HK1197822B - Novel compounds by addition and the preparation method thereof - Google Patents

Description

Novel addition compound and method for producing same

The present application is a divisional application of an invention patent application having chinese application No. 201080038349.4 (the name of the original application is "novel addition compound, method for purifying and manufacturing condensed polycyclic aromatic compound, solution for forming organic semiconductor film, and novel α -diketone compound", the date of application of the original application is 8/24/2010).

Technical Field

The present invention relates to a novel addition compound and an organic semiconductor device, and methods for producing the same. In addition, the present invention relates to intermediates for such novel addition compounds, as well as solutions containing such novel addition compounds and methods of use thereof. The present invention relates to a method for purifying and producing a condensed polycyclic aromatic compound, and more particularly to a method for purifying and producing a condensed polycyclic aromatic compound which can be suitably used as an organic semiconductor compound. The present invention relates to a novel solution for forming an organic semiconductor film and a method for using the solution for forming an organic semiconductor film. The present invention also relates to an organic semiconductor device obtained using such a solution for forming an organic semiconductor film. 4 th the present invention relates to a novel α -diketone compound and an organic semiconductor device, and methods for producing them. In addition, the present invention relates to intermediates for such novel α -diketone compounds, as well as solutions containing such novel α -diketone compounds and methods of use thereof.

Background

Various studies have been made on the use of organic semiconductor compounds in organic semiconductor layers used for organic Thin Film Transistors (TFTs), organic carrier transport layers, organic light emitting devices, and the like. In particular, a thin film transistor having an organic semiconductor layer made of an organic semiconductor compound is expected to replace a conventional silicon-based transistor as a low-cost and lightweight device. Further, the organic semiconductor layer is expected to be applied to smart labels, light weight displays, and the like by utilizing advantages specific to organic materials such as light weight and flexibility.

Therefore, many studies have been made on organic semiconductor compounds for forming an organic semiconductor layer (patent documents 1 to 4, and non-patent documents 1 and 4). Among these organic semiconductor compounds, a condensed polycyclic aromatic compound is known to be preferable in terms of stability of materials, mobility of carriers, and the like.

Furthermore, the Diels-Alder (Diels-Alder) reaction is known in the field of organic synthesis. This reaction is a reaction in which a compound having a double bond or a triple bond is added to the 1-position and the 4-position of a compound having a conjugated double bond to form a cyclic compound having a 6-membered ring. Further, addition of hexachlorocyclopentadiene to naphthalene by the diels-alder reaction has been proposed (non-patent documents 2 and 3).

Further, a precursor is known which is a soluble precursor of pentacene as an example of an organic semiconductor compound, and which can be decomposed by light irradiation to obtain pentacene (non-patent document 4).

Patent document

Patent document 1 Japanese patent laid-open No. 2006-89413

Patent document 2, Japanese patent laid-open No. 2008-290963

Patent document 3 International publication WO2006/077888

Patent document 4 International publication No. 2008/050726

Non-patent document

Non-patent document 1: "facility Synthesis of high Pi-Extended heterologous nes, Diaphtho [2,3-b:2 ', 3' -f ] chalcogenono [3,2-b ] chalcogenones, and therir application to Field-Effect Transistors", Tatsuya Yama moto, and Kazuo Takiya, J.am. chem.Soc.,2007,129(8), pp 2224-2225

Non-patent document 2: "Dienophilic Reactions of Aromatic Double Bonds in the synthesis of beta-sulfonated naphthaleness", A.A.Danish, M.Silverman, Y.A.Tajima, J.Am.chem.Soc.,1954,76(23), pp 6144-

Non-patent document 3: "Tandem Diels-Alder-Diels-Alder Reaction displaying highStereoseiecectricity: Reaction of hexachlorocyclopropetadine with Naphthalene.", Lacourcelle, Claire; poite, Jean Claude; baldy, Andre; jaud, Joel; negrel, JeanClaude; chanon, Michel, Acta Chemica Scandinavica 47,0092-

Non-patent document 4: "Photo Precursor for Pentacene", Hidematsu Uno, et al, Elsevier, Tetrahedron Letters 46(2005)1981-

Disclosure of Invention

(1 st invention)

In the formation of the organic semiconductor layer, a solution method (casting, spin coating, printing, or the like) in which a solution containing an organic semiconductor compound is applied to a substrate and then the solvent is removed, and a vapor deposition method in which an organic semiconductor compound is vapor-deposited on a substrate are known. The known solution method is generally preferable in terms of production cost, production speed, and the like.

However, it is known that a condensed polycyclic aromatic compound which is preferable as an organic semiconductor compound is not polar and has high crystallinity, and therefore is difficult to dissolve in a solution. Therefore, when an organic semiconductor layer is formed using a condensed polycyclic aromatic compound, particularly a low-molecular condensed polycyclic aromatic compound, a vapor deposition method is generally used.

Accordingly, the present invention 1 provides a novel addition compound capable of forming an organic semiconductor layer composed of a condensed polycyclic aromatic compound by a solution method, and a solution containing the novel addition compound. In addition, in the present invention, an organic semiconductor film (organic semiconductor layer) and an organic semiconductor device obtained by using such a novel addition compound are provided. In addition, the present invention also provides a method for synthesizing such a novel addition compound.

(2 nd invention)

As described above, it is known that a condensed polycyclic aromatic compound is preferable as the organic semiconductor compound for forming the organic semiconductor layer. In addition, fused polycyclic aromatic compounds used for such applications are required to have very high purity.

Although many methods for producing a condensed polycyclic aromatic compound have been proposed, it is a matter of course that a substance which becomes an impurity in a final condensed polycyclic aromatic compound is used in a synthesis reaction. In order to remove such impurities, solvent cleaning, vacuum sublimation purification, and the like are performed. However, since the condensed polycyclic aromatic compound has high crystallinity, impurities may be incorporated into the crystal structure. Such impurities incorporated in the crystals cannot be sufficiently purified by a conventional purification method such as solvent washing.

Accordingly, the present invention 2 provides a method for purifying and producing a condensed polycyclic aromatic compound, which solves the above problems, and particularly provides a method for purifying and producing a condensed polycyclic aromatic compound preferably used as an organic semiconductor compound.

(3 rd invention)

In the formation of the organic semiconductor layer, a solution method (casting, spin coating, printing, or the like) in which a solution containing an organic semiconductor compound is applied to a substrate and then the solvent is removed, and a vapor deposition method in which an organic semiconductor compound is vapor-deposited on a substrate are known. The known solution method is generally preferable in terms of production cost, production speed, and the like.

However, it is known that a condensed polycyclic aromatic compound which is preferable as an organic semiconductor compound is not polar and has high crystallinity, and therefore is difficult to dissolve in a solution. Therefore, when an organic semiconductor layer is formed using a condensed polycyclic aromatic compound, particularly a low-molecular condensed polycyclic aromatic compound, a vapor deposition method is generally used.

Therefore, the present invention 3 provides a novel solution for forming an organic semiconductor film, which enables an organic semiconductor layer (organic semiconductor film) composed of a condensed polycyclic aromatic compound to be stably formed by a solution method, and a method for using the solution for forming an organic semiconductor film. In addition, the present invention provides an organic semiconductor device obtained using such a solution for forming an organic semiconductor film.

(4 th invention)

In the formation of the organic semiconductor layer, a solution method (casting, spin coating, printing, or the like) in which a solution containing an organic semiconductor compound is applied to a substrate and then the solvent is removed, and a vapor deposition method in which an organic semiconductor compound is vapor-deposited on a substrate are known. The known solution method is generally preferable in terms of production cost, production speed, and the like.

However, it is known that a condensed polycyclic aromatic compound which is preferable as an organic semiconductor compound is not polar and has high crystallinity, and therefore is difficult to dissolve in a solution. Therefore, when an organic semiconductor layer is formed using a condensed polycyclic aromatic compound, particularly a low-molecular condensed polycyclic aromatic compound, a vapor deposition method is generally used.

Accordingly, the 4 th invention provides a novel α -diketone compound capable of forming an organic semiconductor layer composed of a condensed polycyclic aromatic compound by a solution method, and a solution containing the novel α -diketone compound. In addition, in the present invention, an organic semiconductor film (organic semiconductor layer) and an organic semiconductor device obtained by using such a novel α -diketone compound are provided. In addition, the present invention also provides a method for synthesizing such a novel α -diketone compound.

(1 st invention)

The present inventors have found that an addition compound having a structure in which a specific compound is added to a compound such as dinaphthothiophene (dinaphhthothiophene) can solve the above-mentioned problems, and have arrived at the present invention 1.

The addition compound of the present invention has a structure in which a compound (II) having a double bond such as hexachlorocyclopentadiene is added to a condensed polycyclic aromatic compound of the following formula (I) such as dinaphthothiophene via the double bond so as to be disengageably:

Ar₁Ar₂Ar₃(I)

Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar₂selected from a substituted or unsubstituted aromatic ring moiety consisting of 1 aromatic ring and a substituted or unsubstituted fused aromatic ring moiety in which 2 to 5 aromatic rings are fused,

Ar₁and Ar₂Having at least 2 carbon atoms in total to form a fused aromatic ring, and

Ar₂and Ar₃Having at least 2 carbon atoms in total to form a fused aromatic ring.

The solution containing the adduct compound of the present invention is a solution obtained by dissolving the adduct compound of the present invention in an organic solvent.

The method of the present invention for manufacturing an organic semiconductor film comprises the steps of: a step of coating the solution containing an adduct compound of the present invention on a substrate to produce a film; and then subjecting the film to reduced pressure and/or heating to remove the compound (II) having a double bond from the addition compound, thereby obtaining an organic semiconductor film composed of the condensed polycyclic aromatic compound of the formula (I).

The method of the present invention for manufacturing an organic semiconductor device comprises a step of generating an organic semiconductor film by the method of the present invention for manufacturing an organic semiconductor film.

The organic semiconductor device of the present invention has an organic semiconductor film made of a condensed polycyclic aromatic compound of formula (I) having a structure in which a compound (II) having a double bond is removed from an addition compound of the present invention, and the organic semiconductor film contains the addition compound of the present invention. In addition, the organic semiconductor device of the present invention has an organic semiconductor film having a crystal of the condensed polycyclic aromatic compound of formula (I) having a major axis diameter exceeding 5 μm.

The other novel addition compound (intermediate addition compound) of the present invention can be used as an intermediate for synthesizing the addition compound of the present invention, and is a compound to which a compound (II) having a double bond is added.

The method of the present invention for synthesizing the addition compound of the present invention comprises a step of mixing the condensed polycyclic aromatic compound of the formula (I) with the compound (II) having a double bond. In addition, other methods of the present invention for synthesizing the addition compound of the present invention comprise a step of reacting 2 molecules of the intermediate addition compound of the present invention.

The "addition compound" in the present invention means any compound having a structure in which the compound (II) having a double bond is added to the condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be releasable, and is not limited by a specific synthesis method thereof. The addition compound of the present invention may be an addition compound having a structure in which 1 molecule of the compound (II) having a double bond is added to the condensed polycyclic aromatic compound of the formula (I), or an addition compound having a structure in which 2 molecules, 3 molecules, or 4 molecules or more of the compounds (II) having a double bond are added to the condensed polycyclic aromatic compound of the formula (I).

In the present invention, the "aromatic ring" means a conjugated ring as in the case of a benzene ring, and examples thereof include an aromatic heterocyclic ring such as a furan ring, a thiophene ring, a pyrrole ring and an imidazole ring in parallel with the benzene ring. In addition, in the present invention, "stereoisomer" means the isomerism of a compound having the same structural formula due to the difference in the stereoconfiguration of atoms or groups of atoms therein, and includes optical isomers, geometric isomers, rotational isomers and the like.

(2 nd invention)

The inventors of the present invention have found that a fused polycyclic aromatic compound can be purified and produced by using an addition-elimination reaction, and have arrived at the invention 2.

The method of the present invention for purifying a condensed polycyclic aromatic compound of the following formula (I) comprises the following steps (a) to (d):

Ar₁Ar₂Ar₃(I)

(Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar₂selected from a substituted or unsubstituted aromatic ring moiety consisting of 1 aromatic ring and a substituted or unsubstituted fused aromatic ring moiety in which 2 to 5 aromatic rings are fused,

Ar₁and Ar₂Having at least 2 carbon atoms in total to form a fused aromatic ring, and

Ar₂and Ar₃At least 2 carbon atoms in total to form a fused aromatic ring);

(a) a step of providing a crude product of a condensed polycyclic aromatic compound of the formula (I),

(b) a step of providing a compound (II) having a double bond and being detachably added to the condensed polycyclic aromatic compound of the formula (I),

(c) a step of mixing the condensed polycyclic aromatic compound of the formula (I) with the compound (II) having a double bond to obtain a mixed solution in which an addition compound of these compounds is at least partially dissolved, and

(d) and (3) separating the condensed polycyclic aromatic compound of the formula (I) from the mixed solution to obtain a purified condensed polycyclic aromatic compound of the formula (I).

The method of the present invention for producing a condensed polycyclic aromatic compound includes a step of purifying a crude product of the condensed polycyclic aromatic compound by the method of the present invention. In addition, another method of the present invention for producing a condensed polycyclic aromatic compound includes a step of obtaining a condensed polycyclic aromatic compound from an addition compound of the condensed polycyclic aromatic compound.

In the present invention, the "addition compound" means any compound having a structure in which the compound (II) having a double bond is added to the condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be releasable, and is not limited by a specific synthesis method thereof. The addition compound of the present invention may be an addition compound having a structure in which 1 molecule of the compound (II) having a double bond is added to the condensed polycyclic aromatic compound of the formula (I), or an addition compound having a structure in which 2 molecules, 3 molecules, or 4 molecules, or more compounds (II) having a double bond are added to the condensed polycyclic aromatic compound of the formula (I).

In the present invention, the "aromatic ring" means a conjugated ring as in the case of a benzene ring, and for example, an aromatic heterocyclic ring such as a furan ring, a thiophene ring, a pyrrole ring, or an imidazole ring may be used in parallel with the benzene ring. In addition, in the present invention, "stereoisomer" means the isomerism of a compound having the same structural formula due to the difference in the stereoconfiguration of atoms or groups of atoms therein, and includes optical isomers, geometric isomers, rotational isomers and the like.

(3 rd invention)

The present inventors have found that the above problems can be solved by a solution for forming an organic semiconductor film containing an addition compound having a structure in which a specific compound is added to a compound such as dinaphthothiophene or the like, and have arrived at invention 3.

The solution of the present invention for forming an organic semiconductor film contains an organic solvent, a1 st addition compound dissolved in the organic solvent, and a crystallization inhibitor dissolved in the organic solvent and inhibiting crystallization of the 1 st addition compound.

Wherein the 1 st addition compound has a structure in which a1 st compound (II') having a double bond is added to a condensed polycyclic aromatic compound of the following formula (I) via the double bond so as to be releasable:

Ar₁Ar₂Ar₃(I)

(Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar₂selected from a substituted or unsubstituted aromatic ring moiety consisting of 1 aromatic ring and a substituted or unsubstituted fused aromatic ring moiety in which 2 to 5 aromatic rings are fused,

Ar₁and Ar₂Having at least 2 carbon atoms in total to form a fused aromatic ring, and

Ar₂and Ar₃Having at least 2 carbon atoms in total to form a fused aromatic ring).

The crystallization inhibitor is at least 1 compound selected from the following (a) to (c):

(a) a2 nd addition compound having a structure in which a2 nd compound (II') having a double bond is added to the condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be releasable,

(b) a1 st compound (II') having a double bond and being capable of being added to the condensed polycyclic aromatic compound of the formula (I) via the double bond releasably, and

(c) has a double bond and can be added to the fused polycyclic aromatic compound of the formula (I) via the double bond so as to be disengageable from the compound (II) 2.

The method of the present invention for producing an organic semiconductor film comprises the steps of: a step of applying the solution of the present invention for forming an organic semiconductor film to a substrate to produce a film; and then subjecting the film to pressure reduction and/or heating to remove the 1 st compound (II') having a double bond from the 1 st addition compound to obtain an organic semiconductor film composed of the condensed polycyclic aromatic compound of the formula (I). In addition, the method of the present invention for manufacturing an organic semiconductor device includes a step of forming an organic semiconductor film by the method of the present invention for forming an organic semiconductor film.

An organic semiconductor device of the present invention has an organic semiconductor film made of an organic semiconductor compound having the following formula (I), the organic semiconductor film containing a1 st addition compound in which a1 st compound (II') having a double bond is added to a condensed polycyclic aromatic compound of the following formula (I) so as to be releasable via the double bond, and at least 1 compound selected from the following compounds (a) to (c):

Ar₁Ar₂Ar₃(I)

(Ar₁～Ar₃as described below).

In the present invention, the 1 st and 2 nd "addition compounds" mean any compounds having a structure in which the 1 st compound (II ') and the 2 nd compound (II') each having a double bond are added to the condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be releasable, and are not limited by the specific synthesis method thereof. The addition compound may be an addition compound having a structure in which 1 molecule of the 1 st compound (II ') and/or the 2 nd compound (II') having a double bond is added to the condensed polycyclic aromatic compound of the formula (I), or an addition compound having a structure in which 2 molecules, 3 molecules, 4 molecules, or more than these of the 1 st compound (II ') and/or the 2 nd compound (II') having a double bond is added to the condensed polycyclic aromatic compound of the formula (I).

In the present invention, the "aromatic ring" means a conjugated ring as in the case of a benzene ring, and examples thereof include an aromatic heterocyclic ring such as a furan ring, a thiophene ring, a pyrrole ring and an imidazole ring in parallel with the benzene ring. In addition, in the present invention, "stereoisomer" means the isomerism of a compound having the same structural formula due to the difference in the stereoconfiguration of atoms or groups of atoms therein, and includes optical isomers, geometric isomers, rotational isomers and the like.

In the following description, for the sake of simplicity, "1 st addition compound" and "2 nd addition compound" may be collectively referred to as "addition compound". Similarly, the "1 st compound (II ') having a double bond" and the "2 nd compound (II') having a specific double bond" may be collectively referred to as "compound (II) having a double bond" for the sake of simplicity.

(4 th invention)

The present inventors found that an α -diketone compound having a specific structure can solve the above problems, and arrived at the present invention 4.

The α -diketone compound of the present invention has the following formula (i) (a) -X):

Ar_1XAr_2(a)Ar_3X(I(a)-X)

(Ar_1Xand Ar_3XEach independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties, and at least one of these aromatic rings is substituted with a bicyclic α -dione moiety of formula (X):

Ar_2(a)selected from a substituted or unsubstituted aromatic heterocyclic moiety consisting of 1 aromatic heterocyclic ring and a substituted or unsubstituted condensed aromatic heterocyclic moiety condensed with 2 to 5 aromatic heterocyclic rings,

Ar_1Xand Ar_2(a)Having at least 2 carbon atoms in total to form a fused ring, and

Ar_2(a)and Ar_3XHaving at least 2 carbon atoms in total to form a fused ring.

The solution containing an α -diketone compound of the present invention is a solution in which the α -diketone compound of the present invention is dissolved in an organic solvent.

The method of the present invention for manufacturing an organic semiconductor film comprises the steps of: a step of applying the solution containing an α -diketone compound of the present invention to a substrate to produce a film; and then irradiating the film with light to decompose a bicyclic α -diketone moiety of the α -diketone compound to form a benzene ring moiety, thereby obtaining an organic semiconductor film composed of a condensed polycyclic aromatic compound.

The method of the present invention for manufacturing an organic semiconductor device comprises a step of generating an organic semiconductor film by the method of the present invention for manufacturing an organic semiconductor film.

The organic semiconductor device of the present invention has an organic semiconductor film made of a condensed polycyclic aromatic compound, and the organic semiconductor film further contains the α -diketone compound of the present invention.

Other novel α -diketone compounds (intermediate α -diketone compounds) of the present invention are compounds that can be used as intermediates for synthesizing the α -diketone compounds of the present invention.

The method of the present invention for synthesizing the α -diketone compound of the present invention comprises the steps of hydrolyzing and oxidizing the condensed polycyclic aromatic compound to which vinylene carbonate is added. In addition, other methods of the present invention for synthesizing the α -diketone compounds of the present invention comprise the steps of: a step of reacting 2 molecules of the intermediate α -diketone compound of the present invention, or a step of reacting 1 molecule of the intermediate α -diketone compound of the present invention with 1 molecule of a compound having a structure obtained by decomposing a bicyclic α -diketone moiety of the intermediate α -diketone compound.

Further, the α -diketone compound of the present invention is not limited to a compound in which one 1-molecule bicyclic α -diketone moiety in the aromatic ring is substituted, but may be a compound in which 2 or more 1-molecule bicyclic α -diketone moieties in the aromatic ring are substituted.

In the present invention, the "aromatic ring" means a conjugated ring as in the case of a benzene ring, and examples thereof include an aromatic heterocyclic ring such as a furan ring, a thiophene ring, a pyrrole ring and an imidazole ring in parallel with the benzene ring. In addition, in the present invention, "stereoisomer" means the isomerism of a compound having the same structural formula due to the difference in the stereoconfiguration of atoms or groups of atoms therein, and includes optical isomers, geometric isomers, rotational isomers and the like. Further, in the present invention, the term "substituted or unsubstituted" as used with respect to an aromatic ring or the like means that the aromatic ring or the like has a substituent or no substituent on the ring.

(1 st invention)

The novel addition compound of the present invention is obtained by adding a compound (II) having a double bond such as hexachlorocyclopentadiene to a condensed polycyclic aromatic compound of the formula (I) dinaphthothiophenothiophene via the double bond so as to be releasable by diels-alder reaction. The novel addition compound of the present invention can increase the solubility in a solvent by an increase in polarity and/or a decrease in crystallinity due to the addition of the compound (II) having a double bond. Therefore, the novel addition compound of the present invention can form an organic semiconductor layer made of a condensed polycyclic aromatic compound by a solution method which is generally easier than the vapor deposition method.

(2 nd invention)

The method of the present invention for purifying a condensed polycyclic aromatic compound can be used in place of or together with conventional purification methods such as solvent washing and vacuum sublimation purification, and can realize purification which has not been achieved conventionally. This is considered to be because in the method of the present invention of refining the fused polycyclic aromatic compound of formula (I), the compound (II) having a double bond is added to the fused polycyclic aromatic compound of formula (I), whereby the polarity of the fused polycyclic aromatic compound of formula (I) is increased and/or the crystallinity is decreased, thereby increasing the solubility of the fused polycyclic aromatic compound of formula (I) in the compound (II) having a double bond and an arbitrary solvent.

Further, by the method of the present invention for producing a condensed polycyclic aromatic compound of formula (I), a condensed polycyclic aromatic compound of formula (I) having a purity which has not been achieved in the past and/or from which impurities which have been difficult to remove in the past have been removed can be produced.

(3 rd invention)

The 1 st and 2 nd addition compounds are compounds obtained by adding a compound (II) having a double bond such as hexachlorocyclopentadiene to a condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be disengageable by Diels-Alder reaction. The addition compound can increase solubility in a solvent by increasing polarity and/or decreasing crystallinity due to addition of the compound (II) having a double bond. Therefore, the solution for forming a semiconductor film of the present invention containing the addition compound can form an organic semiconductor layer made of a condensed polycyclic aromatic compound by a solution method which is generally easier than the vapor deposition method.

In addition, the solution for forming a semiconductor film of the present invention contains a specific compound as a crystallization inhibitor, and thus, when an organic semiconductor film is formed by a solution method, crystallization of the 1 st addition compound is inhibited, whereby an excellent organic semiconductor film can be provided and/or an organic semiconductor film can be efficiently provided.

(4 th invention)

The novel α -diketone compound of the present invention can have relatively large solubility in a solvent due to the increase in polarity and/or decrease in crystallinity caused by the bicyclic α -diketone moiety. In addition, the novel α -diketone compound of the present invention can obtain a condensed polycyclic aromatic compound, particularly a condensed polycyclic aromatic compound useful as an organic semiconductor compound, by decomposing the bicyclic α -diketone moiety by light irradiation to form a benzene ring moiety, particularly by light irradiation to decompose the bicyclic α -diketone moiety into a benzene ring moiety and carbon monoxide to obtain a benzene ring moiety.

Therefore, the novel α -diketone compound of the present invention can form an organic semiconductor layer composed of a condensed polycyclic aromatic compound by a solution method which is generally easier than the vapor deposition method. In addition, the novel α -diketone compound of the present invention can reduce or eliminate the necessity of heating when obtaining a condensed polycyclic aromatic compound by decomposition, and thus can promote the formation of an organic semiconductor layer on an organic substrate requiring a relatively low temperature process.

Drawings

FIG. 1 is a schematic diagram of the structure of a Field Effect Transistor (FET) used in example 1-1A and comparative example 1-1A.

FIG. 2 is a graph showing the output characteristics of the field effect transistor obtained in example 1-1A.

FIG. 3 is a graph showing the transfer characteristics of the field effect transistor obtained in example 1-1A.

FIG. 4 is a graph showing the thermal release characteristics of the addition compounds of examples 1 to 10A.

Fig. 5 is a graph showing the output characteristics of the field effect transistors obtained in examples 1 to 10A.

Fig. 6 is a graph showing transfer characteristics of the field effect transistors obtained in examples 1 to 10A.

Fig. 7 is a graph showing NMR results for the residual adduct compounds in the organic semiconductor films obtained in examples 1 to 10A.

Fig. 8 is a photomicrograph showing the crystalline state of DNTT in the channel portion of the organic semiconductor film obtained in examples 1 to 10A.

Fig. 9 is a polarization microscope photograph showing the crystal state of DNTT of the organic semiconductor film obtained in examples 1 to 10C.

Fig. 10 is a polarization microscope photograph showing the crystal state of DNTT of the organic semiconductor films obtained in examples 1 to 10D.

Fig. 11 is a polarization microscope photograph showing the crystal state of DNTT of the organic semiconductor film obtained in examples 1 to 10E.

Fig. 12 is a polarization microscope photograph showing the crystal state of DNTT of the organic semiconductor film obtained in examples 1 to 10F.

Fig. 13 is a polarization microscope photograph showing the crystal state of DNTT of the organic semiconductor film obtained in examples 1 to 10G.

FIG. 14 is a diagram conceptually showing a mode of the purification method of the present invention.

FIG. 15 is a graph showing the results of NMR (nuclear magnetic resonance spectroscopy) analysis of DNTT (purified products 1 to 3) of example 2-1.

FIG. 16 is a graph showing the release characteristics of DNTT-phenylmaleimide 1 adduct (DNTT-1PMI) (endo form, exo form) obtained in example 2-1.

FIG. 17 is a photograph showing a solid obtained from the solution for forming an organic semiconductor film of example 3-1.

FIG. 18 is a photograph showing the organic semiconductor film of the FET obtained from the solution for forming an organic semiconductor film of example 3-1.

FIG. 19 is a photograph showing a solid obtained from the solution for forming an organic semiconductor film of comparative example 3-1.

FIG. 20 is a photograph showing the organic semiconductor film of the FET obtained from the solution for forming an organic semiconductor film of comparative example 3-1.

Detailed Description

"the invention of item 1

Addition Compounds

The addition compound of the present invention has a structure in which a compound (II) having a double bond is added to a condensed polycyclic aromatic compound of the following formula (I) via a double bond so as to be releasable:

Ar₁Ar₂Ar₃(I)

(Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar₂selected from a substituted or unsubstituted aromatic ring moiety consisting of 1 aromatic ring and a substituted or unsubstituted fused aromatic ring moiety in which 2 to 5 aromatic rings are fused,

Ar₁and Ar₂Having at least 2 carbon atoms in total to form a fused aromatic ring, and

Ar₂and Ar₃Having at least 2 carbon atoms in total to form a fused aromatic ring).

In the addition compound of the present invention, the fact that the compound (II) having a double bond is "disengageably" added to the condensed polycyclic aromatic compound of the formula (I) means that the addition compound of the present invention is capable of releasing the compound (II) having a double bond, particularly capable of releasing and removing the compound (II) having a double bond, without decomposing the condensed polycyclic aromatic compound of the formula (I) by, for example, reducing pressure and/or heating.

For example, the addition compound of the present invention is obtained by adding a compound of the following formula (II-1) as an example of the compound (II) having a double bond to a compound of the following formula (I-4) as an example of the condensed polycyclic aromatic compound of the formula (I), and thereby is a compound of the following formula (III-1) or a stereoisomer thereof:

(Y is each independently an element selected from the group consisting of chalcogens, and

the fused benzene ring being substituted or unsubstituted)

(R is independently selected from hydrogen, halogen, hydroxyl, amido, sulfydryl, cyano, alkyl with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, alkynyl with 2-10 carbon atoms, alkoxy with 1-10 carbon atoms, substituted or unsubstituted aromatic group with 4-10 carbon atoms, ester group with 1-10 carbon atoms, ether group with 1-10 carbon atoms, ketone group with 1-10 carbon atoms, amino group with 1-10 carbon atoms, amido group with 1-10 carbon atoms, imido group with 1-10 carbon atoms and thioether group with 1-10 carbon atoms);

(Y and R, and the fused benzene ring portion are the same as described above).

Further, for example, the addition compound of the present invention is obtained by adding a compound of the following formula (II-6) as an example of the compound (II) having a double bond to a compound of the following formula (I-4) as an example of the condensed polycyclic aromatic compound of the formula (I), and thus is a compound of the following formula (III-6) or a stereoisomer thereof:

(Y is each independently an element selected from the group consisting of chalcogens, and

the fused benzene ring moiety is substituted or unsubstituted);

(R and R)_rIndependently selected from hydrogen, halogen, hydroxyl, amido, sulfydryl, cyano, alkyl with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, and 2-EAn alkynyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, an ether group having 1 to 10 carbon atoms, a ketone group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, an amide group having 1 to 10 carbon atoms, an imide group having 1 to 10 carbon atoms, and a thioether group having 1 to 10 carbon atoms);

(Y, R and R_rAnd the fused benzene ring portion is the same as described above).

Method for synthesizing addition Compound 1

The addition compound of the present invention can be produced by a method including a step of mixing the condensed polycyclic aromatic compound of the formula (I) and the compound (II) having a double bond. In this case, the compound (II) having a double bond may be used by being dissolved in a solvent or may be used alone. Here, as the solvent, any solvent capable of dissolving the compound (II) having a double bond can be used. Examples of the solvent that can be used include aprotic polar solvents such as N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, and ethyl acetate; diethyl ether, tetrahydrofuran, diisopropyl ether, diglyme, 1, 4-diEther solvents such as alkanes; benzene, toluene, xylene,Aromatic hydrocarbons such as 1,3, 5-trimethylbenzene; aliphatic hydrocarbons such as hexane and heptane; and halogen-containing solvents such as dichloromethane, chloroform, dichloroethane, and the like.

In the synthesis of the addition compound of the present invention, when the condensed polycyclic aromatic compound of (I) and the compound having a double bond (II) are mixed, the reaction can be accelerated by heating and/or light irradiation. The reaction temperature in the synthesis of the addition compound of the present invention may be determined in consideration of the production rate, the stability of the components, the boiling point of the components, and the like, and may be, for example, a temperature of 20 ℃ or higher, 50 ℃ or higher, 100 ℃ or higher, 180 ℃ or lower, 200 ℃ or lower, or 220 ℃ or lower. The reaction time may be, for example, 1 minute or more, 10 minutes or more, 30 minutes or more, 1 hour or more, and 1 day or less, 3 days or less, 5 days or less, or 10 days or less.

Intermediate addition Compound and method for synthesizing addition Compound 2

The intermediate addition compound of the present invention has a structure in which a compound (II) having a double bond is added to a compound (I') through the double bond:

Ar₁Q(I’)

{Ar₁selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties, and

q has the following formula and structure Ar₁A part of the fused aromatic ring of (1):

(Y is an element selected from chalcogen).

Specifically, for example, the compound of formula (I') may be a compound of the following formula:

the intermediate addition compound of the present invention can be obtained by adding a compound (II) having a double bond to the compound of formula (I'). The reaction conditions for the addition reaction can be referred to the description of the reaction for adding the compound (II) having a double bond to the compound of formula (I).

The method for synthesizing the above-mentioned addition compound of the present invention from the above-mentioned intermediate addition compound comprises the following steps (a) and (b):

(a) reacting 2 molecules of the intermediate addition compound of the present invention to give a compound of the formula:

Ar₁Q＝QAr₁

(Q ═ Q represents the following structure:

) Then, then

(b) By reacting the above formula Ar₁Q＝QAr₁The resulting compound of (a) is reacted with iodine.

By this method, an addition compound of the present invention having a structure in which a compound (II) having a double bond is added to a condensed polycyclic aromatic compound of the following formula (I (a1)) via the double bond so as to be releasable can be produced:

Ar₁Ar_2(a1)Ar₁(I(a1))

(Ar₁selected from the group consisting of substituted or unsubstituted fused aromatic ring moieties fused with 2 to 5 aromatic rings,

Ar_2(a1)is a fused aromatic ring moiety of the formula (a1) below, and

Ar₁and Ar_2(a1)Having at least 2 carbon atoms in total to form a fused aromatic ring).

Further, with respect to the conditions of the method for synthesizing the above-mentioned addition compound of the present invention from the above-mentioned intermediate addition compound and the like,reference is made to the description of non-patent document 1. That is, for example, in the reaction of 2 molecules of the intermediate addition compound in the step (a), tetrachloromethane/zinc (TiCl) can be used in tetrahydrofuran₄/Zn) catalyst. In addition, formula Ar in step (b)₁(Q＝Q)Ar₁The reaction with iodine can be carried out in chloroform (i.e., chloroform) (CHCl)₃) Is carried out in (1).

Condensed polycyclic aromatic Compound of formula (I)

With respect to the condensed polycyclic aromatic compound of the formula (I), Ar₁And Ar₃Each of which may be independently selected from substituted or unsubstituted fused aromatic ring moieties fused with 2 to 5 aromatic rings, particularly 2 to 4 aromatic rings. Ar (Ar)₁And Ar₃The compound (II) having a double bond, which is a diene moiety or a diene affinity moiety, can be selected so as to be capable of being added to the moiety releasably when a diels-alder reaction is carried out. Here, the aromatic ring is especially a substituted or unsubstituted benzene ring. In addition, Ar₁And Ar₃May be the same or different.

Thus, Ar₁And Ar₃May each independently be a benzene ring moiety selected from the following (b1) to (b4) substituted or unsubstituted:

further, regarding the condensed polycyclic aromatic compound of the formula (I), Ar₂Is a substituted or unsubstituted aromatic ring moiety composed of 1 aromatic ring, or a substituted or unsubstituted fused aromatic ring moiety in which 2 to 5, particularly 2 to 3 aromatic rings are fused.

Thus, Ar₂May be an aromatic ring moiety or a fused aromatic ring moiety selected from the following (a1) to (a4) substituted or unsubstituted:

(Y 'S are each independently an element selected from chalcogens, particularly oxygen (O), sulfur (S), selenium (Se), and tellurium (Te), particularly sulfur, and Y' S may be the same or partially different.

The condensed polycyclic aromatic compound of the formula (I) is preferably an organic semiconductor compound, that is, an organic compound exhibiting properties as a semiconductor. The fused polycyclic aromatic compound of the formula (I) may be selected from the following substituted or unsubstituted fused polycyclic aromatic compounds of the formulae (I-1) to (I-5). These condensed polycyclic aromatic compounds have high stability, and therefore can be stably maintained when the compound (II) having a double bond is removed from the addition compound of the present invention, particularly when the compound (II) is removed by heat, particularly at a relatively high temperature and/or for a long time. Therefore, when these compounds are used, the elimination of the compound (II) having a double bond from the addition compound of the present invention can be carried out at a high ratio.

(Y 'S are each independently an element selected from chalcogens, particularly an element selected from oxygen (O), sulfur (S), selenium (Se), and tellurium (Te), especially sulfur; Y' S may be the same or partially different).

The fused polycyclic aromatic compound of formula (I) and the synthesis thereof are not particularly limited, and patent documents 1 to 5 and non-patent document 1 can be referred to.

The aromatic ring moiety and/or the fused aromatic ring moiety of the fused polycyclic aromatic compound of the formula (I) may be substituted with a substituent selected from the group consisting of a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, an ether group having 1 to 20 carbon atoms, a ketone group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, an imide group having 1 to 20 carbon atoms, and a thioether group having 1 to 20 carbon atoms.

Compound (II) having double bond

The compound (II) having a double bond may be any compound capable of being added to the condensed polycyclic aromatic compound of the formula (I) releasably. Thus, for example, the compound (II) having a double bond may be any compound which is releasably added as a dienophile (dienophile) or conjugated diene to the condensed polycyclic aromatic compound of the formula (I) by a diels-alder reaction. Further, the compound (II) having a double bond may be Ar which can be added disengageably to the condensed polycyclic aromatic compound particularly of the formula (I)₁、Ar₂And Ar₃At least 1 aromatic ring moiety or fused aromatic ring moiety in (A), especially Ar of a fused polycyclic aromatic compound of formula (I)₁And Ar₃Any compound of at least 1 fused aromatic ring moiety in (a).

When the compound (II) having a double bond is a diene affibody, the compound (II) having a double bond may be any of the following formulae (II-A1) and (II-B1):

(R_a、R_b、R_cand R_dEach independently selected from a bond, hydrogen, halogen, hydroxyl group, amide group, mercapto group, cyano group, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, ester group having 1 to 10 carbon atoms, ether group having 1 to 10 carbon atoms, ketone group having 1 to 10 carbon atoms, amino group having 1 to 10 carbon atoms, amide group having 1 to 10 carbon atoms, imide group having 1 to 10 carbon atoms, and ester group having 1 to 10 carbon atoms1 to 10 of a thioether group,

R_aand R_bMay be bonded to each other to form a ring, and

R_cand R_dMay bond to each other to form a ring).

The compound of the formula (II-A1) is preferable because the presence of a carbon-oxygen double bond moiety is more electrophilic than the carbon-carbon double bond moiety adjacent to the carbon atom, and thus promotes the Diels-Alder reaction as a dienophile. Similarly, the compound of the formula (II-B1) is preferable because the presence of oxygen is more electrophilic than the carbon-carbon double bond portion adjacent to the oxygen atom, and thus promotes the Diels-Alder reaction as a dienophile.

When the compound (II) having a double bond is a dienophile, the compound (II) having a double bond may be any of the following formulae (II-A2) and (II-B2):

(R_b、R_c、R_dand R_eEach independently selected from a bond, hydrogen, halogen, hydroxyl group, amide group, mercapto group, cyano group, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, ester group having 1 to 10 carbon atoms, ether group having 1 to 10 carbon atoms, ketone group having 1 to 10 carbon atoms, amino group having 1 to 10 carbon atoms, amide group having 1 to 10 carbon atoms, imide group having 1 to 10 carbon atoms, and thioether group having 1 to 10 carbon atoms,

R_eand R_bMay be bonded to each other to form a ring, and

R_cand R_dMay bond to each other to form a ring).

The compound of the formula (II-A2) is preferably used because the presence of 2 carbon-oxygen double bond moieties promotes Diels-Alder reaction as a dienophile because the carbon-carbon double bond moieties between these carbon atoms are relatively electrophilic. Similarly, the compound of the formula (II-B2) is preferably a diene-compatible compound because the carbon-carbon double bond portion between these oxygen atoms is relatively electrophilic due to the presence of 2 oxygen atoms and thus promotes the Diels-Alder reaction.

When the compound (II) having a double bond is a dienophile, the compound (II) having a double bond may be any of the following formulae (II-A3) and (II-B3):

(R_cand R_dEach independently selected from a bond, hydrogen, halogen, hydroxyl group, amide group, mercapto group, cyano group, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, ester group having 1 to 10 carbon atoms, ether group having 1 to 10 carbon atoms, ketone group having 1 to 10 carbon atoms, amino group having 1 to 10 carbon atoms, amide group having 1 to 10 carbon atoms, imide group having 1 to 10 carbon atoms, and thioether group having 1 to 10 carbon atoms,

R_cand R_dMay be bonded to each other to form a ring,

n is an integer of 1 to 5, and

z is selected from the group consisting of a bond (-), oxygen (-), methylene carbon (-C (R-), and oxygen (-O-)_r)₂-) and ethylenic carbon (-C (R)_r) α), carbonyl (-C (═ O) -), nitrogen (-N (R)_r) -, and sulfur (-S-), and n is 2 or more, each may be different (R)_rEach independently selected from hydrogen, halogen, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, carbon atomAn alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, an ether group having 1 to 10 carbon atoms, a ketone group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, an amide group having 1 to 10 carbon atoms, an imide group having 1 to 10 carbon atoms, and a thioether group having 1 to 10 carbon atoms)).

The compound of the formula (II-A3) is preferable because the existence of 2 carbon-oxygen double bond moieties and the carbon-carbon double bond moieties between these carbon atoms are relatively electrophilic and promotes Diels-Alder reaction as a dienophile. Similarly, the compound of formula (II-B3) is preferably a diene-based affibody because the carbon-carbon double bond portion between the oxygen atoms is relatively electrophilic due to the presence of 2 oxygen atoms, and thus promotes Diels-Alder reaction. Further, the compounds of the above formula (II-A3) or (II-B3) are structurally stable because a double bond forms a part of a cyclic structure, and therefore, these compounds are preferably added to the condensed polycyclic aromatic compound of the formula (I) so as to be releasable.

In addition, the compound (II) having a double bond of a conjugated diene type is added as a dienophile and/or a conjugated diene to the condensed polycyclic aromatic compound of the formula (I) in a diels-alder reaction in combination with the condensed polycyclic aromatic compound of the formula (I).

The compound (II) having a double bond may be a compound having a cyclic moiety. The double bond is preferably a part of a cyclic structure because the compound (II) having a double bond can be structurally stabilized, and thus the compound (II) having a double bond can be added to the condensed polycyclic aromatic compound of the formula (I) in a releasable manner.

Thus, for example, the compound (II) having a double bond may be any of the following formulae (II-1) to (II-12):

(R and R)_rEach independently selected from the group consisting of hydrogen, halogen, hydroxyl, amide, mercapto, cyano, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkynyl having 2 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, ester group having 1 to 10 carbon atoms, ether group having 1 to 10 carbon atoms, ketone group having 1 to 10 carbon atoms, amino group having 1 to 10 carbon atoms, amide group having 1 to 10 carbon atoms, imide group having 1 to 10 carbon atoms, and thioether group having 1 to 10 carbon atoms).

The compound (II) having a double bond may be a conjugated diene type compound, for example, any of the compounds represented by the formulae (II-1) to (II-3) and (II-8). The compound (II) having a double bond may be any of diene affinity type compounds, for example, compounds represented by any of the formulae (II-4) to (II-6), formula (II-9), and formulae (II-10) to (II-12). The compound (II) having a double bond may be a compound having a cyclic moiety, for example, any of the compounds represented by the formulae (II-1) to (II-6), the formula (II-8), and the formulae (II-10) to (II-12).

Furthermore, R and R for any of the compounds of formulae (II-1) to (II-12)_rAs the substituent for the aromatic group having 4 to 10 carbon atoms, a substituent capable of substituting the aromatic ring moiety or the condensed aromatic ring moiety of the condensed polycyclic aromatic compound of the formula (I) may be referred to.

Hereinafter, any of the compounds represented by the following formulae (II-1) to (II-12) will be described in more detail.

Compound of the formula (II-1)

(R is as defined above)

In particular, with respect to the compound of formula (II-1), each R is independently selected from hydrogen and halogen. When R is halogen, each R may independently be an element selected from fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and a combination thereof, particularly an element selected from fluorine (F), chlorine (Cl), and a combination thereof, especially chlorine. Thus, the compound of the formula (II-1) may be, for example, hexafluorocyclopentadiene, hexachlorocyclopentadiene, hexabromocyclopentadiene, 5-difluorotetrachlorocyclopentadiene, or 5, 5-dibromotetrachlorocyclopentadiene, particularly hexachlorocyclopentadiene. When all R's are hydrogen, the compound of the formula (II-1) is cyclopentadiene.

Compound of the formula (II-2)

(R is as defined above)

With respect to the compound of formula (II-2), in particular, each R is independently selected from hydrogen and halogen. When all R's are hydrogen, the compound of the formula (II-2) is furan.

Compound of the formula (II-3)

(R and R)_rAs described above)

With respect to the compound of formula (II-3), in particular, each R is independently selected from hydrogen and halogen. Especially R_rAn ester group having 1 to 10 carbon atoms, such as methyl ester. Therefore, the compound of the formula (II-3) may be a compound in which R is hydrogen and Rr is an alkyl ester group having 1 to 10 carbon atoms, that is, an alkyl carboxylate pyrrole, for example, a methyl carboxylate pyrrole in which R is hydrogen and Rr is a methyl ester group.

Compounds of the formula (II-4)

(R and R)_rAs described above)

With respect to the compound of the formula (II-4), especially R_rA group other than hydrogen, that is, a relatively large group is preferable because it promotes the elimination of the compound of formula (II-4) from the addition compound of the condensed polycyclic aromatic compound of formula (I) and the compound of formula (II-4) by heating or the like.

Compound of the formula (II-5)

(R is as defined above)

As to the compound of the formula (II-5), in particular, a compound in which R are all hydrogen is maleic anhydride. The compound of the formula (II-5) can be therefore considered as maleic anhydride or a compound in which a hydrogen group thereof is substituted.

Compound of the formula (II-6)

(R and R)_rAs described above)

With respect to the compound of formula (II-6), in particular, each R is independently selected from hydrogen and halogen. Especially R_rIs an alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, such as a hydroxyphenyl group.

Thus, for example, a compound of formula (II-6) as described above may be such that R is hydrogen and R is_rN-methylmaleimide being methyl, R being hydrogen and R_rN-ethylmaleimide which is ethyl. Further, for example, the compound of the above formula (II-6) may be such that R is hydrogen and R is_rA compound which is a substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, i.e., an aromatic maleimide, particularly RIs hydrogen and R_rN-phenylmaleimide which is phenyl, or hydroxyphenylmaleimide which R is hydrogen and Rr is hydroxyphenyl.

Compounds of the formula (II-7)

(R_rAs described above)

With respect to the compound of the formula (II-7), in particular R_rSelected from alkyl groups having 1 to 10 carbon atoms. The compound of the formula (II-7) may therefore be in particular R_rCompounds which are alkyl, i.e. N-sulfonylacylamides, e.g. R_rN-sulfonylacetamides which are methyl.

Compounds of the formula (II-8)

(R is as defined above)

With respect to the compound of formula (II-8), in particular, each R is independently selected from hydrogen and halogen. When R is halogen, each R is independently an element selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and combinations thereof. When all R's are hydrogen, the compound of the formula (II-8) is anthracene.

Compounds of the formula (II-9)

(R_rAs described above)

With respect to the compound of the formula (II-9), in particular R_rSelected from alkyl groups having 1 to 10 carbon atoms. The compound of the formula (II-9) may therefore be in particular R_rA compound which is an alkyl group,I.e. tricyanocarboxylic acid alkyl-ethylenes, e.g. R_rTricyanocarboxylic acid methyl-ethylene as methyl group.

Compounds of the formula (II-10)

(R and R)_rAs described above)

A Compound of the formula (II-11)

(R is as defined above)

With respect to the compound of formula (II-11), in particular, each R is independently selected from hydrogen and halogen. When all R's are hydrogen, the compound of the formula (II-2) is vinylene carbonate.

Compounds of the formula (II-12)

(R and R)_rAs described above)

Solutions containing addition Compounds

The solution containing the adduct compound of the present invention is obtained by dissolving the adduct compound of the present invention in a solvent, particularly an organic solvent.

The solution containing the addition compound of the present invention may contain the addition compound of the present invention at any concentration, for example, at a concentration of 0.01 to 20 mass%, 0.05 to 10 mass%, 0.1 to 5 mass%.

As a solvent that can be used in the solution containing the addition compound,any solvent capable of dissolving the addition compound of the present invention may be used. Examples of usable solvents include aprotic polar solvents such as N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, and ethyl acetate; diethyl ether, tetrahydrofuran, diisopropyl ether, diglyme, 1, 4-diEther solvents such as alkanes; benzene, toluene, xylene,Aromatic hydrocarbons such as 1,3, 5-trimethylbenzene; aliphatic hydrocarbons such as hexane and heptane; and halogen-containing solvents such as dichloromethane, chloroform, dichloroethane, and the like.

When the adduct compound of the present invention has stereoisomers, the solution of the present invention is, for example, a solution in which the adduct compound of the present invention and at least one of its stereoisomers are dissolved in a solvent, and the ratio of the stereoisomer having the lowest thermal desorption temperature { the stereoisomer having the lowest thermal desorption temperature among the adduct compound and its stereoisomers/the adduct compound and its stereoisomers } may be more than 50 mol%, more than 70 mol%, more than 90 mol%, more than 95 mol%, relative to the total of the adduct compound and its stereoisomers.

In addition, when the addition compound of the present invention has an exo form (exo form) and an endo form (endo form) as stereoisomers, the solution of the present invention is, for example, one containing the exo form and the endo form of the addition compound of the present invention in a solvent, and the ratio of the stereoisomers whose thermal dissociation temperature is low { the stereoisomer whose thermal dissociation temperature is low in the exo and endo forms/(exo + endo form) } may be more than 50 mol%, more than 70 mol%, more than 90 mol%, more than 95 mol%, relative to the total of the exo form and endo form of the addition compound of the present invention. Thus, the solution of the invention is, for example, one in which the exo and endo forms of the adduct compound of formula (III-6) are dissolved in a solvent, and the ratio of exo { exo/(exo + endo) } may be more than 50 mol%, more than 70 mol%, more than 90 mol%, more than 95 mol%, or more than 99 mol% relative to the total of exo and endo forms of the adduct compound.

Here, in the case where the solution containing an addition compound of the present invention contains a stereoisomer having a relatively low thermal dissociation temperature in a relatively large proportion, when the compound (II) having a double bond is dissociated and removed from the solution by heating to obtain an organic semiconductor film composed of the condensed polycyclic aromatic compound of the formula (I), the dissociation can be started from a relatively low temperature. Therefore, in this case, the generation of an organic semiconductor film at a relatively low temperature can be promoted.

Further, in the diels-alder reaction, a reaction product having a substituent on the opposite side to the main bridge is defined as an endo form, and a reaction product having a substituent on the same side as the main bridge is defined as an exo form.

Method for producing organic semiconductor film

The method of the present invention for producing an organic semiconductor film comprises the steps of: a step of applying the solution containing an addition compound of the present invention to a substrate to produce a film; and then subjecting the film to reduced pressure and/or heating to remove the compound (II) having a double bond from the addition compound, thereby obtaining an organic semiconductor film composed of the condensed polycyclic aromatic compound of the formula (I).

The coating of the solution on the substrate can be carried out in any manner, and can be carried out by, for example, a casting method, a spin coating method, a printing method, or the like. The coating of the solution on the substrate may be carried out by simply dropping the solution on the substrate.

When the compound (II) is eliminated and removed by heating and/or reduced pressure, any condition under which the condensed polycyclic aromatic compound of the formula (I) is not substantially decomposed may be used. Thus, the compound (II) can be eliminated or removed by heating at a temperature of, for example, 80 ℃ or higher, 100 ℃ or higher, 120 ℃ or higher, or 140 ℃ or higher, and 200 ℃ or lower, 220 ℃ or lower, 240 ℃ or lower, or 260 ℃ or lower. In addition, the detachment and removal of the compound (II) may be carried out, for example, under vacuum or atmospheric pressure. Further, the elimination and removal of the compound (II) may be carried out, for example, under a nitrogen atmosphere or under an atmospheric atmosphere. In particular, since the condensed polycyclic aromatic compound of formula (I) can be easily produced, it is preferable to remove and eliminate compound (II) in an atmospheric atmosphere at atmospheric pressure.

In the method of the present invention for producing an organic semiconductor film, the compound (II) having a double bond can be detached and removed by rapid heating, that is, heating at a heating rate of, for example, 100 ℃/min, 200 ℃/min, 400 ℃/min, 600 ℃/min, 800 ℃/min, or more than 1000 ℃/min. Such rapid heating may be achieved by: for example, a substrate having a film is directly contacted with a heated object such as a heated electric heater; introducing the substrate having the film into a heated region such as a heated furnace; irradiating electromagnetic waves such as infrared rays and microwaves to the film side or the substrate side; or any several of them may be performed simultaneously. The rapid heating may be carried out to a temperature higher by 3 ℃ or more, 5 ℃ or more, or 10 ℃ or more than the temperature at which the compound (II) having a double bond starts to be desorbed and removed.

When the compound (II) having a double bond is detached and removed by rapid heating in this manner, an organic semiconductor film having a large crystal of the condensed polycyclic aromatic compound of the formula (I), for example, a crystal of the condensed polycyclic aromatic compound of the formula (I) having a major axis diameter of more than 5 μm can be formed.

This is considered to be because when the compound (II) having a double bond is detached and removed by rapid heating in this manner, rearrangement due to thermal motion of the condensed polycyclic aromatic compound of the formula (I) is caused together with detachment and removal of the compound (II) having a double bond, and crystallization of the condensed polycyclic aromatic compound of the formula (I) is promoted by crystallinity of the condensed polycyclic aromatic compound of the formula (I). In contrast, when the compound (II) having a double bond is eliminated and removed by slow heating, the compound (II) having a double bond is eliminated from the addition compound, and crystallization of the condensed polycyclic aromatic compound of formula (I) proceeds at a plurality of sites to generate a plurality of crystal nuclei, whereby the crystals of the condensed polycyclic aromatic compound of formula (I) become fine in the finally obtained organic semiconductor film.

Method for manufacturing organic semiconductor device

The method of the present invention for manufacturing an organic semiconductor device comprises the step of forming an organic semiconductor film by the method of the present invention for forming an organic semiconductor film. In addition, the method may further include a step of forming an electrode layer and/or a dielectric layer on the upper side or the lower side of the organic semiconductor film as desired.

Organic semiconductor device

The organic semiconductor device of the present invention is an organic semiconductor device having an organic semiconductor film made of a condensed polycyclic aromatic compound of formula (I) having a structure in which a compound (II) having a double bond is removed from an addition compound of the present invention, and the organic semiconductor film contains the addition compound of the present invention.

Here, the organic semiconductor film contains the addition compound of the present invention means that the organic semiconductor film contains the addition compound of the present invention in a detectable amount. Thus, for example, the molar ratio of the addition compound of the present invention may be in excess of 1ppm, in excess of 10ppm, in excess of 100ppm, in excess of 1,000ppm, or in excess of 10,000ppm (1%). The proportion of the addition compound of the present invention may be 10 mol% or less, 5 mol% or less, 3 mol% or less, 1 mol% or less, 0.1 mol% or less, or 0.01 mol% or less.

The organic semiconductor device of the present invention may have characteristics as an organic semiconductor device, even if it contains the condensed polycyclic aromatic compound of the formula (I) and the addition compound of the present invention. That is, when the organic semiconductor film of the organic semiconductor device of the present invention is produced from the adduct compound of the present invention, the organic semiconductor device of the present invention can have characteristics as a semiconductor device even if the thermal desorption reaction of the adduct compound of the present invention does not proceed completely. This is preferable because it makes the production of the organic semiconductor device of the present invention or the organic semiconductor film thereof easy.

In addition, another organic semiconductor device of the present invention is an organic semiconductor device having an organic semiconductor film having a crystal of a condensed polycyclic aromatic compound of the following formula (I) having a major axis diameter of more than 5 μm, more than 10 μm, more than 20 μm, more than 30 μm, more than 40 μm, more than 50 μm, more than 60 μm, more than 70 μm, more than 80 μm, more than 90 μm, or more than 100 μm:

Ar₁Ar₂Ar₃(I)

(Ar₁、Ar₂and Ar₃As described above).

In such an organic semiconductor device of the present invention, the organic semiconductor film can improve semiconductor characteristics of the organic semiconductor film, such as carrier mobility and on/off ratio, by having large crystals.

The organic semiconductor film used for these organic semiconductor devices of the present invention can be obtained by a method for forming an organic semiconductor film, particularly the method of the present invention for producing an organic semiconductor film, including, for example, a solution method, that is, a step of applying a solution to a substrate and then removing the solvent from the solution.

Further, another organic semiconductor device of the present invention is an organic semiconductor device having an organic semiconductor film, the organic semiconductor film being made of a condensed polycyclic aromatic compound of formula (I) having a structure in which a compound (II) having a double bond is removed from an addition compound of the present invention, the organic semiconductor film containing the addition compound of the present invention, and the organic semiconductor film having a crystal of the condensed polycyclic aromatic compound of formula (I) having a major axis of more than 5 μm.

In particular, the organic semiconductor device of the present invention is a thin film transistor having a source electrode, a drain electrode, a gate insulating film, and an organic semiconductor film, and is a thin film transistor in which the source electrode and the drain electrode are insulated from the gate electrode by the gate insulating film, and a current flowing from the source electrode to the drain electrode through the organic semiconductor is controlled by a voltage applied to the gate electrode. In addition, the organic semiconductor device of the present invention is particularly a solar cell having an organic semiconductor film as an active layer. In addition, in the present invention, the "organic semiconductor device" means a device having an organic semiconductor film, and other layers such as an electrode layer and a dielectric layer may be made of an inorganic material or an organic material.

"the invention of item 2

Refining method

The method of the present invention for purifying a condensed polycyclic aromatic compound of the following formula (I) comprises the following steps (a) to (d):

Ar₁Ar₂Ar₃(I)

(Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar₂selected from a substituted or unsubstituted aromatic ring moiety consisting of 1 aromatic ring and a substituted or unsubstituted fused aromatic ring moiety in which 2 to 5 aromatic rings are fused,

Ar₁and Ar₂Having at least 2 carbon atoms in total to form a fused aromatic ring, and

Ar₂and Ar₃At least 2 carbon atoms in total to form a fused aromatic ring);

(a) a step of providing a crude product of a condensed polycyclic aromatic compound of the formula (I),

(b) a step of providing a compound (II) having a double bond and being detachably added to the condensed polycyclic aromatic compound of the formula (I),

(c) mixing the condensed polycyclic aromatic compound of formula (I) with the compound (II) having a double bond to obtain a mixed solution in which an addition compound of the compounds is at least partially dissolved, and

(d) and (3) separating the condensed polycyclic aromatic compound of the formula (I) from the mixed solution to obtain a purified condensed polycyclic aromatic compound of the formula (I).

A method for refining, step (a)

In step (a), a crude product of the fused polycyclic aromatic compound of formula (I) is provided. The crude product of the fused polycyclic aromatic compound of formula (I) provided herein can be obtained by any synthetic method. In general, the condensed polycyclic aromatic compound of formula (I) can be obtained by a synthesis method using a halogen element and/or a metal element or a compound thereof, and/or an aromatic compound as a reaction medium, a raw material, a catalyst, and the like (see, for example, patent documents 1 to 5 and non-patent document 1, particularly patent document 2 mentioned above). Therefore, according to the purification method of the present invention, these elements or compounds contained as impurities in the crude product of the condensed polycyclic aromatic compound of the formula (I) can be at least partially removed.

Furthermore, since purification by the method of the present invention can be facilitated, it is preferable to pre-purify the crude product of formula (I) used in step (a), for example, by washing with a solvent.

The condensed polycyclic aromatic compound of the formula (I) is exemplified more specifically below.

A method for refining, step (b)

Providing in step (b) a compound (II) having a double bond and being releasably added to the fused polycyclic aromatic compound of formula (I). Further, the fact that the compound (II) having a double bond is "detachably" added to the condensed polycyclic aromatic compound of the formula (I) means that the compound (II) having a double bond can be removed without decomposing the condensed polycyclic aromatic compound of the formula (I) by, for example, reducing pressure and/or heating the addition compound of the condensed polycyclic aromatic compound of the formula (I) and the compound (II) having a double bond.

The compound (II) having a double bond is exemplified in more detail below.

A method for refining, step (c)

In the step (c), the condensed polycyclic aromatic compound of the formula (I) and the compound (II) having a double bond are mixed to obtain a mixed solution in which an addition compound of these compounds is at least partially dissolved. The addition compound is exemplified in more detail below.

The solvent may be used together with the compound (II) having a double bond, or the compound (II) having a double bond may be used alone. As the solvent that can be used here, any solvent that can dissolve the addition compound obtained in step (c) can be used. Examples of usable solvents include aprotic polar solvents such as N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, and ethyl acetate; diethyl ether, tetrahydrofuran, diisopropyl ether, diglyme, 1, 4-diEther solvents such as alkanes; benzene, toluene, xylene,Aromatic hydrocarbons such as 1,3, 5-trimethylbenzene; aliphatic hydrocarbons such as hexane and heptane; and halogen-containing solvents such as dichloromethane, chloroform, dichloroethane, and the like.

In addition, a radical scavenger such as hydroquinone may be used in combination for the purpose of promoting the removal of impurities from the crude product of the compound of formula (I) and suppressing the polymerization by the self-polymerization caused by the radical polymerization of the compound (II) having a double bond.

In the step (c), when the condensed polycyclic aromatic compound of (I) and the compound having a double bond (II) are mixed, the addition-elimination reaction may be promoted by heating and/or light irradiation. The temperature of the mixed liquid in the step (c) may be determined in consideration of the rate of addition reaction, stability of components, boiling point of components, and the like, and may be, for example, 20 ℃ or higher, 50 ℃ or higher, 100 ℃ or higher, 180 ℃ or lower, 200 ℃ or lower, or 220 ℃ or lower. The mixed solution may be kept for a predetermined period, for example, for 1 minute or more, 10 minutes or more, 30 minutes or more, 1 hour or more, and 1 day or less, 3 days or less, 5 days or less, or 10 days or less.

For reference, a schematic diagram of a scheme for separating impurities from the crude product of the condensed polycyclic aromatic compound of formula (I) in the mixed solution of the step (c) is shown in fig. 14, but the present invention is not limited thereto.

The left 100 of the formula in fig. 14 represents an initial state of a mixture of the condensed polycyclic aromatic compound of formula (I) (crude product) containing impurities in a crystalline state and the compound (II) having a double bond. In such a mixture, as shown by the middle side 200 of the formula in fig. 14, the compound (II) having a double bond is added to the condensed polycyclic aromatic compound of the formula (I) so as to be disengageably, and the crystallinity of the condensed polycyclic aromatic compound of the formula (I) is lowered and/or the polarity of the compound is increased, whereby the condensed polycyclic aromatic compound of the formula (I) is dissolved in the mixed solution.

Since the compound (II) having a double bond is releasably added to the condensed polycyclic aromatic compound of the formula (I), the left 100, middle 200 and right 300 states of the formula in fig. 14 are in a balanced relationship with each other. However, since the amount of impurities is generally small compared to the compound (II) having a double bond and any solvent, when the fused polycyclic aromatic compound of formula (I) is crystallized from the state of the middle side 200 of the formula of fig. 14, the probability of doping impurities is low, and it can be understood that the balance is shifted from the state of the left side 100 of fig. 14 to the states of the middle side 200 and the right side 300 of fig. 14.

A method of refining, step (d)

In the step (d), a purified condensed polycyclic aromatic compound of the formula (I) can be isolated from the mixed solution obtained in the step (c). Here, the condensed polycyclic aromatic compound of formula (I) in a purified crystalline state in the state of the right side 300 in fig. 14 can be separated by filtration or the like because of its low solubility in the liquid mixture.

Further, the addition compound in the state of middle side 200 of fig. 14 can detach and remove the compound (II) having a double bond from the condensed polycyclic aromatic compound of formula (I) by, for example, reducing pressure and/or heating without decomposing the condensed polycyclic aromatic compound of formula (I). This is because, as described above, the compound (II) having a double bond is added to the condensed polycyclic aromatic compound of the formula (I) disengageably.

When the compound (II) is eliminated or removed by heating and/or reduced pressure, any condition under which the condensed polycyclic aromatic compound of the formula (I) is not substantially decomposed may be used. Therefore, the compound (II) can be eliminated or removed by heating at a temperature of, for example, 80 ℃ or higher, 100 ℃ or higher, 120 ℃ or higher, or 140 ℃ or higher, and 200 ℃ or lower, 220 ℃ or lower, 240 ℃ or lower, or 260 ℃ or lower. In addition, the detachment and removal of the compound (II) may be carried out, for example, under vacuum or atmospheric pressure. Further, the compound (II) may be desorbed and removed, for example, under a nitrogen atmosphere or an atmospheric atmosphere.

The purified condensed polycyclic aromatic compound of formula (I) obtained in step (d) may be further purified, for example, by sublimation purification.

Method for producing condensed polycyclic aromatic Compound 1

The 1 st process of the present invention for producing a fused polycyclic aromatic compound of formula (I) comprises a step of refining a crude product of the fused polycyclic aromatic compound of formula (I) by the process of the present invention.

Method for producing condensed polycyclic aromatic Compound 2

The 2 nd process of the present invention for producing a condensed polycyclic aromatic compound of the formula (I) comprises removing and removing the compound (II) from an addition compound having a structure in which the compound (II) having a double bond is added to the condensed polycyclic aromatic compound of the formula (I) so as to be disengageable, particularly removing and removing the compound (II) by heating and/or reduced pressure.

When the compound (II) is eliminated and removed by heating and/or reduced pressure, any condition under which the condensed polycyclic aromatic compound of the formula (I) is not substantially decomposed may be used. Therefore, the compound (II) can be eliminated or removed by heating at a temperature of, for example, 80 ℃ or higher, 100 ℃ or higher, 120 ℃ or higher, or 140 ℃ or higher, and 200 ℃ or lower, 220 ℃ or lower, 240 ℃ or lower, or 260 ℃ or lower. In addition, the detachment and removal of the compound (II) may be carried out, for example, under vacuum or atmospheric pressure. Further, the compound (II) may be desorbed and removed, for example, under a nitrogen atmosphere or an atmospheric atmosphere. Since the condensed polycyclic aromatic compound of the formula (I) can be easily produced, it is particularly preferable to carry out the elimination and removal of the compound (II) in an atmospheric atmosphere at atmospheric pressure.

In the methods 1 and 2 of the present invention for producing a condensed polycyclic aromatic compound of formula (I), the condensed polycyclic aromatic compound of formula (I) can be obtained in the form of powder. However, the form of the condensed polycyclic aromatic compound of the formula (I) obtained by the method of the present invention is not limited to powder.

Method for manufacturing organic semiconductor film

The method of the present invention for manufacturing an organic semiconductor film includes a step of manufacturing a condensed polycyclic aromatic compound by the method of the present invention, and then obtaining an organic semiconductor film from the obtained condensed polycyclic aromatic compound of formula (I) by, for example, a vapor deposition method.

Method for manufacturing organic semiconductor device

The method of the present invention for manufacturing an organic semiconductor device comprises the step of forming an organic semiconductor film by the method of the present invention for forming an organic semiconductor film. The method may further include a step of forming an electrode layer and/or a dielectric layer on the upper side or the lower side of the organic semiconductor film.

(others)

The addition products, the condensed polycyclic aromatic compound of formula (I), the compound (II) having a double bond, the organic semiconductor device, and the like can be referred to the description of the above invention 1.

"the invention of item 3

Solution for forming organic semiconductor film

The solution of the present invention for forming an organic semiconductor film contains an organic solvent, a1 st addition compound dissolved in the organic solvent, and a crystallization inhibitor dissolved in the organic solvent and inhibiting crystallization of the 1 st addition compound.

Wherein the 1 st addition compound has a structure in which a1 st compound (II') having a double bond is added to a condensed polycyclic aromatic compound of the following formula (I) via the double bond so as to be releasable:

Ar₁Ar₂Ar₃(I)

(Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar₂selected from a substituted or unsubstituted aromatic ring moiety consisting of 1 aromatic ring and a substituted or unsubstituted fused aromatic ring moiety in which 2 to 5 aromatic rings are fused,

Ar₁and Ar₂Having at least 2 carbon atoms in total to form a fused aromatic ring, and

Ar₂and Ar₃Having at least 2 carbon atoms in total to form a fused aromatic ring).

The crystallization inhibitor may be at least one compound selected from the following (a) to (c):

(a) a2 nd addition compound having a structure in which a2 nd compound (II') having a double bond is added to the condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be releasable,

(b) the 1 st compound (II ') having a double bond, which compound (II') is capable of being added to the fused polycyclic aromatic compound of the formula (I) via a double bond in a releasable manner, and

(c) the 2 nd compound (II ") having a double bond, which compound (II") is capable of being added to the fused polycyclic aromatic compound of the formula (I) via a double bond.

In the solution of the present invention for forming an organic semiconductor film, the 1 st addition compound has a structure in which the compound (II') having a double bond is added to the condensed polycyclic aromatic compound of formula (I), and thus has a relatively high solubility in a solvent due to increased polarity and/or decreased crystallinity as compared with the condensed polycyclic aromatic compound of formula (I). Therefore, the solution of the present invention can form an organic semiconductor layer made of a condensed polycyclic aromatic compound by a solution method. Specifically, for example, the solution of the present invention is applied to a substrate to prepare a film, and then the film is subjected to reduced pressure and/or heating to remove the 1 st compound (II') having a double bond from the 1 st addition compound, thereby obtaining an organic semiconductor film composed of the condensed polycyclic aromatic compound of the formula (I).

In addition, the solution of the present invention for forming an organic semiconductor film contains a crystallization inhibitor, and thereby, crystallization is inhibited when the organic semiconductor film is formed by a solution method, whereby an excellent organic semiconductor film can be provided and/or an organic semiconductor film can be efficiently provided.

The solution for forming an organic semiconductor film of the present invention may contain the 1 st addition compound at any concentration, and for example, the 1 st addition compound may be contained at a concentration of 0.01 to 20 mass%, 0.05 to 10 mass%, 0.1 to 5 mass%.

As the solvent that can be used in the solution for forming an organic semiconductor film of the present invention, any solvent that can dissolve the 1 st addition compound can be used. Examples of solvents which can be used are N-methylpyrrolidone, dimethyl sulfoxide and ethyl acetateAprotic polar solvents such as nitrile and ethyl acetate; diethyl ether, tetrahydrofuran, diisopropyl ether, diglyme, 1, 4-diEther solvents such as alkanes; benzene, toluene, xylene,Aromatic hydrocarbons such as 1,3, 5-trimethylbenzene; aliphatic hydrocarbons such as hexane and heptane; and halogen-containing solvents such as dichloromethane, chloroform, dichloroethane, and the like.

When the 1 st addition compound has a stereoisomer, the solution of the present invention is, for example, a solution in which the 1 st addition compound and at least 1 of its stereoisomers are dissolved in a solvent, and the ratio of the stereoisomer having the lowest thermal desorption temperature { the stereoisomer having the lowest thermal desorption temperature among the addition compound and its stereoisomers/the addition compound and its stereoisomers } may be more than 50 mol%, more than 70 mol%, more than 90 mol%, more than 95 mol%, relative to the total of the addition compound and its stereoisomers.

In addition, when the 1 st addition compound has exo and endo forms as stereoisomers, the solution of the present invention is, for example, one containing exo and endo forms of the 1 st addition compound in a solvent, and the ratio of stereoisomers whose thermal desorption temperature is low { stereoisomers/(exo + endo forms) } in which thermal desorption temperature is low in the exo and endo forms may be more than 50 mol%, more than 70 mol%, more than 90 mol%, more than 95 mol% relative to the total of exo and endo forms of the 1 st addition compound. Thus, the solution of the invention is, for example, one in which the exo and endo forms of the adduct compound of formula (III-6) are dissolved in a solvent, and the ratio of exo { exo/(exo + endo) } may be more than 50 mol%, more than 70 mol%, more than 90 mol%, more than 95 mol%, or more than 99 mol% relative to the total of exo and endo forms of the adduct compound.

Here, in the case where the 1 st solution containing the addition compound contains a stereoisomer having a relatively low thermal dissociation temperature in a relatively large proportion, when the compound (II) having a double bond is dissociated and removed from the solution by heating to obtain an organic semiconductor film composed of the condensed polycyclic aromatic compound of the formula (I), the dissociation can be started from a relatively low temperature. Therefore, in this case, the generation of an organic semiconductor film at a relatively low temperature can be promoted.

Further, in the diels-alder reaction, a reaction product in which a substituent is present on the opposite side of the main bridge is defined as an endo form, and a reaction product in which a substituent is present on the same side as the main bridge is defined as an exo form.

Solution-crystallization inhibitor-No. 2 addition Compound for Forming organic semiconductor film

In one embodiment, the crystallization inhibitor contained in the solution of the present invention is a2 nd addition compound having a structure in which a2 nd compound (II ") having a double bond is added to the condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be disengageable.

Here, the 2 nd addition compound has the same condensed polycyclic aromatic compound of the formula (I) as the 1 st addition compound. That is, the same as the 1 st addition compound except that the 2 nd addition compound (II ') is added with the 2 nd compound (II ") having a double bond instead of the 1 st compound (II') having a double bond.

Therefore, the part of the condensed polycyclic aromatic compound of formula (I) in the 2 nd addition compound has a relatively large affinity for the part of the 1 st addition compound, particularly the condensed polycyclic aromatic compound of formula (I) in the 1 st addition compound. However, the 1 st addition compound and the 2 nd addition compound are different in structure with respect to the 1 st and 2 nd compounds (II') and (II ") having a double bond, and therefore are relatively difficult to crystallize in the formation of an organic semiconductor film by a solution method.

The 1 st and 2 nd addition compounds each have a structure in which the 1 st and 2 nd compounds (I ') and (II') each having a double bond are added to the condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be disengageable. Thus, when the 1 st and 2 nd addition compounds are removed and removed from the 1 st and 2 nd compounds (II ') and (II') having a double bond by, for example, heating and/or reducing pressure, both the condensed polycyclic aromatic compound of the formula (I) are formed.

Therefore, for example, when the concentration of the 1 st addition compound contained in the solution is constant, the content of the fused polycyclic aromatic compound of the formula (I) in the solution can be substantially increased by further containing the 2 nd addition compound in the solution.

The solution for forming an organic semiconductor film of the present invention may contain the 2 nd addition compound as a crystallization inhibitor in an arbitrary amount that can be dissolved in a solvent, and for example, the molar ratio of the 2 nd addition compound to the 1 st addition compound (2 nd addition compound/1 st addition compound) may be 0.1 mol% or more, 1 mol% or more, 10 mol% or more, 30 mol% or more, or 50 mol% or more. Here, the molar ratio of 100 mol% means that the number of moles of the 1 st addition compound contained in the solution for forming an organic semiconductor film is the same as the number of moles of the 2 nd addition compound.

Solution for forming organic semiconductor film-crystallization inhibitor-Compounds (II') and (II) No. 1 and 2

In another embodiment, the crystallization inhibitor contained in the solution of the present invention is the 1 st compound (II') having a double bond. The 1 st compound (II ') having a double bond used as the crystallization inhibitor is the same as the 1 st compound (II') having a double bond constituting the 1 st addition compound which is added to the condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be disengageable. Therefore, the 1 st compound (II') having a double bond used as a crystallization inhibitor may be added to the condensed polycyclic aromatic compound of the formula (I) via the double bond so as to be releasable.

In another embodiment, the compound (2') is a2 nd compound (II ″), and the 2 nd compound (II ″) has a double bond and can be added to the fused polycyclic aromatic compound of the formula (I) via the double bond so as to be disengageable. That is, the 1 st compound (II ") having a double bond used as the crystallization inhibitor is different from the 1 st compound (II') having a double bond constituting the 1 st addition compound which is added to the condensed polycyclic aromatic compound of the formula (I) via a double bond in a releasable manner. However, the 1 st compound (II ") having a double bond used as the crystallization inhibitor may be added to the condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be disengageable, similarly to the 1 st compound (II') having a double bond.

The 1 st and 2 nd compounds (II ') and (II ″) having a double bond used as the crystallization inhibitor are each detachably added to the fused polycyclic aromatic compound of the formula (I) via a double bond by the same mechanism as that of the 1 st addition compound formed by detachably adding the 1 st compound (II') having a double bond to the fused polycyclic aromatic compound of the formula (I) to form the 1 st addition compound, and/or show affinity for the fused polycyclic aromatic compound of the formula (I), whereby the polarity of the 1 st addition compound is further increased and/or crystallization of the 1 st addition compounds with each other can be prevented when the organic semiconductor film is formed by the solution method.

The solution for forming an organic semiconductor film of the present invention may contain the 1 st and 2 nd compounds (II ') and (II ") having a double bond as a crystallization inhibitor in an arbitrary amount soluble in a solvent, for example, the molar ratio of the 1 st and 2 nd compounds (II ') and (II") to the 1 st addition compound (the 1 st and/or 2 nd compounds (II ') and (II ")/the 1 st addition compound) may be 0.1 mol% or more, 1 mol% or more, 10 mol% or more, 30 mol% or more, or 50 mol% or more. Here, the molar ratio of 100 mol% means that the number of moles of the 1 st addition compound contained in the solution for forming an organic semiconductor film is the same as the number of moles of the 1 st and/or 2 nd compounds (II') and (II ").

Method for producing organic semiconductor film

The method of the present invention for producing an organic semiconductor film comprises the steps of: a step of coating the solution for forming an organic semiconductor film of the present invention on a substrate to produce a film; then, the film is subjected to pressure reduction and/or heating to remove and remove the compound (II) having a double bond from the 1 st addition compound and the optionally used 2 nd addition compound, thereby obtaining an organic semiconductor film composed of the condensed polycyclic aromatic compound of the formula (I).

The coating of the solution on the substrate can be carried out in any manner, and can be carried out by, for example, a casting method, a spin coating method, a printing method, or the like. The coating of the solution on the substrate may be carried out by simply dropping the solution on the substrate.

When the compound (II) is eliminated and removed by heating and/or reduced pressure, any condition under which the condensed polycyclic aromatic compound of the formula (I) is not substantially decomposed may be used. Thus, the compound (II) can be eliminated or removed by heating at a temperature of, for example, 80 ℃ or higher, 100 ℃ or higher, 120 ℃ or higher, or 140 ℃ or higher, and 200 ℃ or lower, 220 ℃ or lower, 240 ℃ or lower, or 260 ℃ or lower. In addition, the detachment and removal of the compound (II) may be carried out, for example, under vacuum or atmospheric pressure. Further, the elimination and removal of the compound (II) may be carried out, for example, under a nitrogen atmosphere or under an atmospheric atmosphere. Since the condensed polycyclic aromatic compound of the formula (I) can be easily produced, it is particularly preferable to carry out the elimination and removal of the compound (II) in an atmospheric atmosphere at atmospheric pressure.

Method for manufacturing organic semiconductor device

The method of the present invention for manufacturing an organic semiconductor device comprises the step of forming an organic semiconductor film by the method of the present invention for forming an organic semiconductor film. The method may further include a step of forming an electrode layer and/or a dielectric layer on the upper side or the lower side of the organic semiconductor film.

Organic semiconductor device

An organic semiconductor device of the present invention is an organic semiconductor device having an organic semiconductor film, the organic semiconductor film being made of an organic semiconductor compound having the following formula (I), and the organic semiconductor film containing a1 st addition compound in which a1 st compound (II') having a double bond is added to a condensed polycyclic aromatic compound of the following formula (I) via the double bond so as to be releasable, and at least one compound selected from the following compounds (a) to (c):

Ar₁Ar₂Ar₃(I)

(Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar₂selected from a substituted or unsubstituted aromatic ring moiety consisting of 1 aromatic ring and a substituted or unsubstituted fused aromatic ring moiety in which 2 to 5 aromatic rings are fused,

Ar₁and Ar₂Having at least 2 carbon atoms in total to form a fused aromatic ring, and

Ar₂and Ar₃At least 2 carbon atoms in total to form a fused aromatic ring);

(a) a2 nd addition compound having a structure in which a2 nd compound (II') having a double bond is added to the condensed polycyclic aromatic compound of the formula (I) via a double bond so as to be releasable,

(b) a1 st compound (II ') having a double bond, which compound (II') is capable of being added to the condensed polycyclic aromatic compound of the formula (I) via the double bond releasably, and

(c) a2 nd compound (II ') having a double bond, which compound (II') can be added to the condensed polycyclic aromatic compound of the formula (I) via the double bond.

Here, the organic semiconductor film contains the 1 st addition compound and at least 1 compound selected from the above-mentioned (a) to (c) means that the organic semiconductor film contains these compounds in detectable amounts. Thus, for example, the molar ratio of these compounds relative to the organic semiconducting compound of formula (I) may exceed 1ppm, exceed 10ppm, exceed 100ppm, exceed 1,000ppm, or exceed 10,000ppm (1%). The proportion of these compounds to the organic semiconductor compound having the formula (I) may be 10 mol% or less, 5 mol% or less, 3 mol% or less, 1 mol% or less, 0.1 mol% or less, or 0.01 mol% or less.

The organic semiconductor device of the present invention may have characteristics as an organic semiconductor device, although it contains the condensed polycyclic aromatic compound of the formula (I) and also contains the 1 st addition compound and at least 1 compound selected from the above-mentioned compounds (a) to (c). That is, when the organic semiconductor film of the organic semiconductor device of the present invention is produced from the solution for forming an organic semiconductor film of the present invention, the organic semiconductor device of the present invention can have characteristics as a semiconductor device even if the thermal dissociation reaction of the addition compound and the removal of the crystallization inhibitor are not completely performed. This is preferable because it makes the production of the organic semiconductor device of the present invention or the organic semiconductor film thereof easy.

In particular, the organic semiconductor device of the present invention is a thin film transistor having a source electrode, a drain electrode, a gate insulating film, and an organic semiconductor film, and is a thin film transistor in which the source electrode and the drain electrode are insulated from the gate electrode by the gate insulating film, and a current flowing from the source electrode to the drain electrode through the organic semiconductor is controlled by a voltage applied to the gate electrode. In addition, the organic semiconductor device of the present invention is particularly a solar cell having an organic semiconductor film as an active layer.

(others)

The addition products, the condensed polycyclic aromatic compound of the formula (I), the compound (II) having a double bond, and the like can be referred to the description of the above invention 1.

"the invention of item 4

Alpha-diketone compound

The α -diketone compound of the present invention has the following formula (i) (a) -X):

Ar_1XAr_2(a)Ar_3X(I(a)-X)

(Ar_1Xand Ar_3XEach independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties, and these aromatic ringsAt least one of the rings is partially substituted with a bicyclic α -dione of formula (X):

Ar_2(a)selected from a substituted or unsubstituted aromatic heterocyclic moiety consisting of 1 aromatic heterocyclic ring and a substituted or unsubstituted condensed aromatic heterocyclic moiety condensed with 2 to 5 aromatic heterocyclic rings,

Ar_1Xand Ar_2(a)Having at least 2 carbon atoms in total to form a fused ring, and

Ar_2(a)and Ar_3XAt least 2 carbon atoms in total to form a fused ring }.

With respect to the α -dione compound of the present invention, Ar_1XAnd Ar_3XEach independently selected from 2 to 5 aromatic rings, particularly 2 to 4 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties, and at least one of these aromatic rings is substituted with a bicyclic α -dione moiety of formula (X):

in addition, for example, Ar_1XAnd Ar_3XEach independently selected from substituted or unsubstituted fused benzene ring moieties in which 2 to 5 benzene rings, particularly 2 to 4 substituted or unsubstituted benzene rings are fused, and at least one of these benzene rings is substituted with the above-mentioned bicyclic α -dione moiety₁And Ar₃May be the same or different.

Thus Ar_1XAnd Ar_3XEach independently selected from the group consisting of substituted or unsubstituted fused benzene ring moieties of the following (b1) to (b4), and at least one of these benzene rings is substituted with the aforementioned bicyclic α -dione moiety:

with respect to the α -dione compound of the present invention, Ar_2(a)Selected from a substituted or unsubstituted aromatic heterocyclic moiety consisting of 1 aromatic heterocyclic ring, or a substituted or unsubstituted fused aromatic heterocyclic moiety fused with 2 to 5, particularly 2 to 3 aromatic heterocyclic rings. Here, the aromatic heterocyclic ring may be, for example, an aromatic heterocyclic ring having the following structure:

(Y is each an element selected from chalcogens, particularly oxygen (O), sulfur (S), selenium (Se), and tellurium (Te), more particularly sulfur).

Thus, Ar_2(a)May be a fused aromatic heterocyclic moiety selected from the group consisting of the following (a1), (a3) and (a4) substituted or unsubstituted:

(Y's are each independently an element selected from chalcogens, and may be the same or partially different).

The α -diketone compound of the present invention decomposes a bicyclic α -diketone moiety into a phenyl ring moiety by irradiation with light, thereby producing a condensed polycyclic aromatic compound of the following formula (i (a)):

Ar₁Ar_2(a)Ar₃(I(a))

(Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar_2(a)selected from substituted or unsubstituted aromatic heterocyclic ring systems consisting of 1 aromatic heterocyclic ringSubstituted aromatic heterocyclic moiety, and 2 to 5 aromatic heterocyclic fused substituted or unsubstituted fused aromatic heterocyclic moieties,

Ar_1Xand Ar_2(a)Having at least 2 carbon atoms in total to form a fused ring, and

Ar_2(a)and Ar_3XHaving at least 2 carbon atoms in total to form a fused ring).

With respect to the condensed polycyclic aromatic compound of the formula (I), (a), Ar₁And Ar₃Each independently selected from 2 to 5 aromatic rings, particularly 2 to 4 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties. Here, the aromatic ring is particularly a substituted or unsubstituted benzene ring. In addition, Ar₁And Ar₃May be the same or different.

Thus, Ar₁And Ar₃May be a benzene ring moiety selected from the above (b1) to (b4) each independently substituted or unsubstituted.

With respect to the condensed polycyclic aromatic compound of the formula (I), Ar_2(a)Is a substituted or unsubstituted aromatic heterocyclic moiety composed of 1 aromatic heterocyclic ring, or a substituted or unsubstituted fused aromatic heterocyclic moiety fused with 2 to 5, particularly 2 to 3 aromatic heterocyclic rings.

Thus, Ar_2(a)May be an aromatic heterocyclic moiety or a fused aromatic heterocyclic moiety selected from the group consisting of the above (a1), (a3) and (a4) which may be substituted or unsubstituted.

The condensed polycyclic aromatic compound of the formula (i (a)) is preferably an organic semiconductor compound, i.e., an organic compound exhibiting properties as a semiconductor. The fused polycyclic aromatic compound of the formula (I (a)) may be selected from the following substituted or unsubstituted fused polycyclic aromatic compounds of the formulae (I-1) to (I-5). Since these condensed polycyclic aromatic compounds have high stability, when a condensed polycyclic aromatic compound of the formula (i (a)) is produced from the α -diketone compound of the present invention, the condensed polycyclic aromatic compound of the formula (i (a)) can be stably maintained. That is, in this case, even when heating is performed during the production of the condensed polycyclic aromatic compound of formula (i (a)), the condensed polycyclic aromatic compound of formula (i (a)) can be stably maintained. Therefore, in this case, a condensed polycyclic aromatic compound of the formula (I), (a)) can be produced from the α -diketone compound of the present invention at a high ratio.

(each Y is independently an element selected from chalcogens).

The fused polycyclic aromatic compound of the formula (i (a)) and the synthesis thereof are not particularly limited, and patent documents 1 to 5 and non-patent document 1 may be cited.

Specifically, for example, the α -diketone compound of the present invention is a compound represented by the following formulae (i) (a) -X1) to (i (a) -X5), or a stereoisomer thereof:

(Y is an element each independently selected from chalcogens, and

the fused benzene ring moiety is substituted or unsubstituted).

Here, the compounds of formulae (I), (a) -X1) to (I (a) -X5) or stereoisomers thereof are partially decomposed into benzene ring portions by irradiation with light, whereby a compound of formula (I-4) below, which is an example of a condensed polycyclic aromatic compound, can be produced:

(Y is each independently an element selected from the group consisting of chalcogens, and

the fused benzene ring being substituted or unsubstituted)

The aromatic ring and the like are substituted with a substituent selected from the group consisting of a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, an ether group having 1 to 20 carbon atoms, a ketone group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, an imide group having 1 to 20 carbon atoms, and a thioether group having 1 to 20 carbon atoms.

[ 1 st Synthesis method of alpha-diketone Compound ]

The α -diketone compound of the present invention can be synthesized by a method comprising the following steps (a) to (c):

(a) a step of providing a condensed polycyclic aromatic compound to which vinylene carbonate is added, the condensed polycyclic aromatic compound having a structure in which vinylene carbonate is added to a condensed polycyclic aromatic compound represented by formula (I) (a) below via a double bond thereof so as to be releasable:

Ar₁Ar_2(a)Ar₃(I(a))

(Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar_2(a)selected from a substituted or unsubstituted aromatic heterocyclic moiety consisting of 1 aromatic heterocyclic ring and a substituted or unsubstituted condensed aromatic heterocyclic moiety condensed with 2 to 5 aromatic heterocyclic rings,

Ar₁and Ar_2(a)Having at least 2 carbon atoms in total to form a fused ring, and

Ar_2(a)and Ar₃At least 2 carbon atoms in total to form a fused ring);

(b) a step of hydrolyzing the condensed polycyclic aromatic compound to which vinylene carbonate is added to obtain an α -diol compound in which a portion corresponding to vinylene carbonate is converted into an α -diol portion:

(c) a step of oxidizing the α -diol compound to convert the α -diol moiety into an α -diketone moiety.

The condensed polycyclic aromatic compound to which vinylene carbonate is added, which is used as a raw material in the step (a) of the method, can be produced by a method comprising the steps of: a step of adding vinylene carbonate to the condensed polycyclic aromatic compound of the formula (i) (a), particularly a step of adding these compounds by mixing them. In this case, vinylene carbonate may be used by dissolving it in a solvent, or may be used alone. Here, as the solvent, any solvent capable of dissolving vinylene carbonate can be used. Examples of usable solvents include aprotic polar solvents such as N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, and ethyl acetate; diethyl ether, tetrahydrofuran, diisopropyl ether, diglyme, 1, 4-diEther solvents such as alkanes; benzene, toluene, xylene,Aromatic hydrocarbons such as 1,3, 5-trimethylbenzene; aliphatic hydrocarbons such as hexane and heptane; and halogen-containing solvents such as dichloromethane, chloroform, dichloroethane, and the like.

In the synthesis of the condensed polycyclic aromatic compound to which vinylene carbonate is added, when the condensed polycyclic aromatic compound of (i (a)) and vinylene carbonate are mixed, the reaction may be accelerated by heating and/or light irradiation. The reaction temperature in the synthesis of the condensed polycyclic aromatic compound to which vinylene carbonate is added may be determined in consideration of the rate of formation, stability of components, boiling point of components, and the like, and may be, for example, a temperature of 20 ℃ or higher, 50 ℃ or higher, 100 ℃ or higher, 180 ℃ or lower, 200 ℃ or lower, or 220 ℃ or lower. The reaction time may be, for example, 1 minute or more, 10 minutes or more, 30 minutes or more, 1 hour or more, and 1 day or less, 3 days or less, 5 days or less, or 10 days or less.

Specifically, for example, Dinaphthothiophene (DNTT) which is a condensed polycyclic aromatic compound and vinylene carbonate are mixed inVinylene carbonate is added to DNTT by diels-alder addition reaction in a solvent while stirring under heating under nitrogen, thereby obtaining dinaphthothiophene (a compound of formula (1) below) to which vinylene carbonate is added, which is a condensed polycyclic aromatic compound to which vinylene carbonate is added. Then, dinaphthothiophene added with vinylene carbonate was obtained as a solid by filtration, followed by washing with chloroform.

For the hydrolysis in step (b) of this method, for example, dinaphthothiophene (the compound of formula (1) above) to which vinylene carbonate is added, provided in step (b), is added to ethanol, and further sodium hydroxide is added, and reflux is performed to obtain an α -diol compound (the compound of formula (2) below) in which a portion corresponding to vinylene carbonate is converted into an α -diol portion. In addition, regarding the hydrolysis reaction in the step (b), non-patent document 4 can be referred to.

For the oxidation in step (c) of this method, for example, the α -diol compound obtained in step (b) is reacted in a mixed solution of dimethyl sulfoxide, trifluoroacetic anhydride, triethylamine, and dichloromethane while cooling, and the α -diol compound is oxidized to convert the α -diol moiety into an α -diketone moiety, thereby obtaining an α -diketone compound (the compound of formula (3) below). In addition, for the oxidation reaction in the step (c), non-patent document 4 can be referred to.

In another embodiment of this method, in order to provide dinaphthothiophene added with vinylene carbonate as an example of the condensed polycyclic aromatic compound added with vinylene carbonate used as a raw material in the step (a), 2-methylthio-3-naphthaldehyde obtained as shown in patent document 5 is added to a tetrahydrofuran solvent under a nitrogen stream, vinylene carbonate is added thereto, and then the reaction is carried out at a reflux temperature to obtain adducts (compounds of the following formulae (4) and (5)) obtained by adding vinylene carbonate to 2-methylthio-3-naphthaldehyde. The procedure shown in example 1 of patent document 5 was followed for the addition product to bond 2 molecules of the addition product, thereby obtaining dinaphthothiophene with vinylene carbonate added.

[2 nd Synthesis method of intermediate alpha-diketone Compound and alpha-diketone Compound ]

The intermediate α -diketone compound of the present invention has the following formula (i (a')):

Ar_1XQ (I(a)’)

{Ar_1Xselected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties, and at least one of said aromatic rings is substituted with a bicyclic α -dione moiety of formula (X) below, and:

q has the following formula and structure Ar_1XA part of the fused ring of (a):

(Y is an element selected from chalcogen).

Specifically, for example, the compound of formula (i (a)') may be any one of the following compounds or a stereoisomer thereof:

(Y is an element selected from chalcogen elements, and

the benzene ring moiety is substituted or unsubstituted).

The intermediate α -diketone compound of the present invention can be obtained by adding vinylene carbonate to a compound of the following formula (I') and then hydrolyzing and oxidizing the resulting compound:

Ar₁Q (I’)

{Ar₁selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties, and

q has the following formula and structure Ar₁A part of the fused aromatic ring of (1):

(Y is an element selected from chalcogen elements) }

For the addition reaction, hydrolysis reaction and oxidation reaction for obtaining the intermediate α -diketone compound, reference may be made to the description of the 1 st synthesis method of the α -diketone compound described above.

Specifically, in order to obtain the intermediate α -diketone compound of the present invention, for example, an adduct obtained by adding vinylene carbonate (the compounds of formulae (4) and (5) above) to 2-methylthio-3-naphthaldehyde is added to ethanol, and further sodium hydroxide is added thereto, followed by reflux to obtain an α -diol compound (compounds of formulae (6) and (7) below) in which a portion corresponding to the vinylene carbonate is converted into an α -diol portion. For the hydrolysis reaction, non-patent document 4 can be referred to.

Then, the α -diol compound (the compounds of the above formulae (6) and (7)) is reacted in a mixed solution of dimethyl sulfoxide, trifluoroacetic anhydride, triethylamine and dichloromethane while cooling, and the α -diol compound is oxidized to convert the α -diol moiety into an α -diketone moiety, thereby obtaining the intermediate α -diketone compound (the compounds of the formulae (8) and (9)) of the present invention. For the oxidation reaction, non-patent document 4 can be referred to.

The method for synthesizing the α -diketone compound of the present invention from the above intermediate α -diketone compound comprises the following steps (a) and (b):

(a) a step of reacting 2 molecules of the intermediate α -diketone compound of the present invention, or 1 molecule of the intermediate α -diketone compound of the present invention with 1 molecule of a compound having a structure which decomposes a bicyclic α -diketone moiety of the intermediate α -diketone compound of the present invention to form a benzene ring moiety to obtain a compound of the following formula:

Ar_1XQ＝QAr_1X

{ Q ═ Q denotes the following structure:

(Y is an element selected from chalcogen); and

(b) with the formula Ar_1XQ＝QAr_1XAnd (d) reacting the obtained compound with iodine.

According to this method, the α -diketone compound of the present invention of the following formula (I (a1) -X) can be synthesized:

Ar_1XAr_2(a1)Ar_1X(I(a1)-X)

(Ar_1Xselected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties, and at least one of said aromatic rings is substituted with a bicyclic α -dione moiety of formula (X):

Ar_2(a1)is a condensed aromatic heterocyclic moiety of the following formula (a1) (Y is an element selected from chalcogen), and

Ar_1Xand Ar_2(a1)Having at least 2 carbon atoms in total to form a fused ring).

Further, with respect to the conditions and the like of the method for synthesizing the α -dione compound of the present invention from the intermediate α -dione compound, reference is made to the description of non-patent document 1, that is, for example, the reaction of 2 molecules of the intermediate α -dione compound in the step (a) can utilize tetrachloromethane/zinc (TiCl) in tetrahydrofuran₄/Zn) catalyst. In addition, the stepsFormula Ar in step (b)₁(Q＝Q)Ar₁The reaction with iodine can be carried out in chloroform (i.e., chloroform) (CHCl)₃) Is carried out in (1).

In this method, for example, the intermediate α -diketone compound of the present invention (the compounds of the above formulas (8) and (9)) is subjected to the procedure shown in example 1 of patent document 5, and 2 molecules of the adduct are bonded to obtain dinaphthothiophene carbonate (any of the compounds of the following formulas (3-1) to (3-5)) added with vinylene carbonate.

Solutions containing alpha-diketone compounds

The solution containing an α -diketone compound of the present invention is obtained by dissolving the α -diketone compound of the present invention in a solvent, particularly an organic solvent.

The solution containing the α -diketone compound may contain the α -diketone compound of the present invention at any concentration, and for example, the α -diketone compound of the present invention may be contained at a concentration of 0.01 to 20 mass%, 0.05 to 10 mass%, 0.1 to 5 mass%.

As the solvent usable in the solution containing α -dione compound, any solvent can be used which can dissolve the α -dione compound of the present invention, and examples of the solvent usable include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, and ethyl acetate, diethyl ether, tetrahydrofuran, diisopropyl ether, diglyme, and 1, 4-diglymeEther solvents such as alkanes; benzene, toluene, xylene,Aromatic hydrocarbons such as 1,3, 5-trimethylbenzene; aliphatic hydrocarbons such as hexane and heptane; and twoAnd halogen-containing solvents such as methyl chloride, chloroform, dichloroethane, and the like.

Method for producing organic semiconductor film

The method of the present invention for producing an organic semiconductor film comprises the following steps (a) and (b):

(a) a step of applying the solution containing an α -diketone compound of the present invention to a substrate to produce a film, and

(b) a step of irradiating the film with light to decompose a bicyclic α -diketone moiety of the α -diketone compound to form a benzene ring moiety, thereby obtaining an organic semiconductor film composed of a condensed polycyclic aromatic compound represented by the following formula (i (a):

Ar₁Ar_2(a)Ar₃(I(a))

(Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar_2(a)selected from a substituted or unsubstituted aromatic heterocyclic moiety consisting of 1 aromatic heterocyclic ring and a substituted or unsubstituted condensed aromatic heterocyclic moiety condensed with 2 to 5 aromatic heterocyclic rings,

Ar₁and Ar_2(a)Having at least 2 carbon atoms in total to form a fused ring, and

Ar_2(a)and Ar₃Having at least 2 carbon atoms in total to form a fused ring).

The coating of the solution on the substrate can be carried out in any manner, and can be carried out by, for example, a casting method, a spin coating method, a printing method, or the like. The coating of the solution on the substrate may be carried out by simply dropping the solution on the substrate.

In the irradiation of light for obtaining the condensed polycyclic aromatic compound of the formula (i (a)) from the α -diketone compound, light of an arbitrary wavelength and/or intensity that can achieve such decomposition may be irradiated. Among them, decomposition is generally achieved by visible light to ultraviolet light.

Further, the method may further comprise a step of removing impurities other than the condensed polycyclic aromatic compound of the formula (I (a)) by reducing the pressure and/or heating together with or after the light irradiation. In this case, any condition under which the condensed polycyclic aromatic compound of the formula (I (a)) is not substantially decomposed may be used. Therefore, the heating may be performed at a temperature of, for example, 40 ℃ or more, 60 ℃ or more, 80 ℃ or more, 100 ℃ or more, 120 ℃ or more, or 140 ℃ or more, and 200 ℃ or less, 220 ℃ or less, 240 ℃ or less, or 260 ℃ or less. In addition, the decomposition of the α -diketone compound of the present invention and/or the removal of impurities may be carried out, for example, under vacuum or atmospheric pressure. Further, the decomposition of the α -diketone compound and/or the removal of impurities of the present invention may be performed, for example, under a nitrogen atmosphere or under an atmospheric atmosphere. Since the process is easy, it is particularly preferable to carry out the decomposition of the α -diketone compound and/or the removal of impurities of the present invention in an atmospheric atmosphere at atmospheric pressure.

Method for manufacturing organic semiconductor device

The method of the present invention for manufacturing an organic semiconductor device comprises the step of forming an organic semiconductor film by the method of the present invention for forming an organic semiconductor film. In addition, the method may further include a step of forming an electrode layer and/or a dielectric layer on the upper side or the lower side of the organic semiconductor film as desired.

Organic semiconductor device

The organic semiconductor device of the present invention is an organic semiconductor device having an organic semiconductor film made of a condensed polycyclic aromatic compound of the following formula (i (a)), and the organic semiconductor film further contains an α -diketone compound of the present invention:

Ar₁Ar_2(a)Ar₃(I(a))

(Ar₁and Ar₃Each independently selected from 2 to 5 aromatic ring fused substituted or unsubstituted fused aromatic ring moieties,

Ar_2(a)selected from a substituted or unsubstituted aromatic heterocyclic moiety consisting of 1 aromatic heterocyclic ring and a substituted or unsubstituted condensed aromatic heterocyclic moiety condensed with 2 to 5 aromatic heterocyclic rings,

Ar₁and Ar_2(a)Having at least 2 carbon atoms in total to form a fused ring, and

Ar_2(a)and Ar₃Having at least 2 carbon atoms in total to form a fused ring).

Here, the organic semiconductor film contains the α -diketone compound of the present invention means that the organic semiconductor film contains the α -diketone compound of the present invention in a detectable amount. Thus, for example, the mole ratio of the α -diketone compound of the present invention may exceed 1ppm, exceed 10ppm, exceed 100ppm, exceed 1,000ppm, or exceed 10,000ppm (1%). The proportion of the α -diketone compound of the present invention may be 10 mol% or less, 5 mol% or less, 3 mol% or less, 1 mol% or less, 0.1 mol% or less, or 0.01 mol% or less.

Such an organic semiconductor device of the present invention may have characteristics as an organic semiconductor device, even if it contains the α -diketone compound of the present invention in addition to the condensed polycyclic aromatic compound of the formula (I). That is, when the organic semiconductor film of the organic semiconductor device of the present invention is produced from the α -diketone compound of the present invention, the organic semiconductor device of the present invention has characteristics as a semiconductor device even if the thermal dissociation reaction of the α -diketone compound of the present invention does not proceed completely. This is preferable because it makes the production of the organic semiconductor device of the present invention or the organic semiconductor film thereof easy.

In particular, the organic semiconductor device of the present invention is a thin film transistor having a source electrode, a drain electrode, a gate insulating film, and an organic semiconductor film, and is a thin film transistor in which the source electrode and the drain electrode are insulated from the gate electrode by the gate insulating film, and a current flowing from the source electrode to the drain electrode through the organic semiconductor is controlled by a voltage applied to the gate electrode. In addition, the organic semiconductor device of the present invention is particularly a solar cell having an organic semiconductor film as an active layer.

Examples

In the following examples and comparative examples, the structure of the target compound can be determined by 1H-NMR (1H-nuclear magnetic resonance spectroscopy), MS (mass spectrometry), and elemental analysis, if necessary, unless otherwise specified. The machine used is as follows.

¹H-NMR：JEOL ECA-500(500MHz)

MS：Shimazu QP-5050A

Elemental analysis: parkin Elmer2400CHN type element analyzer

The conditions for computer simulation of the addition reaction were as follows.

Semi-empirical method

Procedure MOPAC3.0

AM1 Hamilton

Structure optimization by EF method

Non-empirical method

Procedure Gaussian 03

Correlation exchange function B3LYP

Basis function system 6-31G (d)

Structure optimization Berny algorithm

In the computer simulation, the heat of formation of the raw material compound and the heat of formation of the addition compound of these compounds were determined, and the possibility of realization of the reaction for producing the addition compound was evaluated. Here, it is considered that the reaction for producing the addition compound can be achieved when the value of the difference (relative heat of formation) between the total heat of formation of the raw material compounds and the heat of formation of the addition compound of these compounds is larger than-20 kcal/mol (endothermic), that is, when the addition reaction is an exothermic reaction or a slightly endothermic reaction. The value of the relative heat generation is relatively small, and for example, an endothermic reaction in which the value of the relative heat generation is more than-20 kcal/mol or an exothermic reaction of 20kcal/mol or less is considered to be reversible. Further, MOPAC has very high reliability when considering only carbon and hydrogen, but has high reliability of Gaussian when containing elements other than carbon and hydrogen.

EXAMPLE 1-1A

To 100mg (0.293mmol) of dinaphthothiophene (DNTT, MW-340.46, structural formula shown below) synthesized by the method shown in patent document 2, 20g (47.66mmol) of hexachlorocyclopentadiene (HCCPD, MW-272.77, structural formula shown below) was added, and the reaction temperature was maintained at 160 ℃ for 24 hours.

Then, the reaction product was cooled to obtain dinaphthothiophene (DNTT-2hccpd (tts), mw.886.00, 20mg, 0.0225 mmol) to which 2 molecules of hexachlorocyclopentadiene were added, with a yield of 7.7%, and a structural formula shown below.

The DNTT-2HCCPD (TTs) obtained as described above was purified by High Performance liquid chromatography (Agilent1100Series HPLC: High Performance liquid chromatography, SHISEIDO CAPCELL PAKC18TYPE UG120, solvent acetonitrile/water).

The results of the analysis for DNTT-2HCCPD (TTs) are shown below:

¹H-NMR(500MHz，CDCl₃):8.43(s，1H)，8.39(s，1H)，8.33(s，1H)，8.24(s，1H)，8.05(m，1H)，7.96(m，1H)，7.55(m，2H)，4.20(d，J＝9.5Hz，1H)，4.16(d，J＝9.5Hz，1H)，3.64(d，J＝8.9Hz，2H)

Anal.Calcd for C₃₂H₁₂Cl₁₂S₂:C，43.37；H，1.37

Found:C，41.9；H，1.3

MS(70eV，DI):340m/z

mass analysis (MS) measurements (340m/z) were consistent with DNTT (molecular weight 340.46), indicating that DNTT-2HCCPD (TTs) were detached and DNTT regenerated by HCCPD exposure to mass analysis (70eV, DI).

The DNTT-2hccpd (tts) obtained in the above synthesis was dissolved in toluene to a concentration of 0.2 mass%, thereby preparing a solution for semiconductor device fabrication.

Then, for 300nm with SiO₂An n-doped silicon wafer (sheet resistance 0.005. omega. cm) having an oxide film was subjected to UV ozone treatment (AI UV-ozone cleaning apparatus OC-250615-D + A, EYE GRAPHICS K.K.) for 20 minutes. Further, a 10 mmol/toluene solution of octadecyltrichlorosilane (ODTS, shin-Etsu chemical LS-6495) was prepared, and in this solution, the silicon substrate subjected to UV ozone treatment was immersed for 24 hours. Then, a source/drain gold electrode having a channel length of 50 μm and a channel width of 1.5mm was formed on a silicon substrate by a vacuum evaporation method (Sanyu Electron, resistance heating type deposition apparatus: SVC-700 TM/700-2).

While heating the silicon substrate to 40 ℃, a solution for manufacturing a semiconductor device was dropped on the channel portion to volatilize the solvent, thereby forming a thin layer made of DNTT-2hccpd (tts). The thus-produced element was heat-treated at 180 ℃ for 1 hour under vacuum to produce an organic semiconductor element. A schematic diagram of the obtained organic semiconductor element is shown in fig. 1. In the organic semiconductor element shown in fig. 1, a dielectric layer 5 as silicon oxide is formed on a substrate (gate electrode) 7 as a silicon wafer, source and drain electrodes 2 and 3 are stacked on the dielectric layer 5, and then an organic semiconductor 1 is stacked.

Performing organic semiconductor propertiesThe result shows that the p-type semiconductor has a carrier mobility of 2 × 10-⁵cm²Vs, on/off ratio 113, threshold voltage 14.4V. Fig. 2 and 3 show the output characteristics and transfer characteristics of a Field Effect Transistor (FET), respectively. Here, in fig. 2, the vertical axis represents the leakage current (I)_D(A) And the abscissa represents the drain voltage (V)_D(V)). In fig. 3, the vertical axis represents the leakage current (I)_D(A) The abscissa represents the gate voltage (V)_G(V))。

Comparative example 1-1A

The DNTT alone, which was not added to HCCPD, was added to toluene at a concentration of 0.2 mass%, but hardly dissolved. Therefore, DNTT alone cannot be used with the solution method.

EXAMPLES 1-1B

The addition reaction of Dinaphthothiophene (DNTT) with Hexachlorocyclopentadiene (HCCPD) was confirmed by computer simulation using the semi-empirical method described above (MOPAC).

The results are shown in the following table. Furthermore, in the semi-empirical Method (MOPAC) described above, the heat of formation of DNTT was 117.29kcal/mol and the heat of formation of HCCPD was 5.86 kcal/mol.

[ Table 1]

The addition positions in table 1 are shown by the following chemical formulas, and they are the positions where HCCPD is centered at "c", "z" is the position of the end on the same side (zusammen) as the neighboring sulfur (S) atom, and "e" is the position of the end on the opposite side (entgegen) to the neighboring sulfur (S) atom, and are added to DNTT.

In table 1, "anti" indicates that HCCPD is added from the opposite side to the conjugate surface of DNTT, and "iso" indicates that 2HCCPD are added to the same end of DNTT. Further, "anti" when 3 or more HCCPDs are added indicates that the binding conformation between HCCPDs at opposite ends adjacent to each other is "anti".

As can be understood from the results in table 1, when only 1HCCPD is added to DNTT, HCCPD is added to DNTT at the position of the same side of the terminal as the nearby sulfur (S) atom (addition position "z", notation "DNTT-1 HCCPD (t)") and at the position of the opposite side of the terminal as the nearby sulfur (S) atom (addition position "e", notation "DNTT-1 HCCPD (tb)"). Further, it is understood that when another HCCPD is further added to the addition compound, the HCCPD is further added to the same terminal as the terminal to which the HCCPD has been added (addition position "iso") (notation "DNTT-2 HCCPD (TTs)").

This result of further addition of HCCPD to the same terminus as the terminus to which HCCPD had been added (addition position "iso") in the case of addition of 2 HCCPDs to DNTT corresponded to the result obtained in example 1-1A. Thus, the adequacy of applying computer simulations in diels-alder reactions can be understood.

EXAMPLES 1-2A

1750mg (5.14mmol) of dinaphthothiophene (DNTT, MW-340.46), 17.83g (169.62mmol, 3300 mol%) of N-sulfonyl acetamide (NSAA, MW105.12, structural formula shown below), and metal catalyst reagent CH₃ReO₃(ACROS A0245387, MW249.23)12.81mg (0.05mmol) were mixed in chloroform solvent and refluxed at 63 ℃ for 15.5 hours under nitrogen. Thus, a diels-alder addition reaction of DNTT and NSAA was performed.

Then, a solid was obtained by filtration, which was washed with chloroform. It was confirmed that 1.82g of the obtained green solid was an impurity containing the starting material.

Hexane was added to the filtrate to conduct recrystallization, and 0.2636g of a yellow solid (31.5mg) was obtained by filtration. The solid was separated by HPLC to obtain 31.5mg of an adduct in which 1 molecule of NSAA was added to DNTT (DNTT-1NSAA, Mw: 445.58, yield 1.4 mol%). The structural formula of the addition compound is shown below.

The analysis results for the obtained DNTT-1NSAA are shown below.

¹H-NMR(600MHz，CDCl₃):8.42(s，2H)，8.38(s，2H)，8.05(m，2H)，7.95(m，2H)，7.54(m，4H)，2.03(s，3H)

MS(70eV，DI):339.85m/z

The mass analysis (MS) measurements (339.85m/z) were consistent with DNTT (molecular weight 340.46), indicating exposure of DNTT-1NSAA to conditions of mass analysis (70eV, DI) whereby NSAA is detached and DNTT is regenerated.

EXAMPLES 1-2B

The addition reaction of Dinaphthothiophene (DNTT) with N-sulfonyl acetamide (NSAA) was confirmed by computer simulation using the semi-empirical Method (MOPAC) and the non-empirical method (Gaussian) described above.

The results are shown in the following table. Furthermore, in the semi-empirical Method (MOPAC) described above, the heat of formation of DNTT was 117.56kcal/mol and the heat of formation of NSAA was-49.27 kcal/mol.

[ Table 2]

TABLE 2

In the addition position in table 2, as shown in the following chemical formula, the carbon of DNTT was numbered, and the carbon to which the nitrogen (N) atom and the sulfur (S) atom of NSAA were coordinated was identified.

From the results in table 2, it is understood that the reaction of adding NSAA to DNTT can be achieved, and in this case, NSAA is added to the central position of DNTT.

EXAMPLES 1 to 3

The addition reaction of Dinaphthothiophene (DNTT) with cyclopentadiene (CPD, structural formula shown below) was confirmed by computer simulation using the semi-empirical Method (MOPAC) and non-empirical method (Gaussian) described above.

The results are shown in the following table. Furthermore, in the semi-empirical Method (MOPAC) described above, the heat of formation of DNTT was 117.56kcal/mol and the heat of formation of CPD was 37.97 kcal/mol.

[ Table 3]

TABLE 3

The addition positions in Table 3 are exemplified below. Further, the notation "CPD-CPD" in table 3 indicates an addition compound to which 2 CPDs are added.

From the results in table 3, it can be understood that the addition reaction of CPD to DNTT can be achieved.

EXAMPLES 1 to 4

The addition reaction of Dinaphthothiophene (DNTT) with furan (FRN, formula shown below) was confirmed by computer simulation using the semi-empirical Method (MOPAC) and non-empirical method (Gaussian) described above.

The results are shown in the following table. Furthermore, in the semi-empirical Method (MOPAC) described above, the heat of formation of DNTT was 117.56kcal/mol and the heat of formation of FRN was 2.96 kcal/mol.

[ Table 4]

TABLE 4

The addition positions in table 4 are exemplified below. Note that the symbol "FRN-FRN" in table 4 indicates an addition compound to which 2 FRNs are added.

From the results in table 4, it is understood that the addition reaction of FRN to DNTT can be achieved.

EXAMPLES 1 to 5

The addition reaction of Dinaphthothiophene (DNTT) with anthracene (ANTH, structural formula shown below) was confirmed by computer simulation using the semi-empirical Method (MOPAC) and the non-empirical method (Gaussian) described above.

The results are shown in the following table. In addition, in the above semi-empirical Method (MOPAC), the heat of formation of DNTT was 117.56kcal/mol, and the heat of formation of ANTH was 62.92 kcal/mol.

[ Table 5]

TABLE 5

The addition positions for table 5 are shown below.

From the results of table 5, it can be understood that the addition reaction of ANTH to DNTT can be achieved.

EXAMPLES 1 to 6

The addition reaction of Dinaphthothiophene (DNTT) with tricyano-carboxylic acid methyl ester-ethylene (TCPM, structural formula shown below) was confirmed by computer simulation using the semi-empirical Method (MOPAC) and non-empirical method (Gaussian) described above.

The results are shown in the following table. Furthermore, in the semi-empirical Method (MOPAC) described above, the heat of formation of DNTT was 117.56kcal/mol and the heat of formation of TCPM was 40.24 kcal/mol.

[ Table 6]

TABLE 6

"light" and "heat" in the reaction conditions of the addition reaction of table 6 mean that the addition reaction proceeds by light and heat, respectively. The addition positions in table 6 are exemplified below.

From the results of Table 6, it can be understood that the addition reaction of TCPM to DNTT can be achieved.

EXAMPLES 1 to 7

The addition reaction of Dinaphthothiophene (DNTT) with methyl carboxylate pyrrole (NMPC, formula shown below) was determined by computer simulation using the semi-empirical Method (MOPAC) and non-empirical method (Gaussian) described above.

The results are shown in the following table. Furthermore, in the semi-empirical Method (MOPAC) described above, the heat of formation of DNTT was 117.56kcal/mol and the heat of formation of NMPC was-30.46 kcal/mol.

[ Table 7]

TABLE 7

"light" and "heat" in the reaction conditions of the addition reaction of table 7 mean that the addition reaction proceeds by light and heat, respectively. The addition positions in table 7 are exemplified below.

From the results in Table 7, it can be understood that addition reaction of NMPC to DNTT can be achieved.

EXAMPLES 1 to 8

The addition reaction of Dinaphthothiophene (DNTT) with hydroxyphenyl-maleimide (hopim, structural formula shown below) was confirmed by computer simulation using the semi-empirical Method (MOPAC) and non-empirical method (Gaussian) described above.

The results are shown in the following table. In addition, in the semi-empirical Method (MOPAC) described above, the heat of formation of DNTT was 117.56kcal/mol and the heat of formation of HOPMI was-38.13 kcal/mol.

[ Table 8]

TABLE 8

"light" and "heat" in the reaction conditions of the addition reaction of table 8 mean that the addition reaction proceeds by light and heat, respectively. The addition positions in table 8 are exemplified below.

From the results in Table 8, it is understood that the addition reaction of HOPMI to DNTT can be achieved.

EXAMPLES 1 to 9

The addition reaction of Dinaphthothiophene (DNTT) with vinylene carbonate (VC (vinylene carbonate), structural formula shown below) was confirmed by computer simulation using the semi-empirical Method (MOPAC) and the non-empirical method (Gaussian) described above.

The results are shown in the following table. Furthermore, in the semi-empirical Method (MOPAC) described above, the heat of formation of DNTT was 117.56kcal/mol and the heat of formation of VC was-59.30 kcal/mol.

[ Table 9]

TABLE 9

"light" and "heat" in the reaction conditions of the addition reaction of table 9 mean that the addition reaction proceeds by light and heat, respectively.

The addition positions in Table 9 are shown by the following chemical formulae.

M position: 2-7

L position: 4-5

Z position: 3-6

A T position: 3-4, or 5-6

C position: 7b-14b

From the results in Table 9, it is understood that addition reaction of VC to DNTT can be achieved.

EXAMPLES 1 to 10A

500mg (1.47mmol) of dinaphthothiophene (DNTT, MW-340.46) synthesized by the method shown in patent document 2, 2.54g (14.7mmol, 1000 mol% based on DNTT) of N-phenylmaleimide (PMI, MW-173.16, structural formula shown below) were used as free radicalsHydroquinone based scavenger (MW110.1)16.2mg (1 mol% based on N-phenylmaleimide group) inThe mixture was stirred at 160 ℃ for 2 hours under nitrogen. Thus, diels-alder addition reaction of DNTT and PMI proceeds.

After the reaction, a solid was obtained by filtration and washed with chloroform. The solid was confirmed to be DNTT (raw material) by NMR (yield 422.3mg, yield 84.5 mol%).

The filtrate was separated by HPLC (high performance Liquid Chromatography, Agilent1100Series HPLC: high Performance Liquid Chromatography, SHISEIDO CAPCELL PAK C18TYPE UG120, solvent: acetonitrile/water), to obtain 113.2mg of an adduct compound in which 1 molecule of PMI was added to DNTT (DNTT-1PMI, Mw 513.63, yield 15.0 mol%).

The DNTT-1PMI obtained was a mixture of 2 stereoisomers ("stereoisomer A" and "stereoisomer B", respectively). The results of analysis of these stereoisomers are shown below. Further, from the results of NMR, it can be estimated that the stereoisomer A is an endo form, and the stereoisomer B is an exo form.

DNTT-1PMI (stereoisomer A)

¹H-NMR(600MHz，CDCl₃):8.30(S、1H)、8.23(S、1H)、7.95(m、1H)、7.89(m、1H)、7.50(m、2H)、7.47(m、2H)、7.25(m、2H)、7.12(t、J＝7.3Hz，1H)、7.07(dd、J＝7.3Hz、7.7Hz，2H)、6.50(d、J＝7.7Hz、2H)、5.30(d、J＝3.3Hz，1H)、5.22(d、J＝3.3Hz，1H)、3.54(dd、J＝3.3Hz，8.1Hz，1H)、3.51(dd、J＝3.3Hz、8.1Hz、1H)

MS(70eV，DI):514.10m/z

DNTT-1PMI (stereoisomer B)

¹H-NMR(600MHz，CDCl₃):8.33(s、1H)、8.25(s、1H)、7.97(m、1H)、7.90(m、1H)、7.49(m、2H)、7.42(m、1H)、7.40(m、1H)、7.31(m、1H)、7.30(m、2H)、7.26(m、2H)、6.53(m、2H)、5.22(d、J＝3.3Hz、1H)、5.18(d、J＝3.3Hz、1H)、3.59(dd、J＝3.3Hz，8.4Hz，1H)、3.56(dd、J＝3.3Hz、8.4Hz、1H)

MS(70eV，DI):513.05m/z

The detection values of Mass Spectrometry (MS) were substantially identical to DNTT-1PMI (Mw: 513.63).

The thermal dissociation properties of DNTT-1PMI (stereoisomers A and B) were evaluated by differential thermal Scale analysis (Rigaku TG-DTATG8120) and temperature rise analysis at 1 ℃/min under nitrogen. Accordingly, for DNTT-1PMI (stereoisomer A), the weight loss was 31.9 wt% over the temperature range from 195 ℃ to 260 ℃. In addition, for DNTT-1PMI (stereoisomer B), the weight loss was 32.7 wt% over the temperature range from 155 ℃ to 260 ℃. The results are shown in FIG. 4. In the case where PMI is thermally dissociated from DNTT-1PMI (MW 513.63) by retro diels-alder reaction, weight reduction was-33.7 wt% (calculated value), and thus the analysis result of DNTT-1PMI (stereoisomers a and B) showed that PMI is dissociated by heating. Furthermore, it was confirmed by NMR that the sample after thermal desorption agrees with DNTT.

A bottom-contact bottom-gate FET (Field effect Transistor) device was fabricated as follows using DNTT-1 PMIs (stereoisomers a and B), respectively.

The substrate is SiO at 300nm₂SiO of oxide film n-doped silicon wafer (sheet resistance 0.005. omega. cm)₂The oxide film was formed with a source/drain gold electrode having a channel length of 50 μm and a channel width of 1.5mm (bottom contact).

While heating the substrate to 50 ℃, a3 wt% solution of DNTT-1PMI (stereoisomers a and B) in chloroform was dropped onto the channel portion of the substrate, and rapidly volatilized to obtain a film, and then the film was heated to obtain an organic semiconductor film. Here, DNTT-1PMI (stereoisomer A) was heated at 200 ℃ for 2 hours while starting from room temperature at a heating rate of about 20 ℃/min under nitrogen. In addition, DNTT-1PMI (stereoisomer B) was heated from room temperature at a heating rate of about 20 ℃/min under nitrogen or atmospheric air, and was heated at 160 ℃ for 2 hours.

The characteristics of the obtained organic semiconductor film were evaluated, and p-type semiconductor characteristics were exhibited. In addition, the mobility of the carrier is 0.01 to 0.0001cm²Vs and an on/off ratio of 10³～10⁵. That is, semiconductor characteristics can be obtained not only when DNTT-1PMI (stereoisomer B) is heated under nitrogen but also when it is heated under the atmosphere. Fig. 5 and 6 show the output characteristics and transfer characteristics of a Field Effect Transistor (FET), respectively. Here, in fig. 5, the vertical axis represents the leakage current (I)_D(A) And the abscissa represents the drain voltage (V)_D(V)). In fig. 6, the vertical axis represents the leakage current (I)_D(A) The abscissa represents the gate voltage (V)_G(V))。

Fig. 8 shows the result of observing the crystal state of DNTT in the channel portion of the organic semiconductor film obtained by DNTT-1PMI (stereoisomer B) with a polarization microscope. From the observation of the channel portion by the polarization microscope, it was confirmed that after the organic semiconductor film was obtained by heating, fine crystal particles of about 1 μm were formed on the entire surface of the organic semiconductor film. Thus, it was confirmed that the PMI was detached from DNTT-1PMI by heating to form DNTT crystals.

With respect to the above FET element having an organic semiconductor film obtained from DNTT-1PMI (stereoisomer B), the presence or absence of residual DNTT-1PMI (stereoisomers a and B) in the organic semiconductor film was confirmed by NMR. The results are shown in FIG. 7. In addition, in FIG. 7, "DNTT", "DNTT-1 PMI (A)", "DNTT-1 PMI (B)", and "FETDNTT-1 PMI (B)" respectively show the results of analysis of the organic semiconductor films obtained from DNTT, DNTT-1PMI (stereoisomer A), DNTT-1PMI (stereoisomer B), and DNTT-1PMI (stereoisomer B).

From FIG. 7, not only NMR peaks corresponding to DNTT but also NMR peaks corresponding to both DNTT-1PMI (stereoisomers A and B) were observed in the organic semiconductor film obtained from DNTT-1PMI (stereoisomer B). That is, it was confirmed that sufficient semiconductor characteristics can be provided even when DNTT-1PMI (stereoisomers a and B) remains in the organic semiconductor film.

Here, DNTT has low solubility, and thus peaks are difficult to observe by NMR. On the other hand, DNTT-1PMI (stereoisomers A and B) had high solubility, and NMR peaks corresponding to the dissolved fraction were observed. Therefore, the ratio of DNTT-1PMI to DNTT in the organic semiconductor film cannot be determined from the NMR results. As can be understood from the increase in noise, the peak of "DNTT" in fig. 7 has a larger magnification than other peaks. In addition, it was found that the NMR peak of DNTT-1PMI (stereoisomers A and B) detected in the organic semiconductor film was approximately the same size as the peak of DNTT, and that the residual DNTT-1PMI (stereoisomers A and B) was slightly smaller.

EXAMPLES 1 to 10B

The addition reaction of Dinaphthothiophene (DNTT) with N-phenylmaleimide was confirmed by computer simulation using the semi-empirical Method (MOPAC) and non-empirical method (Gaussian) described above.

The results are shown in the following table. Furthermore, in the semi-empirical Method (MOPAC) described above, the heat of formation of DNTT was 117.56kcal/mol and the heat of formation of PMI was 5.83 kcal/mol.

[ Table 10]

The addition positions in Table 10 are shown by the following chemical formulae.

M position: 2-7

C position: 7b-14b

Z position: 3-6

MM bit: 2-7 and 9-14

ZZ position: 3-6 and 10-13

MZ bit and ZM bit: 2-7 and 10-13

From the results in table 10, it is understood that the addition reaction of 1 molecule of PMI to 1 molecule of DNTT and the addition reaction of 2 molecules of PMI to 1 molecule of DNTT can be achieved.

EXAMPLES 1 to 10C

A1.5 wt% solution of DNTT-1PMI (stereoisomer A) synthesized in examples 1-10A in chloroform was dropped on a base material and dried on a hot plate at 50 ℃ to form a thin film of DNTT-1PMI (stereoisomer A) on a substrate. Here, the substrate is 300nm with SiO₂An n-doped silicon wafer (sheet resistance 0.005. omega. cm, thickness about 0.5mm) having an oxide film.

The substrate having the DNTT-1PMI (stereoisomer a) film was placed on a heating plate heated to 210 ℃ under the atmosphere with tweezers, and rapidly heated and held for 3 minutes. By this rapid heating, phenylmaleimide was detached from DNTT-1PMI (stereoisomer A) to precipitate DNTT. In this rapid heating, a change from colorless to yellow in the film was visually observed for about 15 seconds. Considering that the thermal dissociation temperature of DNTT-1PMI (stereoisomer A) is 195 ℃, it can be said that about 200 ℃ is reached in about 15 seconds, which corresponds to a temperature rise rate of about 800 ℃/min.

Fig. 9 shows the results of observation of DNTT deposited on the substrate by a polarization microscope. As shown in fig. 9, crystal particles of DNTT having a major axis diameter exceeding 100 μm were precipitated.

For the substrate on which DNTT is precipitated, a source with a channel length of 50 mu m and a channel width of 1.5mm is preparedGold leakage electrode, thereby fabricating an organic semiconductor element (bottom gate top contact). The characteristics of the obtained organic semiconductor film were evaluated, and as a result, p-type semiconductor characteristics were exhibited. In addition, the mobility of the carrier is 0.2 to 0.001cm²Vs and an on/off ratio of 10⁴～10⁶。

EXAMPLES 1 to 10D

DNTT was precipitated in the same manner as in example 1-10C, except that the substrate having a thin film of DNTT-1PMI (stereoisomer a) was placed on a hot plate heated to 205 ℃ with tweezers, and rapidly heated and held for 5 minutes. In this rapid heating, a change from colorless to yellow in the film was visually observed for about 15 seconds. Considering that the thermal dissociation temperature of DNTT-1PMI (stereoisomer A) is 195 ℃, it can be said that about 200 ℃ is reached in about 15 seconds, which corresponds to a temperature rise rate of about 800 ℃/min.

Fig. 10 shows the results of observation of DNTT deposited on the substrate by a polarization microscope. As shown in fig. 10, crystal particles of DNTT having a major axis diameter exceeding 100 μm were precipitated.

EXAMPLES 1 to 10E

DNTT was precipitated in the same manner as in examples 1 to 10C, except that the substrate having a thin film of DNTT-1PMI (stereoisomer a) was placed on a hot plate at room temperature with tweezers, heated from room temperature to 210 ℃ (heating rate of about 20 ℃/min) for 10 minutes in an atmospheric atmosphere, and then kept isothermally at 210 ℃ for 3 minutes.

Fig. 11 shows the results of observation of DNTT deposited on the substrate by a polarization microscope. As shown in fig. 11, fine DNTT crystal particles of about 1 μm were precipitated.

EXAMPLES 1 to 10F

DNTT was precipitated in the same manner as in example 1-10C except that DNTT-1PMI (stereoisomer B) synthesized in example 1-10A was used in place of DNTT-1PMI (stereoisomer a), and the substrate having the thin film of DNTT-1PMI (stereoisomer B) was placed on a hot plate heated to 170 ℃ with tweezers, rapidly heated, and held for 15 minutes. In this rapid heating, a change from colorless to yellow in the film was visually observed for about 15 seconds. Considering that the thermal desorption temperature of DNTT-1PMI (stereoisomer B) is 155 ℃, it can be said that about 160 ℃ is reached in about 15 seconds, which corresponds to a temperature rise rate of about 640 ℃/min.

Fig. 12 shows the results of observation of DNTT deposited on the substrate by a polarization microscope. As shown in fig. 12, crystal particles of DNTT having a major axis diameter exceeding 20 μm were precipitated.

EXAMPLES 1 to 10G

DNTT was precipitated in the same manner as in example 1 to 10C except that DNTT-1PMI (stereoisomer B) synthesized in example 1 to 10A was used in place of DNTT-1PMI (stereoisomer a), and the substrate having the thin film of DNTT-1PMI (stereoisomer B) was placed on a hot plate at room temperature using tweezers, and then heated from room temperature to 170 ℃ (heating rate of about 20 ℃/min) for 8 minutes in an atmospheric atmosphere, and thereafter kept isothermally at 170 ℃ for 15 minutes.

Fig. 13 shows the results of observation of DNTT deposited on the substrate by a polarization microscope. As shown in fig. 13, fine DNTT crystal particles of about 1 μm were precipitated.

EXAMPLES 1 to 11

The addition reaction of naphthalene formaldehyde (NAL, structural formula shown below) with N-phenylmaleimide (PMI, structural formula shown below) was confirmed by computer simulation using the semi-empirical Method (MOPAC) and the non-empirical method (Gaussian) described above.

Also, the addition reaction of 3-methylthio-2-naphthaldehyde (MTNAL, structural formula shown below) and N-phenylmaleimide (PMI, structural formula shown below) was confirmed by computer simulation.

The results are shown in the following table. Further, in the semi-empirical Method (MOPAC) described above, the heat of formation of NAL was 9.58kcal/mol, the heat of formation of MTNAL was 12.28kcal/mol, and the heat of formation of PMI was 5.83 kcal/mol.

[ Table 11]

TABLE 11

"heat" in the reaction conditions of the addition reaction of table 9 means that the addition reaction proceeds by heat.

The addition positions in table 11 are shown below:

m position: 1-4

Z position: 8-5

From the results in table 11, it can be understood that the addition reaction of PMI to NAL and the addition reaction of PMI to MTNAL can be achieved. In addition, it can be understood from the results of Table 11 that both the following inner and outer shapes can be formed.

EXAMPLES 1 to 12

500mg (1.47mmol) of dinaphthothiophene (DNTT, MW-340.46), 1.63g (14.7mmol, 1000 mol% based on DNTT) of N-methylmaleimide (MMI, MW-111.1), and 16.2mg (1 mol% based on N-methylmaleimide) of hydroquinone (MW110.1) as a radical scavenger were added to the solutionThe mixture was stirred at 160 ℃ for 2 hours under nitrogen. Thus, Diels-Alder addition reaction of DNTT and MMI was carried out.

Then, a solid was obtained by filtration, and washed with chloroform. The solid was confirmed to be DNTT (raw material) by NMR (yield 343.5mg, yield 68.7 mol%).

The filtrate was separated by HPLC to obtain 113.2mg of an adduct compound having 1 molecule of MMI added to DNTT (DNTT-1MMI, Mw: 451.56, yield 28.5 mol%). The structural formula of the addition compound is shown below.

The resulting DNTT-1MMP is a mixture of 2 stereoisomers ("stereoisomer A" and "stereoisomer B", respectively). The results of analysis of these stereoisomers are shown below. Further, from the results of NMR, it can be estimated that the stereoisomer A is an endo form, and the stereoisomer B is an exo form.

DNTT-1MMI (stereoisomer A)

¹H-NMR(600MHz，CDCl₃):8.28(s，1H)，8.19(s，1H)，7.94(m，1H)，7.88(m，1H)，7.47(m，2H)，7.46(m，1H)，7.42(m，1H)，7.21(m，2H)，5.18(d，J＝2.9Hz，1H)，5.11(d，J＝2.9Hz，1H)，3.37(dd，J＝2.9Hz，7.7Hz，1H)，3.35(dd，J＝2.9Hz，7.7Hz，1H)，2.53(s，3H)

MS(70eV，DI):451.00m/z

DNTT-1MMI (stereoisomer B)

¹H-NMR(600MHz，CDCl₃):8.32(s，1H)，8.23(s，1H)，7.95(m，1H)，7.89(m，1H)，7.49(m，2H)，7.33(m，1H)，7.31(m，1H)，7.17(m，2H)，5.11(d，J＝3.3Hz，1H)，5.07(d，J＝3.3Hz，1H)，3.43(dd，J＝3.3Hz，8.4Hz，1H)，3.40(dd，J＝3.3Hz，8.4Hz，1H)，2.52(s，3H)

MS(70eV，DI):451.30m/z

The mass analysis (MS) measurements were substantially identical to DNTT-1MMI (Mw: 451.56).

The thermal release properties of the DNTT-1MMI were evaluated by differential thermal Scale analysis as in examples 1-10A. Accordingly, with respect to DNTT-1MMI (stereoisomer A), thermal desorption was caused at a temperature range of 220 ℃ to 260 ℃. In addition, since the sample of DNTT-1MMI (stereoisomer B) was trace, the evaluation of thermal dissociation characteristics could not be performed.

With respect to DNTT-1MMI (stereoisomer A), an organic semiconductor film was obtained as in examples 1 to 10A, and semiconductor characteristics were evaluated. Here, heating for obtaining the organic semiconductor film was performed at 225 ℃ for 2 hours under nitrogen. The characteristics of the obtained organic semiconductor film were evaluated, and the results showed p-type semiconductor characteristics. In addition, the mobility of the carrier is 0.01 to 0.0001cm²Vs and an on/off ratio of 10³～10⁵。

EXAMPLES 1 to 13

500mg (1.47mmol) of dinaphthothiophene (DNTT, MW-340.46), 2.63g (14.7mmol, 1000 mol% based on DNTT) of N-cyclohexylmaleimide (CHMI, MW-179.22), and 16.2mg (1 mol% based on N-phenylmaleimide) of hydroquinone (MW110.1) as a radical scavenger were added to the solutionThe mixture was stirred at 160 ℃ for 2 hours under nitrogen. The Diels-Alder addition reaction of DNTT with CHMI was thereby carried out.

Then, a solid was obtained by filtration, and washed with chloroform. The solid was confirmed to be DNTT (raw material) by NMR (yield 478.5mg, yield 95.7 mol%).

The filtrate was separated by HPLC to obtain 28.9mg of an adduct having 1 molecule of CHMI added to DNTT (DNTT-1CHMI, Mw: 519.13, yield 2.1 mol%). The structural formula of the addition compound is shown below.

The results of the analysis of the obtained DNTT-1CHMI are shown below. Furthermore, with respect to DNTT-1CHMI, no stereoisomer was obtained.

¹H-NMR(600MHz，CDCl₃):8.31(s，1H)，8.23(s，1H)，7.95(m，1H)，7.89(m，1H)，7.48(m，2H)，7.33(m，1H)，7.32(m，1H)，7.17(m，2H)，5.08(d，J＝3.4Hz，1H)，5.05(d，J＝3.4Hz，1H)，3.51(m，1H)，3.33(dd，J＝3.4Hz，8.3Hz，1H)，3.30(dd，J＝3.4Hz，8.3Hz，1H)，1.68(m，4H)，1.58(m，1H)，1.09(m，3H)，0.84(m，2H)

MS(70eV，DI):519.20m/z

The measurement value of Mass Spectrometry (MS) substantially agreed with DNTT-1CHMI (Mw: 519.13).

The thermal release properties of DNTT-1CHMI were evaluated by differential thermal Scale analysis as in examples 1-10A. Accordingly, with respect to DNTT-1CHMI, thermal desorption was caused at a temperature ranging from 200 ℃ to 280 ℃.

With respect to DNTT-1CHMI, an organic semiconductor film was obtained as in examples 1 to 10A, and semiconductor characteristics were evaluated. Here, heating for obtaining the organic semiconductor film was performed at 210 ℃ for 2 hours under nitrogen. The characteristics of the obtained organic semiconductor film were evaluated, and the results showed p-type semiconductor characteristics. The mobility of the carrier is 0.01 to 0.0001cm²Vs and an on/off ratio of 10³～10⁵。

EXAMPLES 1 to 14

2000mg (5.87mmol) of dinaphthothiophene (DNTT, MW-340.46), 10.99g (58.7mmol, based on DNTT) of N-benzylmaleimide (BZMI, MW-187.19)1000 mol%), hydroquinone (MW110.1) as radical scavenger 64.8mg (1 mol% based on N-benzylmaleimide group) inThe mixture was stirred at 160 ℃ for 4 hours under nitrogen. Thus, the Diels-Alder addition reaction of DNTT and BZMI proceeds.

Then, a solid was obtained by filtration, and washed with chloroform. This solid was confirmed to be DNTT (raw material) by NMR (yield 980mg, yield 49.0 mol%).

The filtrate was separated by HPLC to obtain 659.2mg of an adduct having 1 molecule of BZMI added to DNTT (DNTT-1BZMI, Mw 527.10, yield 21.3 mol%). The structural formula of the addition compound is shown below.

The results of the analysis of the obtained DNTT-1BZMI are shown below. Furthermore, with respect to DNTT-1BZMI, no stereoisomers were obtained.

¹H-NMR(600MHz，CDCl₃):8.31(s，1H)，8.22(s，1H)，7.95(m，1H)，7.89(m，1H)，7.48(m，2H)，7.23(m，2H)，7.18(t，J＝7.3Hz，1H)，7.14(dd，J＝7.3Hz，7.3Hz，2H)，6.99(m，2H)，6.75(d，J＝7.3Hz，2H)，5.08(d，J＝3.3Hz，1H)，5.05(d，J＝3.3Hz，1H)，4.28(s，2H)，3.44(dd，J＝3.3Hz，8.4Hz，1H)，3.41(dd，J＝3.3Hz，8.4Hz，1H)

MS(70eV，DI):527.95m/z

The measurement value of Mass Spectrometry (MS) substantially agreed with DNTT-1BZMI (Mw: 527.10).

The thermal release properties of DNTT-1BZMI were evaluated by differential thermal Scale analysis as in examples 1-10A. Accordingly, with respect to DNTT-1BZMI, thermal desorption was induced in the temperature range of 190 ℃ to 260 ℃.

For DNTT-1BZMI, organic semiconductor films were obtained as in examples 1-10A, and semiconductor characteristics were evaluated. Here, heating for obtaining the organic semiconductor film was performed at 200 ℃ for 2 hours under nitrogen. The characteristics of the obtained organic semiconductor film were evaluated, and the results showed p-type semiconductor characteristics. Each having a carrier mobility of 0.01 to 0.0001cm²Vs, on/off ratio of 10³～10⁵。

EXAMPLES 1 to 15

500mg (1.47mmol) of dinaphthothiophene (DNTT, MW-340.46), 2.25g (14.7mmol, 1000 mol% based on DNTT) of N-tert-butylmaleimide (TBMI, MW-153.18), and 16.2mg (1 mol% based on N-tert-butylmaleimide) of hydroquinone (MW110.1) as a radical scavenger were added to the solutionThe mixture was stirred at 160 ℃ for 4 hours under nitrogen. Thus, a diels-alder addition reaction of DNTT and TBMI proceeded.

Then, a solid was obtained by filtration, and washed with chloroform. The solid was confirmed to be DNTT (raw material) by NMR (yield 486mg, yield 97.2 mol%).

The filtrate was separated by HPLC to obtain 2.1mg of an adduct compound obtained by adding 1 molecule of TBMI to DNTT (DNTT-1TBMI, Mw: 493.64, yield 0.29 mol%). The structural formula of the addition compound is shown below.

The results of the analysis for DNTT-1TBMI are shown below. Furthermore, with respect to DNTT-1TBMI, no stereoisomer was obtained.

¹H-NMR(600MHz，CDCl₃):8.31(s，1H)，8.22(s，1H)，7.95(m，1H)，7.89(m，1H)，7.48(m，2H)，7.35(m，1H)，7.33(m，1H)，7.18(m，2H)，5.06(d，J＝3.3Hz，1H)，5.02(d，J＝3.3Hz，1H)，3.23(dd，J＝3.3Hz，8.8Hz，1H)，3.16(dd，J＝3.3Hz，8.8Hz，1H)，2.59(s，9H)

EXAMPLES 1 to 16

500mg (1.47mmol) of dinaphthothiophene (DNTT, MW-340.46), 1.44g (14.7mmol, 1000 mol% based on DNTT) of maleic anhydride (MA, MW-98.06), and 16.2mg (1 mol% based on maleic anhydride) of hydroquinone (MW110.1) as a radical scavenger in the presence of a catalystThe mixture was stirred at 160 ℃ for 4 hours under nitrogen. Thus, a Diels-Alder addition reaction of DNTT and MA was carried out.

Then, a solid was obtained by filtration, and washed with chloroform. The solid was confirmed to be DNTT (raw material) by NMR (yield 472.2mg, yield 94.4 mol%).

The filtrate was separated by HPLC to obtain 32.2mg of an adduct compound in which 1 molecule of MA was added to DNTT (DNTT-1MA, Mw: 438.52, yield 5.0 mol%). The structural formula of the addition compound is shown below.

The analysis results of the obtained DNTT-1MA are shown below.

¹H-NMR(600MHz，CDCl₃):8.31(s，1H)，8.22(s，1H)，7.95(m，1H)，7.89(m，1H)，7.48(m，2H)，7.23(m，2H)，7.00(m，2H)，5.09(d，J＝3.3Hz，1H)，5.05(d，J＝3.3Hz，1H)，3.44(dd，J＝3.3Hz，8.4Hz，1H)，3.41(dd，J＝3.3Hz，8.4Hz，1H)

MS(70eV，DI):341.31m/z

Mass analysis (MS) measurements were consistent with DNTT (molecular weight 340.46), indicating that exposure of DNTT-1MA to mass analysis (70eV, DI) resulted in MA detachment and regeneration of DNTT.

EXAMPLE 2-1

In the following examples 2-1 to comparative examples 2-2, the structure of the target compound was determined by 1H-NMR (1H-nuclear magnetic resonance spectrum) and MS (mass spectrometry) as required. The machine used is as follows.

¹H-NMR：JNM-A-600(600MHz)

MS：Shimazu QP-5050A

(Generation of DNTT)

Using 9.59g (61.4mmol) of 2-naphthaldehyde (MW ═ 156.18) as a starting material according to the method described in Supporting Information of non-patent document 1, 4.03g (11.8mmol, yield 38.56%) of Dinaphthothiophene (DNTT) (MW ═ 340.46, structural formula shown below) was obtained.

(purification of DNTT by solvent washing)

The DNTT thus obtained was washed with chloroform and hexane solvents, and then filtered through a filter. The color of DNTT (refined product 1) at this time was yellow with gray. Since the pure DNTT was yellow, it was considered that the reason why the DNTT (purified product 1) was colored gray was that the DNTT solid was doped with iodine used during the production of DNTT. As shown in fig. 15, it was confirmed by NMR (nuclear magnetic resonance spectroscopy) that the DNTT (purified product 1) contained aromatic impurities. The impurity content of DNTT (purified product 1) is based on¹The proton ratio of the H-NMR data was calculated to be about 11 mol%.

(purification of DNTT by the method of the present invention)

N-Phenylmaleimide (PMI) (MW 1) was added to 500mg of DNTT (purified product 1)73.16)2.54g (118.3mmol, 1000 mol% based on DNTT), hydroquinone (MW110.1) as radical scavenger 16.2mg (1 mol% based on N-phenylmaleimide group) anda solvent was added to the mixture, and the mixture was stirred at 160 ℃ for 2 hours under a nitrogen atmosphere. Thus, Diels-Alder addition reaction of DNTT with N-phenylmaleimide was carried out.

Then, a solid of the mixed solution was obtained by filtration, and the obtained solid was washed with chloroform. The solid was identified as DNTT (purified product 2) by NMR (yield 422.3mg, yield 84.4 mol%). The DNTT (purified product 2) was yellow, and it was confirmed that a coloring component presumed to be iodine was removed. As shown in fig. 15, it was confirmed by NMR (nuclear magnetic resonance spectroscopy) that the impurity aromatic organic component that could be seen in DNTT (purified product 1) was removed from DNTT (purified product 2).

(purification by sublimed DNTT)

For DNTT, further high purity is essential in order to obtain organic semiconductor characteristics. Thus, DNTT (purified product 2) obtained as described above was purified by further performing sublimation purification 3 times to obtain DNTT (purified product 3).

(preparation of FET element)

A top-contact bottom-gate Field Effect Transistor (FET) element was produced by a vapor deposition method using DNTT (purified product 3).

In particular, for 300nm with SiO₂An n-doped silicon wafer (sheet resistance 0.005. omega. cm) having an oxide film was subjected to UV ozone treatment (AI UV-ozone cleaning apparatus OC-250615-D + A, EYE GRAPHICS K.K.) for 20 minutes to obtain a UV ozone-treated silicon substrate. In addition, a 10 mmol/toluene solution of octadecyltrichlorosilane (ODTS, shin-Etsu chemical LS-6495) was prepared, and the UV ozone-treated silicon substrate was immersed in this solution for 24 hours. Then, vacuum evaporation (SanyuElectron, resistive addition)Thermal vapor deposition apparatus: SVC-700TM/700-2), a thin film of about 50nm was formed by DNTT (refined 3), and then source/drain gold electrodes having a channel width of 50 μm and a channel length of 1.5mm were formed on the DNTT (top contact).

The FET device was measured for semiconductor characteristics, and the characteristics of the p-type semiconductor were shown. Further, the degree of carrier mobility was 1.3cm²Vs, on/off ratio of 10⁷。

EXAMPLE 2-2

The filtrate obtained by purification of DNTT by the method of the present invention in example 2-1 was separated by HPLC (High Performance Liquid Chromatography, Agilent1100Series HPLC: High Performance Liquid Chromatography, SHISEIDO CAPCELL PAK C18TYPE UG120, solvent: acetonitrile/water) to obtain a dinaphthothiophenothiophene-phenylmaleimide 1 adduct of the following formula (DNTT-1PMI, stereoisomeric endo form, exo form, Mw 513.63, yield 113.2mg, yield 15.0 mol%).

The results of the analysis of DNTT-1PMI (endo-and exo-type) are shown in (1) and (2) below, respectively.

(1) DNTT-1PMI (inner type)

¹H-NMR(600MHz，CDCl₃):8.30(S、1H)、8.23(S、1H)、7.95(m、1H)、7.89(m、1H)、7.50(m、2H)、7.47(m、2H)、7.25(m、2H)、7.12(t、J＝7.3Hz，1H)、7.07(dd、J＝7.3Hz、7.7Hz，2H)、6.50(d、J＝7.7Hz、2H)、5.30(d、J＝3.3Hz，1H)、5.22(d、J＝3.3Hz，1H)、3.54(dd、J＝3.3Hz，8.1Hz，1H)、3.51(dd、J＝3.3Hz、8.1Hz、1H)

MS(70eV，DI):514.10m/z

(2) DNTT-1PMI (exterior)

¹H-NMR(600MHz，CDCl₃):8.33(s、1H)、8.25(s、1H)、7.97(m、1H)、7.90(m、1H)、7.49(m、2H)、7.42(m、1H)、7.40(m、1H)、7.31(m、1H)、7.30(m、2H)、7.26(m、2H)、6.53(m、2H)、5.22(d、J＝3.3Hz、1H)、5.18(d、J＝3.3Hz、1H)、3.59(dd、J＝3.3Hz，8.4Hz，1H)、3.56(dd、J＝3.3Hz、8.4Hz、1H)

MS(70eV，DI):513.05m/z

The detection values (514.10m/z and 513.05m/z) by Mass Spectrometry (MS) were consistent with DNTT-phenylmaleimide 1 adduct (DNTT-1PMI) (Mw 513.63).

The thermal release characteristics of DNTT-1 PMIs (endo form and exo form) are confirmed by differential thermal balance analysis (Rigaku TG-DTA TG8120, nitrogen atmosphere, 1 ℃/min temperature rise analysis) as shown in FIG. 16, wherein the weight reduction at 195 ℃ to 260 ℃ is 31.9 wt% for the endo form and 32.7 wt% for the exo form, respectively.

The calculated weight loss of PMI when thermally detached by inverse Diels-Alder reaction from DNTT-1PMI (MW. 513.63) was 33.7 wt%, which is in agreement with the analysis result. In addition, it was confirmed that the pattern after thermal desorption was more consistent with DNTT than NMR.

DNTT-1PMI (endo form, exo form) was heated to 260 ℃ in a nitrogen atmosphere to obtain 64.2mg of purified DNTT (purified product 2'). The DNTT (purified product 2') was yellow, and it was confirmed that a coloring component presumed to be iodine was removed. As shown in fig. 15, it was confirmed that the DNTT (purified product 2') was free of aromatic organic components as impurities that could be seen in the DNTT (purified product 1) by NMR (nuclear magnetic resonance spectroscopy).

The DNTT (purified product 2 of example 2-1) from the solid obtained by filtration and the DNTT (purified product 2' of example 2-2) from the PMI of DNTT-1 were combined to give a yield of 486.5mg and a yield of 97.3 mol%.

Comparative example 2-1

The DNTT (purified product 1) of example 2-1 was purified 3 times by the sublimation purification method to obtain DNTT (purified product 3') in the same manner as in example 2-1, except that the purification of DNTT by the method of the present invention was not performed. The DNTT after sublimation purification was slightly pale in gray color, but the gray component could not be removed.

Using the DNTT (purified product 3') thus obtained, an FET element was produced by a vapor deposition method in the same manner as in example 2-1. The FET device was measured for semiconductor characteristics, and the result showed characteristics of a p-type semiconductor. Further, the degree of carrier mobility was 0.023cm²Vs, on/off ratio of 10⁴. Therefore, the FET device of comparative example 2-1 is significantly inferior to the FET device of example 2-1.

Comparative examples 2 and 2

The DNTT (purified product 1) of example 2-1 was put under a nitrogen atmosphereThe mixture was stirred at 160 ℃ for 2 hours to purify the solvent. In this purification, the coloration of the DNTT (purified product 1) was maintained without change in gray color. Therefore, it is considered that iodine doped in the DNTT (purified product 1) solid was not removed in the purification.

EXAMPLE 3-1

In this example, a solution for forming an organic semiconductor film containing 2 kinds of addition compounds was prepared, and the state of deposition as a solid was confirmed.

The procedure was carried out in the same manner as in examples 1 to 10A described above to obtain an addition compound (DNTT-1PMI (stereoisomer A)) in which 1 molecule of N-Phenylmaleimide (PMI) was added to Dinaphthothiophene (DNTT). Here, it is assumed from the results of NMR that this DNTT-1PMI (stereoisomer A) is an endo form. Further, 1 molecule of N-Cyclohexylmaleimide (CHMI) was added to dinaphthothiophene (DNTT-1CHMI) in the same manner as in examples 1 to 13 described above.

DNTT-1PMI and DNTT-1CHMI were added to chloroform in an amount of 1.0 mass% in total to obtain a solution for forming an organic semiconductor film. Here, the molar ratio of DNTT-1PMI to DNTT-1CHMI is 1: 1.

evaluation of crystallization

The solution for forming an organic semiconductor film was dropped on a silicon wafer, and chloroform, a solvent, was evaporated in the atmosphere at normal temperature to precipitate a solid. The precipitated state of the solid was observed with a microscope. The results are shown in FIG. 17. Here, fig. 17(a) is a photograph showing the entire solid matter, and fig. 17(b) is an enlarged photograph (500 times) of the solid matter.

As can be understood from fig. 17, it was confirmed that the solid substance precipitated in a film form and did not substantially crystallize. This is considered to be because the solution for forming an organic semiconductor film contains 2 kinds of addition compounds, and crystallization is suppressed when the solvent is volatilized to precipitate a solid.

Manufacture of FET

A bottom-contact bottom-gate fet (field effect transistor) element was produced using the organic semiconductor film forming solution in the following manner.

The substrate is SiO at 300nm₂SiO of oxide film n-doped silicon wafer (sheet resistance 0.005. omega. cm)₂The oxide film was formed with a source/drain gold electrode having a channel length of 50 μm and a channel width of 1.5mm (bottom contact).

The organic semiconductor film-forming solution is dropped at room temperature onto a channel portion of a base material, and the solution is rapidly volatilized to obtain a film, and then the film is heated to obtain an organic semiconductor film. Then, the film was heated at 210 ℃ for 2 hours under nitrogen, to obtain an organic semiconductor film.

The film was observed before and after heating under nitrogen. The results are shown in FIG. 18. Here, fig. 18(a) shows the observation result before heating (annealing), and fig. 18(b) shows the observation result after heating. As can be understood from fig. 18, fine crystal particles are deposited over the entire organic semiconductor film by heating.

For the organic semiconductor film of the obtained FETThe characteristics proceed, showing p-type semiconductor characteristics. In addition, the degree of carrier mobility is 0.01cm at most²Vs and on/off ratio of at most 10⁵。

EXAMPLE 3-2

In this example, a solution for forming an organic semiconductor film containing an addition compound and a compound constituting the addition compound was prepared, and the state of deposition as a solid was confirmed.

The procedure was carried out in the same manner as in examples 1 to 10A described above to obtain an addition compound (DNTT-1PMI (stereoisomer A)) in which 1 molecule of N-Phenylmaleimide (PMI) was added to Dinaphthothiophene (DNTT). As a result of NMR, it was presumed that the DNTT-1PMI (stereoisomer A) is an endo form.

DNTT-1PMI in an amount of 1.0 mass% and 1 mol% of PMI relative to DNTT-1PMI were added to chloroform to obtain a solution for forming an organic semiconductor film.

Evaluation of crystallization

The solution for forming an organic semiconductor film was dropped on a silicon wafer, and chloroform, a solvent, was evaporated in the atmosphere at normal temperature to precipitate a solid. The precipitated state of the solid was observed with a microscope, and it was confirmed that the solid precipitated in a film form and did not substantially crystallize. This is considered to be because the solution for forming an organic semiconductor film contains an addition compound and a compound constituting the addition compound, and crystallization is suppressed when the solvent is volatilized to precipitate a solid.

Manufacture of FET

Using the solution for forming an organic semiconductor film, a bottom-contact bottom-gate FET element was produced in the same manner as in example 3-1. The characteristics of the organic semiconductor film of the obtained FET were evaluated, and p-type semiconductor characteristics were exhibited. In addition, the degree of carrier mobility is 0.01cm at most²Vs and on/off ratio of at most 10⁵。

EXAMPLES 3 to 3

In this example, a solution for forming an organic semiconductor film containing an addition compound and a compound constituting the addition compound was prepared, and the state of deposition as a solid was confirmed.

The procedure was carried out in the same manner as in examples 1 to 13 to obtain an addition compound (DNTT-1CHMI) in which 1 molecule of N-Cyclohexylmaleimide (CHMI) was added to Dinaphthothiophene (DNTT).

DNTT-1CHMI in an amount of 1.0 mass% and PMI in 1 mol% relative to DNTT-1CHMI were added to chloroform to obtain a solution for forming an organic semiconductor film.

Evaluation of crystallization

The solution for forming an organic semiconductor film was dropped on a silicon wafer, and chloroform, a solvent, was evaporated in the atmosphere at normal temperature to precipitate a solid. The precipitated state of the solid was observed with a microscope, and it was confirmed that the solid precipitated in a film form and did not substantially crystallize. This is considered to be because the solution for forming an organic semiconductor film contains an addition compound and a compound constituting the addition compound, and crystallization is suppressed when the solvent is volatilized to precipitate a solid.

Manufacture of FET

Using the solution for forming an organic semiconductor film, a bottom-contact bottom-gate FET element was produced in the same manner as in example 3-1. The characteristics of the organic semiconductor film of the obtained FET were evaluated, and p-type semiconductor characteristics were exhibited. In addition, the degree of carrier mobility is 0.01cm at most²Vs and on/off ratio of at most 10⁵。

Comparative example 3-1

In this comparative example, a solution for forming an organic semiconductor film containing only an addition compound was prepared, and the state of deposition as a solid was confirmed.

The procedure was carried out in the same manner as in examples 1 to 10A described above to obtain an addition compound (DNTT-1PMI (stereoisomer A)) in which 1 molecule of N-Phenylmaleimide (PMI) was added to Dinaphthothiophene (DNTT). Here, it can be estimated from the results of NMR that this DNTT-1PMI (stereoisomer A) is endo-type.

DNTT-1PMI was added to chloroform in an amount of 1.0 mass%, to obtain a solution for forming an organic semiconductor film.

Evaluation of crystallization

The solution for forming an organic semiconductor film was dropped on a silicon wafer, and chloroform, a solvent, was evaporated in the atmosphere at normal temperature to precipitate a solid. The results are shown in FIG. 19. Here, fig. 19 is a magnified photograph (500 times) of the solid matter.

As can be understood from fig. 19, the solid substance precipitated in the form of particles, and no film of the solid substance was obtained. This is considered to be because the crystallization of DNTT-1PMI proceeded while the solvent was volatilized from the organic semiconductor film-forming solution.

Manufacture of FET

Using the solution for forming an organic semiconductor film, a bottom-contact bottom-gate FET element was produced in the same manner as in example 3-1. The characteristics of the organic semiconductor film of the obtained FET were evaluated, but the characteristics as a semiconductor were not obtained. The obtained organic semiconductor film of the FET was observed with a polarizing microscope. The results are shown in FIG. 20. As can be understood from fig. 20, the organic semiconductor forms particles, and no path of the organic semiconductor film is formed in the channel between the electrodes.

EXAMPLE 4-1

The addition reaction of Dinaphthothiophene (DNTT) with vinylene carbonate (VC (vinylene carbonate), structural formula shown below) was confirmed by computer simulation using the semi-empirical Method (MOPAC) and the non-empirical method (Gaussian) described above.

The results are shown in the following table. In addition, in the semi-empirical Method (MOPAC) described above, the heat of formation of DNTT was 117.56kcal/mol and the heat of formation of VC was-59.30 kcal/mol.

[ Table 12]

TABLE 1

"light" and "heat" in the reaction conditions of the addition reaction of table 1 each mean that the addition reaction proceeds by light and heat.

The addition positions in table 1 are shown by the following chemical formulae.

M position: 2-7

L position: 4-5

Z position: 3-6

A T position: 3-4, or 5-6

C position: 7b-14b

As is understood from the results in Table 1, the addition reaction of DNTT to VC can be achieved.

Description of the symbols

1 organic semiconductor

2 source electrode

3 drain electrode

5 dielectric layer (silicon oxide)

7 silicon wafer substrate (Gate electrode)

10 organic semiconductor element

Claims (31)

1. An addition compound having a structure in which a compound (II) having a double bond is detachably added to a substituted or unsubstituted fused polycyclic aromatic compound of the following formula (I-4) via the double bond:

wherein each Y is independently an element selected from the group consisting of chalcogens,

the compound (II) having a double bond has any one of the following formulas (II-1) to (II-12),

in the formula, R and R_rEach independently selected from the group consisting of hydrogen, halogen, hydroxyl, amide, mercapto, cyano, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkynyl having 2 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, ester group having 1 to 10 carbon atoms, ether group having 1 to 10 carbon atoms, ketone group having 1 to 10 carbon atoms, amino group having 1 to 10 carbon atoms, amide group having 1 to 10 carbon atoms, imide group having 1 to 10 carbon atoms, and thioether group having 1 to 10 carbon atoms, and

the condensed polycyclic aromatic compound of the formula (I-4) is substituted by a substituent independently selected from halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, an ether group having 1 to 20 carbon atoms, a ketone group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, an imide group having 1 to 20 carbon atoms, and a thioether group having 1 to 20 carbon atoms.

2. The addition compound according to claim 1, wherein the compound (II) having a double bond can be detached from the fused polycyclic aromatic compound of the formula (I-4) by reducing pressure and/or heating.

3. The addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-6):

4. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-1):

5. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-2):

6. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-3):

7. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-4):

8. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-5):

9. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-7):

10. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-8):

11. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-9):

12. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-10):

13. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-11):

14. the addition compound according to claim 1 or 2, the compound (II) having a double bond has the following formula (II-12):

15. the addition compound of claim 1, which is a compound having the following formula (III-1) or a stereoisomer thereof:

each Y is independently an element selected from the group consisting of chalcogens,

r is independently selected from hydrogen, halogen, alkyl with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, alkynyl with 2-10 carbon atoms, alkoxy with 1-10 carbon atoms, aromatic group with 4-10 carbon atoms, ester group with 1-10 carbon atoms, ether group with 1-10 carbon atoms, ketone group with 1-10 carbon atoms, amino group with 1-10 carbon atoms, amide group with 1-10 carbon atoms, imide group with 1-10 carbon atoms and thioether group with 1-10 carbon atoms, and R is selected from hydrogen, halogen, alkyl with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, alkynyl with 2-10 carbon atoms, alkoxy with 1-10 carbon atoms, aromatic group with 4-10 carbon atoms

The fused benzene ring moiety is substituted or unsubstituted.

16. The addition compound of claim 1, which is a compound having the following formula (III-6) or a stereoisomer thereof:

each Y is independently an element selected from the group consisting of chalcogens,

r and R_rEach independently selected from hydrogen, halogen, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms,An aromatic group having 4 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, an ether group having 1 to 10 carbon atoms, a ketone group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, an amide group having 1 to 10 carbon atoms, an imide group having 1 to 10 carbon atoms, and a sulfide group having 1 to 10 carbon atoms, and

the fused benzene ring moiety is substituted or unsubstituted.

17. The adduct compound of claim 16, which is an external adduct.

18. A solution containing an adduct compound, which is obtained by dissolving the adduct compound according to any one of claims 1 to 17 in a solvent.

19. The solution according to claim 18, wherein the adduct compound according to any one of claims 1 to 17 and at least 1 stereoisomer thereof are dissolved in a solvent, and the ratio of the stereoisomer having the lowest thermal dissociation temperature among the adduct compound and the stereoisomers thereof to the total of the adduct compound and the stereoisomers thereof, that is, the stereoisomer having the lowest thermal dissociation temperature among the adduct compound and the stereoisomers thereof/(the adduct compound and the stereoisomers thereof) exceeds 50 mol%.

20. The solution according to claim 19, wherein the exo and endo forms of the adduct compound according to any one of claims 1 to 17 are contained in a solvent, and the ratio of the stereoisomer having a low thermal dissociation temperature to the total of the exo and endo forms of the adduct compound, i.e., the stereoisomer having a low thermal dissociation temperature in the exo and endo forms/(exo + endo forms), exceeds 50 mol%.

21. The solution according to claim 18, wherein the exo and endo forms of the adduct compound of claim 16 are contained in a solvent, and the ratio of exo to the total of exo and endo forms of the adduct compound, i.e., exo/(exo + endo form), exceeds 50 mol%.

22. A method of forming an organic semiconductor film, comprising the steps of:

a step of applying the solution containing an addition compound according to any one of claims 18 to 21 to a substrate to produce a film, and then

And (II) removing and eliminating the compound (II) having a double bond from the addition compound by heating and/or reducing the pressure of the film to obtain an organic semiconductor film composed of the substituted or unsubstituted fused polycyclic aromatic compound of the formula (I-4).

23. The method according to claim 22, wherein the detachment and removal of the compound (II) having a double bond is performed by heating at a heating rate exceeding 100 ℃/min.

24. The method of claim 22 or 23, wherein the heating is performed by: a mode in which the substrate having the film is directly brought into contact with a heated object, a mode in which the substrate having the film is introduced into a heated region, and/or a mode in which electromagnetic waves are radiated to the film side or the substrate side.

25. The method according to claim 23, wherein the organic semiconductor film has a crystal of the condensed polycyclic aromatic compound of the formula (I-4) having a major axis diameter exceeding 5 μm.

26. The method of claim 22 or 23, the detaching and removing being performed at atmospheric pressure.

27. A method of manufacturing an organic semiconductor device comprising the step of forming an organic semiconductor film by the method of any one of claims 22 to 26.

28. An organic semiconductor device having an organic semiconductor film made of a substituted or unsubstituted condensed polycyclic aromatic compound of the formula (I-4), and containing the addition compound of any one of claims 1 to 17.

29. The organic semiconductor device according to claim 28, which is a thin film transistor having a source electrode, a drain electrode, a gate insulating film, and the organic semiconductor film, wherein the source electrode and the drain electrode are insulated from the gate electrode by the gate insulating film, and wherein a current flowing from the source electrode to the drain electrode through the organic semiconductor is controlled by a voltage applied to the gate electrode.

30. The method for synthesizing an organic compound according to any one of claims 1 to 17, comprising a step of mixing the substituted or unsubstituted fused polycyclic aromatic compound of the formula (I-4) with the compound (II) having a double bond.

31. The method for producing an addition compound according to any one of claims 1 to 17, comprising the steps of:

(a) a step of providing an addition compound having a structure in which a compound (II) having a double bond is added to a compound of the following formula (I') via the double bond:

Ar₁Q (I’)

Ar₁a fused benzene ring of the following (b4) which is substituted or unsubstituted:

q has the following formula and structure Ar₁A part of the fused aromatic ring of (1):

y is an element selected from the group consisting of chalcogens, and

the fused benzene ring (b4) is substituted by a substituent independently selected from the group consisting of a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, an ether group having 1 to 20 carbon atoms, a ketone group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, an imide group having 1 to 20 carbon atoms, and a thioether group having 1 to 20 carbon atoms;

(b) a step of reacting 2 molecules of the addition compound to obtain a compound of the following formula:

formula Ar₁Q＝QAr₁

Wherein Q represents the following structure:

then the

(c) Reacting said formula Ar₁Q＝QAr₁The step of reacting the resulting compound with iodine.