JP4528000B2 - π-Electron Conjugated Molecule-Containing Silicon Compound and Method for Producing the Same - Google Patents

Description

  The present invention relates to a π-electron conjugated molecule-containing silicon compound and a method for producing the same, and more specifically, a π-electron conjugated molecule-containing silicon compound that is a novel conductive or semiconductive substance useful as an electrical material and the production thereof. Regarding the method.

  In recent years, semiconductors using inorganic materials are easy to manufacture, easy to process, can respond to device enlargement, and can be expected to reduce costs due to mass production, and synthesize organic compounds with more functions than inorganic materials. Because of this, research and development of semiconductors (organic semiconductors) using organic compounds has been conducted, and the results have been reported.

In particular, it is known that a TFT having a large mobility can be produced by using an organic compound containing a π-electron conjugated molecule. As this organic compound, pentacene has been reported as a representative example (for example, IEEE Electron Device Lett., 18, 606-608 (1997): Non-Patent Document 1). Here, when an organic semiconductor layer is formed using pentacene and a TFT is formed using this organic semiconductor layer, a field effect mobility is 1.5 cm ² / Vs, and a TFT having a mobility higher than that of amorphous silicon is constructed. It has been reported that this is possible.

  However, when an organic semiconductor layer for obtaining a higher field effect mobility than amorphous silicon as described above is required, a vacuum process such as a resistance heating vapor deposition method or a molecular beam vapor deposition method is required. In addition to being complicated, a film having crystallinity can be obtained only under certain specific conditions. Further, since the adsorption of the organic compound film on the substrate is physical adsorption, there is a problem that the adsorption strength of the film to the substrate is low and the film is easily peeled off. Furthermore, in order to control the molecular orientation of the organic compound in the film to some extent, the orientation control by rubbing or the like is usually performed in advance on the substrate on which the film is formed. It has not yet been reported that the molecular alignment and orientation of the compound at the interface between the organic compound and the substrate can be controlled.

  On the other hand, with regard to the regularity and crystallinity of the film that has a great influence on the field-effect mobility, which is a representative guideline for the characteristics of this TFT, in recent years its production is simple, so that self-organization using organic compounds is possible. Membranes have attracted attention, and research on the use of these membranes has been made.

  A self-assembled film is a film in which a part of an organic compound is bonded to a functional group on a substrate surface, has very few defects, and has high order, that is, crystallinity. Since this self-assembled film has a very simple manufacturing method, it can be easily formed on a substrate. Usually, as a self-assembled film, a thiol film formed on a gold substrate and a silicon-based compound film formed on a substrate (for example, a silicon substrate) capable of protruding a hydroxyl group on the surface by a hydrophilization treatment are known. Yes. Of these, silicon compound films are attracting attention because of their high durability. The silicon-based compound film has been conventionally used as a water-repellent coating, and has been formed using a silane coupling agent having an alkyl group having a high water-repellent effect or a fluorinated alkyl group as an organic functional group.

However, the conductivity of the self-assembled film is determined by the organic functional group in the silicon-based compound contained in the film, but commercially available silane coupling agents contain π-electron conjugated molecules in the organic functional group. There are no compounds, so it is difficult to impart conductivity to the self-assembled film. Accordingly, there is a need for a silicon-based compound suitable for devices such as TFTs and containing a π-electron conjugated molecule as an organic functional group.
As such a silicon compound, a compound having one thiophene ring as a functional group at the end of a molecule and a thiophene ring bonded to a silicon atom via a linear hydrocarbon group has been proposed (for example, Patent No. 1). No. 2889768: Patent Document 1).

IEEE Electron Device Lett. , 18, 606-608 (1997) Japanese Patent No. 2889768

  However, the compounds proposed above can produce a self-assembled film that can be chemically adsorbed to a substrate, but can be used for electronic devices such as TFTs. A thin film could not always be produced.

  In order to obtain high order, that is, high crystallinity, a high attractive interaction must be exerted between molecules. The intermolecular force is composed of an attractive term and a repulsion term, the former being inversely proportional to the sixth power of the intermolecular distance and the latter being inversely proportional to the twelfth power of the intermolecular distance. Therefore, the intermolecular force obtained by adding the attractive force term and the repulsive term has the relationship shown in FIG. Here, the minimum point (arrow part in the figure) in FIG. 11 is the intermolecular distance when the highest attractive force acts between the molecules due to the balance between the attractive term and the repulsive term. That is, in order to obtain higher crystallinity, it is important to make the intermolecular distance as close as possible to the minimum point. Therefore, originally, in vacuum processes such as resistance heating vapor deposition and molecular beam vapor deposition, high orderliness is achieved by controlling the intermolecular interaction between π-electron conjugated molecules only under certain conditions. That is, crystallinity is obtained. Thus, it becomes possible to express high electrical conduction characteristics only with the crystallinity constructed by the intermolecular interaction.

On the other hand, the above compound may be chemically adsorbed to the substrate by forming a two-dimensional network of Si-O-Si, and there is a possibility that ordering due to intermolecular interaction between specific long-chain alkyls may be obtained. However, since one thiophene molecule as a functional group only contributes to the π-electron conjugated system, there is a problem that the interaction between molecules is weak and the spread of the π-electron conjugated system essential for electrical conductivity is very small. there were. Even if the number of thiophene molecules, which are the above functional groups, can be increased, the factor that forms the order of the film matches the intermolecular interaction between the long-chain alkyl part and the thiophene part. It is difficult to make it.
Furthermore, as an electrical conduction characteristic, a single thiophene molecule that is a functional group has a large HOMO-LUMO energy gap, and there is a problem that sufficient carrier mobility cannot be obtained even when used as an organic semiconductor layer in a TFT or the like. Existed.

  The present invention has been made in view of the above problems, and can be easily crystallized by a simple manufacturing method to form an organic thin film, and the obtained organic thin film is firmly adsorbed on the substrate surface, The purpose of the present invention is to provide a compound for producing an organic thin film having high orderability, crystallinity, and electrical conduction characteristics while preventing physical peeling, and further used as an electronic device such as a TFT. In this case, it is an object to provide a novel π-electron conjugated molecule-containing silicon compound that can ensure sufficient carrier mobility and a method for producing the same.

  As a result of diligent studies to achieve the above object, in order to produce an organic thin film that can be applied to an electronic device such as a TFT, a two-dimensional network of Si-O-Si is formed and chemically bonded to the substrate. At the same time, the order (crystallinity) of the organic thin film is controlled by the interaction of molecules (here, π-electron conjugated molecules) formed on the two-dimensional network of Si—O—Si, that is, intermolecular force. The inventors have found that this is possible and have invented a novel silicon compound containing a π-electron conjugated molecule.

That is, according to the present invention, the formula R-SiX ¹ X ² X ³ (I)
(In the formula, R is an organic residue of a π-electron conjugated system in which 5 to 10 units selected from a group derived from a monocyclic aromatic hydrocarbon and a monocyclic heterocyclic compound are bonded to each other; (It may have a functional group, and X ¹ , X ² and X ³ are the same or different and are groups which give a hydroxyl group by hydrolysis.)
Represented by
The unit may be bonded via a vinylene group,
The functional group is a linear alkyl group having 1 to 30 carbon atoms;
The SiX ¹ X ² X ³ group is directly bonded to the unit;
There is provided a π-electron conjugated molecule-containing silicon compound in which the monocyclic aromatic hydrocarbon and the monocyclic heterocyclic compound are benzene and thiophene, respectively .

Thus, a compound having an organic residue formed by bonding units constituting a π-electron conjugated system and having a functional group capable of reacting with moisture, -SiX ¹ X ² X ³ , is, for example, Since a two-dimensional network of Si—O—Si can be formed by the chemical adsorption method, there is an advantage that an organic thin film having a high degree of order (crystallinity) can be formed.

Also according to the present invention, the formula R-Li (II)
(In the formula, R is an organic residue of a π-electron conjugated system in which 5 to 10 units selected from a group derived from a monocyclic aromatic hydrocarbon and a monocyclic heterocyclic compound are bonded to each other; (It may have a functional group.)
A compound represented by
Formula Y-SiX ¹ X ² X ³ (III)
(In the formula, X ¹ , X ² and X ³ are the same or different and are groups which give a hydroxyl group by hydrolysis, and Y is a hydrogen atom, a halogen atom or a lower alkoxy group.)
Is reacted with a compound represented by
Formula R-SiX ¹ X ² X ³ (I)
(In the formula, R, X ¹ , X ² and X ³ are as defined above.)
In give π electron conjugate molecule-containing silicon compound represented by,
The unit may be bonded via a vinylene group,
The functional group is a linear alkyl group having 1 to 30 carbon atoms;
The SiX ¹ X ² X ³ group is directly bonded to the unit;
A method for producing a π-electron conjugated molecule-containing silicon compound is provided, wherein the monocyclic aromatic hydrocarbon and the monocyclic heterocyclic compound are benzene and thiophene, respectively .

Furthermore, according to the present invention, the formula R-MgX (IV)
(In the formula, R is an organic residue of a π-electron conjugated system in which 5 to 10 units selected from a group derived from a monocyclic aromatic hydrocarbon and a monocyclic heterocyclic compound are bonded to each other; (It may have a functional group.)
A compound represented by
Formula Y-SiX ¹ X ² X ³ (III)
(In the formula, X ¹ , X ² and X ³ are the same or different and are groups which give a hydroxyl group by hydrolysis, and Y is a hydrogen atom, a halogen atom or a lower alkoxy group.)
To a Grignard reaction with a compound represented by
Formula R-SiX ¹ X ² X ³ (I)
(In the formula, R, X ¹ , X ² and X ³ are as defined above.)
In give π electron conjugate molecule-containing silicon compound represented by,
The unit may be bonded via a vinylene group,
The functional group is a linear alkyl group having 1 to 30 carbon atoms;
The SiX ¹ X ² X ³ group is directly bonded to the unit;
A method for producing a π-electron conjugated molecule-containing silicon compound is provided, wherein the monocyclic aromatic hydrocarbon and the monocyclic heterocyclic compound are benzene and thiophene, respectively .

According to the present invention, the compound of the formula (I) is chemically adsorbed to the substrate and formed into a crystal of the film by forming a two-dimensional network of Si—O—Si formed between silicon compounds having π-electron conjugated molecules. Because the intermolecular interaction acting between π-electron conjugated molecules, which is a short-range force necessary for crystallization, works efficiently, it has a very high stability and highly crystallized organic thin film Can be configured. Therefore, compared to a film produced by physical adsorption on the substrate, the obtained film can be strongly adsorbed on the surface of the substrate and physical peeling can be prevented.
Moreover, it becomes possible to easily produce the above compound.

  In addition, the silicon compound-derived network that forms the organic thin film and the organic residue that forms the upper part are directly bonded to each other, and due to the intermolecular interaction between the silicon-compound-derived network and the π-conjugated molecule, high ordering (crystal The organic thin film can be formed. Thereby, carriers are smoothly moved by hopping conduction in a direction perpendicular to the molecular plane. In addition, since high conductivity is obtained in the molecular axis direction, the conductive material can be widely applied not only to organic thin film transistor materials but also to solar cells, fuel cells, sensors, and the like.

The silicon compound containing a π-electron conjugated molecule of the present invention (hereinafter simply referred to as a silicon compound) is represented by the formula (I), that is, R—SiX ¹ X ² X ³ .
In the formula (I), R is a π-electron conjugated organic residue in which 3 to 10 units selected from a group derived from a monocyclic aromatic hydrocarbon and a monocyclic heterocyclic compound are bonded, You may have a functional group at the terminal.
Examples of the monocyclic aromatic hydrocarbon constituting the unit include benzene, toluene, xylene, mesitylene, cumene, cymene, styrene, divinylbenzene and the like. Of these, benzene is particularly preferred.

Examples of the hetero atom contained in the monocyclic heterocyclic compound include oxygen, nitrogen, and sulfur. Specific heterocyclic compounds include oxygen atom-containing compounds such as furan, nitrogen atom-containing compounds such as pyrrole, pyridine, pyrimidine, pyrroline, imidazoline, and pyrazoline, sulfur atom-containing compounds such as thiophene, oxazole, isoxazole, and the like. Nitrogen and oxygen atom-containing compounds, sulfur and nitrogen atom-containing compounds such as thiazole and isothiazole, and the like, among which thiophene is particularly preferable.
3 to 10 of the above units are bonded to form a π-electron conjugated organic residue. Furthermore, it is more preferable that 3 to 8 units are combined in consideration of yield, economy, and mass production.

  A plurality of these units may be connected in a branched manner, but are preferably connected in a linear shape. Moreover, the same unit may couple | bond with the organic residue, all different units may couple | bond, and several types of units may couple | bond together in regular or random order. In addition, the position of the bond may be any of 2,5-position, 3,4-position, 2,3-position, 2,4-position, etc. when the constituent molecule of the unit is a 5-membered ring, Of these, the 2,5-position is preferred. In the case of a 6-membered ring, any of 1,4-position, 1,2-position, 1,3-position and the like may be used, but among them, 1,4-position is preferable.

  For example, specific examples of R include biphenyl, bithiophenyl, terphenyl, terthienyl, quarterphenyl, quarterthiophene, quinkephenyl, quinkethiophene, hexylphenyl, hexthiophene, and thienyl-oligophenylene (see the compound of formula (3)) ), Phenyl-oligo-oligothienylene (see compound of formula (4)), group derived from block oligomer (see compound of formula (5) or (6)).

  The organic residue may have a functional group at the terminal. Specific examples of the functional group include a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, Substituted or unsubstituted alkoxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Examples thereof include a substituted alkoxycarbonyl group, a carboxyl group, and an ester group. Among these functional groups, a functional group that does not inhibit crystallization of the organic thin film due to steric hindrance is preferable. Therefore, among the above functional groups, a linear alkyl group having 1 to 30 carbon atoms is particularly preferable.

  Furthermore, a vinylene group may be located between the units. Examples of hydrocarbons that give a vinylene group include alkenes, alkadienes, and alkatrienes. Alkenes include compounds having 2 to 4 carbon atoms, such as ethylene, propylene, butylene and the like. Of these, ethylene is preferable. Examples of the alkadiene include compounds having 4 to 6 carbon atoms, butadiene, pentadiene, hexadiene and the like. Examples of the alkatriene include compounds having 6 to 8 carbon atoms such as hexatriene, heptatriene, and octatriene.

The group that gives a hydroxyl group by hydrolysis in X ¹ , X ^2, and X ³ is not particularly limited, and examples thereof include a halogen atom or a lower alkoxy group. Examples of halogen atoms include fluorine, chlorine, iodine and bromine atoms. Examples of the lower alkoxy group include an alkoxy group having 1 to 4 carbon atoms. For example, a methoxy group, an ethoxy group, an n-propoxy group, a 2-propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and the like, some of which are further functional groups (trialkylsilyl). Group, another alkoxy group, etc.). X ¹ , X ² and X ³ may be the same, but not all may be the same, and two or all of them may be different. Especially, it is preferable that all are the same.

  Specific examples of the silicon compound of the present invention include those shown below.

(In the formula, n is 2 to 8, m is 2 to 5, and a + b is 3 to 10.)
The method for synthesizing the silicon compound of the present invention will be described below.

The silicon compound of the present invention is
A compound represented by the formula R-Li (II) and a formula Y-SiX ¹ X ² X ³ (III) (wherein X ¹ , X ² , X ³ and Y are as defined above). Reacting with the compound represented, or
-It can be obtained by subjecting a compound represented by the formula R-MgX (IV) (wherein R and X are as defined above) and a compound represented by the formula (III) to Grignard reaction. it can.

The compound of formula (II) or (IV) is obtained, for example, by reacting a compound represented by RH with alkyllithium, or a compound represented by R—X (X is a halogen atom). Alternatively, it can be obtained by reacting with metallic magnesium or the like.
Examples of the alkyl lithium used in this reaction include lower (about 1 to 4 carbon atoms) alkyl lithium such as n-butyl lithium, s-butyl lithium, and t-butyl lithium. The amount to be used is preferably 1 to 5 mol, more preferably 1 to 2 mol, relative to 1 mol of compound R-X. Examples of the alkyl magnesium halide include ethyl magnesium bromide and methyl magnesium chloride. The amount used is preferably 1 to 10 mol, more preferably 1 to 4 mol, relative to 1 mol of the raw material compound RH.

  For example, the reaction temperature is preferably −100 to 150 ° C., more preferably −20 to 100 ° C. The reaction time is, for example, about 0.1 to 48 hours. The reaction is usually carried out in an organic solvent that does not affect the reaction. Examples of the organic solvent that does not adversely influence the reaction include aliphatic or aromatic hydrocarbons such as hexane, pentane, benzene, and toluene, ether solvents such as diethyl ether, dipropyl ether, dioxane, and tetrahydrofuran (THF). These can be used alone or as a mixture. Of these, diethyl ether and THF are preferable. The reaction may optionally use a catalyst. As the catalyst, a known catalyst such as a platinum catalyst, a palladium catalyst, or a nickel catalyst can be used.

The method for synthesizing the silicon compound of the present invention will be described more specifically below. The reaction temperature and reaction time in the following synthesis method are the same as those described above, for example, −100 to 150 ° C. and 0.1 to 48 hours.
In the following, a synthesis example of a precursor of an organic residue composed of a unit derived from benzene, which is an example of a monocyclic aromatic hydrocarbon, and a unit derived from thiophene, which is an example of a monocyclic heterocyclic compound. Show. However, a precursor can be formed also for a heterocyclic compound containing a nitrogen atom or an oxygen atom in the same manner as a nitrogen-containing heterocyclic compound such as thiophene.

As a method for synthesizing a precursor composed of units derived from benzene or thiophene, a method using a Grignard reaction after first halogenating a reaction site of benzene or thiophene is effective. If this method is used, a precursor in which the number of benzene or thiophene is controlled can be synthesized. In addition to the method of applying the Grignard reagent, it can be synthesized by coupling using an appropriate metal catalyst (Cu, Al, Zn, Zr, Sn, etc.).
Furthermore, for thiophene, in addition to the method using a Grignard reagent, the following synthesis method can be used.

That is, first, the 2′-position or 5′-position of thiophene is halogenated (eg, chlorinated). Examples of the halogenation method include treatment with 1 equivalent of N-chlorosuccinimide (NCS) and phosphorous oxychloride (POCl ₃ ). As the solvent at this time, for example, a chloroform / acetic acid (AcOH) mixed solution or DMF can be used. In addition, by reacting halogenated thiophenes with a catalyst of tris (triphenylphosphine) nickel (tris (triphenylphosphine) nickel: (PPh ₃ ) 3Ni) in a DMF solvent, the resulting halogenated portion Thiophenes can be bonded directly.

Furthermore, divinyl sulfone is added to the halogenated thiophene and coupled to form a 1,4-diketone body. Subsequently, in a dry toluene solution, Lawesson Reagent (LR) or P ₄ S ₁₀ is added, and the mixture is refluxed overnight in the former case and about 3 hours in the latter case, thereby causing a ring-closing reaction. As a result, a precursor having one thiophene greater than the total number of coupled thiophenes can be synthesized.
Using the above reaction of thiophene, the number of thiophene rings can be increased.

The precursor can be halogenated at the terminal in the same manner as the raw material used for the synthesis. Therefore, after the precursor is halogenated, for example, by reacting with SiCl ₄ , a silicon compound having a silyl group at the terminal and having an organic residue consisting only of units derived from benzene or thiophene (simple benzene) Or a simple thiophene compound) can be obtained.

  As an example, the following (A) to (D) show examples of a method for synthesizing a precursor of an organic residue composed only of benzene or thiophene and a method for silylation of the precursor. In addition, in the synthesis example of the precursor which consists only of the following thiophene, only the reaction from the trimer of thiophene to the hexamer or heptamer was shown. However, by reacting with thiophene having a different number of units, precursors other than the 6 or 7 mer can be formed. For example, thiophene tetramer or pentamer can be formed by coupling 2-chlorothiophene and then reacting 2-chlorobithiophene chlorinated with NCS in the same manner as described below. Furthermore, if thiophene tetramer is chlorinated with NCS, thiophene 8 or 9-mer can also be formed.

As a method of obtaining a precursor of a block type organic residue by directly bonding a unit in which a predetermined number of units derived from thiophene and benzene are bonded, there is a method using a Grignard reaction, for example. If the precursor is reacted with SiCl ₄ or HSi (OEt) ₃ , the target silicon compound can be obtained. Of the above compounds, compounds having a silyl group as a terminal alkoxy group can be synthesized in a state of being bonded to a raw material in advance because of their relatively low reactivity. As a synthesis example in this case, the following method can be applied.

First, after halogenating (for example, brominating) a silyl group and a reverse terminal of simple benzene or simple thiophene compound, a functional group bonded to the silyl group is converted from a halogen to an alkoxy group by a Grignard reaction. Subsequently, it can be debrominated and boronated by applying n-BuLi, B (O-iPr) ₃ . The solvent at this time is preferably ether. In addition, the reaction in the case of boronation is a two-stage process. In order to stabilize the reaction, the first stage is performed at −78 ° C., and the second stage is gradually increased from −78 ° C. to room temperature. It is preferable to make it. On the other hand, an intermediate of a block type compound is prepared from a Grignard reaction using benzene or thiophene having a halogen group (for example, bromo group) at both ends.

In this state, the unreacted bromo group and the above boronated compound are developed in, for example, a toluene solvent, and in the presence of Pd (PPh ₃ ) ₄ and Na ₂ CO ₃ at a reaction temperature of 85 ° C. If the reaction is allowed to proceed completely, coupling can occur. As a result, a silicon compound having a silyl group at the terminal of the block type compound can be synthesized.

An example of a synthetic route for silicon compounds (E) and (F) using such a reaction is shown below. A compound having a halogen group (for example, bromo group) and a trichlorosilyl group at both ends of a unit derived from benzene or thiophene is p-phenylene or 2,5-thiophenediyl and a halogenating agent (for example, NBS). It can be formed by halogenating both ends by the reaction with and then reacting with SiCl ₄ and trichlorosilylating one of them.

As a method for synthesizing a precursor in which units derived from benzene or thiophene and vinyl groups are alternately bonded, for example, the following method can be applied. That is, after preparing a raw material having a methyl group at the reaction site of benzene or thiophene, both ends thereof are used with 2,2′-azobisisobutyronitrile (AIBN) and N-bromosuccinimide (NBS). Brominated. Thereafter, PO (OEt) ₃ is reacted with the bromo compound to form an intermediate. Subsequently, the above precursor can be formed by reacting a compound having an aldehyde group at the terminal with an intermediate, for example, using NaH in a DMF solvent. In addition, since the obtained precursor has a methyl group at the terminal, for example, if the methyl group is further brominated and the above synthetic route is applied again, a precursor having a larger number of units can be formed.

If the obtained precursor is brominated using, for example, NBS, the portion can be reacted with SiCl ₄ . Therefore, a silicon compound having SiCl ₃ at the terminal can be formed. An example of a synthesis route for precursors (G) to (I) and silicon compound (J) having different lengths using such a reaction is shown below.

For any compound, a raw material having a side chain (for example, an alkyl group) at a predetermined position can also be used. That is, for example, when 2-octadecyl terthiophene is used as a raw material, 2-octadecyl sexual thiophene can be obtained as a precursor (A) by the above synthesis route. Accordingly, 2-octadecylsecthiothiophene trichlorosilane can be obtained as the silicon compound (C). Similarly, if a raw material having a side chain in advance at a predetermined position is used, a compound having any of the compounds (A) to (J) and having a side chain can be obtained.
The raw materials used in the above synthesis examples are general-purpose reagents that can be obtained and used from reagent manufacturers. The CAS number of the raw material and the purity of the reagent when obtained from Kishida Chemical as a reagent manufacturer are shown below.

The silicon compound thus obtained can be isolated and purified from the reaction solution by known means such as phase transfer, concentration, solvent extraction, fractional distillation, crystallization, recrystallization, chromatography and the like. This silicon compound can be formed into a film as follows, for example.
First, a silicon compound is dissolved in a non-aqueous organic solvent such as hexane, chloroform, or carbon tetrachloride. A substrate on which an organic thin film is to be formed (preferably a substrate having active hydrogen such as a hydroxyl group or a carboxyl group) is immersed in the obtained solution and pulled up. Alternatively, the obtained solution may be applied to the substrate surface. Thereafter, it is washed with a non-aqueous organic solvent, washed with water, left to stand or dried by heating to fix the organic thin film.

This organic thin film may be used directly as an electric material, or may be used after further treatment such as electrolytic polymerization. By using this material, it is possible to obtain a highly ordered (crystallized) organic thin film with a Si—O—Si network and a small distance between adjacent π-electron conjugated molecules. Further, when the units are arranged in a straight chain, the adjacent units are not coupled to each other, and the distance between the adjacent units is small, so that a highly crystallized organic thin film can be obtained.
Hereinafter, the silicon compound of the present invention and the production method thereof will be specifically described with reference to examples.

Example 1: Synthesis of terphenyltrichlorosilane by Grignard method In a 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 1.5 mol of terphenyl was dissolved in carbon tetrachloride, NBS, AIBN was added and stirred for 3 hours, followed by filtration under reduced pressure to obtain bromoterphenyl. Subsequently, in a 500 ml glass flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, 0.5 mol of metal magnesium and 300 ml of THF (tetrahydrofuran) were charged, and 0.5 mol of bromoterphenyl was added at 50 to 60 ° C. Was added dropwise from a dropping funnel over 2 hours, and after completion of dropping, the mixture was matured at 65 ° C. for 2 hours to prepare a Grignard reagent.

A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel is charged with 1.0 mol of SiCl ₄ (tetrachlorosilane) and 300 ml of toluene, cooled on ice, and at an internal temperature of 20 ° C. or less, a Grignard reagent Was added over 2 hours, and after completion of the dropwise addition, maturation was performed at 30 ° C. for 1 hour (Grignard reaction).
Then, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted tetrachlorosilane were stripped from the filtrate, and this solution was distilled to obtain the title compound in a yield of 50%. .

When the infrared absorption spectrum measurement was performed for the obtained compound, absorption derived from SiC was observed at 1080 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.
Moreover, when the ultraviolet-visible absorption spectrum measurement of the solution containing a compound was performed, absorption was observed by wavelength 280nm. This absorption was attributed to the π → π * transition of the terphenyl molecule contained in the molecule, and it was confirmed that the compound contained a terphenyl molecule.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed. Direct NMR measurement of the resulting compound is impossible due to the high reactivity of the compound, so the compound was reacted with ethanol (hydrogen chloride generation was confirmed), and the terminal chlorine was converted to an ethoxy group. Then, measurement was performed.
7.95 ppm to 7.35 ppm (m) (from 13H aromatics)
2.60 ppm (m) (derived from 3H ethoxy group)
From these results, it was confirmed that the obtained compound was terphenyltrichlorosilane represented by the formula (1).

Example 2: Synthesis of terthiophene trichlorosilane by Grignard method In a 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 1.0 mol of terthiophene was dissolved in carbon tetrachloride, NBS, AIBN was added and stirred for 2.5 hours, followed by filtration under reduced pressure to obtain bromoterthiophene. continue,
A 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel is charged with 0.5 mol of metal magnesium and 300 ml of THF (tetrahydrofuran), and 0.5 mol of bromoterthiophene is added dropwise at 50 to 60 ° C. It dropped over 2 hours from the funnel, and after completion of dropping, the mixture was matured at 65 ° C. for 2 hours to prepare a Grignard reagent.
A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 1.5 mol of SiCl ₄ (tetrachlorosilane) and 300 ml of toluene, cooled on ice, and at an internal temperature of 20 ° C. or lower, the Grignard reagent Was added over 2 hours, and after completion of the dropwise addition, maturation was performed at 30 ° C. for 1 hour (Grignard reaction).

Then, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted tetrachlorosilane were stripped from the filtrate, and this solution was distilled to obtain the title compound in a yield of 55%. .
When the obtained compound was subjected to infrared absorption spectrum measurement, SiC-derived absorption was observed at 1060 cm ⁻¹ , confirming that the compound had a SiC bond.
Moreover, when the ultraviolet-visible absorption spectrum measurement of the solution containing a compound was performed, absorption was observed by wavelength 360nm. This absorption was attributed to the π → π * transition of the terthiophene molecule contained in the molecule, and it was confirmed that the compound contained the terthiophene molecule.

Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed. Since this compound cannot be directly measured by NMR due to the high reactivity of the compound, the compound was reacted with ethanol (hydrogen chloride generation was confirmed), and the terminal chlorine was replaced with an ethoxy group. Measurements were made later.
7.50 ppm to 7.00 ppm (m) (derived from 7H thiophene ring)
2.20 ppm (m) (derived from 3H ethoxy group)
From these results, it was confirmed that this compound was terthiophene trichlorosilane represented by the formula (2).

Example 3: Synthesis of terthiophene trichlorosilane using Li A 300-liter tetrahydrofuran solution containing 1.0 mol of terthiophene was charged into a 1-liter glass flask equipped with a stirrer, a thermometer, and a dropping funnel, and cooled to -78 ° C. Then, 1.0 mol of n-butyllithium was slowly added dropwise, and then stirred for 1 hour to prepare a lithium salt of terthiophene having a structure represented by formula (8).

Next, a tetrahydrofuran solution of tetrachlorosilane was added and stirred overnight, and then lithium chloride, toluene and unreacted tetrachlorosilane were removed from the reaction solution. The solution was then distilled to give the title compound in 45% yield.
The obtained compound was measured for infrared absorption spectrum and nuclear magnetic resonance. As a result, absorption was observed at the same position as the compound shown in Example 2, so that the compound produced in Example 2 was used. It was confirmed that it was terthiophene trichlorosilane represented by (2).

Example 4: Preparation of organic thin film and measurement of semiconductor properties A silicon substrate prepared by preparing a toluene solution containing the π-electron conjugated molecule-containing silicon compound obtained in Example 2 and having a hydroxyl group protruding from the surface in advance by hydrophilization treatment Was immersed in a toluene solution to form an organic thin film.
In the ultraviolet-visible absorption spectrum, terthiophene absorption was observed at a wavelength of 360 nm, which confirmed that the silicon compound was adsorbed on the substrate surface.

In addition, a peak was confirmed at 2θ = 22.7 ° in X-ray diffraction, and it was found that a crystalline film having a plane spacing of 0.392 nm was formed. This is because the terthiophene trichlorosilane of the present invention is chemisorbed on the substrate by the two-dimensional network of Si-O-Si formed between the silicon compounds, and at a short distance force necessary for crystallization of the film. It can be expected that an intermolecular interaction acting between π-electron conjugated molecules works efficiently, so that it has a very high stability and constitutes a highly crystallized organic thin film. .
As a result, it was shown that the compound of the present invention can be used as an organic thin film forming material with high crystallinity.

Moreover, in order to investigate the semiconductor characteristic which the produced organic thin film has, as shown in FIG. 4, what provided the blocking electrode 21 and the counter electrode 22 on both sides of the organic thin film 23 was produced. In this system, when a light pulse is applied to the blocking electrode from the direction indicated by the arrow in a state where a voltage is applied between the electrode 21 and the electrode 22, carriers are generated on the electrode 21 side and sequentially move to the electrode 22. If this is detected by the detector 24, the mobility can be evaluated from the carrier movement time and the carrier distribution state (transient photocurrent measurement method). As a result of measuring the mobility of the organic film of terthiophene trichlorosilane using this measurement method, it was 1 × 10 ⁻¹ cm ² / Vs.
From this result, it was shown that the compound of the present invention can be used as a material having semiconductor characteristics. Moreover, when the mobility of the compounds (1) to (7) described above was measured in the same manner, it was confirmed that they had similar semiconductor characteristics.

Example 5: Electrical conductivity measurement of organic thin film with terthiophene trichlorosilane (perpendicular to substrate)
A silicon substrate imparted with conductivity (0.1 to 0.2 Ω · cm) by high doping is immersed for 1 hour in a mixed solution of hydrogen peroxide and concentrated sulfuric acid (mixing ratio 3: 7), and the substrate surface is Hydrophilic treatment was performed. Thereafter, the substrate obtained was immersed in a terthiophene trichlorosilane solution having a concentration of 10 mM dissolved in a non-aqueous solvent (for example, n-hexadecane) in an inert atmosphere for 5 minutes, and then slowly lifted. Cleaning was performed to form a film on the substrate.

About the obtained organic thin film, as a result of measuring the electrical conductivity in the film thickness direction (perpendicular to the substrate) of the organic thin film using SPM (scanning probe microscope), it is as high as 10 ⁻⁴ S / cm or higher. A value was obtained.
Thereby, it can be predicted that conductivity in the direction of the molecular axis constituting the organic thin film can be obtained.

Example 6: Electrical conductivity measurement of organic thin film with quarterthiophene trichlorosilane (parallel to substrate)
As shown in FIG. 1, electrode terminals 2a and 2b were formed on a quartz substrate 1 by vapor deposition of Au. Thereafter, a direct current power source for applying a predetermined voltage between both terminals 2a and 2b and an ammeter conductivity measuring means 4 for detecting a current between both terminals 2a and 2b are provided. The degree was measured.
As a result of the electrical conductivity measurement with the electrode terminals thus produced, values of 10 ⁻⁵ to 10 ⁻⁷ S / cm were shown.

As a result of measuring the mobility by the same method as in Example 4, ie, the transient photocurrent measurement method, the mobility of the quarterthiophenetrichlorosilane organic thin film was 1 × 10 ⁻¹ cm ² / Vs.
From these results, the organic thin film has excellent conductivity in the direction perpendicular to the substrate and excellent semiconductor characteristics in the plane direction. That is, it became clear that the electric characteristics were anisotropic in the vertical direction and the planar direction.

Example 7 Production of Organic Thin Film Transistor In order to produce the organic thin film transistor shown in FIG. 2, first, chromium was deposited on the silicon substrate 10 to form the gate electrode 15.
Next, after depositing an insulating film 16 made of a silicon nitride film by a plasma CVD method, vapor deposition was performed in the order of chromium and gold, and a source electrode 13 and a drain electrode 14 were formed by a normal lithography technique.

  Subsequently, after the obtained substrate was subjected to surface hydrophilization treatment by immersing it in a mixed solution of hydrogen peroxide and concentrated sulfuric acid, this substrate was immersed in a 20 mM terthiophene trichlorosilane solution under anaerobic conditions. The organic semiconductor layer 12 was formed by lifting and solvent cleaning.

  About the obtained organic-semiconductor layer 12, it has confirmed that the silicon compound was adsorb | sucking to the substrate surface from the ultraviolet-visible absorption spectrum having seen terthiophene absorption in wavelength 360nm. In addition, a peak was confirmed at 2θ = 22.7 ° in X-ray diffraction, and it was found that a crystalline film having a plane spacing of 0.392 nm was formed. Therefore, it can be said that this crystalline film has regularly formed adjacent terthiophene molecules as shown in FIG. That is, π-conjugated molecules are bonded to the surface of the insulating film 16 via siloxane bonds, but are not bonded between adjacent organic molecules. That is, as shown in Example 4, it is reasonable to infer that the adjacent terthiophene molecules were able to form a crystalline film having high order by mutual molecular interaction.

Thereby, in the produced organic thin film transistor, hopping conduction is likely to occur when a voltage is applied from the outside, so that the on-current can be increased. In other words, at the time of ON, since the distance between adjacent molecules is small due to the interaction between induced dipoles, an environment in which hopping conduction is likely to occur is generated and the ON current can be increased.
Moreover, since there is no direct covalent bond between π-electron conjugated molecules (adjacent molecules) bonded to Si included in the two-dimensional network of Si—O—Si, the leakage current at OFF is reduced. It is possible.

The organic thin film transistor obtained above had a field effect mobility of 1 × 10 ⁻¹ cm ² / Vs, an on / off ratio of about 6 digits, and good performance was obtained.
From the above, the novel substance according to the present invention can provide an organic thin film having conductivity that is anisotropic in the molecular axis direction and the direction perpendicular to the molecular plane and having high crystallinity. become.

Example 8: Preparation of Organic Thin Film Transistor Using 2-Octyl-Kinkkethiophene Triethoxysilane In the same manner as in Example 7, the prepared electrode-attached substrate was mixed with 5 mM 2-octyl-kink quinkethiophene triethoxysilane toluene and A 2-octyl-quinkethiophene triethoxysilane film was formed by immersing in a hydrochloric acid mixed solution for a certain time (for example, 10 minutes), thereby forming an organic semiconductor layer and an organic thin film transistor. The characteristics of the formed organic thin film transistor are shown in FIG. As a result, the organic thin film transistor formed had a field effect mobility of 1.5 × 10 ⁻¹ cm ² / Vs and an on / off ratio of about 6 digits.

Example 9: Preparation of organic thin-film transistor using 2-dodecyl-septithiophene trichlorosilane In the same manner as in Example 7, the prepared electrode-attached substrate was placed in a 2 mM 2-dodecyl-septithiophenetriethoxysilane solution in toluene. The organic thin film transistor was formed by forming a 2-dodecyl-septithiophene trichlorosilane film by immersing the film in a certain time (for example, 5 minutes) to form an organic semiconductor layer. The characteristics of the formed organic thin film transistor are shown in FIG. As a result, the organic thin film transistor formed had a field effect mobility of 1.7 × 10 ⁻¹ cm ² / Vs and an on / off ratio of about 6 digits.

Example 10: Preparation of organic thin film transistor using 2-hexadecyl-quarterphenyltrimethoxysilane In the same manner as in Example 7, the prepared electrode-attached substrate was placed in a toluene solution of 3 mM 2-hexadecyl-quaterphenyltrimethoxysilane. By immersing for a certain time (for example, 60 minutes), a 2-hexadecyl-quarterphenyltrimethoxysilane film was formed, an organic semiconductor layer was formed, and an organic thin film transistor was formed. The characteristics of the formed organic thin film transistor are shown in FIG. As a result, the organic thin film transistor formed had a field effect mobility of 1.3 × 10 ⁻¹ cm ² / Vs and an on / off ratio of about 6 digits.

Example 11: Preparation of organic thin-film transistor using 2-hexadecyl-octiphenyltrimethoxysilane In the same manner as in Example 7, the prepared electrode-attached substrate was fixed in a 3 mM 2-hexadecyl-octiphenyltrimethoxysilane toluene solution. By immersing for a time (for example, 60 minutes), a 2-hexadecyl-octylphenyltrimethoxysilane film was formed, an organic semiconductor layer was formed, and an organic thin film transistor was formed. The characteristics of the formed organic thin film transistor are shown in FIG. As a result, the organic thin film transistor formed had a field effect mobility of 1.6 × 10 ⁻¹ cm ² / Vs and an on / off ratio of about 6 digits.

Example 12: Preparation of an organic thin film transistor using an organosilicon compound (Chemical E: where n ₁ = n ₃ = 2 and n ₂ = 1) In the same manner as in Example 7, the prepared electrode-attached substrate was prepared at a concentration of 1 mM. The compound thin film was formed by immersing in a THF solution of the organosilicon compound represented by (Chemical Formula E) for a predetermined time (for example, 15 minutes). Thus, an organic semiconductor layer was formed, and an organic thin film transistor was formed. The characteristics of the formed organic thin film transistor are shown in FIG. As a result, the organic thin film transistor formed had a field effect mobility of 1.1 × 10 ⁻¹ cm ² / Vs and an on / off ratio of about 6 digits.

Example 13: Preparation of an organic thin film transistor using an organosilicon compound (Chemical Formula F: where n ₄ = n ₆ = 2 and n ₅ = 3) In the same manner as in Example 7, the prepared electrode-attached substrate was prepared at a concentration of 1 mM. The compound film was formed by immersing in a xylene solution of an organosilicon compound represented by (Chemical Formula F) for a certain time (for example, 10 minutes). Thus, an organic semiconductor layer was formed, and an organic thin film transistor was formed. The characteristics of the formed organic thin film transistor are shown in FIG. As a result, the organic thin film transistor formed had a field effect mobility of 2.2 × 10 ⁻¹ cm ² / Vs and an on / off ratio of about 6 digits.

Example 14 Synthesis of an organosilicon compound having the following structural formula (Chemical Formula E; where n ₁ = n ₃ = 2 and n ₂ = 3)

  About the said compound, it synthesize | combined with the following methods. That is, Intermediate 1 and Intermediate 2 are formed from dibromodiphenyl. Intermediate 3 is also formed from terthiophene and Grignard reagent (see below). By subjecting these to a coupling reaction, the target compound is formed. Specifically, it is as follows.

Formation of Intermediate 1 First, in a 500 ml glass flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, 1.5 mol of metallic magnesium and 200 ml of toluene were charged, and 0.5 mol of dibromobiphenyl in toluene was added. A Grignard reagent substituted with one bromo group was prepared by adding over 30 minutes and ripening at 65 ° C. for 2 hours after completion of the dropwise addition. Subsequently, a 1 liter glass flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was charged with 1.0 mol of tetrachlorosilane and 200 ml of toluene, cooled with ice, and the above Grignard at an internal temperature of 15 ° C. The reagent was added over 1 hour, and after the dropwise addition, the mixture was matured for 1 hour. Subsequently, the reaction solution was filtered under reduced pressure to remove unreacted materials, and then dissolved in diethyl ether, and then charged into a 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel. A 0 mol CH ₃ —CH ₂ —O—MgBr ether solution was added dropwise over 1 hour and then refluxed at 70 ° C. for 12 hours to form Intermediate 1 (yield 60%).

Formation of Intermediate 2 First, 0.5 mol of n-butyllithium was charged into a 500 ml glass flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, and cooled to −78 ° C., and then Intermediate 1 was dropped. Add using a funnel over 30 minutes, followed by addition of 1.5 moles of bis (pinacolato) diboron followed by increasing the internal temperature of the vessel from −78 ° C. to room temperature over 12 hours. Proceeded. After completion of the reaction, 2M hydrochloric acid was added to form intermediate 2 (yield 60%).

Formation of Intermediate 3 First, 1.0 mol of terthiophene was dissolved in carbon tetrachloride, NBS was added, azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the mixture was stirred for 6 hours. Dibromoterthiophene was obtained by filtration under reduced pressure.
Further, 1.0 mol of biphenyl was dissolved in carbon tetrachloride, and then NBS was added and stirred in the presence of AIBN for 2 hours to form bromobiphenyl, followed by stirring, reflux condenser, temperature A 500 ml glass flask equipped with a total addition funnel was charged with 1.5 mol of magnesium metal and 200 ml of toluene, and 0.5 mol of a bromodiphenyl toluene solution was added over 30 minutes. Grignard reagents were prepared by time maturation.

  Subsequently, dibromoterthiophene is dissolved in diethyl ether, charged into a 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel, and the Grignard reagent is added dropwise over 2 hours, and then refluxed for 18 hours. This allowed the reaction to proceed. Then, it filtered under reduced pressure and the intermediate body 3 was obtained by stripping an unreacted substance (yield 50%).

Formation of target compound Toluene solution of intermediate 2 above, 3 mol% Pd (PPh) 3 and a small amount of sodium carbonate aqueous solution were sequentially charged into a 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel. Subsequently, the toluene solution of Intermediate 3 was added using a dropping funnel, and then reacted at 85 ° C. for 12 hours to form the target compound (Suzuki coupling).

When the infrared absorption spectrum measurement was performed for the formed target compound, absorption derived from SiC was confirmed at 1065 cm ⁻¹ , and it was confirmed that the compound contained SiC bonds. Furthermore, the nuclear magnetic resonance measurement of the compound was performed.
7.5 ppm to 7.2 ppm (m) (derived from 17H phenyl skeleton)
7.1 ppm to 6.9 ppm (m) (derived from 6H thiophene skeleton)
3.8 ppm to 3.7 ppm (m) (derived from 6H ethoxy group methylene)
1.4 ppm to 1.2 ppm (m) (derived from 9H ethoxy group methyl group)
From these results, it was confirmed that this compound was a compound represented by the above structural formula.

Example 15
Synthesis of a compound of an organosilicon compound having the following structural formula (Chemical formula J; where nγ = 2)

About the said compound, it synthesize | combined with the following methods.
First, α-bromoxylene (50 mM) and triethyl phosphite (60 mM) were charged into a 200 ml eggplant flask, and the reaction was allowed to proceed by raising the temperature to 140 ° C. while stirring. The temperature was further raised to 180 ° C., the residue of triethyl phosphite was destroyed, and then cooled to form 4- (methyl-benzyl) -phosphonic acid (4- (Methyl-benzy) -phosphonic acid). Subsequently, to a 500 ml glass flask equipped with a stirrer, a thermometer and a dropping funnel, 10 mM sodium hydroxide was added to dry DMF in an argon atmosphere to bring the solution temperature to 0 ° C., and then the 4- (methyl-benzyl)- Slowly add a DMF solution (50 ml) of phosphonic acid (4- (Methyl-benzy) -phosphonic acid) (8 mM) and trans-4-stilbenecarboxaldehyde (7 mM) and stir for 24 hours. The reaction was allowed to proceed. After completion of the reaction, the product was extracted with ethanol to give 4-[(E) -2- [4-{(E) -2-phenylvinyl} -phenyl] -vinyl] -phenylmethane (4-{( E) -2- [4-{(E) -2-phenylvinyl} -phenyl] -vinyl} -phenylmethane) (compound G) was synthesized. Further, Compound G was dissolved in carbon tetrachloride, NBS was added, AIBN was added, and the mixture was stirred for 2 hours, followed by filtration under reduced pressure to synthesize Intermediate 4 represented by the following structural formula.

  Subsequently, the intermediate 4 was charged into a 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 1.0 mol of tetrachlorosilane and 200 ml of toluene were charged, ice-cooled, and an internal temperature of 10 ° C. The intermediate 4 was added over 1 hour, and after the dropwise addition, the mixture was matured for 1 hour, thereby synthesizing the compound represented by the above structural formula.

When an infrared absorption spectrum measurement was performed on the formed target compound, absorption derived from SiC was confirmed at 1070 cm ⁻¹ , and it was confirmed that the compound contained SiC bonds. Furthermore, the nuclear magnetic resonance measurement of the compound was performed. Since this compound is highly reactive and cannot be directly measured by NMR, it was measured after reacting with ethanol and replacing the terminal chlorine with an ethoxy group.
7.4 ppm to 7.2 ppm (m) (derived from 12H phenyl skeleton)
7.1 ppm to 7.0 ppm (m) (derived from 4H vinyl group skeleton)
3.8 ppm to 3.7 ppm (m) (derived from 6H ethoxy group methylene)
2.5 ppm to 2.4 ppm (m) (derived from 3H methyl group)
1.4 ppm to 1.2 ppm (m) (derived from 9H ethoxy group methyl group)
From these results, it was confirmed that this compound was a compound represented by the above structural formula.

It is a figure which shows the structure for evaluating the electrical conductivity of the film | membrane using the pi-electron conjugated molecule containing silicon compound of this invention. It is a schematic sectional drawing of the organic thin-film transistor using the pi-electron conjugated molecule containing silicon compound of this invention. It is a conceptual diagram which shows the molecular arrangement | sequence of the organic film part in FIG. It is the schematic for demonstrating the measurement of the mobility by a transient photocurrent measuring method. It is a characteristic view of the organic thin-film transistor in the 8th Example of this invention. It is a characteristic view of the organic thin-film transistor in the 9th Example of this invention. It is a characteristic view of the organic thin-film transistor in the 10th Example of this invention. It is a characteristic view of the organic thin-film transistor in the 11th Example of this invention. It is a characteristic view of the organic thin-film transistor in the 12th Example of this invention. It is a characteristic view of the organic thin-film transistor in the 13th Example of this invention. It is a figure for demonstrating the relationship between intermolecular distance and intermolecular force.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Quartz substrate 2a, 2b Electrode terminal 3 Organic thin film 4 Ammeter conductivity measuring means 10 Silicon substrate 12 Organic semiconductor layer 13 Source electrode 14 Drain electrode 15 Gate electrode 16 Insulating film 21 Blocking electrode 22 Counter electrode 23 Organic thin film 24 Detector

Claims (9)

Formula R-SiX ¹ X ² X ³ (I)
(In the formula, R is an organic residue of a π-electron conjugated system in which 5 to 10 units selected from a group derived from a monocyclic aromatic hydrocarbon and a monocyclic heterocyclic compound are bonded to each other; (It may have a functional group, and X ¹ , X ² and X ³ are the same or different and are groups which give a hydroxyl group by hydrolysis.)
Represented by
The unit may be bonded via a vinylene group,
The functional group is a linear alkyl group having 1 to 30 carbon atoms;
The SiX ¹ X ² X ³ group is directly bonded to the unit;
A π-electron conjugated molecule-containing silicon compound in which the monocyclic aromatic hydrocarbon and the monocyclic heterocyclic compound are benzene and thiophene, respectively .   The π-electron conjugated molecule-containing silicon compound according to claim 1, wherein R is an organic residue containing a vinylene group between units. ^2. The π-electron conjugated molecule-containing silicon compound according to claim ¹ , wherein X ¹ , X ^2, and X ³ are all the same type of halogen atom or lower alkoxy group. Formula R-Li (II)
(In the formula, R is an organic residue of a π-electron conjugated system in which 5 to 10 units selected from a group derived from a monocyclic aromatic hydrocarbon and a monocyclic heterocyclic compound are bonded to each other; (It may have a functional group.)
A compound represented by
Formula Y-SiX ¹ X ² X ³ (III)
(In the formula, X ¹ , X ² and X ³ are the same or different and are groups which give a hydroxyl group by hydrolysis, and Y is a hydrogen atom, a halogen atom or a lower alkoxy group.)
Is reacted with a compound represented by
Formula R-SiX ¹ X ² X ³ (I)
(In the formula, R, X ¹ , X ² and X ³ are as defined above.)
In give π electron conjugate molecule-containing silicon compound represented by,
The unit may be bonded via a vinylene group,
The functional group is a linear alkyl group having 1 to 30 carbon atoms;
The SiX ¹ X ² X ³ group is directly bonded to the unit;
The method for producing a π-electron conjugated molecule-containing silicon compound, wherein the monocyclic aromatic hydrocarbon and the monocyclic heterocyclic compound are benzene and thiophene, respectively . Formula R-MgX (IV)
(In the formula, R is an organic residue of a π-electron conjugated system in which 5 to 10 units selected from a group derived from a monocyclic aromatic hydrocarbon and a monocyclic heterocyclic compound are bonded to each other; (It may have a functional group.)
A compound represented by
Formula Y-SiX ¹ X ² X ³ (III)
(In the formula, X ¹ , X ² and X ³ are the same or different and are groups which give a hydroxyl group by hydrolysis, and Y is a hydrogen atom, a halogen atom or a lower alkoxy group.)
To a Grignard reaction with a compound represented by
Formula R-SiX ¹ X ² X ³ (I)
(In the formula, R, X ¹ , X ² and X ³ are as defined above.)
In give π electron conjugate molecule-containing silicon compound represented by,
The unit may be bonded via a vinylene group,
The functional group is a linear alkyl group having 1 to 30 carbon atoms;
The SiX ¹ X ² X ³ group is directly bonded to the unit;
The method for producing a π-electron conjugated molecule-containing silicon compound, wherein the monocyclic aromatic hydrocarbon and the monocyclic heterocyclic compound are benzene and thiophene, respectively . The group R is halogenated at a predetermined bonding position of a raw material compound selected from a monocyclic aromatic hydrocarbon and a monocyclic heterocyclic compound, and then subjected to a Grignard reaction one or more times, whereby a predetermined number of The method for producing a π-electron conjugated molecule-containing silicon compound according to claim 4 or 5 derived from a compound obtained by bonding a raw material compound. A step in which a unit constituting the group R is derived from thiophene, the group R is halogenated at a predetermined bonding position of thiophene, and then the obtained halogenated thiophene is reacted in the presence of NCS or POCl ₃ to bond them. The method for producing a π-electron conjugated molecule-containing silicon compound according to claim 4 or 5 derived from a compound obtained by bonding a predetermined number of thiophenes by repeating at least once. The unit constituting the group R is derived from thiophene, the group R is halogenated at a predetermined bonding position of thiophene, and then the resulting halogenated thiophene and divinylsulfone are reacted to form thiophene on both sides of the succinyl group. A bonded 1,4-diketone is obtained, and then a step of ring-closing reaction of the 1,4-diketone in the presence of Low Wesson's agent or P ₄ S ₁₀ is repeated one or more times to bind a predetermined number of thiophenes. The manufacturing method of the pi-electron conjugated molecule containing silicon compound of Claim 4 or 5 derived from the compound obtained by making it do. The methyl group of the raw material compound selected from the monocyclic aromatic hydrocarbon and monocyclic heterocyclic compound in which the group R has a methyl group at a predetermined bonding position is halogenated, and then the halogen is converted to a pentavalent phosphorus compound And the step of reacting the obtained compound with a raw material compound selected from a monocyclic aromatic hydrocarbon having a aldehyde group at a predetermined bonding position and a monocyclic heterocyclic compound is repeated at least once. 6. The method for producing a π-electron conjugated molecule-containing silicon compound according to claim 4 or 5 derived from a compound obtained by bonding a predetermined number of raw material compounds.

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