JP5881363B2 - Novel aromatic polymer - Google Patents

Description

  The present invention relates to a novel aromatic polymer. The present invention also relates to a method for synthesizing and using such a novel aromatic polymer.

  Various studies have been made on organic semiconductor compounds for use in organic semiconductor layers 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 the current silicon-based transistor as a low-cost and lightweight device. In addition, the organic semiconductor layer is expected to be applied to smart tags, lightweight displays, and the like by utilizing advantages specific to organic materials such as being lightweight and flexible.

  Therefore, many studies have been made on organic semiconductor compounds for forming an organic semiconductor layer (Patent Documents 1 to 5 and Non-Patent Documents 1 to 3).

  Among these organic semiconductor compounds, condensed polycyclic aromatic compounds, particularly dinaphthothienothiophene (DNTT) represented by the following formula, or a substituted polycyclic aromatic compound having a similar structure or a similar structure, It has been found that material stability, carrier mobility, semiconductor properties, etc. are preferred.

  However, since the condensed polycyclic aromatic compound has strong aromaticity and high crystallinity, the solubility in an organic solvent or the like is extremely low, and it has been difficult to use in a coating method. Therefore, when obtaining an organic semiconductor film using a condensed polycyclic aromatic compound, it has been common to obtain an organic semiconductor thin film made of a condensed polycyclic aromatic compound by vapor deposition.

  Although the above DNTT has a slight solubility in organic solvents due to the small number of condensed rings, it still achieves sufficient solubility for industrial use in solution methods. There was not (patent document 4).

  In addition, low molecular organic semiconductor compounds having sufficient solubility to be used in a solution method, such as dioctylbenzothienobenzothiophene (C8-BTBT), are also known. When such a low molecular organic semiconductor compound is used However, there is a tendency that the size of crystals precipitated from the solution process varies greatly and the characteristics of the organic semiconductor film obtained thereby become non-uniform. Therefore, in an element using such an organic semiconductor film, when a thin film transistor (TFT) array is formed, the characteristics between the elements may vary. Further, when the low molecular organic semiconductor compound as described above is used in a solution method, the viscosity of the solution is low, and thus an organic semiconductor film having a sufficient thickness is obtained, and a semiconductor film is formed on a hydrophobic surface. It was not easy.

  In addition, in order to obtain an organic semiconductor thin film by using a condensed polycyclic aromatic compound such as DNTT in a coating method, a precursor that has high solubility and decomposes to generate such a condensed polycyclic aromatic compound is used. Have also been proposed (Patent Document 5, Non-Patent Documents 2 and 3).

JP 2006-89413 A JP 2008-290963 A International Publication WO2006 / 077788 International Publication WO2008 / 050726 International Publication WO2011 / 024804

“Facile Synthesis of Highly π-Extended Heteroarenes, Dinaphtho [2,3-b: 2 ′, 3′-f] charcogenopheno [3,2-b] charcogenophenes, and Tyrapt Applied”. Kazuo Takimiya, J.A. Am. Chem. Soc. , 2007, 129 (8), pp 2224-2225. H. Uno et a1. , Photoprecursor for pentacene, Tetrahedron Letters, 2005, Vol. 46, no. 12, PP. 1981-1983 WANG, Y.M. etal, Synthesis, charactrization, and reactionsof 6,13-disclosed 2, 3, 9, 10-tetrakis (trimethylsylly 1) pentacene derivatives, Tetrahedron V, 1 7 63, no. 35, pp. 8586-8597

  As described above, DNTT has a slight solubility in organic solvents due to the small number of condensed rings, but still achieves sufficient solubility for industrial use in solution processes. (Patent Document 4).

  In addition, when a low molecular organic semiconductor compound having sufficient solubility is used in a solution method, there is a problem in that the characteristics between elements using the obtained organic semiconductor film vary. Furthermore, even when such a low molecular weight organic semiconductor compound is used in a solution method, the viscosity of the solution is low, and thus a sufficiently thick organic semiconductor film is obtained, and a semiconductor film formation is formed on a hydrophobic surface. There was a problem that it was not easy.

  Accordingly, the present invention provides an aromatic polymer that at least partially eliminates the above problems, as well as methods for the synthesis and use of such novel aromatic polymers.

  The inventors of the present invention have found that the above problems can be at least partially solved by an aromatic polymer having two or more condensed polycyclic aromatic moieties having a structure similar to DNTT, and have arrived at the present invention. .

  The aromatic polymer of the present invention has two or more condensed polycyclic aromatic moieties represented by the following formula (IV):

(G ₁ and G ₂ are each independently selected from the group consisting of a bond, a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of G ₁ and G ₂ is a bond,
B is a fused ring having at least one benzene ring moiety;
Y is independently selected from chalcogen, and A _{1 to} A ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and two adjacent groups are bonded to each other to form an aromatic group. Group may be formed).

  In the aromatic polymer of the present invention, the condensed polycyclic aromatic moiety has a bond or the like on the benzene ring adjacent to the central condensed heterocycle, so that the condensed polycyclic aromatic moiety provides relatively high solubility. can do. This is because the benzene ring adjacent to the fused heterocycle at the center of the fused polycyclic aromatic moiety, that is, a bond near the center of the fused polycyclic aromatic moiety, reduces the crystallinity of this moiety. This is considered to be due to the fact that the solubility increases and the polarity of this part increases due to the polarity of this bond and the like.

  In addition, although the general formula of Patent Document 4 includes DNTT in which hydrogen of the condensed benzene ring is substituted, specifically, DNTT in which the position farthest from the central condensed heterocycle is substituted It is only disclosed, and the embodiment in which the benzene ring adjacent to the central condensed heterocycle is substituted is not specifically disclosed. Further, Patent Document 4 does not disclose a specific method for synthesizing DNTT in which a benzene ring adjacent to a central condensed heterocycle is substituted.

  The present invention also relates to a method for synthesizing and using the aromatic polymer of the present invention. Moreover, this invention relates to the solution containing the aromatic polymer of this invention, an organic-semiconductor film, an organic-semiconductor device, etc.

It is a molecular structure ORTEP figure based on the single-crystal structure analysis about TIPS2 substitution DNTT obtained by the reference example 2. FIG. It is a crystal packing (stereo) figure about the TIPS2 substituted DNTT obtained in Reference Example 2. It is a figure which shows the transfer characteristic of the FET characteristic about the organic-semiconductor element obtained in the reference example 3.

(Definition)
In the description of the present specification, in order to simplify the description, “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, and the number of carbon atoms” A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms The description of “an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms” is expressed as “an alkyl group or the like”.

  Here, the “alkylsilylalkynyl group having 1 to 40 carbon atoms” may be a trialkylsilylalkynyl group having 1 to 40 carbon atoms, particularly a trialkylsilylalkynyl group having the following formula:

(R _{1 to} R ₃ are each independently an alkyl group having 1 to 10 carbon atoms, particularly a group consisting of a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. Group selected).

  In the description herein, “chalcogen” means oxygen, sulfur, selenium, tellurium and polonium, especially sulfur and selenium, more particularly sulfur.

  In the description herein, “halogen” means fluorine, chlorine, bromine, iodine, and astatine, especially chlorine, bromine, and iodine, more particularly bromine.

  In the description of the present specification, a “substituted or unsubstituted aromatic group having 4 to 20 carbon atoms” formed by bonding two adjacent groups to each other is, for example, a substituted or unsubstituted group having the following structure: May be an aromatic group of:

  In the description of the present specification, Patent Document 5 can be referred to as the diene-type alkene with respect to “substituent (D) having 2 to 20 carbon atoms added to the benzene ring by the diene-type alkene”. Patent Document 5 can be referred to for a method of adding such a diene-type alkene to the benzene ring of the condensed polycyclic aromatic moiety.

  In addition, as described in Patent Document 5, such a diene-type alkene added to the benzene ring of the condensed polycyclic aromatic moiety reduces the crystallinity of the condensed polycyclic aromatic moiety, thereby The solubility of the aromatic polymer of the present invention having a condensed polycyclic aromatic moiety can be increased. Further, when a semiconductor film is produced by using the aromatic polymer of the present invention having such a condensed polycyclic aromatic moiety in a solution method, by heating the coating film of the solution containing this moiety, In conjunction with the removal of the solvent, the diene-type alkene can be eliminated and removed.

  Specifically, the “substituent (D) having 2 to 20 carbon atoms added to the benzene ring by a diene-type alkene” is, for example, the following formulas (B-1a) and (B-2a), particularly the following formula ( Mention may be made of compounds of the following formulas (B-1c) and (B-2c): B-1b) and (B-2b), more particularly:

(R _a , R _b , R _c and R _d are each independently a bond, hydrogen, halogen, hydroxyl group, amide group, mercapto group, cyano group, alkyl group having 1 to 10 carbon atoms, or 2 to 10 carbon atoms. An alkenyl 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 selected from the group consisting of C 1-10 sulfide groups,
R _a and R _b may be bonded to each other to form a ring,
R _c and R _d may be bonded to each other to form a ring,
n is an integer of 1 to 5; and Z is a bond (-), oxygen (-O-), methylene carbon (-C (R _r ) _2- ), ethylenic carbon (-C (R _r ) =), Carbonyl group (—C (═O) —), nitrogen (—N (R _r ) —), and sulfur (—S—), and n is 2 or greater Sometimes each may be different (R _r is independently 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, carbon An alkoxy group having 1 to 10 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, and 1 to 1 carbon atoms; 10 ketone groups, 1-10 carbon atom amino groups, 1-10 carbon atoms Selected from the group consisting of an amide group, an imide group having 1 to 10 carbon atoms, and a sulfide group having 1 to 10 carbon atoms)).

  More specifically, examples of the diene-type alkene include compounds represented by the following formulas (B-1-1) to (B-2-3):

(R and R _r are each independently 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, or 2 to 2 carbon atoms. 10 alkynyl groups, alkoxy groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic groups having 4 to 10 carbon atoms, ester groups having 1 to 10 carbon atoms, ether groups 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 having 1 to 10 carbon atoms Selected from the group consisting of groups).

(Aromatic polymer)
The aromatic polymer of the present invention has two or more condensed polycyclic aromatic moieties represented by the following formula (IV):

(G ₁ and G ₂ are each independently selected from the group consisting of a bond, a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of G ₁ and G ₂ is a bond,
B is a fused ring having at least one benzene ring moiety;
Y is each independently selected from chalcogen, and A _{1 to} A ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _4. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

  Here, the condensed polycyclic aromatic moiety is represented, for example, by the following formula (IV-1):

(G _{1 to} G ₄ are each independently selected from the group consisting of a bond, a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of G _{1 to} G ₄ is a bond,
Y is each independently selected from chalcogens, and A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _8. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

Here, in the condensed polycyclic aromatic moiety of the formula (IV-1), for example, G ₂ and G ₃ are a bond, and G ₁ and G ₄ are a hydrogen atom.

  This fused polycyclic aromatic moiety of formula (IV-1) may in particular be a moiety represented by the following formula (IV-1-1):

  The condensed polycyclic aromatic moiety is represented, for example, by the following formula (IV-2):

(G ₁ and G ₂ are each independently selected from the group consisting of a bond, a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of G ₁ and G ₂ is a bond,
D is a substituent having 2 to 20 carbon atoms added to the benzene ring by a diene-type alkene,
Y is each independently selected from chalcogens, and A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _8. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

Here, in the condensed polycyclic aromatic moiety of the formula (IV-2), for example, both G ₁ and G ₂ are a bond.

  The fused polycyclic aromatic moiety of formula (IV-2) may in particular be a compound represented by the following formula (IV-2-1):

(G ₂ and G ₃ are a bond, and R _r is as described above).

The aromatic polymer of the present invention has, for example, a repeating unit of the following formula (V):
-{(T _T )-(Q _Q )}-(V)
(T _T is the fused polycyclic aromatic moiety; and Q _Q is a bond or a divalent group).

  Moreover, the aromatic polymer of this invention has a repeating unit of a following formula (V-1), for example:

(G ₁ and G ₄ are each independently selected from the group consisting of a bond, a hydrogen atom, a halogen atom, an alkyl group, etc .;
Each Y is independently selected from chalcogen,
A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group and the like, and two adjacent ones of A _{1 to} A ₈ are bonded to each other to form 4 to 4 carbon atoms. 20 substituted or unsubstituted aromatic groups may be formed, and Q _Q is a bond or a divalent group).

Note that the bond as Q _Q is not particularly limited as long as it can be bonded to an adjacent unit, and may be, for example, a single bond, a double bond, or a triple bond.

In addition, the divalent group as Q _Q is not particularly limited as long as it can be bonded to an adjacent unit. For example, a hydrocarbon having 1 to 40 carbon atoms which may be accompanied by a heteroatom such as oxygen or nitrogen In particular, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, and a substituted or unsubstituted divalent aromatic having 4 to 20 carbon atoms. Group, divalent ketone group having 2 to 10 carbon atoms, divalent amino group having 1 to 20 carbon atoms, divalent amide group having 1 to 20 carbon atoms, divalent imide group having 1 to 20 carbon atoms , A divalent sulfide group having 1 to 20 carbon atoms, and a divalent alkylsilylalkynyl group having 1 to 40 carbon atoms.

  For example, the aromatic polymer of the present invention has a molecular weight obtained by gel permeation chromatography (GPC) in terms of polystyrene of 1,000 or more, 2,000 or more, 3,000 or more, 4,000 or more, or 5,000. That's all. In addition, for example, the aromatic polymer of the present invention may have a molecular weight obtained by GPC in terms of polystyrene of 500,000 or less, 100,000 or less, 100,000 or less, 50,000 or less, or 30,000 or less.

(Synthesis method)
The method for synthesizing the aromatic polymer of the present invention includes the following steps:

  (A) Providing a composition containing an organic solvent and a condensed polycyclic aromatic compound represented by the following formula (II):

(X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of X ₁ and X ₂ is a halogen atom,
B is a fused ring having at least one benzene ring moiety;
Y is each independently selected from chalcogen, and A _{1 to} A ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _4. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms);

(B) A binding compound having two or more moieties capable of substituting at least one halogen atom of X ₁ and X ₂ is added to the composition, and the two or more condensed polycyclic aromatic compounds are bonded to each other. Step.

  Various portions are known as the portion capable of substituting the halogen atom of the binding compound used in the step (b), that is, the portion capable of substituting the halogen of the aromatic halide. Reactions using such moieties include: Mizorogi-Heck reaction, Negishi coupling, Ueda-Kosugi-Still coupling, Sonogashira coupling, Suzuki-Miyaura coupling, Buchwald-Heartwig reaction, Kumada-Tamao-Ko Coupling reactions such as Liu coupling are known. Heating may be performed to promote this coupling reaction.

The outline of each coupling reaction is as follows (Ar is an aromatic moiety, X is a halogen, R is hydrogen, an alkyl group, etc.):
(1) Mizorogi-Heck reaction Ar-X + H ₂ C = CHR (+ Pd catalyst) → Ar-HC = CHR
(2) Negishi coupling Ar-X + R-Zn-X (+ Pd catalyst) → Ar-R
(3) Ueda / Kosugi / Still coupling Ar-X + R-Sn-R ' ₃ (+ Pd catalyst) → Ar-R
(4) Sonogashira coupling Ar-X + R-C≡C-H (+ Pd catalyst) + base → Ar-C≡C-R
(5) Suzuki-Miyaura coupling Ar-X + R-B (OH) ₂ (+ Pd catalyst) + base → Ar-R
(6) Buchwald-Hartwig reaction Ar-X + R-NH ₂ (+ Pd catalyst) + base → Ar-NHR
(7) Kumada, Tamao, Collie coupling Ar-X + R-Mg-X (+ Ni catalyst) → Ar-R

  Examples of the organic solvent that can be used here include any organic solvent that can dissolve and / or disperse the condensed polycyclic aromatic compound represented by the formula (II). Specifically, examples of the organic solvent include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, and ethyl acetate; diethyl ether, tetrahydrofuran, diisopropyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, and the like. Ether solvents; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene (ie 1,3,5-trimethylbenzene); aliphatic hydrocarbons such as hexane and heptane; and dichloromethane, chloroform, dichloroethane, etc. Halogen-containing solvents can be considered.

  The addition of the binding compound to the composition containing the condensed polycyclic aromatic compound represented by the formula (II) can be performed by any method. For example, the binding compound is added as it is, or the binding compound is organically added in advance. It can be added after diluting with a solvent. In addition, heating may be performed to promote the reaction between the compound represented by formula (II) and the binding compound.

  The compound of the above formula (II) is represented by, for example, the following formula (II-1):

(X _{1 to} X ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of X _{1 to} X ₄ is a halogen atom,
Y is each independently selected from chalcogens, and A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _8. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

In the compound of the above formula (II-1), for example, X ₂ and X ₃ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group and the like, and at least one of X ₂ and X ₃ is A halogen atom; and X ₁ and X ₄ are hydrogen atoms.

  The compound of the above formula (II) is particularly represented by the following formula (II-1-1):

  The compound of the above formula (II) is represented, for example, by the following formula (II-2):

(X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of X ₁ and X ₂ is a halogen atom,
D is a substituent having 2 to 20 carbon atoms added to the benzene ring by a diene-type alkene,
Y is each independently selected from chalcogens, and A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _8. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

Here, in the compound of the formula (II-2), for example, both X ₁ and X ₂ are halogen atoms.

  This compound of formula (II-2-1) may in particular be a compound of formula (I-2-1)

(R _r is as described above).

In the compounds of formula (I), in particular of formula (I-1) or (I-2), A ₁ , A ₄ , A ₅ and A ₈ , in particular A _{1 to} A ₈ , may be hydrogen atoms. In the compound of formula (I), particularly of formula (I-1) or (I-2), Y may be a sulfur atom.

(Aromatic polymer-containing solution)
The aromatic polymer-containing solution of the present invention contains an organic solvent and the aromatic polymer of the present invention that is at least partially dissolved in the organic solvent.

  This aromatic polymer-containing solution can contain the aromatic polymer of the present invention at an arbitrary concentration. For example, the aromatic polymer of the present invention is 0.01 to 10% by mass, 0.05 to 5%. It can contain with the density | concentration of a mass% and 0.1-3 mass%.

  Examples of the organic solvent that can be used here include any organic solvent that can dissolve and dissolve the aromatic polymer of the present invention. Specifically, examples of the organic solvent include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, and ethyl acetate; diethyl ether, tetrahydrofuran, diisopropyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, and the like. Ether solvents; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene (ie 1,3,5-trimethylbenzene); aliphatic hydrocarbons such as hexane and heptane; and dichloromethane, chloroform, dichloroethane, etc. Halogen-containing solvents can be considered.

(Method for producing organic semiconductor film)
The method of the present invention for producing an organic semiconductor film includes the steps of applying the aromatic polymer-containing solution of the present invention to a substrate, and removing the organic solvent from the solution applied to the substrate.

  Application of the solution to the substrate can be performed in any manner, for example, by a casting method, a spin coating method, a printing method, or the like. Moreover, application | coating to the base material of a solution can also be performed only by dripping a solution on a base material.

  The removal of the organic solvent from the solution may be performed simultaneously with the coating step.

  Removal of the organic solvent from the solution can also be facilitated by heating. In this case, any temperature that does not substantially decompose the aromatic polymer of the present invention, for example, 80 ° C. or higher, 100 ° C. or higher, 120 ° C. or higher, or 140 ° C. or higher, 200 ° C. or lower, 220 ° C. or lower, 240 Heating can be performed at a temperature of not higher than 260 ° C. and not higher than 260 ° C. Such heating includes, for example, bringing the substrate coated with the solution into direct contact with a heated object such as a heated electric heater, introducing it into a heated region such as a heated furnace, infrared It can be achieved by irradiation with electromagnetic waves such as microwaves.

  In the aromatic polymer of the present invention intended to form an organic semiconductor film by desorbing an addition compound, for example, an aromatic polymer of the formula (IV-2), for example, the organic solvent is removed. In addition, the substituent represented by D can be eliminated and removed. This elimination reaction can be accelerated by heating.

(Method for manufacturing organic semiconductor device)
The method of the present invention for producing an organic semiconductor device includes the step of producing an organic semiconductor film by the method of the present invention for producing an organic semiconductor film.

  The method may optionally further comprise forming an electrode layer and / or a dielectric layer above or below the organic semiconductor film.

(Organic semiconductor device)
The organic semiconductor device of 1st this invention has the organic-semiconductor film containing the aromatic polymer of this invention.

  Here, the fact that the organic semiconductor film contains the aromatic polymer of the present invention means that the organic semiconductor film contains the aromatic polymer of the present invention in at least a detectable amount.

  Thus, for example, in the aromatic polymer of the present invention intended to constitute the organic semiconductor film as it is, for example, the aromatic polymer of the formula (IV-1), this aromatic polymer is an organic semiconductor. The organic semiconductor film is substantially composed of the aromatic polymer of the present invention.

  In particular, the organic semiconductor device of the present invention is a thin film transistor having a source electrode, a drain electrode, a gate electrode, a gate insulating film, and an organic semiconductor film, wherein the source electrode, the drain electrode, and the gate electrode are insulated by the gate insulating film, The thin film transistor controls the current flowing through the organic semiconductor from the source electrode to the drain electrode by a voltage applied to the gate electrode. In particular, the organic semiconductor device of the present invention is a solar cell having an organic semiconductor film as an active layer. In the context of the present invention, “organic semiconductor device” means a device having an organic semiconductor film, and other layers such as an electrode layer and a dielectric layer are made of an inorganic material or an organic material. It may be made.

  In the following examples, the structure of the target compound was determined by 1H nuclear magnetic resonance spectrum (1H-NMR spectrum), mass spectrometry spectrum (MS), and single crystal structure analysis as necessary.

The equipment used is as follows.
¹ H-NMR: JEOL ECA-500 (500 MHz)
MS: Bruker Autoflex III (MALDI)
Single crystal structure analysis: Rigaku RAXIS RAPIDS
GPC: LC-9101 manufactured by Japan Analytical Industrial Co., Ltd. Column: JAIGEL-6H, JAIGEL-5H

<Reference Example 1>
Dinaphthothienothiophene (DNTT (Dinaphthothenothiophene)) (the following structural formula, MW = 340.46) is obtained by the method shown in Patent Document 2 (Japanese Patent Laid-Open No. 2008-290963 (Nippon Kayaku Co., Ltd., Hiroshima University)). Synthesized.

To 100 mL of mesitylene (ie, 1,3,5 trimethylbenzene) containing 1,000 mg (2.93 mmol) of the above DNTT, 2341 mg (14.65 mmol) of bromine (Br ₂ MW = 159.8) was added, and the reaction temperature was increased. It was kept at 40 ° C. for 4 hours, and then allowed to cool to bromine disubstituted dinaphthothienothiophene (Br2 substituted DNTT) (the following structural formula, Mw = 498.25, 1431 mg, 2.87 mmol, yield 98.1%) Got. The reaction product was purified with chloroform.

  In addition, the substitution position of bromine in Br2-substituted DNTT was determined by the position of triisopropylsilyl (TIPS) group by single crystal structure analysis of TIPS2-substituted DNTT in Reference Example 2.

¹ H-NMR and MS results for the obtained Br2-substituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl 3, 50 ° C.): δ 8.47 (d, J = 8.3 Hz, 2H), 8.44 (s, 2H), 7.97 (d, J = 8.3 Hz, 2H) ), 7.66 (t, J = 8.3 Hz, 2H), 7.59 (t, J = 8.3 Hz, 2H)

  MS (m / z): 497.513 (positive ion observation) (ExactMass: 495.86)

<Reference Example 2>
A triisopropylsilyl (TIPS) group was introduced into the Br2 substituted DNTT synthesized in Reference Example 1 by the Sonogashira coupling method.

Specifically, 191.3 mg of Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) and CuI (Mw = 190.25) with respect to 500 mg (1.0 mmol) of Br 2 -substituted DNTT (Mw = 498.25). 45) 134.1 mg, diisopropylamine (Mw = 101.20) 0.706 mL, CsCO ₃ (Mw = 325.82) 791.6 mg, triisopropylsilylacetylene (Mw = 182.38) 1.698 mL were added, and the pressure was reduced. After degassing and nitrogen replacement 3 times, 35 mL of N, N-dimethylformamide (N, N-DMF) was introduced, vacuum degassing and nitrogen replacement were again performed 3 times at 120 ° C. for 20 hours. The reaction was carried out with stirring.

  As a result, 479.1 mg (68.3 mmol, yield 68.0%) of triisopropylsilylacetylene 2-substituted dinaphthothienothiophene (TIPS2-substituted DNTT, the following structural formula) (Mw = 701.19) was obtained. The solubility of the obtained TIPS2-substituted DNTT in chloroform was 0.2 wt%. DNTT used as a raw material did not substantially dissolve in chloroform.

¹ H-NMR and MS results for the obtained TIPS2-substituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.61 (d, J = 8.0 Hz, 2H), 8.41 (s, 2H), 7.97 (d, J = 8.0 Hz, 2H), 7.63 (dd, J = 8.0 Hz, 8.0 Hz 2H), 7.57 (dd, J = 8.0 Hz, 8.0 Hz, 2H), 1.40 to 1.47 (m, 6H), 1 .34 (d, J = 6.9 Hz, 36H)

  MS (m / z): 700.3 (ExactMass: 700.30)

  The single crystal structure analysis results for the obtained TIPS2-substituted DNTT are shown below.

a = 8.2044 (5) Å
b = 8.4591 (6) Å
c = 14.488 (1) Å
α = 88.475 (4) °
β = 89.336 (3) °
γ = 89.555 (4) °
V = 1005.1 (1) ^{３ 3}

  In addition, a molecular structure ORTEP (Oak Ridge Thermal Ellipsoid Plot) diagram and a crystal packing (stereo) diagram based on the single crystal structure analysis of this TIPS2-substituted DNTT body are shown in FIGS. 1 and 2, respectively.

<Reference Example 3>
The TIPS2-substituted DNTT (Mw = 701.19) obtained in Reference Example 2 was dissolved in chloroform at a concentration of 0.2 wt% to prepare a semiconductor element manufacturing solution.

Next, UV-ozone treatment for 20 minutes (eye UV-ozone cleaning apparatus OC-250615-D + A, iGraphics) on 300 nm n-doped silicon wafer with SiO ₂ oxide film (surface resistance 1 ⁻¹⁰ Ω · cm) Ltd.). Further, a 1,1,1,3,3,3-hexamethyldisilazane ((HMDS) 1,1,1,3,3,3-hexylmethyldisilazane) 10 mmol / toluene solution was prepared, The silicon substrate that had been subjected to UV ozone treatment was immersed for 24 hours to hydrophobize the silicon substrate. Thereafter, a source / drain gold electrode having a channel width of 50 μm and a channel length of 1.5 mm was produced by vacuum deposition (Sanyu Electronics, resistance heating deposition apparatus: SVC-700TM / 700-2).

  While heating the silicon substrate to 40 ° C., a solution for forming a semiconductor element was dropped on the channel portion to evaporate the solvent, thereby forming a thin layer made of TIPS2-substituted DNTT. The device thus fabricated was heat-treated at 70 ° C. for 1 hour under vacuum to remove the chloroform solvent by drying, thereby fabricating an organic semiconductor device.

When the organic semiconductor characteristics of the obtained organic semiconductor element were measured, a p-type semiconductor was shown. Further, this organic semiconductor element had a carrier mobility of 1 × 10 ⁻³ cm ² / Vs, an on / off ratio of 10 ⁵ , and a threshold voltage of −26V. FIG. 3 shows the transfer characteristics of FET characteristics for this organic semiconductor element. Here, in FIG. 3, when the drain voltage (V _D ) is −80 V, the drain current (I _D (A) or I _D ^1/2 (A ^1/2 )) (vertical axis) and the gate voltage (V _G (V)) (horizontal axis).

<Reference Example 4>
In the same manner as in Reference Example 1, dinaphthothienothiophene (DNTT (Dinaphthothienothiophene)) (MW = 340.46) was synthesized.

  12.68 g (73.25 mmol) of N-phenylmaleimide (MW = 173.17) was added to 500 mL of mesitylene (ie, 1,3,5 trimethylbenzene) containing 5,000 mg (14.65 mmol) of the above DNTT, and the reaction The temperature was maintained at 160 ° C. for 4 hours, and then allowed to cool, purified by preparative purification, and dinaphthothienothiophene-N-phenylmaleimide 1 adduct (DNTT-PMI1 adduct) in which one N-phenylmaleimide was added to DNTT. , A mixture of stereoisomeric Endo and Exo isomers) (the following structural formula, Mw = 513.63), and 376 mg (0.73 mmol, yield 4.9%) were obtained. In addition, the reaction product fractionated the stereoisomer by HPLC, and obtained 132 mg of Endo forms and 151 mg of Exo forms.

To 50 mL of mesitylene containing 151 mg (0.29 mmol) of DNTT-PMI1 adduct (Exo isomer), 235 mg (1.47 mmol) of bromine (Br ₂ , MW = 159.8) was added, and the reaction temperature was brought to 40 ° C. It was kept for 1 hour, and then allowed to cool to 186 mg of bromine 2-substituted dinaphthothienothiophene-N-phenylmaleimide 1-adduct (Br2-substituted DNTT-PMI1 adduct) (the following structural formula, Mw = 673.44). 276 mmol, yield 95.2%).

¹ H-NMR and MS results for the obtained Br2-substituted DNTT-1PMI adduct are shown below.

¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.39 (d, J = 7.7 Hz, 1H), 8.29 (d, J = 7.7 Hz, 1H), 7.67 (dd, J = 7 .7 Hz, 1H), 7.64 (dd, J = 7.7 Hz, 1H), 7.41-7.44 (m, 2H), 7.31-7.32 (m, 3H), 7.27 ˜7.29 (m, 2H), 6.52 to 6.54 (m, 2H), 5.25 (d, J = 3.2 Hz, 1H), 5.23 (d, J = 3.2 Hz, 1H), 3.59 (dd, J = 3.2 Hz, 8.3 Hz, 1H), 3.55 (dd, J = 3.2 Hz, 8.3 Hz, 1H)

  MS (m / z): 497.513 (ExactMass: 670.92)

  In MS, it is presumed that Br2-substituted DNTT (ExactMass: 497.86) in which N-phenylmaleimide was eliminated from the Br2-substituted DNTT-PMI1 adduct was estimated.

<Reference Example 5>
A triisopropylsilyl (TIPS) group was introduced into the Br2-substituted DNTT-PMI1 adduct synthesized in Reference Example 4 by the Sonogashira coupling method.

Specifically, Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) 28.1 mg, CuI (Br2 substituted DNTT-PMI1 adduct (Mw = 673.44) 100 mg (0.148 mmol)) Mw = 190.45) 20.0 mg, diisopropylamine (Mw = 101.20) 0.11 mL, triisopropylsilylacetylene (Mw = 182.38) 0.1 mL were added, and vacuum degassing and nitrogen substitution were performed three times. After that, 7 mL of N, N-dimethylformamide (N, N-DMF) was introduced, vacuum degassing and nitrogen substitution were again performed three times, and the reaction was performed by stirring at 120 ° C. for 20 hours.

  Thereby, triisopropylsilylacetylene 2 substituted dinaphthothienothiophene-phenylmaleimide 1 adduct (exo form) (TIPS2 substituted DNTT-PMI1 adduct (exo form)) (the following structural formula, Mw = 876.37) 74.9 mg (85.4 mmol, yield 57.7%) was obtained.

¹ H-NMR and MS results for the obtained TIPS2-substituted DNTT-PMI1 adduct (exo form) are shown below.

¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.52 to 8.54 (m, 1H), 8.43 to 8.45 (m, 1H), 7.60 to 7.64 (m, 2H), 7.43 to 7.46 (m, 2H), 7.31 to 7.33 (m, 3H), 7.25 to 7.29 (m, 2H), 6.52 to 6.54 (m, 2H) ), 5.29 (d, J = 3.4 Hz, 1H), 5.21 (d, J = 3.4 Hz, 1H), 3.62 (dd, J = 3.4 Hz, 8.3 Hz, 1H) 3.56 (dd, J = 3.4 Hz, 8.3 Hz, 1H), 1.36 to 1.43 (m, 6H), 1.31 (d, J = 2.9 Hz, 12H), 1. 30 (d, J = 4.0Hz, 24H)

  MS (m / z): 873.078 (Exact Mass: 875.37)

<Example 1>
The Br2-substituted DNTT synthesized in Reference Example 1 was reacted with 1,6-heptadiyne by Sonogashira coupling method to polymerize DNTT.

Specifically, Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) 110 mg (0.15 mmol), CuI (Mw) with respect to Br2 substituted DNTT (Mw = 498.25) 200 mg (0.41 mmol) = 190.45) 60 mg (0.31 mmol) and Cs ₂ CO ₃ (Mw = 325.8) 170 mg (0.53 mmol) were added, and vacuum degassing and nitrogen substitution were performed 5 times. Next, 0.14 ml (1.00 mmol) of diisopropylamine (Mw = 101.2, d = 0.72 g / cm ³ ), 14 ml of dimethylformamide, 1,6-heptadiine (Mw = 92.14, d = 0. 81 g / cm ³ ) 0.20 ml (1.70 mmol) was added, vacuum degassing and nitrogen substitution were again performed 5 times, and the reaction was performed by stirring at 120 ° C. for 12 hours.

  As a result, a 1,6-heptadiyne-linked dinaphthothienothiophene polymer (the following structural formula) was obtained. The molecular weight of polystyrene conversion by gel permeation chromatography (GPC) was 5,000 or more (polystyrene conversion). The solubility of the obtained polymer in chloroform was 0.1 wt% or more. DNTT used as a raw material did not substantially dissolve in chloroform.

１，６−ヘプタジイン結合ジナフトチエノチオフェン重合体（Ｒ＝Ｃ_３Ｈ_６）

1,6-heptadiyne-linked dinaphthothienothiophene polymer (R = C ₃ H ₆ )

<Example 2>
The Br2 substituted DNTT synthesized in Reference Example 1 was reacted with 1,9-decadiyne by Sonogashira coupling method to polymerize DNTT.

Specifically, for 200 mg (0.41 mmol) of Br2 substituted DNTT (Mw = 498.25), 100 mg (0.14 mmol) of Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90), CuI (Mw = 190.45) 60 mg (0.31 mmol) and Cs ₂ CO ₃ (Mw = 325.8) 170 mg (0.53 mmol) were added, and vacuum degassing and nitrogen substitution were performed 5 times. Next, 0.14 ml (1.00 mmol) of diisopropylamine (Mw = 101.2, d = 0.72 g / cm ³ ), 14 ml of dimethylformamide, 1,9-decadiine (Mw = 134.22, d = 0. 82 g / cm ³ ) 0.28 ml (1.70 mmol) was added, vacuum degassing and nitrogen replacement were again performed 5 times, and the reaction was performed by stirring at 120 ° C. for 12 hours.

  As a result, a 1,9-decadiyne-linked dinaphthothienothiophene polymer (the following structural formula) was obtained. The molecular weight of polystyrene conversion by gel permeation chromatography (GPC) was 5,000 or more (polystyrene conversion). The solubility of the obtained polymer in chloroform was 0.1 wt% or more.

１，６−ヘプタジイン結合ジナフトチエノチオフェン重合体（Ｒ＝Ｃ_１０Ｈ_１４）

1,6-heptadiyne-linked dinaphthothienothiophene polymer (R = C ₁₀ H ₁₄ )

Claims (10)

Have a repeating unit represented by the following formula (V-1), and the molecular weight obtained in terms of polystyrene by gel permeation chromatography, of 1,000 or more, Fang aromatic polymer:

(G ₁ and G ₄ are each independently a bond, a hydrogen atom, a halogen atom, 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, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 carbon atom Selected from the group consisting of ˜20 imide groups, C 1-20 sulfide groups, and C 1-40 alkylsilylalkynyl groups,
Each Y is independently selected from chalcogen,
A _{1 to} A ₈ are each independently a hydrogen atom, a halogen atom, 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, or the number of carbon atoms. A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Selected from the group consisting of an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms, and two adjacent ones of A _{1 to} A ₈ are bonded to each other A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms may be formed, and Q _Q is a divalent group). The polymer according to claim 1 , which has a molecular weight of 3,000 or more . (A) A step of providing a composition containing an organic solvent and a condensed polycyclic aromatic compound represented by the following formula (II-1) :

(X ₁ and X ₄ are each independently a hydrogen atom, a halogen atom, 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, or a carbon atom. A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Selected from the group consisting of an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms ,
X ₂ and X ₃ are halogen atoms ,
Y is independently selected from chalcogen, and A _{1 to} A ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon C2-C20 alkynyl group, C4-C20 substituted or unsubstituted aromatic group, C2-C10 ketone group, C1-C20 amino group, C1-C1 Selected from the group consisting of 20 amide groups, imide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, and alkylsilylalkynyl groups having 1 to 40 carbon atoms, and A _{1 to} A ₄ Two adjacent ones may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms);
(B) adding a bonding compound having two or more moieties capable of substituting the halogen atoms of X ₂ and X ₃ to the composition to bond the two or more condensed polycyclic aromatic compounds to each other;
The method for synthesizing an aromatic polymer according to claim 1 , comprising: The reaction in step (b) is the Mizorogi / Heck reaction, Negishi coupling, Ueda / Kosugi / Still coupling, Soto coupling, Suzuki / Miyaura coupling, Buchwald / Heartwig reaction, Kumada / Tamao / Colle cup 4. The method of claim 3 , wherein the method is accomplished by a coupling reaction selected from the group consisting of rings. The method according to claim 3 or 4 , wherein X ₁ and X ₄ are hydrogen atoms. The method according to claim 5 , wherein the condensed polycyclic aromatic compound is represented by the following formula (II-1-1):

An aromatic polymer-containing solution containing an organic solvent and the aromatic polymer according to claim 1 or 2 which is at least partially dissolved in the organic solvent. Applying the solution of claim 7 to a substrate;
Removing the organic solvent from the solution applied to a substrate;
A method for producing an organic semiconductor film, comprising: The manufacturing method of an organic-semiconductor device including the step which manufactures an organic-semiconductor film by the method of Claim 8 . The organic-semiconductor device which has an organic-semiconductor film containing the polymer of Claim 1 or 2 .

Images