternatively, it represents a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent.
R ⁵ and R ⁶ may be the same or different.
Hydrogen atom, halogen atom, cyano group, nitro group, nitroso group,
A linear or branched alkyl fluoride group having 1 to 20 carbon atoms, which may have a substituent,
Aryl fluoride group having 6 to 36 carbon atoms, which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
Alternatively, it represents a sulfonyl group having 0 to 20 carbon atoms which may have a substituent.
R ² and R ³ and R ⁵ and R ⁶ may be coupled to each other to form a ring. ] The perylene derivative compound according to claim 1, which is represented by the following general formula (2).

[In the formula, R ¹ and R ⁴ are the same,
Hydrogen atom, halogen atom,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have a substituent,
Alternatively, it represents a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent.
R ² is a hydroxyl group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 5 to 10 carbon atoms, which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkoxy group having 5 to 10 carbon atoms, which may have a substituent,
A thio group having 0 to 18 carbon atoms which may have a substituent,
An amino group having 0 to 20 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have a substituent,
Alternatively, it represents a heterocyclic group having 5 to 36 ring-forming atoms which may have a substituent.
R ⁵ is a halogen atom, a cyano group, a nitro group, a nitroso group,
A linear or branched alkyl fluoride group having 1 to 20 carbon atoms, which may have a substituent,
Aryl fluoride group having 6 to 36 carbon atoms, which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
Alternatively, it represents a sulfonyl group having 0 to 20 carbon atoms which may have a substituent. ] The perylene derivative compound according to claim 1 or 2, wherein in the general formula (1), ^{at least one of the substituents of R 1} and R ^{4 is a fluorine atom.} In the general formula (1), ^{at least one of R 2} and R ³ may have a hydroxyl group or a substituent as a linear or branched alkoxy group having 1 to 20 carbon atoms, or a substituent. The perylene derivative compound according to claim 1 to 3, which is a thio group having 0 to 18 carbon atoms which may have. In the general formula (1), ^{at least one of R 5} and R ^{6 is} a linear or branched alkyl fluoride group having 1 to 20 carbon atoms which may have a cyano group or a substituent. The perylene derivative compound according to any one of claims 1 to 4. The perylene derivative compound according to any one of claims 1 to 5, wherein the solubility in an aromatic organic solvent or a halogen-based organic solvent at 25 ± 2 ° C. is 0.02 to 5% by mass. A composition for an organic semiconductor containing the perylene derivative compound according to any one of claims 1 to 6. An organic semiconductor device using the composition for organic semiconductor according to claim 7. An organic thin film transistor using the organic semiconductor device according to claim 8.

Images