JP2014055117A - Phenacene precursor compound and ink comprising the same, organic film using the same and production method thereof, electronic device, and organic thin film transistor - Google Patents

Abstract

［(X₁、X₂)または(Y₁、Y₂）のうち少なくともいずれか一対はともにＨであり、残りの一対はともに置換または無置換のアシルオキシ基である。R₁、R₂はＨまたはハロゲンである。R₃、R₄は水Ｈ、ハロゲン、置換および無置換のアルキル基またはアルコシキ基またはチオアルコキシ基から選択される基であり、同一でも異なっていてもよい。］
【選択図】図１Provided are a phenacene precursor compound, an ink, an organic film, and an electronic device that are excellent in solvent solubility and storage stability and can be converted into a phenacene compound by an external stimulus.
A phenacene precursor compound having a partial structure represented by the following general formula (I) or the like is obtained at a terminal site of a molecular structural formula, and an organic semiconductor layer 1 is formed using an ink obtained by dissolving this in a solvent. An organic thin film transistor is formed.

[At least one pair of (X ₁ , X ₂ ) or (Y ₁ , Y ₂ ) is both H, and the remaining pairs are both substituted or unsubstituted acyloxy groups. R ₁ and R ₂ are H or halogen. R ₃ and R ₄ are groups selected from water H, halogen, substituted and unsubstituted alkyl groups, alkoxy groups or thioalkoxy groups, which may be the same or different. ]
[Selection] Figure 1

Description

  The present invention relates to a precursor of a π-electron conjugated compound, and more specifically, a phenacene precursor compound that can be converted into a phenacene compound, an ink using the same, a method for producing an organic film, an electronic device including the organic film, and an organic The present invention relates to a thin film transistor.

  Since π-conjugated compounds have an extended π-electron system, they are excellent in hole transport and electron transport. For example, electroluminescent materials, organic semiconductor materials (see, for example, Patent Documents 1 and 2 and Non-Patent Documents 1 and 2) Widely applied to pigments, pigments, etc. As π-conjugated materials are widely used in this way, the obstacle is that many of the π-conjugated compounds have high planarity and rigidity, and thus the interaction between molecules is very strong. It is mentioned that the solubility in is poor. For example, with respect to pigments, dispersion becomes unstable as the pigments aggregate. Taking an organic semiconductor as an example, there is a problem that it is difficult to apply a solution process because it is hardly soluble, and vapor deposition such as vacuum deposition is required.

In contrast, a precursor compound into which a reactive substituent that solubilizes an organic compound containing a π-conjugated compound is introduced is given an external stimulus to eliminate the substituent to obtain the target compound. Methods have been proposed (see, for example, Patent Documents 3 and 4 and Non-Patent Document 3). In this method, for example, the Boc group is removed by heating the pigment precursor having a structure in which an amino group or an alcoholic or phenolic hydroxy group in the pigment molecule is modified with a t-butoxycarbonyl group (Boc group). It is something to be released.
However, this method has limitations on applicable compounds because the substituent needs to be linked to a nitrogen atom or an oxygen atom. Furthermore, the improvement was calculated | required also from the viewpoint of the preservability of a precursor.

In recent years, the retro Diels-Alder reaction has been actively studied to convert a precursor compound having a high solvent-soluble bulky substituent into pentacene, porphyrin, or phthalocyanine by applying an external stimulus. (For example, see Patent Documents 5 and 6 and Non-Patent Documents 4 to 6).
However, among these examples, tetrachlorobenzene molecules are eliminated from the pentacene precursor, but tetrachlorobenzene has a high boiling point and is difficult to remove out of the reaction system, and its toxicity is a concern. Further, porphyrin and phthalocyanine need to be improved from the viewpoint of storage stability of the compound obtained after the precursor treatment. In addition, since all of them require complicated synthesis, the range of application is narrow, and development of a substitute group that can be synthesized more simply is required.

In addition, a method for converting to a phthalocyanine by desorbing a substituent and replacing it with a hydrogen atom by applying an external stimulus to a solvent-soluble precursor compound having a sulfonate ester-based substituent is proposed. (For example, refer to Patent Document 7).
However, this method has a problem in that the sulfonic acid ester has a high polarity, so the solubility in a nonpolar organic solvent is poor, and the temperature required for conversion from the precursor is relatively high.

  In addition, a method has been proposed in which oligothiophene is obtained by solubilizing by introducing a carboxylic acid ester at the molecular end of oligothiophene and then removing it by applying heat (for example, Patent Document 8, Non-Patent Document). Reference 7). In this method, desorption occurs at a relatively low temperature. However, since olefin remains at the end of the molecule after desorption, this impairs the crystallinity of the compound and greatly reduces the stability to oxygen, moisture, heat, etc. There was a problem of end.

Moreover, a phenacene compound is mentioned as an organic semiconductor material in which a molecular skeleton is formed only by an aromatic ring. A method using a phenacene compound as an active layer of an organic transistor has been proposed (Patent Document 9).
However, since the exemplified phenacene compound has a large molecular size and cannot be dissolved, or is very poor in solubility, it is difficult to form a film by a printing process. Furthermore, it is presumed that at the time of the reaction intermediate compound of these phenacene compounds, the solubility is low and the reaction and purification are difficult.

  The present invention has been made in view of the above prior art, and has excellent solubility in various organic solvents and excellent storage stability, and can be converted into a phenacene compound by external stimulation (for example, application of thermal energy). It is an object of the present invention to provide a phenacene precursor compound, an ink containing the same, an organic film manufacturing method using the ink, an electronic device including the organic film formed by the manufacturing method, and an organic thin film transistor.

As a result of intensive studies, the present inventors have found that the above problems can be solved by synthesizing and using a phenacene precursor compound having a specific structure, and have reached the present invention.
That is, the above problem is solved by a phenacene precursor compound characterized by having a partial structure represented by the following general formula (I) or general formula (II) at the terminal site of the molecular structure of the phenacene compound.

[In Formula (I), at least one pair of (X ₁ , X ₂ )) or (Y ₁ , Y ₂ ) is both a hydrogen atom, and the remaining pairs are both substituted or unsubstituted carbon atoms of 1 or more. Of the acyloxy group. R ₁ and R ₂ are a hydrogen atom or a halogen atom, and may be the same or different. R ₃ and R ₄ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]

[In Formula (II), at least one of X ₃ and Y ₃ is a hydrogen atom, and the other is a substituted or unsubstituted acyloxy group having 1 or more carbon atoms. R ₅ and R ₆ are a hydrogen atom or a halogen atom, and may be the same or different. R ₇ and R ₈ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]

  Further, the above problem is solved by a phenacene precursor compound, wherein the phenacene precursor compound is represented by the following general formula (III) or general formula (IV).

[In the formula (III) or (IV), R _{9 to} R ₃₀ are hydrogen atoms or halogen atoms, which may be the same or different. Z ₁ and Z ₂ are partial structures represented by the following general formula (I) or general formula (II), and may be the same or different. n is an integer of 1-2. ]

[In Formula (I), at least one pair of (X ₁ , X ₂ )) or (Y ₁ , Y ₂ ) is both a hydrogen atom, and the remaining pairs are both substituted or unsubstituted carbon atoms of 1 or more. Of the acyloxy group. R ₁ and R ₂ are a hydrogen atom or a halogen atom, and may be the same or different. R ₃ and R ₄ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]

[In Formula (II), at least one of X ₃ and Y ₃ is a hydrogen atom, and the other is a substituted or unsubstituted acyloxy group having 1 or more carbon atoms. R ₅ and R ₆ are a hydrogen atom or a halogen atom, and may be the same or different. R ₇ and R ₈ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]
Further, the above-mentioned problems are solved by an ink characterized by containing the phenacene precursor compound according to claim 1 or 2 and a solvent.
The above-mentioned problem is solved by a method for producing an organic film formed using an ink according to claim 3, wherein the film formation is performed by a wet process. Is done.
Further, the above-mentioned problem is that a molecular structure represented by the general formula (I) or the general formula (II) of the phenacene compound contained in the organic film by applying an external stimulus to the organic film according to claim 4 Solved by a method of producing an organic film characterized in that the structure of the formula end site is converted from (I) to (Ia) or (II) to (IIa) by a chemical reaction represented by the following formula (1) or formula (2) Is done.

  [Substituents in Formula (1) or Formula (2) are the same as defined in Formula (I) or Formula (II). ]

  Further, the above problem is solved by an organic film formed by the manufacturing method according to any one of claims 4 to 6.

  Moreover, the said subject is solved by the electronic device characterized by comprising the organic film of Claim 7.

  Moreover, the said subject is solved by the organic thin-film transistor characterized by comprising the organic-semiconductor layer which consists of an organic film of Claim 7.

The phenacene precursor compound of the present invention has solubility in various organic solvents by having the partial structure represented by the general formula (I) or the general formula (II) at the terminal site of the molecular structural formula of the phenacene compound. It is excellent in storage stability and can be converted into a phenacene compound by external stimulation (for example, application of thermal energy). For this reason, an ink containing a phenacene precursor compound and a solvent can be used, and film formation (film formation) can be easily performed using the ink. Therefore, an electronic device can be created by a wet process (for example, a printing process). .
In addition, by applying an external stimulus (for example, simple heat treatment) to the formed organic film after the printing process, the terminal end of the molecular structure formula of the phenacene compound represented by the general formula (I) or the general formula (II) The site (solubilizing group) can be structurally converted from (I) to (Ia) or (II) to (IIa) by a chemical reaction to produce a phenacene compound. By such a method, for example, an organic thin film transistor having excellent storage stability and high carrier mobility can be provided.

It is the schematic which shows the structural examples (A) to (C) of the organic thin-film transistor which concerns on this invention.

  As described above, the phenacene precursor compound of the present invention is characterized by having a partial structure represented by the following general formula (I) or general formula (II) at the terminal site of the molecular structure of the phenacene compound. .

[In Formula (I), at least one pair of (X ₁ , X ₂ )) or (Y ₁ , Y ₂ ) is both a hydrogen atom, and the remaining pairs are both substituted or unsubstituted carbon atoms of 1 or more. Of the acyloxy group. R ₁ and R ₂ are a hydrogen atom or a halogen atom, and may be the same or different. R ₃ and R ₄ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]

[In Formula (II), at least one of X ₃ and Y ₃ is a hydrogen atom, and the other is a substituted or unsubstituted acyloxy group having 1 or more carbon atoms. R ₅ and R ₆ are a hydrogen atom or a halogen atom, and may be the same or different. R ₇ and R ₈ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]

  The phenacene compound in the present invention is a polycyclic aromatic ring compound in which a benzene ring is condensed, and the condensed form of the benzene ring is a polyacene compound condensed in zigzag, which is an expanded phenanthrene skeleton. A general term for a group of compounds in a ring mode. In the present invention, the “phenacene precursor compound” may be referred to as a “specific compound”.

  Here, the phenacene precursor compound is preferably one represented by the following general formula (III) or general formula (IV).

[In the formula (III) or (IV), R _{9 to} R ₃₀ are hydrogen atoms or halogen atoms, which may be the same or different. Z ₁ and Z ₂ are partial structures represented by the following general formula (I) or general formula (II), and may be the same or different. n is an integer of 1-2. ]

[In Formula (I), at least one pair of (X ₁ , X ₂ )) or (Y ₁ , Y ₂ ) is both a hydrogen atom, and the remaining pairs are both substituted or unsubstituted carbon atoms of 1 or more. Of the acyloxy group. R ₁ and R ₂ are a hydrogen atom or a halogen atom, and may be the same or different. R ₃ and R ₄ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]

[In Formula (II), at least one of X ₃ and Y ₃ is a hydrogen atom, and the other is a substituted or unsubstituted acyloxy group having 1 or more carbon atoms. R ₅ and R ₆ are a hydrogen atom or a halogen atom, and may be the same or different. R ₇ and R ₈ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]

  Examples of the halogen atom in the general formulas (I) to (IV) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the general formulas (I) and (II), as the substituted or unsubstituted acyloxy group, a formyloxy group, a linear or cyclic aliphatic carboxylic acid which may contain a halogen atom having 2 or more carbon atoms, and carbon Examples include acyloxy groups derived from carboxylic acids such as aromatic carboxylic acids having a number of 4 or more. Specifically, for example, formyloxy group, acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, pentanoyloxy, hexanoyloxy, lauroyloxy group, stearoyloxy group, trifluoroacetyloxy 3,3,3-trifluoropropionyloxy, pentafluoropropionyloxy, cyclopropanoyloxy, cyclobutanoyloxy, cyclohexanoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, pentafluorobenzoyloxy group Etc.
In addition, carbonic acid esters derived from a carbonic acid half ester corresponding to a structure in which an oxygen atom is inserted between the carbonoxy group and the alkyl group or aryl group of the acyloxy group exemplified above can also be mentioned.

R ₃ and R _{4 in} the general formula (I) and R ₇ and R _{8 in} the general formula (II) are selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group, or a thioalkoxy group. Group, which may be the same or different.

  Examples of the substituted and unsubstituted alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecane, hexadecyl, heptadecyl, octadecyl, 3,7-dimethyloctyl, 2-ethylhexyl Group, trifluoromethyl group, trifluorooctyl group, trifluorododecyl group, trifluorooctadecyl group, 2-cyanoethyl group and the like. Examples of the alkoxy group and the alkylthio group include those in which an oxygen atom or a sulfur atom is inserted into the bonding position of the alkyl group to form an alkoxy group or an alkylthio group.

In the general formulas (I) and (II), at least one of (X ₁ , X ₂ )) or (Y ₁ , Y ₂ ) is a substituted or unsubstituted acyloxy group having 1 or more carbon atoms. However, such an acyloxy group preferably has a structure represented by the following general formula (V).

[In the formula (V), R ₃₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxyl group, substituted or unsubstituted A substituted thioalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a cyano group are particularly preferred, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, A substituted or unsubstituted thioalkyl group. Most preferably, it is a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxyl group. ]

  By applying an external stimulus (for example, thermal energy), the enacene precursor compound of the present invention can convert the molecular structural formula terminal site represented by the general formula (I) or the general formula (II) into the formula (1) described below. ) Or the chemical reaction represented by the formula (2) [Chemical Formula 26], the structure is converted from (I) to (Ia) or (II) to (IIa) to be converted into a phenacene compound.

X ₁ -Y ₁ and X ₂ -Y ₂ which are the leaving components of the above formula (1) include, in addition to the halogen atom, the —O— bond site of the substituent constituting the acyloxy group, which is cleaved at the terminal. And corresponding carboxylic acids and carbonic acid half esters substituted for hydrogen. For example, formic acid, acetic acid, pyruvic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, lauric acid, stearic acid, monochloroacetic acid, monofluoroacetic acid, difluoroacetic acid, 2,2-difluoropropionic acid , Trifluoroacetic acid, 3,3,3-trifluoropropionic acid, pentafluoropropionic acid, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclohexanecarboxylic acid, benzoic acid, p-methoxybenzoic acid, pentafluorobenzoic acid, methylhydrogen Examples include carbonate, ethyl hydrogen carbonate, isopropyl hydrogen carbonate, and hexyl hydrogen carbonate. Since these carbonic acid half esters are usually unstable, they may be decomposed to the corresponding alcohol (eg, methanol, ethanol, 2-propanol, hexanol) and carbon dioxide.

The substituent R ₃₁ in the general formula (V) is not particularly limited, and from the viewpoint of solvent solubility and film formability, the intermolecular interaction as a substituent is reduced to some extent and the affinity with the solvent is increased. However, if the volume change before and after the detachment of the substituent is too great, there may be a problem in the uniformity of the thin film in the elimination reaction. However, it is preferable that the substituent is as small as possible. In addition, although it is not yet known, the electron-withdrawing substituent (for example, a halogen-containing alkyl group or a group having a nitro group and a cyano group) is removed so that the degree of polarization of carbonyl oxygen is increased. It is considered preferable in terms of increasing the efficiency of the separation reaction.

In the structure described in the phenacene compound to the general formula (III) or the general formula (IV), for example, when Z ₁ and Z ₂ are aromatic rings, the molecular structural formula terminal site is the general formula (I) and the general formula When it does not have a dissolving group as in (II)], it does not dissolve in a general organic solvent, or dissolves only a very small amount.
Assuming that the application of the phenacene compound to organic electronics materials is assumed, by expanding the conjugated system of the molecules, the area of the electron transfer path is widened and can be used as a good electronics material. However, extending the conjugated system of molecules tends to increase the interaction between molecules, and the solubility in organic solvents and the like is significantly reduced.
Thus, by introducing a substituent that weakens the intermolecular force represented by the general formula (I) or the general formula (II) into the terminal site of the molecular structure of the phenacene compound as in the present invention, the solubility in various solvents is improved. Can be adapted to the printing process.

Furthermore, from the phenacene precursor compound of the present invention, the phenacene compound produced by the elimination of the soluble groups (leaving components X ₁ , Y ₁ and X ₂ , Y ₂ ) by a simple external stimulus, Even if the conjugated system continues to be expanded, there is no bias of electrons in the molecule, so there is no deterioration reaction due to oxygen, water, etc., and it has very high storage stability.

  Further, detailed phenacene precursor compounds (abbreviated as “derivatives”) of the present invention are exemplified in the following structural formulas (1) to (26). However, structural formulas (1) to (26) are examples and are not limited to these.

Below, the synthesis example of a phenacene precursor compound is demonstrated concretely.
The phenacene precursor compounds of the structural formulas (1) to (4) can be produced via a reaction formula shown in the following synthesis route 1.
[Synthetic route 1]

The main points of the reaction formula in the synthesis route 1 are as follows.
-1-2 is produced by Still coupling of 1-1 and a vinyl tin body in the presence of a palladium catalyst.
-1-4 is produced by iodination of the amine derivative of 1-3 by the Sandmeyer reaction.
1-5 is produced by bromination of the benzyl position with azobisisobutyronitrile (AIBN) and N-bromosuccinimide (NBS).
1-6 is produced by esterification with carboxylic acid corresponding to the leaving group in the presence of tetramethylammonium hydroxide pentahydrate.
1-7 is produced by coupling 1-2 and 1-6 using a Heck reaction in the presence of a palladium catalyst.
1-8 is produced via photoreaction and oxidation reaction. That is, when 1-7 is irradiated with ultraviolet light, a photoisomerization reaction occurs, and the photoisomerization reaction results in a hexatriene structure. When this structure is further irradiated with ultraviolet light, a photocyclization reaction occurs. After photoreaction, oxidation reaction occurs with iodine to produce 1-8.

The phenacene precursor compounds of the structural formulas (5) and (6) can be produced via the reaction formula shown in the following synthesis route 2.
[Synthesis route 2]

The main points of the reaction formula in the synthesis route 2 are as follows.
-2-2 is produced by iodination of the amine derivative of 2-1 by the Sandmeyer reaction.
-2-3 is produced by reducing the ketone moiety of 2-2 with sodium borohydride and converting it to hydroxy.
2-4 is produced by esterifying the hydroxyl group of 2-3 with acetic anhydride in the presence of N, N-dimethylaminopyridine (DMAP).
2-5 is produced by bromination of the benzyl position with azobisisobutyronitrile (AIBN) and N-bromosuccinimide (NBS).
2-6 is produced by dehydrohalogenation with sodium methoxide (base).
2-7 is produced by esterification using carboxylic acid corresponding to the leaving group in the presence of DMAP.
2-8 is produced by coupling 2-7 and 1-2 using the Heck reaction in the presence of a palladium catalyst.
・ 2-9 is produced via photoreaction and oxidation reaction. That is, when 2-8 is irradiated with ultraviolet light, a photoisomerization reaction occurs, and the photoisomerization reaction results in a hexatriene structure. When this structure is further irradiated with ultraviolet light, a photocyclization reaction occurs. After the photoreaction, iodine undergoes an oxidation reaction to produce 2-9.

The phenacene precursor compounds of the structural formulas (7) to (9) can be produced via the reaction formula shown in the following synthesis route 3.
[Synthesis route 3]

The main points of the reaction formula in the synthesis route 3 are as follows.
3-2 is produced by Still coupling of 3-1 and a vinyl tin body in the presence of a palladium catalyst.
3-3 is produced by coupling 3-2 and 1-6 using a Heck reaction in the presence of a palladium catalyst.
3-4 is produced via photoreaction and oxidation reaction. That is, when 3-3 is irradiated with ultraviolet light, a photoisomerization reaction occurs, and the photoisomerization reaction results in a hexatriene structure. When this structure is further irradiated with ultraviolet light, a photocyclization reaction occurs. After the photoreaction, iodine undergoes an oxidation reaction to produce 3-4.

The phenacene precursor compounds of the structural formulas (10) to (12) can be produced via the reaction formula shown in the following synthesis route 4.
[Synthesis route 4]

The main points of the reaction formula in the synthesis route 4 are as follows.
4-1 is produced by coupling 3-2 and 2-7 using a Heck reaction in the presence of a palladium catalyst.
-4-2 is produced via photoreaction and oxidation reaction. That is,
When 4-1 is irradiated with ultraviolet light, a photoisomerization reaction occurs, and the photoisomerization reaction results in a hexatriene structure. When this structure is further irradiated with ultraviolet light, a photocyclization reaction occurs. After the photoreaction, an oxidation reaction occurs with iodine to produce 4-2.

The phenacene precursor compounds of the structural formulas (13) to (17) can be produced via the reaction formula shown in the following synthesis route 5.
[Synthesis route 5]

The main points of the reaction formula in the synthesis route 5 are as follows.
5-2 is produced by Still coupling of 5-1 and a vinyl tin body in the presence of a palladium catalyst.
-5-3 is produced by coupling 5-2 and 1-6 in the presence of a palladium catalyst using the Heck reaction.
-5-4 is produced via photoreaction and oxidation reaction. That is, when 5-3 is irradiated with ultraviolet light, a photoisomerization reaction occurs, and the photoisomerization reaction results in a hexatriene structure. When this structure is further irradiated with ultraviolet light, a photocyclization reaction occurs. After the photoreaction, an oxidation reaction occurs with iodine to produce 5-4.

The phenacene precursor compounds of the structural formulas (18) to (20) can be produced via a reaction formula shown in the following synthesis route 6.
[Synthesis route 6]

The main points of the reaction formula in the synthesis route 6 are as follows.
6-1 is produced by coupling 5-2 and 2-7 using a Heck reaction in the presence of a palladium catalyst.
-6-2 is produced via photoreaction and oxidation reaction. That is, when 6-1 is irradiated with ultraviolet light, a photoisomerization reaction occurs, and the photoisomerization reaction results in a hexatriene structure. When this structure is further irradiated with ultraviolet light, a photocyclization reaction occurs. After photoreaction, oxidation reaction occurs with iodine to produce 6-2.

The phenacene precursor compounds of the structural formulas (21) to (23) can be produced via the reaction formula shown in the following synthesis route 7.
[Synthesis route 7]

The main points of the reaction formula in the synthesis route 7 are as follows.
7-2 is produced by Still coupling of 7-1 and a vinyl tin body in the presence of a palladium catalyst.
7-3 is produced by coupling 7-2 and 1-6 in the presence of a palladium catalyst using the Heck reaction.
・ 7-4 is manufactured via photoreaction and oxidation reaction. That is, when 7-3 is irradiated with ultraviolet light, a photoisomerization reaction occurs, and the photoisomerization reaction results in a hexatriene structure. When this structure is further irradiated with ultraviolet light, a photocyclization reaction occurs. After the photoreaction, an oxidation reaction occurs with iodine to produce 7-4.

The phenacene precursor compounds of the structural formulas (24) to (26) can be produced via the reaction formula shown in the following synthesis route 8.
[Synthesis route 8]

The main points of the reaction formula in the synthesis route 8 are as follows.
8-1 is produced by coupling 7-2 and 2-7 using a Heck reaction in the presence of a palladium catalyst.
・ 8-2 is produced via photoreaction and oxidation reaction. That is, when 8-1 is irradiated with ultraviolet rays, a photoisomerization reaction occurs, and the photoisomerization reaction results in a hexatriene structure. When this structure is further irradiated with ultraviolet light, a photocyclization reaction occurs. After the photoreaction, an oxidation reaction occurs with iodine to produce 8-2.

  In addition, a production method in the case where the partial structure represented by the general formula (I) or the general formula (II) is not a phenacene precursor compound having both terminal portions of the molecular structural formula, that is, only at one end portion of the phenacene structure. A phenacene precursor having a structure having the general formula (I) or the general formula (II), or a structure having the general formula (I) at one end of one side and the general formula (II) at the other end As the production method, a reaction for forming an olefin bond may be selectively used in the coupling reaction immediately before the photoisomerization / cyclization / oxidation reaction of the final reaction. For example, a stetyl coupling reaction, a Heck coupling reaction, and the like are possible by introducing a substituent that is selective for bond formation into the compound to be reacted.

[ink]
The ink of the present invention contains at least a phenacene precursor compound and a solvent (such as an organic solvent) that dissolves the precursor. As the organic solvent, generally known organic solvents can be used, and they can be used by mixing. Examples of common organic solvents include dichloromethane, tetrahydrofuran, chloroform, toluene, chlorobenzene, dichlorobenzene, xylene, mesitylene, and N-methylpyrrolidone. Furthermore, in order to adjust the viscosity, a high viscosity solvent, a polymer material, or a thickener may be added.

  The content of the phenacene precursor compound in the ink is preferably adjusted for viscosity and evaporation temperature according to the coating method. For example, in the case of an inkjet solvent, a range of 0.1 wt% to 10 wt% is preferably used. .

  The ink of the present invention can be used in a generally known wet process (wet process), for example, inkjet method, spin coating, dip coating, spray coating, screen printing, gravure printing, blade coating, casting, roll coating. Used for bar coating, die coating and the like.

Next, a method for producing a phenacene compound by an elimination reaction of a phenacene precursor compound will be described.
As described above, the phenacene precursor compound of the present invention imparts an external stimulus to the molecular structural formula terminal site represented by the general formula (I) or the general formula (II) by the following formula (1) or formula. The structure can be converted from (I) to (Ia) or (II) to (IIa) by the chemical reaction shown in (2), and the phenacene compound is converted.

  [Substituents in Formula (1) or Formula (2) are the same as defined in Formula (I) or Formula (II). ]

As described above, the phenacene precursor compound has a detachable solubilizing group and is detached by applying an external stimulus.
Examples of the energy to be applied for the elimination reaction include heat, light, and electromagnetic waves. However, thermal energy or light energy is desirable from the viewpoint of reactivity, yield, and post-processing, and thermal energy is particularly preferable.
That is, an organic film converted from a phenacene precursor compound to a phenacene compound is obtained by forming a coating film by a wet process using the ink and applying an external stimulus.
As a heating method for performing the elimination reaction, a method of heating on a support, a method of heating in an oven, a method of irradiation with microwaves, a method of heating by converting light into heat using a laser, Various methods such as using a photothermal conversion layer can be used, but are not limited thereto.

  The atmosphere for the elimination reaction can be performed in the atmosphere, but in order to eliminate side effects such as oxidation and the influence of moisture, in addition, the elimination of the desorbed components outside the system is promoted. Therefore, it is desirable to carry out under an inert gas atmosphere or under reduced pressure.

[Electronic device]
The phenacene precursor of the present invention and the phenacene compound obtained from the precursor can be used, for example, in an electronic device. That is, an electronic device can be configured by including an organic film formed by a wet process using an ink containing a phenacene precursor compound and a solvent.
An example of an electronic device is a device that has two or more electrodes, the current flowing between the electrodes or the voltage generated is controlled by electricity, light, magnetism, chemical substances, etc., or the applied voltage or current. And a device for generating light, an electric field, and a magnetic field.
In addition, for example, an element that controls current or voltage by application of voltage or current, an element that controls voltage or current by application of a magnetic field, an element that controls voltage or current by the action of a chemical substance, or the like can be given. Examples of this control include rectification, switching, amplification, and oscillation.

Currently, the corresponding devices realized with inorganic semiconductors such as silicon include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements, chemical sensors, etc. Examples include combinations of elements and integrated devices.
In addition, a solar cell that generates an electromotive force by light, or an optical element such as a photodiode or a phototransistor that generates a photocurrent can be used.
An example of an electronic device suitable for applying the specific compound of the present invention is a field effect transistor (FET).
Hereinafter, a field effect transistor (FET) will be described in detail as an example.

[Transistor structure]
1A to 1D are schematic structures of an organic thin film transistor according to the present invention.
The organic semiconductor layer (1) of the organic thin film transistor according to the present invention contains the specific compound of the present invention.
The organic thin film transistor according to the present invention is provided with a source electrode (2), a drain electrode (3) and a gate electrode (4) which are spatially separated, and the gate electrode (4) and the organic semiconductor layer (1). An insulating film (5) may be provided between them. In the organic thin film transistor, the current flowing in the organic semiconductor layer (1) between the source electrode (2) and the drain electrode (3) is controlled (controlled) by applying a voltage to the gate electrode (4).

  The organic thin film transistor according to the present invention can be provided on a support, and a commonly used substrate such as glass, silicon, or plastic can be used as the support. In addition, by using a conductive substrate, it can also be used as a gate electrode, and a structure in which a gate electrode and a conductive substrate are stacked can be used. However, the flexibility of a device to which the organic thin film transistor of the present invention is applied. When characteristics such as light weight, low cost, and impact resistance are desired, a plastic sheet is preferably used as the support.

  Examples of the plastic sheet include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate. Is mentioned.

[Deposition method: Organic semiconductor layer]
The organic film (organic semiconductor layer) of the organic thin film transistor according to the present invention can be formed by vapor deposition such as vacuum deposition. In addition, for example, a thin film can be formed by dissolving in a solvent such as dichloromethane, tetrahydrofuran, chloroform, toluene, chlorobenzene, dichlorobenzene, and xylene and coating on a support. It can also be formed by applying (applying) an external stimulus (for example, heat or light energy) and converting the phenacene precursor compound into a phenacene compound.
These organic semiconductor layers (organic semiconductor thin films) can be prepared by spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, ink jet, and dispensing. In accordance with the material, a suitable solvent is selected from the suitable film forming method and the solvent.

In the organic thin film transistor according to the present invention, the thickness of the organic semiconductor layer is not particularly limited, but a uniform thin film, that is, a thin film having no gap or hole that adversely affects the carrier transport property of the organic semiconductor layer is formed. The thickness is selected. The thickness of the organic semiconductor thin film is generally 1 μm or less, particularly preferably 5 to 200 nm.
In the organic thin film transistor of the present invention, the organic semiconductor layer formed using the specific compound as a component is formed in contact with the source electrode, the drain electrode, and the insulating film.

〔electrode〕
The gate electrode, source electrode, and gate electrode used in the organic thin film transistor according to the present invention are not particularly limited as long as they are conductive materials. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony, lead Tantalum, indium, aluminum, zinc, magnesium, etc., and their alloys, conductive metal oxides such as indium / tin oxide, or inorganic and organic semiconductors whose conductivity has been improved by doping, such as silicon single crystals , Polysilicon, amorphous silicon, germanium, graphite, polyacetylene, polyparaphenylene, polythiophene, polypyrrole, polyaniline, polythienylene vinylene, polyparaphenylene vinylene, a complex of polyethylenedioxythiophene and polystyrenesulfonic acid, and the like.
Of the above-described conductivity, the source electrode and the drain electrode preferably have low electrical resistance at the contact surface with the semiconductor layer.

As a method for forming an electrode, a method of forming an electrode using a known photolithographic method or a lift-off method, using a conductive thin film formed by a method such as vapor deposition or sputtering using the above materials as a raw material, a metal such as aluminum or copper There is a method of etching using a resist by thermal transfer, ink jet or the like on a foil. Alternatively, a conductive polymer solution or dispersion, or a conductive fine particle dispersion may be directly patterned by inkjet, or may be formed from the coating film by lithography, laser ablation, or the like. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as relief printing, intaglio printing, planographic printing, or screen printing can also be used.
Moreover, the organic thin-film transistor which concerns on this invention can provide the extraction electrode from each electrode as needed.

[Insulating film]
Various insulating film materials can be used for the insulating film used in the organic thin film transistor according to the present invention. For example, silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum oxide, tin oxide, vanadium oxide, barium strontium titanate, zirconium barium titanate, lead zirconate titanate, lead lanthanum titanate, titanate Examples thereof include inorganic insulating materials such as strontium, barium titanate, barium magnesium fluoride, bismuth tantalate niobate, and yttrium trioxide. Further, for example, polymer compounds such as polyimide, polyvinyl alcohol, polyvinylphenol, polyester, polyethylene, polyphenylene sulfide, unsubstituted or halogen atom-substituted polyparaxylylene, polyacrylonitrile, cyanoethyl pullulan, and the like can be used.
Further, two or more of the above insulating materials may be used in combination. The material is not particularly limited, but a material having a high dielectric constant and a low electrical conductivity is preferable.

  Examples of the method for producing the insulating film layer using the above materials include a CVD method, a plasma CVD method, a plasma polymerization method, a dry process such as a vapor deposition method, a spray coating method, a spin coating method, a dip coating method, an ink jet method, and a cast method. Examples thereof include wet processes such as coating, blade coating, and bar coating.

[Organic semiconductor / insulating film interface modification by HMDS, etc.]
In the organic thin film transistor according to the present invention, an organic thin film may be provided between these layers for the purpose of improving the adhesion between the insulating film and the organic semiconductor layer, reducing the gate voltage, and reducing the leakage current.
The organic thin film is not particularly limited as long as it does not chemically affect the organic semiconductor layer. For example, an organic molecular film or a polymer thin film can be used. Examples of the organic molecular film include a coupling agent using octyltrichlorosilane, octadecyltrichlorosilane, hexamethylenedisilazane (HMDS), phenyltrichlorosilane and the like as specific examples. As the polymer thin film, the above-described polymer insulating film materials can be used, and these may function as a kind of insulating film. The organic thin film may be subjected to an anisotropic treatment by rubbing or the like.

[Protective layer]
The organic transistor of the present invention is stably driven even in the atmosphere, but a protective layer is used as necessary for protection from mechanical destruction, protection from moisture and gas, or protection for device integration. Can also be provided.

[Applied devices]
The organic thin film transistor according to the present invention can be used as an element for driving display image elements such as liquid crystal, organic EL, and electrophoresis, and by integrating them, a so-called “electronic paper” display can be manufactured. It is.
Further, an IC in which the organic thin film transistor of the present invention is integrated can be used as a device such as an IC tag.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples unless it exceeds the gist.

[Example 1]
The derivative exemplified in the structural formula (14) (phenacene precursor compound) was synthesized according to the following synthesis route.
The synthesis route of the phenacene precursor compound (14) is shown in the following formula, and the procedure is shown in the following synthesis procedures [1] to [8].

Synthesis procedure [1]
<< Synthesis of (E) -1,2-bis (2-bromophenyl) ethane: 2 >>
THF (300 ml) and zinc powder (17.23 ml, 0.263 mol) were placed in a 500 ml four-necked flask and cooled to 0 ° C. with an ice bath. Thereto, titanium tetrachloride (50.0 g, 0.263 mol) was appropriately added and refluxed for 1.5 hours. After cooling to room temperature, 2-bromobenzaldehyde (10.16 ml, 0.0879 mol) was added and refluxed for 5 hours. After cooling to room temperature, the reaction solution was added to a saturated aqueous sodium hydrogen carbonate solution (500 ml) and stirred, and further ethyl acetate (500 ml) was added and stirred overnight. Celite filtration was performed to separate insoluble matters, and the resulting solution was extracted with ethyl acetate. The organic layer was washed with water saturated brine, and then the organic layer was dried over magnesium sulfate. Magnesium sulfate was filtered off and recrystallized with ethyl acetate to obtain 7.0 g (54% yield) of (E) -1,2-bis (2-bromophenyl) ethane: 2.
Identification was performed by NMR. ¹ H-NMR (CDCl 3, TMS) σ: 7.15 (t, 2H, J = 5.5 Hz), 7.34 (t, 2H, J = 5.5 Hz), 7.40 (s, 2H,) 7.60 (dd, 2H, J ₁ = 7.9 Hz, J ₂ = 1.5 Hz), 7.73 (dd, 2H, J ₁ = 7.9 Hz, J ₂ = 1.5 Hz)

Synthesis procedure [2]
<< Synthesis of 1,8-dibromophenanthrene: 3 >>
Cyclohexane (400 ml), (E) -1,2-bis (2-bromophenyl) ethane (3.0 g, 0.0088 mol) and iodine (0.22 g, 0.0017 mol) in a 500 ml four-necked flask Put. Ushio low-pressure mercury lamp was irradiated for 24 hours. The precipitated solid was filtered off and washed with cyclohexane. Recrystallization from toluene gave 1.7 g (yield 57%) of 1,8-dibromophenanthrene: 3. Identified by NMR
¹ H-NMR (CDCl 3, TMS) σ: 7.53 (dd, 2H, J ₁ = 8.1 Hz, J ₂ = 7.7 Hz), 7.94 (d, 2H, J = 8.1 Hz), 8 .31 (s, 2H,), 8.67 (d, 2H, J = 7.7 Hz)

Synthesis procedure [3]
<< Synthesis of 1,8-divinylphenanthrene: 4 >>
Toluene (60 ml), vinyltributyltin (1.47 ml, 0.0050 mol) and 1,8-dibromophenanthrene (0.77 g, 0.0023 mol) were placed in a 200 ml four-necked flask. The mixture was stirred for 45 minutes while bubbling with argon gas. Tetrakistriphenylphosphine palladium (0.23 g, 0.00020 mol) was added and refluxed for 4 hours. The mixture was cooled to room temperature, poured into a saturated aqueous potassium fluoride solution (100 ml) and stirred, and further ethyl acetate (100 ml) was added and stirred. Celite filtration was performed, insolubles were filtered off, and the resulting solution was extracted with ethyl acetate. The organic layer was washed with water saturated brine, and then the organic layer was dried over magnesium sulfate. Magnesium sulfate was filtered off and recrystallized with ethyl acetate to obtain 0.43 g (yield 82%) of 1,8-divinylphenanthrene: 4.
Identification was performed by NMR. ¹ H-NMR (CDCl 3, TMS) σ: 5.52 (dd, 2 H, J ₁ = 17.4 Hz, J ₂ = 1.4 Hz), 5.81 (dd, 2 H, J ₁ = 10.9 Hz, J ₂ = 1.4 Hz), 7.55 (dd, 2H, J ₁ = 17.4 Hz, J ₂ = 10.9 Hz), 7.64 (dd, 2H, J ₁ = 8.0 Hz, J ₂ = 7. 2 Hz), 7.74 (d, 2H, J = 7.2 Hz), 8.10 (s, 2H,), 8.68 (d, 2H, J = 8.0 Hz)

Synthesis procedure [4]
<< Synthesis of 5-iodo-1,2,3,4, -tetrahydronaphthalene: 6 >>
Distilled water (250 ml), concentrated hydrochloric acid (62.5 ml), and 5,6,7,8-tetrahydronaphthalen-1-amine (25.0 ml, 0.16 mol) were placed in a 500 ml four-necked flask. The mixture was heated and stirred until completely dissolved while bubbling argon gas. Sodium nitrite (11.48 g, 0.166 mol) dissolved in distilled water (30 ml) was added dropwise by cooling to 0 ° C. with glares. After stirring for 10 minutes, potassium iodide (27.62 g, 0.166 mol) dissolved in distilled water (50 ml) was added dropwise. The ice greed was removed and the mixture was stirred for 20 minutes. The mixture was heated to 80 ° C. with an oil bath and stirred for 10 minutes. After cooling to 0 ° C. with an ice bath, sodium hydrogen sulfate was added and stirred. Hexane (100 ml) was added and celite filtration was performed. The filtrate was extracted with hexane, washed with distilled water and saturated brine, and the organic layer was dried over magnesium sulfate. Magnesium sulfate was filtered off and hexane was distilled off. The obtained liquid was distilled under vacuum to obtain 16.84 g (yield 41%) of 5-iodo-1,2,3,4, -tetrahydronaphthalene: 6.
Identification was performed by NMR. ¹ H-NMR (CDCl 3, TMS) σ: 1.71-1 · 84 (m, 4H), 2.66 (t, 2H, J = 6.3 Hz), 2.73 (t, 2H, J = 6) .3 Hz), 6.77-6.81 (m, H), 7.04 (d, H, J = 7.2 Hz), 7.66 (d, H, J = 7.6 Hz)

Synthesis procedure [5]
<< Synthesis of 1,4-dibromo-5-iodo-1,2,3,4, -tetrahydronaphthalene: 7 >>
In a 200 ml four-necked flask, carbon tetrachloride (50 ml), 5-iodo-1,2,3,4, -tetrahydronaphthalene (5.0 g, 0.019 mol), N-bromosuccinimide: NBS (6.90 g, 0.039 mol) and azobisisobutyronitrile: AIBN (0.1 g, 0.00058 mol) were added and stirred. The oil bath temperature was gradually raised to 100 ° C. and refluxed for 1 hour. Cooled to room temperature and filtered. The solvent of the obtained filtrate was distilled off to obtain 7.5 g (yield 92%) of 1,4-dibromo-5-iodo-1,2,3,4, -tetrahydronaphthalene: 7.
Identification was performed by NMR. ¹ H-NMR (CDCl 3, TMS) σ: 2.72-2.76 (m, 2H), 2.81-2.85 (m, 2H), 5.53-5.54 (m, H), 5.60-5.62 (m, H), 6.95-6.99 (m, H), 7.35 (d, H, J = 7.8 Hz), 7.83 (d, H, J = 7.8Hz)

Synthesis procedure [6]
<< Synthesis of 5-iodo-1,2,3,4, -tetrahydronaphthalene-1,4-diyl-dihexanonate: 8 >>
Add dimethylformamide: DMF (30 ml), tetramethylammonium hydroxide pentahydrate (0.92 g, 0.0051 mol) and hexanoic acid (0.63 ml, 0.0051 mol) to a 100 ml four-necked flask and stir for 2 hours. did. 1,4-Dibromo-5-iodo-1,2,3,4, -tetrahydronaphthalene (1.0 g, 0.0024 mol) was added and stirred for 48 hours. Distilled water and ethyl acetate were added and extracted into ethyl acetate. Washed with distilled water and saturated brine. The organic layer was dried with magnesium sulfate. Magnesium sulfate was filtered off and the solvent was distilled off. The obtained liquid was separated and purified by column chromatography to obtain 0.7 g (yield 63%) of 5-iodo-1,2,3,4, -tetrahydronaphthalene-1,4-diyl-dihexanonate: 8. It was.
Identification was performed by NMR. ¹ H-NMR (CDCl 3, TMS) σ: 0.86 to 0.89 (m, 6H), 1.25 to 1.35 (m, 8H), 1.58 to 1.62 (m, 4H), 1.63-1.69 (m, 2H), 1.94-1.96 (m, 2H), 2.24-2.38 (m, 4H), 5.89 (t, H, J = 2) .9 Hz), 6.00 (t, H, J = 2.9 Hz), 7.04-7.07 (m, H), 7.36 (d, H, J = 8.0 Hz), 7.89 (D, H, J = 8.0 Hz)

Synthesis procedure [7]
<< Synthesis of Tetrahexanonate Derivative 9 >>
DMF (30 ml), 1,8-divinylphenanthrene (0.20 g, 0.00089 mol), 5-iodo-1,2,3,4-tetrahydronaphthalene-1,4-diyl in a 100 ml four-necked flask -Dihexanonate: 8 (0.78 g, 0.0017 mol), triphenylphosphine (0.0091 g, 0.000034 mol (4 mol%), triethylamine (0.339 ml, 0.0024 mol) were added while argon gas was bubbled. The mixture was stirred for 45 minutes, palladium acetate (0.0039 g, 0.000017 mol (2 mol%)) was added, and the mixture was refluxed for 6 hours at 100 ° C. Cooled to room temperature, filtered through celite, and the resulting solution was extracted with ethyl acetate. The organic layer was washed with water saturated brine, and the organic layer was dried over magnesium sulfate. Magnesium sulfate was filtered off and purified by GPC, and the resulting pale yellow liquid (tetrahexanonate derivative 9) was identified by MS Accurate mass (LC-TofMS) (m / z ): 714.378 (actual value), 714.372 (calculated value)

Synthesis procedure [8]
<< 1,2,3,4,13,14,15,16-octahydro [9] phenacene-1,4,13,16-tetrayl-tetrahexanonate: Synthesis of (14) >>
Cyclohexane (300 ml), tetrahexanonate derivative 9 (0.13 g, 0.000098 mol) obtained above and iodine (0.010 g, 0.000039 mol) were placed in a 500 ml four-necked flask. Ushio low pressure mercury lamp was irradiated for 5 hours. The cyclohexane solution was washed with aqueous sodium thiosulfate solution, water and saturated brine. Purification was performed by GPC, and the resulting liquid (tetrahexanonate derivative 14) was identified by MS. Accurate mass (LC-TofMS) (m / z): 714.336 (actual value), 714.340 (calculated value)

[Example 2]
The derivative exemplified in the structural formula (2) (phenacene precursor compound) was synthesized according to the following synthesis route.
The synthesis route of the phenacene precursor compound (2) is shown in the following formula. The procedure is as follows.

  1,2-Dibromobenzene (Tokyo Kasei product) was used as a starting material and synthesized in the same procedure as in Synthesis Procedures 3, 7, and 8 described in Example 1, and 1,2,3,4,11,12,13, 14-Octahydro [7] phenacene-1,4,11,14-tetrayl-tetrahexanonate: (2) was obtained.

[Example 3]
The derivative exemplified in the structural formula (9) (phenacene precursor compound) was synthesized according to the following synthesis route.
The synthesis route of the phenacene precursor compound (9) is shown in the following formula. The procedure is as follows.

  1,5-Dibronaphthalene (Aldrich product) was used as a starting material and synthesized in the same procedure as Synthesis Procedures 3, 7, and 8 described in Example 1, and 1, 2, 3, 4, 11, 12, 13, 14-Octahydro [8] phenacene-1,4,11,14-tetrayl-tetrahexanonate: (9) was obtained.

[Example 4]
The thermal decomposition behavior of the phenacene precursor compound (14) synthesized in Example 1 was observed using TG-DTA (manufactured by SII under a nitrogen atmosphere). As a result, a weight reduction corresponding to two molecules of hexanoic acid was confirmed. This confirmed that compound (14) was converted to [9] phenacene.

[Example 5]
[Example of production of substrate for organic thin film transistor evaluation]
1,2,3,4,13,14,15,16-octahydro [9] phenacene-1,4,13,16-tetrayl-tetrahexanonate synthesized in Example 1 (14) The field effect transistor (organic thin film transistor) having the structure shown in FIG.
A thermal oxide film having a thickness of 300 nm was used as an insulating film, and an N-doped silicon wafer was used as a substrate and a gate electrode. After cleaning the surface of the oxide film with oxygen plasma, HMDS (hexamethylene disilazane) treatment was performed in the gas phase to change the wettability of the surface of the insulating film. Thereafter, a 100 nm-thickness Au electrode pattern (channel length 10 μm, channel width 50 mm) was formed by known photolithography. Thereafter, the substrate was immersed in an ethanol solution containing 10 mM perfluorobenzenethiol for 18 hours to change the wettability of the surfaces of the source electrode and the drain electrode.
1,2,3,4,13,14,15,16-octahydro [9] phenacene-1,4,13,16-tetrayl-tetrahexanonate obtained in Example 1: (14) to tetrahydrofuran It melt | dissolved and the 0.1 wt% solution was prepared. The prepared solution was cast and then dried in a tetrahydrofuran atmosphere.

The organic semiconductor layer and the silicon oxide film in a different part from the electrode were scraped off, and a conductive paste (conductive paste, manufactured by Fujikura Kasei) was applied to the part and the solvent was dried (this part was used to form silicon as the gate electrode A voltage was applied to the substrate).
As a result of evaluating the electrical characteristics of the FET (field effect transistor) element thus obtained using a semiconductor parameter analyzer 4156C manufactured by Agilent, the characteristics as a p-type transistor element were shown.
The following formula was used to calculate the field effect mobility of the organic thin film transistor.
Ids = μC _in W (Vg−Vth) 2 / 2L
(Where C _in is the capacitance per unit area of the gate insulating film, W is the channel width, L is the channel length, Vg is the gate voltage, Ids is the source / drain current, μ is the mobility, and Vth is the gate where the channel begins to form. Threshold voltage.)
The field effect mobility of the produced organic thin film transistor was 2.50 × 10 ⁻³ cm ² / Vs.

[Example 6]
The organic TFT prepared by the same method as in Example 5 was subjected to heat treatment at 250 ° C., and 1,2,3,4,13,14,15,16-octahydro [9] phenacene-1,4,13,16 -Tetrayl-tetrahexanonate: Conversion from (14) to [9] phenacene was performed.
When the transistor characteristics of this device were evaluated, the field effect mobility was 4.3 × 10 ⁻¹ cm ² / Vs. From this result, it was confirmed that it is a favorable active layer as a p-type organic thin-film transistor.

[Example 7]
The transistor prepared in Example 6 was left in the atmosphere for one month. When the transistor characteristics of this device were evaluated, the field effect mobility was 4.5 × 10 ⁻¹ cm ² / Vs. From this result, it was confirmed that the phenacene structure has high storage stability.

[Example 8]
In the organic semiconductor layer of the transistor prepared in Examples 5 and 6, Bencotton (M-3, manufactured by Asahi Kasei Fibers Co., Ltd.) was impregnated with tetrahydrofuran and dichlorobenzene, and the organic semiconductor layer dissolved after reciprocating once. Or the peeling state was observed.
In the organic semiconductor layer prepared in Example 5, dissolution was confirmed in the case of Bencot soaked with any solvent.
In the organic semiconductor layer from which the dissolving group created in Example 6 was eliminated, peeling or dissolution in Bencott was not confirmed even in the case of Bencot soaked with any solvent, and it was confirmed that the solvent resistance was excellent. .

From the above results, the phenacene precursor compound of the present invention is excellent in solubility in various organic solvents and excellent in storage stability, and is converted to a phenacene compound by elimination of a soluble group by the application of an external stimulus (heat or light energy). To do. For this reason, even a phenacene compound, which has been difficult to form due to its poor solubility, can be formed into an ink by using the phenacene precursor compound of the present invention, and a film can be easily formed using this. Therefore, the electronic device can be created by the printing process.
That is, after forming a film using an ink containing a phenacene precursor compound, external energy (heat or light energy) is applied to the formed organic film to convert it into a phenacene compound (organic semiconductor compound). A continuous organic semiconductor film can be easily obtained. The organic semiconductor film thus formed can be applied to organic electronic devices such as organic thin film transistors. Furthermore, it is expected to be applicable to fields such as optical-electronic devices such as EL light emitting elements, electronic paper, various sensors, and RFIDs (radio frequency identification).

DESCRIPTION OF SYMBOLS 1 Organic-semiconductor layer 2 Source electrode 3 Drain electrode 4 Gate electrode 5 Insulating film

Japanese Patent Laid-Open No. 5-05568 WO2006 / 077788 JP-A-7-188234 JP 2008-226959 A JP 2007-224019 A JP 2008-270843 A JP 2006-352143 A JP 2009-105336 A JP 2009-218333 A

Appl. Phys. Lett. 72, p1854 (1998) J. et al. Am. Chem. Soc. 128, p12604 (2006) Nature, Vol. 388, p. 131, (1997) Advanced Materials, 1999, 11, 480 J. et al. Appl. Phys. 100, p034502 (2006) Appl. Phys. Lett. 84, 12, p2085 (2004) J. et al. Am. Chem. Soc. 126, p1596 (2004)

Claims (9)

A phenacene precursor compound having a partial structure represented by the following general formula (I) or general formula (II) at a terminal site of a molecular structural formula of the phenacene compound.

[In Formula (I), at least one pair of (X ₁ , X ₂ )) or (Y ₁ , Y ₂ ) is both a hydrogen atom, and the remaining pairs are both substituted or unsubstituted carbon atoms of 1 or more. Of the acyloxy group. R ₁ and R ₂ are a hydrogen atom or a halogen atom, and may be the same or different. R ₃ and R ₄ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]

[In Formula (II), at least one of X ₃ and Y ₃ is a hydrogen atom, and the other is a substituted or unsubstituted acyloxy group having 1 or more carbon atoms. R ₅ and R ₆ are a hydrogen atom or a halogen atom, and may be the same or different. R ₇ and R ₈ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ] The phenacene precursor compound is characterized in that the phenacene precursor compound is represented by the following general formula (III) or general formula (IV).

[In the formula (III) or (IV), R _{9 to} R ₃₀ are hydrogen atoms or halogen atoms, which may be the same or different. Z ₁ and Z ₂ are partial structures represented by the following general formula (I) or general formula (II), and may be the same or different. n is an integer of 1-2. ]

[In Formula (I), at least one pair of (X ₁ , X ₂ )) or (Y ₁ , Y ₂ ) is both a hydrogen atom, and the remaining pairs are both substituted or unsubstituted carbon atoms of 1 or more. Of the acyloxy group. R ₁ and R ₂ are a hydrogen atom or a halogen atom, and may be the same or different. R ₃ and R ₄ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]

[In Formula (II), at least one of X ₃ and Y ₃ is a hydrogen atom, and the other is a substituted or unsubstituted acyloxy group having 1 or more carbon atoms. R ₅ and R ₆ are a hydrogen atom or a halogen atom, and may be the same or different. R ₇ and R ₈ are groups selected from a hydrogen atom, a halogen atom, a substituted and unsubstituted alkyl group, an alkoxy group or a thioalkoxy group, and may be the same or different. ]   An ink comprising the phenacene precursor compound according to claim 1 and a solvent.   A method for producing an organic film formed using the ink according to claim 3, wherein the film formation is performed by a wet process. An external stimulus is applied to the organic film according to claim 4, and the molecular structural formula terminal site represented by the general formula (I) or the general formula (II) of the phenacene compound contained in the organic film is represented by the following formula: A method for producing an organic film, wherein the structure is converted from (I) to (Ia) or (II) to (IIa) by a chemical reaction represented by (1) or formula (2).

[The substituent in Formula (1) or (2) is the same as the definition in said Formula (I) or Formula (II). ]   6. The method of manufacturing an organic film according to claim 4, wherein the external stimulus is due to application of thermal energy.   An organic film formed by the manufacturing method according to claim 4.   An electronic device comprising the organic film according to claim 7.   An organic thin film transistor comprising an organic semiconductor layer comprising the organic film according to claim 7.

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