JPWO2015087875A1 - Novel condensed polycyclic aromatic compounds and uses thereof - Google Patents

Abstract

A novel compound, an organic semiconductor material containing the compound, a composition for forming a thin film, a thin film, and an organic semiconductor device are provided. A condensed polycyclic aromatic compound represented by the following general formula (1). In general formula (1), A represents any one of the following general formulas (2) to (4). R1 to R4 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, substituted or unsubstituted Represents a hydrocarbon oxy group, a substituted or unsubstituted hydrocarbon oxycarbonyl group, a substituted or unsubstituted acyl group, or a cyano group, wherein R5 and R6 are each independently a substituted or unsubstituted chain hydrocarbon group. Represents a substituted or unsubstituted hydrocarbon oxy group. X1 and X2 each independently represent an oxygen atom, a sulfur atom or a selenium atom. * 1 is a bond to X1, * 2 is a bond to X2, * 3 is a bond to a carbon atom bonded to R1, and * 4 is a carbon atom bonded to R2. Represents a bond. [Chemical 1] [Chemical 2]

Description

  The present invention relates to a novel condensed polycyclic aromatic compound, an organic semiconductor material containing the same, a composition for forming a thin film, a thin film, an organic semiconductor device, and a method for producing the condensed polycyclic aromatic compound and the organic semiconductor device. is there.

  In recent years, organic semiconductor devices such as organic EL devices, organic transistors, and organic thin film photoelectric conversion devices using organic semiconductor materials have attracted attention and have been put into practical use. Among the basic physical properties of these organic semiconductor devices, carrier mobility is important. For example, in an organic EL device, it is necessary to increase charge transport efficiency for light emission with high efficiency and driving with low voltage, and carrier mobility becomes important. In the organic transistor, the carrier mobility and the on / off ratio that directly affect the switching speed and the performance of the driven device are important.

  Conventionally, in organic semiconductor materials, similarly to inorganic semiconductor materials, p-type (hole transport) organic semiconductor materials (hereinafter referred to as “p-type materials”) and n-type (electron transport) organic semiconductor materials (hereinafter referred to as “n-type”). Material)). For example, in order to produce a logic circuit such as a CMOS (complementary metal oxide semiconductor), a p-type material and an n-type material are required.

  So far, much research has been done on p-type materials, and many reports on materials that can realize high-performance organic semiconductor devices have been made. On the other hand, research on n-type materials has not progressed so much. There are limited n-type materials that can realize high performance organic semiconductor devices.

For example, Patent Documents 1 and 2 and Non-Patent Documents 1 and 2 disclose compounds having a quinoid structure such as oligothiophenquinoid and benzodithiophenquinoid as compounds that can be used as n-type materials. The organic transistors manufactured using the compounds disclosed in Patent Documents 1 and 2 and Non-Patent Documents 1 and 2 are 2.87 × 10 ⁻ in a state where annealing treatment for improving carrier mobility is not performed. ^{7 to} 6.3 × 10 ⁻³ cm ² V ⁻¹ s ⁻¹ (in paragraph [0192] of Patent Document 1, paragraphs [0280] to [0303] of Patent Document 2, and Non-Patent Document 1) (See p4185, right column, lines 10-18, and Non-Patent Document 2, p568, left column, lines 1-5).

International Publication No. 2008-032715 JP 2009-242339 A

J. et al. Am. Chem. Soc. 2002, 124, 4184-4185. Chem. Lett. , 2009, 38, 568-569.

  In organic semiconductor devices, since carrier mobility is important as described above, new compounds that can be used as n-type materials are being developed for the purpose of improving carrier mobility in organic semiconductor devices. .

  The present invention has been made in view of such circumstances, and provides a novel compound that can be used as an n-type material, an organic semiconductor material containing the compound, a composition for forming a thin film, a thin film, and an organic semiconductor device. For the purpose. Another object of the present invention is to provide a method for producing a novel compound that can be used as an n-type material, and a method for producing an organic semiconductor device containing the compound.

  In order to solve the above-mentioned problems, the present inventor has developed a novel condensed polycyclic aromatic compound, studied its applicability as an organic semiconductor material (n-type material), and completed the present invention. It was.

  That is, the condensed polycyclic aromatic compound of the present invention has the general formula (1)

Wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocycle Represents a group, a substituted or unsubstituted hydrocarbon oxy group, a substituted or unsubstituted hydrocarbon oxycarbonyl group, a substituted or unsubstituted acyl group, or a cyano group, and R ₅ and R ₆ are each independently substituted or unsubstituted Represents an unsubstituted chain hydrocarbon group, a substituted or unsubstituted hydrocarbon oxy group, X ₁ and X ₂ each independently represent an oxygen atom, a sulfur atom or a selenium atom, wherein A represents a general formula ( 2) to (4)

R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon. Represents a group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hydrocarbonoxy group, a substituted or unsubstituted hydrocarbonoxycarbonyl group, a substituted or unsubstituted acyl group, or a cyano group, * 1 represents X ₁ represents a bond to X ₂ , * 2 represents a bond to X ₂ , * 3 represents a bond to a carbon atom bonded to R ₁ , and * 4 represents a carbon bonded to R _2. Represents a bond with an atom. ).

  This condensed polycyclic aromatic compound is a novel compound, and since the condensed polycyclic aromatic compound has a polar structure due to a cyano group that attracts electrons, an n-type organic semiconductor in which electrons function as carriers in organic semiconductor devices It is possible to use this material (n-type material). Moreover, the condensed polycyclic aromatic compound of this invention can improve the carrier mobility in an organic-semiconductor device by utilizing for the organic-semiconductor material of an organic-semiconductor device.

  Moreover, the manufacturing method of the condensed polycyclic aromatic compound of this invention is a manufacturing method of the condensed polycyclic aromatic compound represented by the said General formula (1), Comprising: General formula (5)

(In the formula, Y ₁ represents a halogen atom, and R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group. Represents a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hydrocarbonoxy group, a substituted or unsubstituted hydrocarbonoxycarbonyl group, a substituted or unsubstituted acyl group, or a cyano group, and X ₁ and X ₂ each independently represents an oxygen atom, a sulfur atom or a selenium atom, wherein a represents the following general formulas (6) to (8):

R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon. Represents a group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hydrocarbon oxy group, a substituted or unsubstituted hydrocarbon oxycarbonyl group, a substituted or unsubstituted acyl group, or a cyano group, * 1 Represents a bond to X ₁ , * 2 represents a bond to X ₂ , * 3 represents a bond to a carbon atom bonded to R ₁ , and * 4 is bonded to R ₂ Represents a bond with a carbon atom. And a compound represented by the general formula (9)

(Wherein R ₇ represents a substituted or unsubstituted chain hydrocarbon group, or a substituted or unsubstituted hydrocarbon oxy group), and a step of reacting with the compound.

  According to this production method, a novel condensed polycyclic aromatic compound can be produced. In addition, since the condensed polycyclic aromatic compound produced by this production method has a polar structure due to a cyano group that attracts electrons, in an organic semiconductor device, an n-type organic semiconductor material (n-type material) in which electrons act as carriers ) Can be used. Moreover, the condensed polycyclic aromatic compound manufactured by this manufacturing method can improve the carrier mobility in an organic semiconductor device by being utilized for the organic semiconductor material of an organic semiconductor device.

  The organic semiconductor material of the present invention is characterized by containing the above-mentioned condensed polycyclic aromatic compound of the present invention.

  Since this organic semiconductor material contains the condensed polycyclic aromatic compound of the present invention, the carrier mobility in the organic semiconductor device can be improved by being used in the organic semiconductor device.

  Moreover, the composition for thin film formation of this invention is characterized by including the above-mentioned condensed polycyclic aromatic compound of this invention, and a solvent.

  Since this thin film-forming composition contains the above-mentioned condensed polycyclic aromatic compound of the present invention, the thin film formed using this thin film-forming composition is a thin film constituting a semiconductor layer in an organic semiconductor device. Is available.

  Moreover, the thin film of this invention is characterized by including the condensed polycyclic aromatic compound of this invention mentioned above.

  Since this thin film contains the above-mentioned condensed polycyclic aromatic compound of the present invention, it can be used as a thin film constituting a semiconductor layer in an organic semiconductor device.

  The organic semiconductor device of the present invention includes the above-described thin film of the present invention.

  According to this organic semiconductor device, since it includes the above-described thin film of the present invention and the above-described condensed polycyclic aromatic compound of the present invention, carrier mobility is improved.

  The organic transistor of the present invention includes the above-described thin film of the present invention.

  According to this organic transistor, since it includes the above-described thin film of the present invention and the above-described condensed polycyclic aromatic compound of the present invention, carrier mobility is improved.

  Moreover, the manufacturing method of an organic semiconductor device includes the process of apply | coating the above-mentioned composition for thin film formation of this invention on the surface which forms a thin film.

  According to this manufacturing method, the carrier mobility of an organic semiconductor device can be improved by using the thin film-forming composition of the present invention containing the above-described condensed polycyclic aromatic compound of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the novel compound which can be utilized as n-type material, the organic-semiconductor material containing this compound, the composition for thin film formation, a thin film, and an organic-semiconductor device can be provided. Moreover, according to this invention, the manufacturing method of the novel compound which can be utilized as n-type material, and the manufacturing method of the organic-semiconductor device containing this compound can be provided.

It is a schematic sectional drawing which shows some examples of the organic transistor of this invention, (a) is a schematic sectional drawing which shows the example of an aspect of a bottom contact-bottom gate type organic transistor, (b) is a top contact-bottom. It is a schematic sectional drawing which shows the example of an aspect of a gate type organic transistor, (c) is a schematic sectional drawing which shows the example of an aspect of a top contact-top gate type organic transistor, (d) is a top & bottom contact-bottom gate type It is a schematic sectional drawing which shows the example of an aspect of an organic transistor, (e) is a schematic sectional drawing which shows the example of an aspect of an electrostatic induction transistor, (f) is a cross section which shows the example of an aspect of a bottom contact-top gate type organic transistor FIG. It is explanatory drawing for demonstrating the manufacturing method of the top contact-bottom gate type organic transistor as one example of the organic transistor of this invention, (a)-(f) is a schematic cross section which shows each process of the said manufacturing method FIG. It is a schematic sectional drawing which shows an example of the structure of the organic solar cell device as one aspect | mode of the organic-semiconductor device of this invention. It is a figure which shows the electronic absorption spectrum of the condensed polycyclic aromatic compound (compound 112) obtained in Example 1 of this invention. It is a figure which shows the cyclic voltammogram of the condensed polycyclic aromatic compound (compound 112) obtained in Example 1 of this invention.

  The present invention is described in detail below.

[Condensed polycyclic aromatic compound represented by general formula (1)]
The condensed polycyclic aromatic compound represented by the following general formula (1) will be described.

In the general formula (1), R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a hydrocarbon oxy group, or a hydrocarbon oxycarbonyl group. Represents an acyl group or a cyano group, and is preferably a hydrogen atom. R ₅ and R ₆ each independently represent a chain hydrocarbon group or a hydrocarbon oxy group, and a hydrocarbon group or hydrocarbon having a linear or branched alkyl group having 1 to 30 carbon atoms. It is preferably an oxy group, and among these, a linear hydrocarbon oxy group having 4 to 10 carbon atoms is particularly preferable. The aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, hydrocarbon oxy group, hydrocarbon oxycarbonyl group, acyl group, and chain hydrocarbon group may be substituted or unsubstituted. There may be. The substitution position, the number of substitutions, and the type of the substituent are not particularly limited, and when two or more substituents are present, two or more kinds of substituents can be mixed. Examples of the substituent include a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a hydrocarbon oxy group, a hydrocarbon oxycarbonyl group, an acyl group, or a cyano group. X < ₁ > -X < ₂ > represents an oxygen atom, a sulfur atom, or a selenium atom each independently.

  In the general formula (1), A is a group represented by any one of the following general formulas (2) to (4).

In the general formulas (2) to (4), R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, or a hydrocarbon oxy group. Represents a hydrocarbon oxycarbonyl group, an acyl group, or a cyano group, and is preferably a halogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, and of these, a chlorine atom or a carbon number A straight chain alkyl group of 6 to 14 is particularly preferable. The aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, hydrocarbon oxy group, hydrocarbon oxycarbonyl group, and acyl group may be substituted or unsubstituted, respectively. The substitution position, the number of substitutions, and the type of the substituent are not particularly limited, and when two or more substituents are present, two or more kinds of substituents can be mixed. Examples of the substituent include a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a hydrocarbon oxy group, a hydrocarbon oxycarbonyl group, an acyl group, or a cyano group. Similarly, the general formula (2) to (4), * 1 represents a bond to _{X 1,} * 2 denotes a bond to _{X 2,} * 3 is carbon atom bonded to _{R 1} * 4 represents a bond with a carbon atom bonded to R ₂ .

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The aliphatic hydrocarbon group is roughly classified into a chain hydrocarbon group that is a linear or branched aliphatic hydrocarbon group and an alicyclic hydrocarbon group that is a cyclic aliphatic hydrocarbon group.

  Examples of the chain hydrocarbon group include a saturated or unsaturated linear or branched aliphatic hydrocarbon group, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and 4 to 18 carbon atoms. Further preferred. Here, specific examples of the chain hydrocarbon group include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group, allyl group, t-butyl group, and n-pentyl group. N-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-cetyl group, n-heptadecyl group, n-butenyl group, 2-ethyl to Xyl group, 3-ethylheptyl group, 4-ethyloctyl group, 2-butyloctyl group, 3-butylnonyl group, 4-butyldecyl group, 2-hexyldecyl group, 3-octylundecyl group, 4-octyldodecyl group, A 2-octyldodecyl group, a 2-decyltetradecyl group, etc. are mentioned. Among these, a saturated linear or branched aliphatic hydrocarbon group (that is, an alkyl group) is preferable, and n-octyl group, n-decyl group, n-dodecyl group, n-cetyl group, and 2-ethyl group. A xyl group, a 2-butyloctyl group, and a 2-hexyldecyl group are particularly preferable.

  Examples of the alicyclic hydrocarbon group include saturated or unsaturated cyclic aliphatic hydrocarbon groups. Specific examples of the alicyclic hydrocarbon group include a cyclohexyl group, a cyclopentyl group, an adamantyl group, and a norbornyl group. And a cyclic hydrocarbon group having 3 to 12 carbon atoms such as.

  Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a benzopyrenyl group. Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group is particularly preferable.

  Examples of the heterocyclic group include non-condensed heteroaromatic groups such as pyridyl group, pyrazyl group, pyrimidyl group, pyrrolyl group, imidazolyl group, thienyl group, furyl group, pyridonyl group; quinolyl group, isoquinolyl group, indolenyl group, Examples thereof include a condensed heteroaromatic group such as a carbazolyl group, a benzoquinolyl group, an anthraquinolyl group, a benzothienyl group and a benzofuryl group; a pyranyl group and the like. Among these, a pyridyl group and a thienyl group are preferable, and a thienyl group is particularly preferable.

  Examples of the hydrocarbon oxy group include hydrocarbon oxy groups including the chain hydrocarbon group.

  Examples of the hydrocarbon oxycarbonyl group and acyl group include a hydrocarbon oxycarbonyl group containing the chain hydrocarbon group and an acyl group containing the chain hydrocarbon group.

The X ₁ to X ₂ is independently oxygen atom, a sulfur atom or a selenium atom, a sulfur atom are preferred.

In the general formulas (2) to (4), R ₃ and R ₄ are introduced one by one. In the general formulas (2) to (4), the site where R ₃ and R ₄ are introduced is not particularly limited. Specifically, in the above general formula (2), the introduction site of R ₃ may be any of the positions corresponding to the 7-position and the 8-position of the naphthalene skeleton, and the introduction site of R ₄ is the naphthalene skeleton Any of the positions corresponding to the third and fourth positions may be used. In the general formula (3), the introduction site of R ₃ may be any of the positions corresponding to the 5-position and the 6-position of the naphthalene skeleton, and the introduction site of R ₄ may be the 1-position of the naphthalene skeleton and Any of the positions corresponding to the second position may be used. In the general formula (4), the introduction site of R ₃ may be any of the positions corresponding to the 5th and 8th positions of the naphthalene skeleton, and the introduction site of R ₄ is the 1st position of the naphthalene skeleton and Any of the positions corresponding to the fourth position may be used.

[Method for Producing Condensed Polycyclic Aromatic Compound Represented by General Formula (1)]
As shown in the following scheme, the condensed polycyclic aromatic compound represented by the general formula (1) is a reaction of the compound represented by the general formula (5) and the compound represented by the general formula (9). can get. Therefore, the manufacturing method of the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention reacts the compound represented by the general formula (5) with the compound represented by the general formula (9). Process.

_X 1 in the general formula _(5), X 2, _{R 1,} and _{R 2} each are the same as _{X 1,} X 2, _{R 1} and _{R 2} in the above general formula (1). R ₇ represents a chain hydrocarbon group or a hydrocarbon oxy group, and is preferably a hydrocarbon group or a hydrocarbon oxy group having a linear or branched alkyl group having 1 to 30 carbon atoms, and of these, carbon A linear hydrocarbon oxy group having a number of 4 to 10 is particularly preferred. Y ₁ in the general formula (5) represents a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a bromine atom and an iodine atom are preferable.

  Moreover, a in General formula (5) is group represented by either of following General formula (6)-(8).

_R 3, _{R 4} in the general formula (6) to (8), and * 1 * 4, respectively, the general formula (2) - (4) _R 3 in, _{R 4,} and * 1 * The same as 4.

In the general formulas (6) to (8), R ₃ and R ₄ are introduced one by one. In the general formulas (6) to (8), the site where R ₃ and R ₄ are introduced is not particularly limited. Specifically, in the above general formula (6), the introduction site of R ₃ may be any of the positions corresponding to the 7-position and the 8-position of the naphthalene skeleton, and the introduction site of R ₄ is the naphthalene skeleton Any of the positions corresponding to the third and fourth positions may be used. In the general formula (7), the introduction site of R ₃ may be any of the positions corresponding to the 5th and 6th positions of the naphthalene skeleton, and the introduction site of R ₄ is the 1st position of the naphthalene skeleton and Any of the positions corresponding to the second position may be used. In the general formula (8), the introduction site of R ₃ may be any of the positions corresponding to the 5th and 8th positions of the naphthalene skeleton, and the introduction site of R ₄ is the 1st position of the naphthalene skeleton and Any of the positions corresponding to the fourth position may be used.

In the general formula (9), R ₇ represents a substituted or unsubstituted chain hydrocarbon group or a substituted or unsubstituted hydrocarbon oxy group. The chain hydrocarbon group and hydrocarbon oxy group are the same as described above.

  The condensed polycyclic aromatic compound represented by the general formula (1) of the present invention is described, for example, in J. Org. Am. Chem. Soc. , 2010, 132, 10453. It can be synthesized by applying the method described in 1. Specifically, by reacting the compound represented by the general formula (5) with a compound represented by the general formula (9) in the presence of a base in a solvent or in the absence of a solvent, a general formula is obtained. A compound represented by the formula (1) (condensed polycyclic aromatic compound) is obtained. When a compound represented by general formula (6) is used as the compound represented by general formula (5), A is represented by general formula (1) represented by general formula (2). When a compound represented by the general formula (7) is used as the compound represented by the general formula (5), A is represented by the general formula (3). When a compound represented by the general formula (1) is obtained and a compound represented by the general formula (8) is used as the compound represented by the general formula (5), A is represented by the general formula ( The compound represented by the general formula (1) represented by 4) is obtained.

Palladium-based catalysts such as PdCl ₂ (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ , Pd (OAc) ₂ , PdCl ₂ may be used as the catalyst used for the production of the compound represented by the general formula (1). preferable. The amount of the catalyst used is not particularly limited, but is 0.001 to 1 mol, preferably 0.01 to 0.5 mol, relative to 1 mol of the compound represented by the general formula (2). More preferably, it is 0.05-0.3 mol. Also, for example, triphenylphosphine, 1,1′-bis (diphenylphosphino) ferrocene (dppf), 1,2-bis (diphenylphosphino) ethane (dppe), 1,3-bis (diphenylphosphino) propane A phosphine-based ligand such as (dppp) can also be used as the catalyst.

  Examples of the base used for the production of the compound represented by the general formula (1) include inorganic bases such as potassium carbonate, sodium carbonate, potassium hydride and sodium hydride, preferably sodium hydride. The amount of the base used is not particularly limited, but may be a necessary amount for the reaction, preferably 0.1 to 100 mol, preferably 1 to 100 mol, relative to 1 mol of the compound represented by the general formula (5). Is 0.5 to 50 mol, more preferably 1 to 10 mol.

  In the production of the compound represented by the general formula (1), the reaction between the compound represented by the general formula (5) and the compound represented by the general formula (9) may be performed in a solvent, You may carry out in a solvent-free. As the reaction solvent when the above reaction is carried out in a solvent, ether solvents such as diethyl ether, anisole and tetrahydrofuran (THF); amide solvents such as dimethylacetamide and dimethylformamide; acetonitrile, propionitrile, benzonitrile and the like Nitrile solvents; alcohol solvents such as methanol, ethanol, butanol and the like. As the reaction solvent, ether solvents are preferable, and tetrahydrofuran is more preferable. The amount of the solvent used is not particularly limited, but is about 0 to 10,000 mol with respect to 1 mol of the compound represented by the general formula (5).

  As temperature (reaction temperature) at the time of making the compound represented by General formula (5) and the compound represented by General formula (9) react, -50 degreeC-300 degreeC is preferable. Within this range, the reaction temperature may be changed as necessary, more preferably from 0 ° C to 250 ° C, and even more preferably from 10 ° C to 200 ° C.

  Moreover, as for the time (reaction time) with which the compound represented by General formula (5) and the compound represented by General formula (9) are made to react, 10 minutes-1000 hours are preferable. The reaction is preferably completed in a short time, and the reaction time is more preferably 30 minutes to 100 hours, further preferably 30 minutes to 24 hours. Moreover, it is preferable to adjust the reaction temperature, the amount of the catalyst, the base, and the solvent used so that the reaction is completed in a short time.

  After reacting the compound represented by the general formula (5) with the compound represented by the general formula (9), if necessary, from the reaction mixture obtained by the above reaction by a known isolation and purification method. The target product (that is, the condensed polycyclic aromatic compound represented by the general formula (1)) may be isolated and purified. When the target product is used as an organic semiconductor, the target product is often required to have high purity. Therefore, purification is performed by using known methods such as recrystallization, column chromatography, and vacuum sublimation purification. It is preferable. Moreover, you may refine | purify combining these methods as needed.

  A conventionally well-known method can be used as a manufacturing method of the compound (heterocyclic compound) represented by the said General formula (5).

  That is, for example, a compound represented by the following general formula (10) is converted to Chem. Rev. , 2010, 110, 890. The compound represented by the general formula (5) can be produced by halogenation by the method described in 1. In addition, the compound represented by General formula (10) is Org. Lett. , 2012, 14, 4718.

The general formula (10) in _{a, X 1, X 2,} R 1, and _{R 2,} respectively, similar to the general formula (5) in _{a, X 1, X 2,} R 1, and the _{R 2} It is.

[Specific Example of Condensed Polycyclic Aromatic Compound Represented by General Formula (1)]
Specific examples represented by the general formula (1) according to the present invention are shown below.

  First, specific examples (compounds 101 to 157) of the compound represented by the above general formula (1), wherein A in the general formula (1) is a group represented by the above general formula (2). Show. The present invention is not limited to these.

Compounds 101 to 151 are compounds in which X ₁ and X ₂ in the general formula (1) are sulfur atoms, and R ₁ and R ₂ are hydrogen atoms, that is, compounds represented by the following general formula (11). is there.

Tables 1 and 2 show R _{3 to} R ₆ for compounds 101 to 151.

In the compounds 152 and 153, X ₁ and X ₂ in the general formula (1) are oxygen atoms, R ₁ and R ₂ are hydrogen atoms, and R ₅ and R ₆ are hexyloxy (OC ₆ H ₁₃ ) groups. That is, a compound represented by the following structural formula. As shown in the following structural formula, R ₃ and R ₄ of the compound 152 are hydrogen atoms, and R ₃ and R ₄ of the compound 153 are dodecyl (C ₁₂ H ₂₅ ) groups.

In the compounds 154 and 155, X ₁ and X ₂ in the general formula (1) are selenium atoms, R ₁ and R ₂ are hydrogen atoms, and R ₅ and R ₆ are hexyloxy (OC ₆ H ₁₃ ) groups. That is, a compound represented by the following structural formula. As shown in the following structural formula, R ₃ and R ₄ of the compound 154 are hydrogen atoms, and R ₃ and R ₄ of the compound 155 are octyl (C ₈ H ₁₇ ) groups.

In the compounds 156 and 157, X ₁ in the general formula (1) is a sulfur atom, R ₁ and R ₂ are hydrogen atoms, R ₅ and R ₆ are hexyloxy (OC ₆ H ₁₃ ) groups, A compound in which R ₃ and R ₄ are octyl (C ₈ H ₁₇ ) groups, that is, a compound represented by the following structural formula. As shown in the following structural formula, X _{2 of} compound 156 is an oxygen atom, and X _{2 of} compound 157 is a selenium atom.

  Next, specific examples (compounds 201 to 257) of the compound represented by the general formula (1) in which A in the general formula (1) is a group represented by the general formula (3) Show. The present invention is not limited to these.

Compounds 201-251 are compounds in which X ₁ and X ₂ in the general formula (1) are sulfur atoms and R ₁ and R ₂ are hydrogen atoms, that is, compounds represented by the following general formula (12). is there.

Tables 3 and 4 show R _{3 to} R ₆ for compounds 201 to 251.

In the compounds 252 and 253, X ₁ and X ₂ in the general formula (1) are oxygen atoms, R ₁ and R ₂ are hydrogen atoms, and R ₅ and R ₆ are hexyloxy (OC ₆ H ₁₃ ) groups. That is, a compound represented by the following structural formula. As shown in the following structural formula, R ₃ and R ₄ of the compound 252 are hydrogen atoms, and R ₃ and R ₄ of the compound 253 are octyl (C ₈ H ₁₇ ) groups.

In the compounds 254 and 255, X ₁ and X ₂ in the general formula (1) are selenium atoms, R ₁ and R ₂ are hydrogen atoms, and R ₅ and R ₆ are hexyloxy (OC ₆ H ₁₃ ) groups. That is, a compound represented by the following structural formula. As shown in the following structural formula, R ₃ and R ₄ of the compound 254 are hydrogen atoms, and R ₃ and R ₄ of the compound 255 are octyl (C ₈ H ₁₇ ) groups.

In Compounds 256 and 257, X ₁ in the general formula (1) is a sulfur atom, R ₁ and R ₂ are hydrogen atoms, R ₅ and R ₆ are hexyloxy (OC ₆ H ₁₃ ) groups, A compound in which R ₃ and R ₄ are octyl (C ₈ H ₁₇ ) groups, that is, a compound represented by the following structural formula. As shown in the following structural formula, X _{2 of} compound 256 is an oxygen atom, and X _{2 of} compound 257 is a selenium atom.

  Next, specific examples (compounds 301 to 357) of the compound represented by the general formula (1) in which A in the general formula (1) is a group represented by the general formula (4) Show. The present invention is not limited to these.

Compounds 301 to 351 are compounds represented by the following general formula (13), in which X ₁ and X ₂ in the general formula (1) are sulfur atoms and R ₁ and R ₂ are hydrogen atoms. is there.

Tables 5 and ₆ show R _{3 to} R ₆ for compounds 301 to 351.

In the compounds 352 and 353, X ₁ and X ₂ in the general formula (1) are oxygen atoms, R ₁ and R ₂ are hydrogen atoms, and R ₅ and R ₆ are hexyloxy (OC ₆ H ₁₃ ) groups. That is, a compound represented by the following structural formula. As shown in the following structural formula, R ₃ and R ₄ of the compound 352 are hydrogen atoms, and R ₃ and R ₄ of the compound 353 are octyl (C ₈ H ₁₇ ) groups.

In the compounds 354 and 355, X ₁ and X ₂ in the general formula (1) are selenium atoms, R ₁ and R ₂ are hydrogen atoms, and R ₅ and R ₆ are hexyloxy (OC ₆ H ₁₃ ) groups. That is, a compound represented by the following structural formula. As shown in the following structural formula, R ₃ and R ₄ of the compound 354 are hydrogen atoms, and R ₃ and R ₄ of the compound 355 are octyl (C ₈ H ₁₇ ) groups.

In the compounds 356 and 357, X ₁ in the general formula (1) is a sulfur atom, R ₁ and R ₂ are hydrogen atoms, R ₅ and R ₆ are hexyloxy (OC ₆ H ₁₃ ) groups, A compound in which R ₃ and R ₄ are octyl (C ₈ H ₁₇ ) groups, that is, a compound represented by the following structural formula. As shown in the following structural formula, X _{2 of} compound 356 is an oxygen atom, and X _{2 of} compound 357 is a selenium atom.

  Since the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention has a polar structure due to a cyano group that attracts electrons, an n-type organic semiconductor in which electrons function as carriers in an organic semiconductor device It is possible to use this material (n-type material). In addition, the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention can be stably driven in the air when used as an n-type material of an organic transistor. Moreover, the condensed polycyclic aromatic compound of this invention can improve the carrier mobility in an organic-semiconductor device by utilizing for the organic-semiconductor material of an organic-semiconductor device.

[Organic semiconductor materials]
The condensed polycyclic aromatic compound represented by the general formula (1) can be used as an organic semiconductor. Then, the organic-semiconductor material of this invention contains the condensed polycyclic aromatic compound represented by General formula (1). This organic semiconductor material can be used mainly as a material (transistor material) of an organic transistor.

  The organic semiconductor material includes at least one of the condensed polycyclic aromatic compounds represented by the general formula (1) and, if necessary, other than the condensed polycyclic aromatic compounds represented by the general formula (1) of the present invention. Other organic semiconductors (compounds) and / or various additives may be mixed. For example, when the organic semiconductor material of the present invention is used as a transistor material, the organic semiconductor material may contain an additive such as a dopant for the purpose of improving the characteristics of the organic transistor. When the total amount of the organic semiconductor (the total amount of the condensed polycyclic aromatic compound represented by the general formula (1) and the other organic semiconductor) is 100% by weight, the additive is usually 0.01. It may be contained in the organic semiconductor material in the range of 10 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight.

  Since the organic semiconductor material of the present invention contains the condensed polycyclic aromatic compound of the present invention, the carrier mobility in the organic semiconductor device can be improved by being used in the organic semiconductor device.

[Thin Film, Method for Forming the Same, and Composition for Forming Thin Film Used therein]
The thin film of this invention contains the condensed polycyclic aromatic compound represented by General formula (1).

  The thickness of the thin film of the present invention varies depending on its use and is not particularly limited, but is usually 0.1 nm to 10 μm, preferably 0.5 nm to 3 μm, more preferably 1 nm to 1 μm. is there.

  Various methods can be used for forming the thin film of the present invention. Generally, the thin film formation method is roughly classified into a formation method by a vacuum process and a formation method by a solution process, and any of them may be used. Examples of the method for forming a thin film by the vacuum process include resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination, CVD, molecular beam epitaxial growth, and vacuum vapor deposition. In addition, as a thin film forming method by solution process, spin coating method, drop cast method, dip coating method, spray method, die coater method, roll coater method, bar coater method, etc .; flexographic printing, resin relief printing, etc. Letterpress printing method; flat plate printing method such as offset printing method, dry offset printing method, pad printing method; intaglio printing method such as gravure printing method; stencil printing method such as silk screen printing method, photocopier printing method and lingraph printing method; Ink jet printing method; micro contact printing method and the like. The thin film can be formed by one of the above-described forming methods, or can be formed by combining a plurality of the above-described forming methods. Hereinafter, the thin film forming method will be described in detail.

  First, using the organic semiconductor material of the present invention described above (an organic semiconductor material containing a condensed polycyclic aromatic compound represented by the general formula (1)), it is represented by the general formula (1) of the present invention by a vacuum process. A method for forming a thin film containing a condensed polycyclic aromatic compound will be described.

In this method, the organic semiconductor material is evaporated by heating under vacuum in a container such as a crucible or a metal boat, and the evaporated organic semiconductor material is converted into an object (hereinafter referred to as “covered”). A method of adhering (vapor deposition) to the surface (hereinafter referred to as “attachment surface”) of the “kimono”, that is, a vacuum vapor deposition method is preferably employed. The degree of vacuum at the time of this vapor deposition is usually 1.0 × 10 ⁻¹ Pa or less, preferably 1.0 × 10 ⁻³ Pa or less. In addition, the characteristics of the thin film change depending on the temperature of the deposit during vapor deposition (when the thin film is used as a semiconductor layer of an organic semiconductor device (organic transistor) described later, this changes the characteristics of the organic semiconductor device. Therefore, it is preferable to carefully select the temperature of the deposit during vapor deposition. The temperature of the adherend during vapor deposition is usually 0 to 200 ° C, preferably 5 to 180 ° C, more preferably 10 to 150 ° C, still more preferably 15 to 120 ° C, and particularly preferably. 20 to 100 ° C. The deposition rate is usually 0.001 nm / second to 10 nm / second, preferably 0.01 nm / second to 1 nm / second. Moreover, the thickness of the thin film formed from the said organic-semiconductor material is 0.1 nm-10 micrometers normally, Preferably it is 0.5 nm-3 micrometers, More preferably, it is 1 nm-1 micrometer.

  In addition, instead of the method of heating and evaporating the organic semiconductor material to form the thin film and attaching it to the deposition surface, the organic semiconductor material is deposited on the deposition surface using another vacuum process technique. May be formed.

  Next, a general formula (1) of the present invention is obtained by a solution process using a composition (a composition for forming a thin film) containing the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention and a solvent. The method of forming the thin film containing the condensed polycyclic aromatic compound represented by this will be described.

  In the method of forming a thin film by a solution process, first, a condensed polycyclic aromatic compound represented by the general formula (1) is dissolved or dispersed in a solvent to prepare a thin film forming composition. The composition for thin film formation of this invention contains the condensed polycyclic aromatic compound represented by General formula (1) of this invention, and a solvent.

  The solvent used in the composition for forming a thin film is not particularly limited as long as it can form a thin film containing the condensed polycyclic aromatic compound on an adherend. As the solvent, an organic solvent is preferable. Specific examples of the organic solvent include halogenated hydrocarbon solvents such as dichloromethane, chloroform and dichloroethane; ether solvents such as diethyl ether, anisole and tetrahydrofuran; amides such as dimethylacetamide, dimethylformamide and N-methylpyrrolidone. Solvents; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; alcohol solvents such as methanol, ethanol, isopropanol, butanol; fluorinated alcohol solvents such as octafluoropentanol, pentafluoropropanol, ethyl acetate, acetic acid Ester solvents such as butyl, ethyl benzoate and diethyl carbonate; benzene, toluene, xylene, chlorobenzene, mesitylene, ethylbenzene, dichlorobenzene, chloronaphthalene, Aromatic hydrocarbon solvents such as La tetrahydronaphthalene; hexane, cyclohexane, octane, decane, hydrocarbon solvents such as tetralin and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The content of the condensed polycyclic aromatic compound represented by the general formula (1) in the thin film forming composition varies depending on the type of the solvent and the thickness of the thin film to be prepared, but with respect to the total amount of the thin film forming composition. The content is preferably in the range of 0.001 wt% to 20 wt%, and more preferably in the range of 0.01 wt% to 10 wt%. Moreover, the composition for forming a thin film of the present invention may be dissolved or dispersed in the above-mentioned solvent, but is preferably dissolved as a uniform solution.

  The composition for forming a thin film may contain an organic semiconductor other than the condensed polycyclic aromatic compound represented by the general formula (1) and various additives as necessary. For example, when the thin film forming composition of the present invention is used as a material for an organic transistor (transistor material), the thin film forming composition includes a dopant for the purpose of improving the characteristics of the organic transistor. Such additives may be contained. When the total amount of the organic semiconductor (the total amount of the condensed polycyclic aromatic compound represented by the general formula (1) and the other organic semiconductor) is 100% by weight, the additive is usually 0.01 to 10%. It is preferable that the composition is contained in the thin film forming composition within a range of wt%, preferably 0.05 to 5 wt%, more preferably 0.1 to 3 wt%.

  Next, the composition for forming a thin film is applied onto the adherend surface and dried (the solvent is removed). Examples of the method for applying the thin film-forming composition include spin coating, drop casting, dip coating, spraying, die coater, roll coater, bar coater, and the like; flexographic printing, resin relief printing Relief printing methods such as offset printing, dry offset printing, pad printing, etc .; intaglio printing such as gravure printing, stencil printing such as silk screen printing, photocopier printing, lingraph printing, etc. An inkjet printing method; a microcontact printing method; and a method combining a plurality of these methods.

  Furthermore, as a method of forming a thin film similar to the coating method, a thin film monomolecular film containing the condensed polycyclic aromatic compound represented by the general formula (1) is obtained by dropping the thin film forming composition onto the water surface. A Langmuir project method in which a monomolecular film is manufactured and transferred onto a deposition surface and laminated; a method in which liquid crystal or an organic semiconductor material in a melt state is introduced between substrates by a capillary phenomenon, or the like can also be employed.

  In the method of forming a thin film by the solution process, the temperature of the adherend and the composition for forming the thin film is also important when forming the thin film, and the characteristics of the thin film change depending on the temperature of the adherend and the composition for forming the thin film. (When the thin film is used as a semiconductor layer of an organic semiconductor device (organic transistor) to be described later, this changes the characteristics of the organic semiconductor device). It is preferable to carefully select the temperature. The temperature of the adherend and the composition for forming a thin film is usually 0 to 200 ° C, preferably 10 to 120 ° C, more preferably 15 to 100 ° C. Care must be taken because the temperature of the thin film forming composition largely depends on the type of solvent contained in the thin film forming composition.

  The thickness of the thin film formed from the thin film forming composition by a solution process is usually 0.1 nm to 10 μm, preferably 0.5 nm to 3 μm, and more preferably 1 nm to 1 μm.

  The thin film of the present invention can be used as a thin film constituting a semiconductor layer in an organic semiconductor device, particularly an organic transistor.

[Organic semiconductor device and manufacturing method thereof]
An organic semiconductor device can be produced using the condensed polycyclic aromatic compound represented by the above general formula (1) as a material for electronics. The organic semiconductor device of the present invention includes the above-described thin film of the present invention (that is, a thin film containing a condensed polycyclic aromatic compound represented by the general formula (1)).

  The organic semiconductor device of this invention can be manufactured by the manufacturing method including the process of forming the thin film containing the condensed polycyclic aromatic compound represented by General formula (1). In the production of an organic semiconductor device, any of the thin film formation methods of the present invention described above can be used as the thin film formation method containing the condensed polycyclic aromatic compound represented by the general formula (1). A method for forming a thin film by a process, specifically, the above-described composition for forming a thin film of the present invention is applied onto a surface on which a thin film is to be formed, and the condensed polycyclic aromatic represented by the general formula (1) A method of forming a thin film containing a compound is more preferable. Then, the manufacturing method of the organic-semiconductor device of this invention includes the process of apply | coating the composition for thin film formation of this invention on the surface which is going to form a thin film.

  Examples of the organic semiconductor device include organic transistors, photoelectric conversion devices, organic solar cell devices, organic EL devices, organic light emitting transistor devices, and organic semiconductor laser devices. These will be described in detail.

(Organic transistor)
First, the organic transistor will be described in detail.

  The organic transistor includes at least one semiconductor layer composed of a thin film containing a condensed polycyclic aromatic compound represented by the general formula (1), and two electrodes disposed so as to be in contact with the semiconductor layer and separated from each other, And another electrode called a gate electrode disposed so as to face a region (channel region) between the source electrode and the drain electrode, and the surface between the surface in contact with the source electrode and the surface in contact with the drain electrode in the semiconductor layer. The current flowing between the source electrode and the drain electrode is controlled by the voltage applied to the gate electrode.

  In general, an organic transistor having a structure in which a gate electrode is insulated from a semiconductor layer by an insulator layer made of an insulating film (Metal-Insulator-Semiconductor: MIS structure) is often used. A MIS structure using a metal oxide film as an insulating film is called a MOS (Metal-Oxide-Semiconductor) structure. As an organic transistor having another structure, there is a structure (Metal-Semiconductor; MES structure) in which a gate electrode is formed through a Schottky barrier with respect to a semiconductor layer. However, in the case of an organic transistor using an organic semiconductor, A MIS structure is often used.

  Hereinafter, although an organic transistor is demonstrated in detail using FIG. 1, this invention is not limited to these structures.

  FIG. 1 is a schematic cross-sectional view of some embodiments of the organic transistor of the present invention. The organic transistors 10A to 10D and 10F of each embodiment shown in FIGS. 1 (a) to 1 (d) and (f) are a source electrode 1 and a condensed polycyclic aromatic compound represented by the above general formula (1). At least one semiconductor layer 2, a drain electrode 3, an insulator layer 4, a gate electrode 5, and a substrate 6 having a thin film including An organic transistor 10E shown in FIG. 1E includes a source electrode 1, at least one semiconductor layer 2 having a thin film containing a condensed polycyclic aromatic compound represented by the general formula (1), a drain electrode 3, and a gate electrode. 5 is provided. In addition, arrangement | positioning of each layer 2, 4 and the electrodes 1, 3, 5 can be suitably selected by the use of an organic transistor.

  The organic transistors 10 </ b> A to 10 </ b> D and 10 </ b> F are called lateral transistors because current flows in a direction parallel to the substrate 6, the source electrode 1, and the drain electrode 3. The organic transistor 10A and the organic transistor 10F have a structure in which the source electrode 1 and the drain electrode 3 are disposed on the lower surface of the semiconductor layer 2 (the surface close to the substrate 6), and this structure is called a bottom contact structure. . The organic transistor 10B and the organic transistor 10C have a structure in which the source electrode 1 and the drain electrode 3 are arranged on the upper surface of the semiconductor layer 2 (surface far from the substrate 6), and this structure is called a top contact structure. . The organic transistor 10D has a structure in which one of the source electrode 1 and the drain electrode 3 is disposed on the upper surface of the semiconductor layer 2, and the other is disposed on the lower surface of the semiconductor layer 2. This structure is a top-and-bottom structure. It is called a contact structure.

  The organic transistor 10A, the organic transistor 10B, and the organic transistor 10D have a structure in which the gate electrode 5 is disposed below the semiconductor layer 2 (side closer to the substrate 6), and this structure is called a bottom gate structure. In the bottom gate structure, a single conductive substrate (for example, a silicon wafer) may serve as the gate electrode 5 and the substrate 6. The organic transistor 10C and the organic transistor 10F have a structure in which the gate electrode 5 is disposed on the upper side (the side far from the substrate 6) of the semiconductor layer 2, and this structure is called a top gate structure.

  The organic transistor 10A is a bottom contact-bottom gate type organic transistor. The organic transistor 10 </ b> A includes a substrate 6, a gate electrode 5 disposed on the top surface of the substrate 6, an insulator layer 4 disposed on the top surface of the gate electrode 5, and one end portion of the top surface of the insulator layer 4. Source electrode 1 disposed on top, drain electrode 3 disposed on the other end of the upper surface of the insulator layer 4, a central portion (portion excluding both ends) of the upper surface of the insulator layer 4, a source The semiconductor layer 2 is provided on part of the upper surface of the electrode 1 and part of the upper surface of the drain electrode 3.

  The organic transistor 10B is called a top contact-bottom gate type organic transistor. The organic transistor 10B is disposed on the substrate 6, the gate electrode 5 disposed on the upper surface of the substrate 6, the insulator layer 4 disposed on the upper surface of the gate electrode 5, and the upper surface of the insulator layer 4. The semiconductor layer 2 is provided, and the source electrode 1 and the drain electrode 3 are provided on a part of the upper surface of the semiconductor layer 2 so as to be separated from each other.

  The organic transistor 10C is called a top contact-top gate type organic transistor. The organic transistor 10C has a structure often used for an organic transistor using an organic single crystal semiconductor. The organic transistor 10 </ b> C includes a substrate 6, a semiconductor layer 2 disposed on the upper surface of the substrate 6, and a source electrode 1 and a drain electrode disposed on a part of the upper surface of the semiconductor layer 2 so as to be separated from each other. 3 and the upper surface of the semiconductor layer 2 (except for the portion where the source electrode 1 and the drain electrode 3 are disposed), the upper surface of the source electrode 1, and the insulator layer disposed on the upper surface of the drain electrode 3 4 and a gate electrode 5 disposed on the insulator layer 4.

  The organic transistor 10D is called a top & bottom contact-bottom gate type organic transistor. The organic transistor 10 </ b> D includes a substrate 6, a gate electrode 5 disposed on the top surface of the substrate 6, an insulator layer 4 disposed on the top surface of the gate electrode 5, and one end portion of the top surface of the insulator layer 4. A source electrode 1 disposed above, a semiconductor layer 2 disposed on an upper surface of the insulator layer 4 (except for a portion where the source electrode 1 is disposed) and an upper surface of the source electrode 1, And a drain electrode 3 disposed on the end of the upper surface of the semiconductor layer 2 on the side far from the source electrode 1.

  The organic transistor 10E is a kind of organic transistor having a vertical structure in which current flows in a direction perpendicular to the source electrode 1 and the drain electrode 3, and is an electrostatic induction transistor (SIT). The organic transistor 10E includes a source electrode 1 and a drain electrode 3 disposed so as to be parallel and spaced apart from each other, a semiconductor layer 2 disposed so as to be sandwiched between the source electrode 1 and the drain electrode 3, A plurality of gate electrodes 5 embedded in the semiconductor layer 2 in a mesh shape parallel to the source electrode 1 and the drain electrode 3 are provided. In this electrostatic induction transistor (organic transistor 10E), the flow of current in the semiconductor layer 2 spreads in a plane, so that a large amount of carriers 8 are transferred to the source electrode 1 side at a time as shown by arrows in FIG. To the drain electrode 3 side. Further, since the electrostatic induction transistor (organic transistor 10E) is arranged so that the source electrode 1 and the drain electrode 3 are arranged in the vertical direction (direction perpendicular to the semiconductor layer 2), the source electrode 1 and the drain electrode 3 are arranged. Since the distance between can be shortened, the response is fast. Therefore, this electrostatic induction transistor (organic transistor 10E) can be preferably applied to applications such as passing a large current or performing high-speed switching. Although FIG. 1E does not show a substrate, in the normal case, a substrate similar to the substrate 6 is provided outside the source electrode 1 and the drain electrode 3 in the organic transistor 10E.

  The organic transistor 10F is called a bottom contact-top gate type organic transistor. The organic transistor 10 </ b> F includes a substrate 6, a source electrode 1 and a drain electrode 3 disposed on a part of the upper surface of the substrate 6 so as to be separated from each other, and an upper surface of the substrate 6 (however, the source electrode 1 and the drain electrode 3 ), The semiconductor layer 2 disposed on the upper surface of the source electrode 1 and the upper surface of the drain electrode 3, and the insulator layer 4 disposed on the upper surface of the semiconductor layer 2. And a gate electrode 5 disposed on the insulator layer 4.

  Each component in each embodiment will be described.

  The substrate 6 needs to be able to hold each component formed thereon without peeling off. Examples of the substrate 6 include an insulating substrate such as a resin plate, a resin film, paper, a glass plate, a quartz plate, and a ceramic plate; a substrate in which an insulating layer is formed by coating or the like on a conductive substrate made of metal or an alloy; A substrate composed of various combinations such as a combination of a resin and an inorganic material; a conductive substrate such as a semiconductor substrate (for example, a silicon wafer) can be used. Examples of the resin constituting the resin plate and the resin film include, for example, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyamide, polyimide, polycarbonate, cellulose triacetate, and polyetherimide. When a resin film or paper is used as the substrate 6, the organic transistors 10A to 10D and 10F can be made flexible, and the organic transistors 10A to 10D and 10F are flexible and lightweight. Practicality is improved. The thickness of the substrate is usually 1 μm to 10 mm, preferably 5 μm to 5 mm.

For the source electrode 1, the drain electrode 3, and the gate electrode 5, a conductive material is used. Examples of the conductive material include platinum, gold, silver, aluminum, chromium, tungsten, tantalum, nickel, cobalt, copper, iron, lead, tin, titanium, indium, palladium, molybdenum, magnesium, calcium, and barium. Metals such as lithium, potassium and sodium and alloys containing them; conductive oxides such as InO ₂ , ZnO ₂ , SnO ₂ and ITO (indium tin oxide); polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene vinylene, Conductive polymer compounds such as polydiacetylene; semiconductors such as silicon, germanium, and gallium arsenide; carbon materials such as carbon black, fullerene, carbon nanotubes, graphite, and graphene can be used. Further, the conductive polymer compound or the semiconductor may be doped. Examples of dopants used for the doping include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids having acidic functional groups such as sulfonic acid; Lewis acids such as PF ₅ , AsF ₅ and FeCl ₃ ; halogen atoms such as iodine; lithium , Metal atoms such as sodium and potassium. Boron, phosphorus, arsenic and the like are also frequently used as dopants for inorganic semiconductors such as silicon. Further, a conductive composite material in which particles such as carbon black and metal particles are dispersed in the above dopant is also used.

  For the source electrode 1 and the drain electrode 3 that are in contact with the semiconductor layer 2, it is important to select an appropriate work function for reducing contact resistance, surface treatment, and the like.

  Further, the distance (channel length) between the source electrode 1 and the drain electrode 3 is an important factor that determines the characteristics of the organic transistors 10A to 10F. The channel length is usually 0.01 to 300 μm, preferably 0.1 to 100 μm. If the channel length is short, the amount of current that can be extracted increases, but conversely, short channel effects such as the influence of contact resistance occur and control becomes difficult, so an appropriate channel length is required. The length (channel width) of the source electrode 1 and the drain electrode 3 is usually 10 to 10000 μm, preferably 100 to 5000 μm. In addition, this channel width can be made longer by making the electrode structure a comb-shaped structure, etc., and the channel width is made appropriate depending on the required current amount, device structure, etc. There is a need.

  The structures (shapes) of the source electrode 1 and the drain electrode 3 will be described. The structures of the source electrode 1 and the drain electrode 3 may be the same or different.

  In the case of the bottom contact structure, it is generally preferable to form the source electrode 1 and the drain electrode 3 using a lithography method, and to form the source electrode 1 and the drain electrode 3 in a rectangular parallelepiped. Recently, the printing accuracy by various printing methods has been improved, and it has become possible to produce the source electrode 1 and the drain electrode 3 with high accuracy using techniques such as ink jet printing, gravure printing, or screen printing. In the case of a top contact structure in which the source electrode 1 and the drain electrode 3 are provided on the semiconductor layer 2, the source electrode 1 and the drain electrode 3 can be produced by vapor-depositing the conductive material using a shadow mask or the like. It has also become possible to directly print and form the electrode patterns of the source electrode 1 and the drain electrode 3 using a technique such as inkjet printing. The lengths of the source electrode 1 and the drain electrode 3 are the same as the channel width. The widths of the source electrode 1 and the drain electrode 3 are not particularly limited, but are preferably shorter in order to reduce the area of the device within a range where the electrical characteristics can be stabilized. The width of the source electrode 1 and the drain electrode 3 is usually 0.1 to 1000 μm, preferably 0.5 to 100 μm. The thicknesses of the source electrode 1 and the drain electrode 3 are usually 0.1 to 1000 nm, preferably 1 to 500 nm, and more preferably 5 to 200 nm. Although wiring is connected to the source electrode 1 and the drain electrode 3, the wiring is also made of the same material as the source electrode 1 and the drain electrode 3.

As the insulator layer 4, an insulating material is used. Examples of the insulating material include polyparaxylylene, polyacrylate, polymethyl methacrylate, polystyrene, polyvinylphenol, polyamide, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, fluororesin, Polymers such as epoxy resins and phenol resins, and copolymers in which two or more structural units of these polymers are combined; oxides (non-ferroelectric) such as silicon dioxide, aluminum oxide, titanium oxide, tantalum oxide; SrTiO ₃ , BaTiO Ferroelectric oxides such as ₃ ; nitrides such as silicon nitride and aluminum nitride; dielectrics such as sulfides and fluorides can be used. In addition, as the material having the insulating property, a material in which particles of the dielectric (however, a material different from the polymer) are dispersed in a polymer can be used. As the material having the insulating property, a material having high electrical insulation characteristics is preferable in order to reduce the leakage current. Thereby, the thickness of the insulator layer 4 can be reduced, the insulation capacity can be increased, and the current that can be taken out. Can be more. In order to improve the mobility of the semiconductor, it is preferable that the insulator layer 4 is a smooth film that can reduce the surface energy of the surface of the insulator layer 4 and has no unevenness. For this purpose, a self-assembled monolayer insulating layer 4 or a two-layered insulating layer 4 may be formed. The thickness of the insulator layer 4 varies depending on the material, but is usually 0.1 nm to 100 μm, preferably 0.5 nm to 50 μm, more preferably 1 nm to 10 μm.

  The semiconductor layer 2 has a thin film containing the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention. The structure of the semiconductor layer 2 may be a single-layer structure having only the layer made of the thin film of the present invention described above or a multi-layer structure having a plurality of layers including the layer made of the thin film of the present invention described above. Although it is good, the single layer structure is more preferable.

  The thickness of the semiconductor layer 2 is preferably as thin as possible without losing necessary functions. In a horizontal type organic transistor such as the organic transistors 10A to 10D, 10F, etc., if the thickness of the semiconductor layer 2 has a predetermined thickness or more, the characteristics of the organic transistor do not depend on the thickness. Since the leakage current often increases as the thickness of the semiconductor layer 2 increases, the thickness of the semiconductor layer 2 is preferably within an appropriate range. The thickness of the semiconductor layer 2 is usually 0.1 nm to 10 μm, preferably 0.5 nm to 3 μm, more preferably 1 nm to 1 nm in order for the semiconductor layer 2 to perform the function required for the semiconductor layer 2. 1 μm.

  In the organic transistors 10 </ b> A to 10 </ b> F, other layers may be provided as necessary between the above-described components or on the exposed surfaces of the above-described components. For example, a protective layer may be formed directly or via another layer on the semiconductor layer 2 in the organic transistors 10A to 10F. Thereby, the influence of external air such as humidity on the electrical characteristics of the organic transistor can be reduced, and the electrical characteristics of the organic transistor can be stabilized. In addition, electrical characteristics such as the on / off ratio of the organic transistor can be improved.

  Although it does not specifically limit as a material which comprises the said protective layer, For example, various resins, such as acrylic resins, such as an epoxy resin and polymethylmethacrylate, a polyurethane, a polyimide, polyvinyl alcohol, a fluororesin, polyolefin; silicon oxide, aluminum oxide, Inorganic oxides such as silicon nitride; and dielectrics such as nitrides are preferred, and resins (polymers) having low oxygen permeability, moisture permeability, and water absorption are more preferred. As a material constituting the protective layer, a gas barrier protective material developed for an organic EL display can also be used. Although the thickness of a protective layer can employ | adopt arbitrary thickness according to the objective, it is 100 nm-1 mm normally.

  Further, the surface of the semiconductor layer 2 (the surface of the substrate 6, the surface of the insulator layer 4, etc.) is subjected to surface modification or surface treatment in advance before the formation of the semiconductor layer 2, whereby the organic transistors 10 </ b> A to 10 </ b> F. It is possible to improve the characteristics. For example, by adjusting the degree of hydrophilicity / hydrophobicity of the surface on which the semiconductor layer 2 is formed, the quality of the semiconductor layer 2 formed on the surface (for example, the quality of the thin film constituting the semiconductor layer 2 or the film formation) Property) can be improved. In particular, the characteristics of the semiconductor layer 2 made of an organic semiconductor material may vary greatly depending on the state of the layer, such as molecular orientation. Therefore, the surface treatment on the surface on which the semiconductor layer 2 is formed controls the molecular orientation at the interface portion between the surface on which the semiconductor layer 2 is formed and the semiconductor layer 2 formed on the surface, and the semiconductor layer It is considered that the trap site in the base material (substrate 6, insulator layer 4, etc.) on which 2 is formed is reduced, thereby improving characteristics such as carrier mobility of the organic transistor. The trap site refers to a functional group such as a hydroxyl group present in an untreated substrate. When such a functional group is present in the base material on which the semiconductor layer 2 is formed, electrons are attracted to the functional group, and as a result, the carrier mobility of the organic transistor is lowered. Therefore, reducing trap sites in the base material on which the semiconductor layer 2 is formed is often effective for improving characteristics such as carrier mobility of the organic transistor.

  Examples of the surface treatment of the substrate on which the semiconductor layer 2 is formed include, for example, self-assembled monolayer treatment with hexamethyldisilazane, octyltrichlorosilane, octadecyltrichlorosilane, etc .; surface treatment with polymers, etc .; hydrochloric acid, sulfuric acid Acid treatment with acid such as acetic acid; alkali treatment with alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia; ozone treatment; fluorination treatment; plasma treatment with plasma such as oxygen plasma or argon plasma; Langmuir Blodgett film formation process; other insulator or semiconductor thin film formation process; mechanical process; electrical process such as corona discharge; rubbing process using fibers, etc., and combinations of these processes Can do.

  In the organic transistors 10A to 10F described above, a method of providing various layers on the base material (a method of providing the insulator layer 4 on the substrate 6, a method of providing the semiconductor layer 2 on the substrate 6, a semiconductor layer on the insulator layer 4) As the method of providing 2), the above-described vacuum process and solution process can be appropriately employed.

(Manufacturing method of organic transistor)
Next, a method for manufacturing an organic transistor according to the present invention will be described below with reference to FIG. 2, taking the top contact-bottom gate type organic transistor 10B of the embodiment shown in FIG. 1B as an example. This manufacturing method can be similarly applied to organic transistors of other modes such as the organic transistors 10A, 10C to 10F described above.

(1) Preparation of Substrate 6 and Surface Treatment of Substrate 6 In the manufacturing method of organic transistor 10B, first, substrate 6 is prepared (see FIG. 2A), and various necessary layers and electrodes are provided on substrate 6. Thus, the organic transistor 10B is manufactured. As the substrate 6, those described above can be used. It is also possible to perform the above-described surface treatment on the substrate 6. The thickness of the substrate 6 is preferably thin as long as necessary functions are not hindered. Although the thickness of the board | substrate 6 changes also with the material which comprises the board | substrate 6, it is 1 micrometer-10 mm normally, Preferably it is 5 micrometers-5 mm. If necessary, the substrate 6 may have an electrode function.

(2) Formation of Gate Electrode 5 Next, the gate electrode 5 is formed on the substrate 6 (see FIG. 2B). The material described above is used as the material constituting the gate electrode. As a method for forming the gate electrode 5, various methods can be used. For example, a vacuum deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method, a sol-gel method, or the like can be employed. When forming a layer of a material (electrode material) constituting the gate electrode 5, or after forming the layer, it is preferable to pattern the layer so as to have a desired shape as necessary. Various methods can be used as the layer patterning method, and examples thereof include a photolithography method in which patterning and etching of a photoresist are combined. Also, evaporation method using shadow mask: sputtering method; printing method such as ink jet printing, screen printing, offset printing, letterpress printing, etc .; soft lithography method such as micro contact printing method; or a combination of these methods Thus, the layer can be patterned. The thickness of the gate electrode 5 varies depending on the material constituting the gate electrode 5, but is usually 0.1 nm to 10 μm, preferably 0.5 nm to 5 μm, and more preferably 1 nm to 3 μm. When a single conductive substrate serves as both the gate electrode 5 and the substrate 6, the thickness of the single conductive substrate may be larger than the above-described thickness range of the gate electrode 5.

(3) Formation of insulator layer 4 Next, the insulator layer 4 is formed on the gate electrode 5 (see FIG. 2C). As the material constituting the insulator layer 4, the materials described above are used. Various methods can be used to form the insulator layer 4. Examples of methods that can be used for forming the insulator layer 4 include spin coating, spray coating, dip coating, casting, bar coating, blade coating, and other coating methods; screen printing, offset printing, inkjet printing, and the like; Various methods such as a vacuum deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, an ion plating method, a sputtering method, an atmospheric pressure plasma method, and a dry process method such as a CVD method can be used. In addition to the sol-gel method; a method of forming alumite on aluminum or a method of forming silicon oxide on silicon, the surface layer of metal or metalloid is oxidized by a thermal oxidation method or the like as a method of forming the insulator layer 4. A method of forming an oxide film can also be employed.

  Note that, in a portion where the insulator layer 4 and the semiconductor layer 2 are in contact with each other, molecules constituting the semiconductor layer 2 at the interface between the insulator layer 4 and the semiconductor layer 2, for example, a condensation represented by the general formula (1) In order to satisfactorily orient the molecules of the polycyclic aromatic compound, the insulator layer 4 can be subjected to a predetermined surface treatment. As a surface treatment method for the insulator layer 4, the same surface treatment as that for the substrate 6 can be used. The thickness of the insulator layer 4 is preferably as thin as possible because the amount of electricity taken out can be increased by increasing the electric capacity of the insulator layer 4. However, since the leakage current increases as the thickness of the insulator layer 4 is thinner, the thickness of the insulator layer 4 is preferably as thin as possible without impairing its function. The thickness of the insulator layer 4 is usually 0.1 nm to 100 μm, preferably 0.5 nm to 50 μm, more preferably 5 nm to 10 μm.

(4) Formation of Semiconductor Layer 2 Next, a thin film is formed on the insulator layer 4 using an organic semiconductor material or a composition for forming a thin film to obtain the semiconductor layer 2 (see FIG. 2D). In forming the semiconductor layer 2, the thin film forming method of the present invention described above can be used. In this step, the object (attachment) on which the thin film (semiconductor layer) is formed is the insulator layer 4 shown in FIG. 2C, and the surface (attachment surface) on which the thin film (semiconductor layer) is formed is insulated. It is the upper surface of the body layer 4.

(5) Post-processing of Semiconductor Layer 2 The characteristics of the semiconductor layer 2 (see FIG. 2D) formed in this way can be further improved by post-processing. For example, by performing heat treatment as a post-treatment of the semiconductor layer 2, the semiconductor characteristics of the semiconductor layer 2 can be improved and stabilized. This is because the strain in the film generated during the formation of the thin film constituting the semiconductor layer 2 is alleviated, pinholes in the semiconductor layer 2 are reduced, and the arrangement and orientation in the semiconductor layer 2 are controlled. It depends on what you think is possible. Therefore, when the organic transistor of the present invention is manufactured, the above heat treatment is effective for improving the characteristics of the organic transistor. The heat treatment is performed by heating the stacked body including the semiconductor layer 2 (here, the stacked body shown in FIG. 2D) after the semiconductor layer 2 is formed. The temperature of the heat treatment is not particularly limited, but is usually room temperature or higher and 150 ° C. or lower, preferably 40 to 120 ° C., more preferably 45 to 100 ° C. The time for the heat treatment is not particularly limited, but is usually 10 seconds or longer and 24 hours or shorter, preferably 30 seconds or longer and 3 hours or shorter. Regarding the atmosphere of the heat treatment, the heat treatment may be performed in the air, or may be performed in an inert atmosphere such as nitrogen or argon. In addition, the shape of the semiconductor layer 2 can be controlled by the solvent vapor.

  Further, as another post-treatment method for the semiconductor layer 2, the semiconductor layer 2 is treated with an oxidizing gas such as oxygen, a reducing gas such as hydrogen, an oxidizing liquid, or a reducing liquid, thereby oxidizing the semiconductor layer 2. Or the characteristic change of the semiconductor layer 2 by reduction | restoration can also be induced. This can be used for the purpose of increasing or decreasing the carrier density in the semiconductor layer 2, for example.

In addition, the characteristics of the semiconductor layer 2 can be changed by adding a small amount of dopant (element, atomic group, molecule, or polymer) to the semiconductor layer 2 in a technique called doping. For example, oxidizing gases such as oxygen; reducing gases such as hydrogen; acids such as hydrochloric acid, sulfuric acid and sulfonic acid; Lewis acids such as PF ₅ , AsF ₅ and FeCl ₃ ; halogen atoms such as iodine; sodium and potassium The semiconductor layer 2 can be doped with a dopant such as a metal atom; a donor compound such as tetrathiafulvalene (TTF) or phthalocyanine. This is because the semiconductor layer 2 is brought into contact with a gaseous dopant (when the dopant is a gas), the semiconductor layer 2 is immersed in a solution state dopant (when the dopant is in a solution state), or electrochemical doping. This can be achieved by a method of processing. These dopants do not necessarily have to be added after the formation of the semiconductor layer 2, but are added during the synthesis of the material of the semiconductor layer 2 (organic semiconductor material), or the semiconductor layer 2 is formed using a thin film forming composition. In some cases, it may be added to the composition for forming a thin film, or may be added in the process step of forming the semiconductor layer 2. Further, a dopant is added to the material forming the semiconductor layer 2 (organic semiconductor material) and co-evaporated, or the dopant is mixed in an ambient atmosphere when the semiconductor layer 2 is formed (in an environment where the dopant is present). It is also possible to perform doping by accelerating dopant ions in a vacuum and colliding with the semiconductor layer 2.

  These doping effects include changes in electrical conductivity due to increase or decrease in carrier density, changes in carrier polarity (p-type and n-type), changes in Fermi level, and the like.

(6) Formation of Source Electrode 1 and Drain Electrode 3 Next, the source electrode 1 and the drain electrode 3 are formed on the semiconductor layer 2 (see FIG. 2E). The method for forming the source electrode 1 and the drain electrode 3 can be based on the method for forming the gate electrode 5. In forming the source electrode 1 and the drain electrode 3, various additives or the like can be used to reduce the contact resistance with the semiconductor layer 2.

(7) Formation of protective layer 7 In the step of forming the source electrode and the drain electrode 3 described above, the organic transistor 10B (see FIG. 1B and FIG. 2E) is completed. After the formation of the source electrode 1 and the drain electrode 3, a protective layer 7 may be formed on the exposed portion of the upper surface of the semiconductor layer 2, the upper surface of the source electrode 1, and the upper surface of the drain electrode 3 (FIG. 2). (Refer to (f)). When the protective layer 7 is formed on the exposed portion of the upper surface of the semiconductor layer 2, the upper surface of the source electrode 1, and the upper surface of the drain electrode 3, the influence of outside air can be minimized. There is an advantage that the mechanical characteristics can be stabilized.

  As the material for the protective layer 7, the above-mentioned materials are used. Moreover, the thickness of the protective layer 7 can employ | adopt arbitrary thickness according to the objective, Usually, it is 100 nm-1 mm.

  As a method of forming the protective layer 7, various methods can be adopted. When the protective layer 7 is made of a resin, for example, a method of applying a solution containing a resin and drying it to obtain a resin layer; Examples thereof include a method of polymerizing after applying or vapor-depositing a resin monomer. You may perform a crosslinking process after formation of a resin layer. When the protective layer 7 is made of an inorganic material, as a method for forming the protective layer 7, for example, a forming method by a vacuum process such as a sputtering method or a vapor deposition method; a forming method by a solution process such as a sol-gel method can be used. .

  In the organic transistor, in addition to the semiconductor layer, a protective layer can be provided between the constituent elements as necessary. Such a protective layer may help to stabilize the electrical characteristics of the organic transistor.

  Since the organic transistor of the present invention uses an organic semiconductor material containing the condensed polycyclic aromatic compound represented by the general formula (1) as a material constituting the semiconductor layer, it can be manufactured in a relatively low temperature process. Is possible. Therefore, in the organic transistor of the present invention, a flexible material such as a plastic plate or a plastic film that cannot be used under conditions exposed to a high temperature can be used as the substrate. As a result, in the organic transistor of the present invention, by using a flexible material as a substrate, a lightweight and flexible organic semiconductor device that is not easily broken can be realized, and is preferably used as a switching device for an active matrix display. be able to.

  The organic transistor of the present invention can also be used as a digital device or an analog device such as a memory circuit device, a signal driver circuit device, or a signal processing circuit device. Further, by combining these, a display, an IC (integrated circuit) card, an IC tag, or the like can be manufactured. Furthermore, since the organic transistor of the present invention can change its characteristics by an external stimulus such as a chemical substance, it can be used as a sensor.

(Organic EL device)
The organic semiconductor device of the present invention can be used as an organic EL device.

  Organic EL devices have attracted attention because they can be used in applications such as solid, self-luminous large-area color display and illumination, and many developments have been made. The organic EL device has a structure in which two layers of a light emitting layer and a charge transport layer are provided between a counter electrode composed of a cathode and an anode; an electron transport layer, a light emitting layer and a positive electrode laminated between the counter electrodes. Known are those having a structure having three layers of hole transport layers; and those having a structure having three or more layers, and those having a single light emitting layer.

  When the organic semiconductor device of the present invention is used as an organic EL device, the thin film containing the condensed polycyclic aromatic compound represented by the general formula (1) can function as the charge transport layer or the electron transport layer. .

(Photoelectric conversion device)
The organic semiconductor device of the present invention can be used as a photoelectric conversion device by utilizing the semiconductor characteristics of the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention.

  Examples of the photoelectric conversion device include a charge coupled device (CCD) having a function of converting a video signal such as a moving image or a still image into a digital signal as an image sensor that is a solid-state imaging device. The organic semiconductor material containing the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention is inexpensive and can be used for a photoelectric conversion device by making use of large area processability, flexible functionality unique to organic matter, and the like. Use as a material is expected.

(Organic solar cell device)
Using the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention, a flexible and low-cost organic solar cell device can be easily produced. Since the organic solar cell device is a solid-state device, it is advantageous in terms of flexibility and improved life. Conventionally, development of solar cells using organic thin film semiconductors combined with conductive polymers, fullerenes, and the like has been the mainstream, but power generation conversion efficiency is a problem.

  In general, the structure of an organic solar cell device is similar to that of a silicon-based solar cell, in which a layer for generating power (a power generation layer) is sandwiched between an anode and a cathode, and holes and electrons generated by absorbing light are absorbed by each electrode. By receiving it functions as a solar cell. The power generation layer is composed of a p-type donor material, an n-type acceptor material, and other materials such as a buffer layer, and an organic solar cell is used in which an organic material is used.

  Structures include Schottky junctions, heterojunctions, bulk heterojunctions, nanostructure junctions, hybrids, etc. Each material efficiently absorbs incident light and generates charges, and the generated charges (holes and electrons) It functions as a solar cell by separating, transporting and collecting.

  In FIG. 3, the schematic sectional drawing of the example (organic solar cell device 20) of a heterojunction type organic solar cell device is shown.

  The organic solar cell device 20 includes a substrate 21, an anode 22 formed on the upper surface of the substrate 21, a power generation layer 23 formed on the upper surface of the anode 22, and a cathode 24 formed on the upper surface of the power generation layer 23. And the power generation layer 23 is formed on the upper surface of the anode 22, the n-type layer 232 formed on the upper surface of the p-type layer 231, and the upper surface of the n-type layer 232. And the buffer layer 233.

  Next, each component in the organic solar cell device will be described by taking the organic solar cell device 20 shown in FIG. 3 as an example.

  As the material of the substrate 21, the same material as the substrate 6 of the organic transistors 10A to 10F described above can be used.

  As materials constituting the anode 22 and the cathode 24 in the organic solar cell device 20, the same materials as those constituting the source electrode 1, the drain electrode 3 and the gate electrode 5 of the organic transistors 10A to 10F described above are used. it can. Since the anode 22 and the cathode 24 need to capture light efficiently, it is desirable that the anode 22 and the cathode 24 have transparency in the absorption wavelength region of the power generation layer 23. In order for the organic solar cell device 20 to have good solar cell characteristics, the anode 22 and the cathode 24 have a sheet resistance of 20Ω / □ or less and a light transmittance of 85% or more. preferable.

  Even if the power generation layer 23 has a single-layer structure composed of only a thin film containing a condensed polycyclic aromatic compound represented by the general formula (1) of the present invention, the general formula (1) of the present invention. In general, the power generation layer 23 is made of a p-type donor material, although it may have a multilayer structure including a plurality of layers including a thin film containing a condensed polycyclic aromatic compound represented by A p-type layer 231, an n-type layer 232 made of an n-type acceptor material, and a buffer layer 233 are included.

  As a p-type donor material constituting the p-type layer 231, a compound capable of transporting holes can be basically used. Specifically, a polyparaphenylene vinylene derivative, a polythiophene derivative, a polyfluorene derivative, a polyaniline derivative, etc. π-conjugated polymers; carbazole and other polymers having heterocyclic side chains. Examples of the p-type donor material include low molecular compounds such as pentacene derivatives, rubrene derivatives, porphyrin derivatives, phthalocyanine derivatives, indigo derivatives, quinacridone derivatives, merocyanine derivatives, cyanine derivatives, squalium derivatives, and benzoquinone derivatives.

  As the n-type acceptor material constituting the n-type layer 232, an n-type acceptor material containing a condensed polycyclic aromatic compound represented by the general formula (1) of the present invention can be used. That is, the n-type layer 232 is composed of a thin film containing the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention. As the n-type acceptor material constituting the n-type layer 232, the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention may be used alone, or the general formula (1) of the present invention (1). ) And other acceptor materials may be used in admixture. Other acceptor materials to be mixed are basically compounds capable of transporting electrons, oligomers and polymers having pyridine or a derivative thereof as a skeleton, oligomers or polymers having a quinoline or a derivative thereof as a skeleton, benzophenanthrolines or Polymers having the derivatives, polymer materials such as cyanopolyphenylene vinylene derivatives (CN-PPV, etc.); low molecular materials such as fluorinated phthalocyanine derivatives, perylene derivatives, naphthalene derivatives, bathocuproine derivatives, fullerene derivatives such as C60, C70, PCBM Etc.

  As the p-type donor material and the n-type donor material, those capable of efficiently absorbing light and generating electric charges are preferable, and those having a high extinction coefficient are preferable.

  Examples of the material of the buffer layer 233 include copper phthalocyanine, molybdenum trioxide, calcium, nickel oxide, lithium fluoride, and polyethylenedioxythiophene doped with polystyrene sulfonic acid (PEDOT: PSS).

  As a method for forming a thin film for the power generation layer 23 in the organic solar cell device 20, a method similar to the method for forming a semiconductor layer in the organic transistor described above can be employed. The thickness of the power generation layer 23 varies depending on the configuration of the organic solar cell device. However, the thicker the layer is, the thicker the light is absorbed and the short circuit can be prevented. it can. For this reason, the thickness of the power generation layer 23 is preferably about 10 to 500 nm.

(About organic semiconductor laser devices)
Since the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention is a compound having semiconductor characteristics, it is expected to be used as an organic semiconductor laser device.

  That is, if a resonator structure is incorporated in the organic semiconductor device of the present invention and carriers are efficiently injected to sufficiently increase the density of the excited state, it is expected that light is amplified and laser oscillation occurs. Conventionally, only laser oscillation by optical excitation has been observed, and it is extremely difficult to inject high-density carriers required for laser oscillation by electrical excitation into an organic semiconductor device to generate a high-density excitation state. Although it has been proposed, the use of an organic semiconductor device including a thin film containing the compound represented by the general formula (1) of the present invention is expected to cause highly efficient light emission (electroluminescence).

Examples of synthesizing the condensed polycyclic aromatic compounds represented by the general formulas (14) and (15) are shown in Examples 1 to 3 below. In the condensed polycyclic aromatic compound represented by the general formula (14), A is a group represented by the general formula (2), X ₁ and X ₂ are sulfur atoms, and R ₁ and R ₂ Is a compound represented by the general formula (1) in which is a hydrogen atom. In the condensed polycyclic aromatic compound represented by the general formula (15), A is a group represented by the general formula (4), X ₁ and X ₂ are sulfur atoms, and R ₁ and R ₂ Is a compound represented by the general formula (1) in which is a hydrogen atom.

  The synthesis of the condensed polycyclic aromatic compounds represented by the general formulas (14) and (15) could be specifically performed by the methods shown in Examples 1 to 3 below.

  In the synthesis and measurement of compounds in Examples 1 to 3 below, anhydrous distilled solvents were used for reactions and measurements under inert gas, and commercially available primary or special grade solvents were used for the other reactions and measurements. Moreover, the reagent was purified by anhydrous distillation or the like, if necessary, and the other commercially available primary or special grade reagents were used. Daisogel IR-60 (silica gel, active), MERCK Art 1097 Aluminiumoxide 90 (alumina, active) was used for purification by column chromatography, and Silicagel 60F254 (MERCK) was used for TLC. A rotary evaporator was used for distilling off the solvent.

Nuclear magnetic resonance spectroscopy (hereinafter referred to as “ ¹ H-NMR”) was performed using LAMBDA-NMR (395.75 MHz, σ value, ppm, internal reference TMS).

[Example 1]
Under a nitrogen atmosphere, in a 20 mL two-necked flask, hexyl cyanoacetate (1.7 mmol) as a compound represented by the general formula (9), THF (5 mL) as a reaction solvent, and sodium hydride as a base (2.2 mmol) was added and stirred for 30 minutes. Subsequently, 2,7-dibromo-5,10-didodecylnaphtho [1,2-b: 5,6-b ′] dithiophene (0.3 mmol) as a compound represented by the general formula (5), Pd (PPh ₃ ) ₄ (0.07 mmol) as a catalyst was added and refluxed for 15 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, a small amount of 1N hydrochloric acid was added, and the precipitated solid was collected by filtration. Subsequently, the obtained solid was dissolved in dichloromethane (10 mL), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) was added, and the mixture was heated to 80 ° C. After cooling to room temperature, the precipitated solid was collected by filtration to obtain Compound 112 (a compound of Compound No. 112 in Table 1 and a condensed polycyclic aromatic compound represented by the following structural formula) as a dark green solid. .

Compound 112 was obtained with a yield of 47%. In addition, ¹ H-NMR measurement results of Compound 112 were as shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.89 (m, 12H), 1.24-1.42 (m, 48H), 1.68-1.80 (m, 8H) 2.97 (t, 4H), 4.34 (t, 4H), 7.11 (s, 2H), 7.61 (s, 2H)

[Example 2]
The compound represented by the general formula (5) is 2,7-dibromo-5 instead of 2,7-dibromo-5,10-didodecylnaphtho [1,2-b: 5,6-b ′] dithiophene. , 10-dichloronaphtho [1,2-b: 5,6-b ′] dithiophene was used in the same manner as in Example 1 to obtain compound 145 (compound No. 145 in Table 2, A condensed polycyclic aromatic compound represented by the following structural formula was obtained.

Compound 145 was obtained with a yield of 40%. In addition, ¹ H-NMR measurement results of Compound 145 were as shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.80 (t, 6H), 1.24-1.42 (m, 12H), 1.75 (Quin, 4H), 4.45 (T, 4H), 7.79 (s, 2H), 7.94 (s, 2H)

Example 3
The compound represented by the general formula (5) is 2,7-dibromo-4 instead of 2,7-dibromo-5,10-didodecylnaphtho [1,2-b: 5,6-b ′] dithiophene. , 9-dioctylnaphtho [2,3-b: 6,7-b ′] dithiophene was used in the same manner as in Example 1 to obtain compound 310 (compound No. 310 in Table 3, A condensed polycyclic aromatic compound represented by the following structural formula was obtained.

Compound 310 was obtained in 41% yield. Moreover, the measurement result of ¹ H-NMR of the compound 310 was as shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.89 (m, 12H), 1.24-1.42 (m, 32H), 1.68-1.80 (m, 8H) 2.97 (t, 4H), 4.31 (t, 4H), 7.47 (s, 2H), 7.56 (s, 2H)

[Evaluation of physical properties of condensed polycyclic aromatic compounds]
(1) Measurement of electron absorption spectrum (UV-Vis) With respect to each of the compound 112, compound 145, and compound 310 obtained in Examples 1 to 3, an electron absorption spectrum was measured using dichloromethane as a solvent. FIG. 4 shows the relationship between the absorbance and the absorption wavelength (λ / nm) of the compound 112 obtained in Example 1. Similar electron absorption spectra were observed in the compounds 145 and 310 obtained in Examples 2 and 3. Table 7 shows the value of the maximum absorption wavelength λ _max of each compound. For measurement of the electron absorption spectrum (UV-Vis), an ultraviolet-visible near-infrared (UV-Vis-NIR) spectrophotometer “UV-3600” manufactured by Shimadzu Corporation was used.

(2) Measurement of CV (cyclic voltammetry) CV measurement was performed for each of the compounds 112, 145, and 310 obtained in Examples 1-3. Specifically, dichloromethane as a solvent, tetrabutylammonium hexafluorophosphate (n-BuN ₄ PF ₆ , 0.1M) as a supporting salt, a platinum wire as a working electrode and a counter electrode, and a silver / silver chloride electrode as a reference electrode The potential was swept at a rate of 100 mV / sec, and CV measurement was performed. For the CV measurement, an ALS electrochemical analyzer “612D” manufactured by BAS Co., Ltd. was used. FIG. 5 shows the relationship between the current value and the potential (V) in the compound 112 obtained in Example 1. In the compound 112, the compound 145, and the compound 310 obtained in Examples 1 to 3, two sets of redox waves were observed. Table 8 shows the first reduction potential of each compound and the LUMO (lowest empty orbit) level estimated therefrom. Both compounds were found to have high electron accepting ability.

  Next, Examples in which organic semiconductor transistors were produced using the compounds 112, 145, and 310 obtained in Examples 1 to 3 are shown in Examples 4 to 6 below.

Example 4
(Preparation of thin film forming composition)
A thin film-forming composition was prepared by dissolving 0.2 part by weight of the compound 112 obtained in Example 1 in 100 parts by weight of chloroform.

(Production of organic transistors)
In this example, an organic transistor according to an example of the top contact-bottom gate type organic transistor 10B shown in FIG.

In this example, an n-doped silicon wafer (surface resistance of 0.02 Ω · cm or less) having a SiO ₂ thermal oxide film (SiO ₂ film formed by thermal oxidation of silicon) having a thickness of 200 nm on one side is used as an insulator. Used as layer 4, gate electrode 5, and substrate 6. In the organic transistor of this example, the SiO ₂ thermal oxide film has the function of the insulator layer 4, and the n-doped silicon wafer has the functions of the substrate 6 and the gate electrode 5.

On the surface of SiO ₂ thermal oxide film in the n-doped silicon wafer with SiO ₂ thermal oxide film is attached by spin coating, coating the thin film-forming composition, a thin film (organic containing compound 112 having a thickness of 100nm Thin film) was formed as the semiconductor layer 2.

  Next, Au (gold) is vacuum-deposited on the thin film as the semiconductor layer 2 using a shadow mask, so that the source electrode 1 and drain electrode 3 (channel length 50 μm, channel width 1. 5 mm top contact type electrode) was formed to complete the organic transistor.

Example 5
A thin film forming composition was prepared using the compound 145 obtained in Example 2 in place of the compound 112 obtained in Example 1, and an organic transistor was produced using this thin film forming composition. Produced an organic transistor in the same manner as in Example 4.

Example 6
A thin film forming composition was prepared using the compound 310 obtained in Example 3 instead of the compound 112 obtained in Example 1, and an organic transistor was produced using this thin film forming composition. Produced an organic transistor in the same manner as in Example 4.

[Characteristic evaluation of organic transistors]
The characteristic was evaluated about each of the organic transistor produced in Examples 4-6.

The performance of the organic transistor depends on the amount of current that flows when a potential is applied between the source electrode and the drain electrode while a potential is applied to the gate electrode. By measuring this current value, the mobility which is a characteristic of the organic transistor can be determined. The mobility can be calculated from the equation (a) that expresses the electrical characteristics of the carrier species generated in the organic semiconductor layer as a result of applying a gate electric field to SiO ₂ as an insulator.

Id = ZμCi (Vg−Vt) ² / 2L (a)
Where Id is the saturated source / drain current value, Z is the channel width, Ci is the capacitance of the insulator, Vg is the gate potential, Vt is the threshold potential, L is the channel length, and μ is the determined mobility. (Cm ² / Vs). Ci is the dielectric constant of the SiO ₂ insulating film used, Z and L are determined by the device structure of the organic transistor, Id and Vg are determined when measuring the current value of the organic transistor, and Vt can be obtained from Id and Vg. By substituting each value into equation (a), the mobility at each gate potential can be calculated.

  In the performance evaluation of the organic transistors produced in Examples 4 to 6, the produced organic transistor was placed in a prober and the characteristics of the organic transistor were measured using “Semiconductor Parameter Analyzer 4200-SCS” (manufactured by Keithley Instruments). Was measured. Regarding the characteristics of the organic transistor, the drain voltage was set to −100 V, the gate voltage was scanned from 20 V to −100 V, and the drain current-gate voltage characteristics (transfer characteristics) were measured. This measurement was performed in the atmosphere.

  Table 9 below shows the evaluation results of the characteristics of the organic transistors produced in Examples 4 to 6 in the atmosphere.

From Table 9, the organic transistors produced in Examples 4 to 6 have high mobility (specifically, mobility of 10 ⁻² cm ² V ⁻¹ s ⁻¹ or more) and high on / off in the atmosphere. It was found to have an off ratio (specifically, an on / off ratio of 10 ³ or more). Therefore, the condensed polycyclic aromatic compound represented by the general formula (1) of the present invention, such as the compound 112, the compound 145, and the compound 310, is stably driven in the atmosphere in an organic transistor, It is considered that it can be suitably used as an n-type organic semiconductor material (n-type material) of a semiconductor device.

  The condensed polycyclic aromatic compound of the present invention can be suitably used as an n-type organic semiconductor material (n-type material) of an organic semiconductor device. The organic semiconductor device of the present invention can be used in the fields of organic transistors, diodes, capacitors, thin film photoelectric conversion devices, dye-sensitized solar cells, organic EL devices, and the like.

DESCRIPTION OF SYMBOLS 1 Source electrode 2 Semiconductor layer 3 Drain electrode 4 Insulator layer 5 Gate electrode 6 Substrate 7 Protective layer 10A-10F Organic transistor 20 Organic solar cell device 21 Substrate 22 Anode 23 Power generation layer 24 Cathode 231 P-type layer 232 N-type layer 233 Buffer layer

  The present invention can be implemented in various other forms without departing from the spirit or main features thereof. For this reason, the above-described embodiment is merely an example in all respects and should not be interpreted in a limited manner. The scope of the present invention is indicated by the claims, and is not restricted by the text of the specification. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.

  This application claims a priority based on a patent application filed in Japan on December 10, 2013, Japanese Patent Application No. 2013-255317. The contents of all publications, patents, and patent applications (including the above-mentioned Japanese patent application) cited herein are incorporated herein by reference in their entirety.

Claims (17)

General formula (1)

Wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocycle Represents a group, a substituted or unsubstituted hydrocarbon oxy group, a substituted or unsubstituted hydrocarbon oxycarbonyl group, a substituted or unsubstituted acyl group, or a cyano group, and R ₅ and R ₆ are each independently substituted or unsubstituted Represents an unsubstituted chain hydrocarbon group, a substituted or unsubstituted hydrocarbon oxy group, X ₁ and X ₂ each independently represent an oxygen atom, a sulfur atom or a selenium atom, wherein A represents a general formula ( 2) to (4)

R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon. Represents a group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hydrocarbonoxy group, a substituted or unsubstituted hydrocarbonoxycarbonyl group, a substituted or unsubstituted acyl group, or a cyano group, * 1 represents X ₁ represents a bond to X ₂ , * 2 represents a bond to X ₂ , * 3 represents a bond to a carbon atom bonded to R ₁ , and * 4 represents a carbon bonded to R _2. Represents a bond with an atom. The condensed polycyclic aromatic compound characterized by the above-mentioned. The condensed polycyclic aromatic compound according to claim 1,
The condensed polycyclic aromatic compound, wherein the substituted or unsubstituted heterocyclic group is a substituted or unsubstituted heteroaromatic group or a substituted or unsubstituted pyranyl group. The condensed polycyclic aromatic compound according to claim 1 or 2,
The condensed polycyclic aromatic compound, wherein X ₁ and X ₂ are sulfur atoms. The condensed polycyclic aromatic compound according to any one of claims 1 to 3,
The condensed polycyclic aromatic compound, wherein R ₁ and R ₂ are hydrogen atoms. The condensed polycyclic aromatic compound according to any one of claims 1 to 4,
The condensed polycyclic aromatic compound, wherein R ₅ and R ₆ are hydrocarbon oxy groups having a linear or branched alkyl group having 1 to 30 carbon atoms. The condensed polycyclic aromatic compound according to any one of claims 1 to 5, wherein
The condensed polycyclic aromatic compound, wherein R ₃ and R ₄ are halogen atoms. The condensed polycyclic aromatic compound according to any one of claims 1 to 5, wherein
The condensed polycyclic aromatic compound, wherein R ₃ and R ₄ are linear or branched alkyl groups having 1 to 30 carbon atoms. A method for producing a condensed polycyclic aromatic compound represented by the general formula (1) according to claim 1,
General formula (5)

(In the formula, Y ₁ represents a halogen atom, and R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group. Represents a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hydrocarbonoxy group, a substituted or unsubstituted hydrocarbonoxycarbonyl group, a substituted or unsubstituted acyl group, or a cyano group, and X ₁ and X ₂ each independently represents an oxygen atom, a sulfur atom or a selenium atom, wherein a is a general formula (6) to (8).

R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon. Represents a group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hydrocarbon oxy group, a substituted or unsubstituted hydrocarbon oxycarbonyl group, a substituted or unsubstituted acyl group, or a cyano group, * 1 Represents a bond to X ₁ , * 2 represents a bond to X ₂ , * 3 represents a bond to a carbon atom bonded to R ₁ , and * 4 is bonded to R ₂ Represents a bond with a carbon atom. ) And a compound represented by
General formula (9)

(Wherein R ₇ represents a substituted or unsubstituted chain hydrocarbon group, or a substituted or unsubstituted hydrocarbon oxy group), and a reaction step comprising reacting with a compound represented by A method for producing a polycyclic aromatic compound. A method for producing the condensed polycyclic aromatic compound according to claim 8, comprising:
The method for producing a condensed polycyclic aromatic compound, wherein the substituted or unsubstituted heterocyclic group is a substituted or unsubstituted heteroaromatic group or a substituted or unsubstituted pyranyl group.   An organic semiconductor material comprising the condensed polycyclic aromatic compound according to any one of claims 1 to 7. The organic semiconductor material according to claim 10,
An organic semiconductor material, wherein the organic semiconductor material is a transistor material.   A composition for forming a thin film, comprising the condensed polycyclic aromatic compound according to any one of claims 1 to 7 and a solvent. It is a composition for thin film formation of Claim 12, Comprising:
The composition for forming a thin film, wherein the content of the condensed polycyclic aromatic compound is in the range of 0.01% by weight to 10% by weight with respect to the total amount of the composition for forming a thin film.   A thin film comprising the condensed polycyclic aromatic compound according to any one of claims 1 to 7.   An organic semiconductor device comprising the thin film according to claim 14.   An organic transistor comprising the thin film according to claim 14.   A method for producing an organic semiconductor device, comprising a step of applying the composition for forming a thin film according to claim 12 or 13 onto a surface on which a thin film is to be formed.

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