JP2007145984A - Siloxane-based molecular membrane, method for producing the same and organic device using the membrane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a siloxane-based molecular membrane that has extremely high stability and is highly controlled in arrangement and to provide a method for producing the siloxane-based molecular membrane and an organic device using the molecular membrane. <P>SOLUTION: The siloxane-based molecular membrane is formed by using an organic compound represented by general formula Si(A<SP>1</SP>)(A<SP>2</SP>)(A<SP>3</SP>)-B-Si(A<SP>4</SP>)(A<SP>5</SP>)(A<SP>6</SP>) (A<SP>1</SP>-A<SP>6</SP>are each a hydrogen atom, a halogen atom, an alkoxy group or an alkyl group; release reactivity satisfies relation of A<SP>1</SP>-A<SP>3</SP>>A<SP>4</SP>-A<SP>6</SP>; B is a bifunctional organic group) and has a siloxane network on a membrane surface. The organic device has the molecular membrane. The molecular membrane is obtained by a process for forming a single monomolecular membrane by reacting a silyl group containing A<SP>1</SP>-A<SP>3</SP>of the organic compound with a substrate surface, a process for cleaning and removing an unreacted organic compound by using a nonaqueous solvent and a process for forming a siloxane network by an unreacted silyl group existing on the membrane surface side of the monomolecular membrane. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a molecular film in which a siloxane network is constructed from an organosilicon compound. More specifically, the present invention relates to a molecular film in which a molecular film fixed by a substrate and a siloxane network forms a siloxane network on the air interface side (film surface side) opposite to the substrate and forms a siloxane network on both sides of the molecule. The present invention also relates to a method for producing such a siloxane-based molecular film and an organic device using the molecular film.

Conventionally, as a method of modifying the substrate surface, there is a method of chemically adsorbing on the substrate surface using an organosilicon compound. In this approach, the organosilicon compound is immobilized on the substrate by the substrate and a siloxane network.
The organosilicon compound has a silyl group for adsorbing to the substrate, and adsorbs to the substrate and forms a self-assembled film by an interaction derived from the structure of a portion other than the silyl group.

  A self-assembled film is a film in which a part of an organic compound is bonded to a functional group on the surface of a substrate and has very few defects and high order. 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 or a silicon compound film formed on a substrate (for example, a silicon substrate) capable of protruding a hydroxyl group on the surface by a hydrophilic treatment is known. . Among these, a silicon compound film has attracted attention because of its high durability. The silicon 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. In addition, examples of the silicon compound include those having a molecular structure having a phenylene group or an acetylene group. (For example, Patent Documents 1 to 3)

  As such a silicon-based compound, a compound having one thiophene ring as a functional group at the end of a molecule, and the thiophene ring bonded to Si via a linear hydrocarbon group has been proposed (for example, Patent Document 4). ). Further, as a polyacetylene film, a film in which an —Si—O— network is formed on a substrate by a chemical adsorption method and an acetylene group portion is polymerized has been proposed (for example, Patent Document 5). Further, as the organic material, a silicon compound in which a linear hydrocarbon group is bonded to the 2nd and 5th positions of the thiophene ring and the end of the linear hydrocarbon is bonded to the silanol group is used. In addition, an organic device has been proposed in which molecules are polymerized by electric field polymerization or the like to form a conductive thin film, and this conductive thin film is used as a semiconductor layer (for example, Patent Document 6). Furthermore, a field effect transistor using a semiconductor thin film whose main component is a silicon compound having a silanol group in a thiophene ring contained in polythiophene has been proposed (for example, Patent Document 7).

  However, the compound proposed above is a self-assembled film formed by interaction with the substrate and intermolecular interaction, although a self-assembled film that can be chemically adsorbed to the substrate can be produced. Since the film is formed by utilizing the two interactions, for example, when the intermolecular interaction is weak, the film is not formed and the film becomes very unstable. In addition, when a polyacetylene film is formed on a substrate by a chemical adsorption method in order to improve the stability of the film and express electrical properties, a -Si-O-network is formed on the substrate, and the acetylene group portion is polymerized. Since the Si-Si-Si distance and the acetylene bond distance of Si-O-Si- are different, the molecular network is distorted.

  In order to obtain high ordering, 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 in FIG. 10 (arrow part in the figure) 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 ordering, it is important to make the intermolecular distance as close as possible to the minimum point. Therefore, in vacuum processes such as resistance heating vapor deposition and molecular beam vapor deposition, originally, high sequence ordering can be achieved by well controlling the intermolecular interaction between π-electron conjugated molecules only under certain conditions. Is obtained. Thus, it is possible to develop high electric conduction characteristics only with a highly controlled film constructed by 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. For example, since one thiophene molecule that is a functional group only contributes to the π-electron conjugated system, the interaction between the molecules is weak, and the spread of the π-electron conjugated system essential for electrical conductivity is very small. There was a problem. 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.

  In addition, when a film (cumulative film) in which single molecules are accumulated by a chemical adsorption method using a silicon compound having a silyl group at the terminal is formed on the substrate, the reactivity of the terminal silyl group becomes a problem. As a method for adjusting a cumulative film using the chemical adsorption method reported so far, there is, for example, Patent Document 8. In this patent, an alkylsilane compound having trichlorosilyl groups at both ends is used as a compound that causes an adsorption reaction with the substrate. Specifically, after forming a monomolecular film on the substrate surface, a method of forming a cumulative film comprising accumulating the monomolecular film using the trichlorosilyl group remaining on the air interface side of the compound as a new adsorption reaction site It is shown.

However, it is known that the trichlorosilyl group has extremely intense reactivity of elimination reaction of chlorine atoms. When trichlorosilyl groups are present at both ends, the trichlorosilyl group at either end undergoes a hydrolysis reaction during monomolecular film formation. As a result, this silicon compound causes an adsorption reaction with the substrate, and at the same time, bimolecular and trimolecularization occur simultaneously with the unreacted end group as the next adsorption point. Therefore, in the conventional chemical adsorption method using a compound, it has been difficult to form a monomolecular cumulative film with uniform film thickness and high molecular ordering with high reproducibility. In a device using a monomolecular cumulative film with a non-uniform film thickness and a low order of molecular arrangement, carriers are trapped between the cumulative films, resulting in performance degradation.
Japanese Patent Laid-Open No. 1-305094 Japanese Patent Laid-Open No. 5-186531 JP 2002-261317 A IEEE Electron Device Lett. , 18,606-608 (1997) Japanese Patent No. 2889768 Japanese Examined Patent Publication No. 6-27140 Japanese Patent No. 2507153 Japanese Patent No. 2725587 Japanese Patent No. 3292205

  An object of the present invention is to provide a siloxane-based molecular film having very high stability and highly controlled, a method for producing the siloxane-based molecular film, and an organic device using the molecular film. To do.

（式中、Ａ^１〜Ａ^６はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜１０のアルコキシ基または炭素数１〜１８のアルキル基であり、Ａ^１〜Ａ^６は脱離反応性についてＡ^１〜Ａ^３＞Ａ^４〜Ａ^６の関係を満たす；Ｂは２価の有機基である）で表される有機化合物を用いて形成されてなり、膜表面にシロキサンネットワークを有することを特徴とするシロキサン系分子膜に関する。 The present invention relates to a general formula (I);

(In the formula, A ^{1 to} A ⁶ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, and A ^{1 to} A ⁶ are elimination reactivity. Satisfying the relationship of A ^{1 to} A ³ > A ^{4 to} A ⁶ ; B is a divalent organic group), and has a siloxane network on the film surface The present invention relates to a characteristic siloxane-based molecular film.

The present invention also provides
(Formula) H-B-MgX (2)
(Wherein B is a divalent organic group and X is a halogen atom);
^{(Formula) Y 1 -Si (A 1)} (A 2) (A 3) (3)
(Wherein Y ¹ is a halogen atom, and A ^{1 to} A ³ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 18 carbon atoms). Reaction with the compound
^{(Formula) H-B-Si (A} 1) (A 2) (A 3) (4)
Synthesize
In the formula (4), a halogen atom is bonded to B and reacted with magnesium or lithium metal in the presence of ethoxyethane or tetrahydrofuran (THF) (formula) MgX-B-Si (A ¹ ) (A ² ) ^{(A 3)} or ^{LiX-B-Si (A 1} ) (A 2) (A 3) (5)
After synthesizing the compound represented by
^{(Formula) Y 2 -Si (A 4)} (A 5) (A 6) (6)
(In the formula, Y ² is a halogen atom, and A ^{4 to} A ⁶ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 18 carbon atoms, and is eliminated. The above siloxane-based molecular film is produced, wherein the organic compound of the general formula (I) is obtained by reacting with a compound represented by the formula (I) satisfying the relationship of A ^{1 to} A ³ > A ^{4 to} A ^6. On how to do.

The present invention also provides
^{(Formula) X 1 -B-X 2 (} 8)
(Wherein B is a divalent organic group, X ¹ and X ² are different from each other and are a halogen atom), and a Grignard reactant using a metal catalyst comprising magnesium or lithium. And then
^{(Formula) Y 1 -Si (A 1)} (A 2) (A 3) (3)
(Wherein Y ¹ is a halogen atom, and A ^{1 to} A ³ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 18 carbon atoms). Grignard reactant represented by the following formula (formula) Si (A ¹ ) (A ² ) (A ³ ) -B-MgX ² (9)
And then
^{(Formula) Y 2 -Si (A 4)} (A 5) (A 6) (6)
(In the formula, Y ² is a halogen atom, and A ^{4 to} A ⁶ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 18 carbon atoms, and is eliminated. reactivity a ¹ ~A ^3> a ⁴ ~A satisfies the relation ⁶⁾ with a compound of a (by reacting a compound of the formula 9), to obtain an organic compound of the general formula (I) The present invention relates to a method for producing the siloxane-based molecular film.

  The present invention relates to an organic device having the siloxane-based molecular film.

In the present specification, a single monomolecular film means an organic thin film composed of a single monomolecular film.
The monomolecular cumulative film means an organic thin film in which two or more monomolecular films are accumulated (laminated).

  The siloxane molecular film of the present invention is not only chemically adsorbed to the substrate by the two-dimensional siloxane network, but also has a two-dimensional siloxane network formed on the film surface. A certain intermolecular interaction that works between molecules works efficiently. Therefore, it has very high stability and is highly sequence controlled. Therefore, compared to the film produced by physical adsorption to the substrate, the obtained film can be firmly adsorbed to the substrate surface, preventing physical peeling, and improving the physical strength of the film, In addition, a dense film having excellent film surface smoothness can be provided.

  Further, the siloxane-based molecular film of the present invention achieves very high alignment control by the intermolecular interaction derived from the organic compound constituting the film and the two siloxane networks. Moreover, since the siloxane network is formed also on the film surface side of the molecular film, the roughness of the film surface can be suppressed and the film strength can be improved. Thus, carriers are smoothly moved by hopping conduction in a direction (in-plane direction) perpendicular to the molecular axis. 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.

  And the organic compound which comprises the siloxane type molecular film of this invention can be manufactured simply. In addition, when such an organic compound is a material that does not cause carrier transfer, for example, an organic compound in which the B group is a group derived from a saturated hydrocarbon compound in the general formula (I), the alignment is highly controlled, and the film surface is smooth. Since a film having excellent properties can be formed, it can be applied to an insulating material whose film thickness is controlled on the molecular size order.

  Further, the organic compound of the general formula (I) constituting the siloxane-based molecular film of the present invention has silyl groups at both ends, and the elimination reactivity of the group bonded to silicon is different between the silyl groups at both ends. Therefore, the adsorption to the substrate and the adsorption reaction to the film surface can be performed sequentially and selectively with good reproducibility. Thus, the present invention can form a cumulative film with a uniform film shape and molecular orientation and higher reproducibility than the prior art. That is, it is possible to produce a siloxane-based molecular film having high molecular orientation in which molecules are arranged in a highly ordered manner not only in the in-plane direction but also in the film thickness direction.

In addition, since the siloxane-based molecular film of the present invention has a two-dimensional siloxane network on the substrate side and the film surface side, a very stable film can be formed.
When such a siloxane-based molecular film is produced as a monomolecular cumulative film, the molecular film has different electric characteristics in the film thickness direction corresponding to the electric characteristics of a monomolecular layer of several nm thickness which is a structural unit. obtain. As a result, the conductivity, dielectric constant, carrier transfer efficiency, charge injection efficiency at the electrode interface, and the like can be controlled. Furthermore, it can be applied to high density recording, high speed response and / or high sensitivity light / temperature / gas sensor devices.

  Furthermore, since the organic compound constituting the siloxane-based molecular film of the present invention has a self-organizing property, it is not necessary to produce a molecular film having a high degree of alignment in a vacuum, and in the atmosphere. It can be carried out. This means that the production of the siloxane-based molecular film is simple and inexpensive, and therefore has great merit as an industrial process.

  In addition, if the hydrophilic treatment as a pretreatment of the substrate on which the siloxane-based molecular film of the present invention is formed is patterned, anisotropy can be imparted to the electrical characteristics not only in the film thickness direction but also in the film in-plane direction. That is, it becomes possible to prepare organic thin films having different electrical characteristics in a pseudo three-dimensional manner, and the application to next-generation electric devices is also expanded.

  Furthermore, when the siloxane-based molecular film of the present invention is formed as a cumulative film, materials having different conductivity, heat sensitivity, and light sensitivity can be accumulated in the order of several nm in the vertical direction from the substrate. Fields such as high-density recording, high-speed response switch, fine region conductivity, electron and hole injection, electron and hole transport, organic electroluminescence (EL) elements having a heterostructure in the order of nm, such as a light emitting layer, The present invention can be applied to photoelectric conversion elements used for solar cells and the like.

で表される。 (Organic compounds)
The organic compound constituting the siloxane-based molecular film of the present invention has different functional groups with different elimination reactivity at both ends of the molecule, that is, the general formula (I);

It is represented by

In formula (I), A ^{1 to} A ⁶ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 18 carbon atoms, and A ^{1 to} A ⁶ are eliminated. for reactivity satisfy the relation of ^{a 1 ~A 3> a 4 ~A} 6.

In the present invention, elimination reactivity means “ease of group elimination in water”, and the higher the elimination reactivity, the easier the elimination (hydrolysis) of the group in water. .
Further, the relationship of A ^{1 to} A ³ > A ^{4 to} A ⁶ regarding elimination reactivity means that the reactivity of at least one group, preferably all groups, of A ^{1 to} A ³ is A ⁴ to a elimination reactivity of the ⁶ means a higher relationship than the reactivity of the highest group. As long as such a relationship is satisfied, A ^{1 to} A ³ may be the same or different, and A ^{4 to} A ⁶ may also be the same or different.

As described above, the organic compound of the present invention has a silyl group having A ^{4 to} A ⁶ having relatively low elimination reactivity at one end, and the elimination reaction at the other end is higher than that of A ^{4 to} A ^6. A silyl group having a highly functional group as at least one of A ^{1 to} A ³ . Therefore, by adjusting the proton concentration of water, etc., the reactivity of the two silyl groups of the organic compound of the present invention can be controlled for each silyl group, and the adsorption of one silyl group onto the substrate or the organic film surface The reaction and the subsequent adsorption reaction by the other silyl group can be easily controlled. As a result, it is possible to manufacture a single monomolecular film having a uniform film thickness and a high order of molecular arrangement and its accumulated film with good reproducibility.

Examples of the halogen atom that can be A ^{1 to} A ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkoxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, from the viewpoint of solubility and film-forming property of the compound of the present invention. Preferable specific examples of the alkoxy group include, for example, methoxy group, ethoxy group, n- or 2-propoxy group, n-, sec- or tert-butoxy group, n-pentyloxy group, n-hexyloxy group and the like. . On the other hand, if the number of methylene groups in the alkoxy group is too large, crystallization due to aggregation of the carbon chain occurs and a kind of insulating layer is formed, so that the device characteristics are deteriorated.

  The alkyl group has 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, from the viewpoint of the solubility and film-forming property of the compound of the present invention. Preferable specific examples of the alkyl group include, for example, methyl group, ethyl group, n- or 2-propyl group, n-, sec- or tert-butyl group, n-pentyl group, n-hexyl, n-heptyl group, n -An octyl group, n-nonyl group, n-decyl group, etc. are mentioned. On the other hand, if the number of methylene groups in the alkyl group is too large, crystallization due to aggregation of the carbon chain occurs and a kind of insulating layer is formed, so that the device characteristics are deteriorated.

The elimination reactivity of the atoms and groups depends on the basicity of the atoms and groups. In the case of a hydrocarbon group, elimination reactivity depends on the number of methylene groups and the three-dimensional structure. Therefore, the order of elimination reactivity for all atoms and groups cannot be defined in general, but the general order when the alkoxy group and the alkyl group are regarded as one group is as follows.
Group 1; Halogen atom Group 2; Alkoxy group and alkyl group Group 3; Hydrogen atom In the above order, the higher the group number, the lower the elimination reactivity.

Specifically, in the first group, the elimination reactivity of halogen atoms decreases in the order of iodine, bromine, and chlorine.
In the second group, the elimination reactivity of the alkoxy group and alkyl group decreases in the order of alkoxy group and alkyl group when the carbon number is the same, but when the carbon number is different, it depends on the carbon number and the three-dimensional structure. Therefore, it cannot be specified unconditionally. When the number of carbon atoms is different, the order in the alkoxy group or the order in the alkyl group generally becomes lower as the number of carbon atoms increases. From the viewpoint of the three-dimensional structure, the elimination reactivity of alkoxy groups and alkyl groups is generally such that the alkyl groups contained in these groups are primary alkyl groups, secondary alkyl groups, and tertiary alkyl groups. It becomes lower in order.

When it is desired to know the magnitude relationship of elimination reactivity for a specific group (for example, X group and Y group), a silane compound having an X group and a Y group, for example, Si (X) ₂ (Y) ₂ in water After adding and stirring for a certain time, the relationship between them can be known by analyzing the silanes. That is, a group substituted with a hydroxyl group can be said to be a group having relatively high elimination reactivity. When both X and Y groups are substituted with a hydroxyl group, or when both groups are not substituted, the pH of water may be adjusted to a pH at which one group is substituted with a hydroxyl group.
The analysis method is not particularly limited as long as it can confirm the presence or absence of X group, Y group and hydroxyl group, and examples thereof include mass spectrometry and chromatographic analysis.

Preferred combinations of A ^{1 to} A ³ and A ^{4 to} A ^{6 included in} the organic compound of the present invention as described above are shown below.
(1) A ^{1 to} A ³ are each independently selected from a halogen atom, preferably simultaneously a chlorine atom or a bromine atom, in particular a chlorine atom; A ^{4 to} A ⁶ are each independently selected from an alkoxy group; A methoxy group or an ethoxy group, particularly an ethoxy group is preferred at the same time.
(2) A ^{1 to} A ³ are each independently selected from a halogen atom, preferably simultaneously a chlorine atom or a bromine atom, in particular a chlorine atom; A ^{4 to} A ⁶ are each independently selected from an alkyl group; A methyl group or an ethyl group, particularly an ethyl group is preferred at the same time.
(3) A ^{1 to} A ³ are each independently selected from an alkoxy group having 1 to 2 carbon atoms, and preferably are simultaneously a methoxy group or an ethoxy group, particularly a methoxy group; A ^{4 to} A ⁶ are each independently It is selected from alkoxy groups having 3 to 4 carbon atoms, preferably 2-propoxy group, sec- or tert-butoxy group, particularly tert-butoxy group at the same time.
(4) A ^{1 to} A ³ are each independently selected from an alkoxy group having 1 to 2 carbon atoms, and preferably are simultaneously a methoxy group or an ethoxy group, particularly a methoxy group; A ^{4 to} A ⁶ are each independently It is selected from an alkyl group having 3 to 8 carbon atoms, preferably 3 to 4 carbon atoms, and preferably a 2-propyl group, a sec- or tert-butyl group, particularly a tert-butyl group.

  Among the above combinations, the more preferable combinations are the combinations (1) and (2), particularly the combination (1).

（式中、Ｂは式（Ｉ）のＢと同様であって、後で詳述する通りである）。 Specific examples of the compound of the present invention satisfying the combination (1) are shown below.

(In the formula, B is the same as B in formula (I), and will be described in detail later).

（式中、Ｂは式（Ｉ）のＢと同様であって、後で詳述する通りである）。 Specific examples of the compound of the present invention satisfying the combination (2) are shown below.

(In the formula, B is the same as B in formula (I), and will be described in detail later).

（式中、Ｂは式（Ｉ）のＢと同様であって、後で詳述する通りである）。 Specific examples of the compound of the present invention satisfying the above combination (3) are shown below.

(In the formula, B is the same as B in formula (I), and will be described in detail later).

（式中、Ｂは式（Ｉ）のＢと同様であって、後で詳述する通りである）。 Specific examples of the compound of the present invention satisfying the combination (4) are shown below.

(In the formula, B is the same as B in formula (I), and will be described in detail later).

In the present invention, the combination of A ^{1 to} A ³ and A ^{4 to} A ⁶ is not limited to the above combination as long as the elimination reactivity satisfies the relationship of A ^{1 to} A ³ > A ^{4 to} A ^6. .

  In the formula (I), B is not particularly limited as long as it is a divalent organic group. For example, B may or may not exhibit π electron conjugation. That is, B may be a divalent organic group b1 exhibiting π electron conjugation or a divalent organic group b2 not exhibiting π electron conjugation. When B is a divalent organic group b1 exhibiting π-electron conjugation, the obtained organic thin film exhibits excellent electrical characteristics.

  The divalent organic group b1 showing π electron conjugation is a group derived from a molecule containing a skeleton showing π electron conjugation (π electron conjugate skeleton), for example, a residue obtained by removing two hydrogen atoms from the molecule It is. The π-electron conjugated skeleton is appropriately determined according to desired electrical characteristics, may contain a heterocycle, and / or may have a monocyclic or polycyclic structure. Examples of such a π-electron conjugated skeleton include an aromatic skeleton, a heterocyclic skeleton, and a composite skeleton thereof.

  Examples of the π-electron conjugated skeleton-containing molecule (π-electron conjugated compound) from which the organic group b1 can be derived include, for example, monocyclic aromatic compounds, condensed aromatic compounds, monocyclic heterocyclic compounds, and condensed heterocyclic compounds. A ring compound is mentioned.

Examples of monocyclic aromatic compounds include benzene, toluene, xylene, mesitylene, cumene and the like. Of these, linear ones are preferred. In a monocyclic aromatic compound, the term “linear” refers to a divalent organic group in which two hydrogen atoms in an aromatic ring are separated from each other at a point target position (for example, 1,4-position in benzene) of the compound molecule. It means that it can be.
Examples of the condensed aromatic compound include naphthalene, anthracene, naphthacene, pentacene, hexacene, heptacene, octacene, nonacene, azulene, fluorene, pyrene, acenaphthene, perylene, anthraquinone and the like. Of these, linear ones are preferred. In the condensed aromatic compound, the straight chain means that the aromatic ring is linearly or symmetrically condensed, and preferably two hydrogen atoms in the condensed ring are points of the compound molecule with each other. It can be removed at the target position (for example, 1,6-position in naphthalene) to become a divalent organic group. Specific examples include compounds represented by the following general formulas (α1) to (α3) (wherein n is 0 to 10 in the formula (α1)).

  The compound represented by the formula (α1) is a compound containing an acene skeleton, the compound represented by the formula (α2) is a compound containing an acenaphthene skeleton, and the compound represented by the formula (α3) contains a perylene skeleton. A compound. The number of benzene rings constituting the compound containing the acene skeleton of the above formula (α1) is preferably 2 to 12. In particular, in view of the number of synthesis steps and product yield, naphthalene, anthracene, tetracene, pentacene, hexacene, heptacene, octacene, and nonacene having 2 to 9 benzene rings are particularly preferable.

Examples of the monocyclic heterocyclic compound include furan, thiophene, pyridine, pyrimidine, oxazole and the like. Of these, linear ones are preferred. In a monocyclic heterocyclic compound, a straight-chain is a divalent organic compound in which two hydrogen atoms in a heterocyclic ring are separated from each other at a target point (for example, a 2,5-position in thiophene) of the compound molecule. It means that it can be a group.
Examples of the condensed heterocyclic compound include 5- or 6-membered rings containing heteroatoms such as thiophene, pyridine and furan, or 5- or 6-membered rings containing heteroatoms and an aromatic ring. Compounds. Specific examples include indole, quinoline, acridine, benzofuran and the like. Of these, linear ones are preferred. In the condensed heterocyclic compound, the term “linear” means that the heterocycle and the aromatic ring constituting the compound are condensed in a substantially linear shape or in a substantially symmetrical manner, preferably two in the condensed ring. Can be divalent organic groups by being removed from each other at approximately target positions (for example, 4, 9-positions in indole) of the compound molecule.

  The divalent organic group b2 that does not exhibit π-electron conjugation is a group derived from a molecule containing a skeleton that does not exhibit π-electron conjugation (non-π-electron conjugated skeleton), for example, by removing two hydrogen atoms from the molecule. Residue. Examples of the non-π electron conjugated skeleton include saturated aliphatic skeleton materials.

  Examples of the non-π electron conjugated skeleton-containing molecule capable of deriving the organic group b2 include saturated aliphatic compounds.

  Examples of saturated aliphatic compounds include alkanes. Preferable specific examples of alkanes include, for example, linear alkanes having 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms. Of these, linear ones are preferred.

  The organic group B is two or more selected from the group consisting of the above monocyclic aromatic compounds, condensed aromatic compounds, monocyclic heterocyclic compounds, condensed heterocyclic compounds, and saturated aliphatic compounds In particular, it may be a group derived from a linking compound in which 2 to 30, preferably 2 to 8 compounds are bonded by a single bond. The linking compound is preferably a compound in which two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds are bonded, preferably 2 to 10, and particularly 2 to 8.

  Examples of the compound in which two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds are bonded include compounds in which two or more benzene and / or thiophene are bonded. It is preferable that 2 to 10 benzene and / or thiophene are bonded to form a compound. It is more preferable that 2 to 8 benzene and / or thiophene are bonded in consideration of yield, economy, and mass production.

  Although the compound which comprises a connection type compound may be couple | bonded with the branched form, it is preferable that it couple | bonds with the linear form. Further, at least a part of the compounds constituting the linking compound may be the same or all may be different. Furthermore, in the linking compound, different compounds may be bonded in a regular or random order. In addition, the bonding position of the compound constituting the linking compound is preferably a point target position or a substantially point target position of the compound molecule. For example, in the case of thiophene, the 2,5-position is 1; The 4-position is preferred.

As a specific example of a compound in which two or more monocyclic aromatic compounds are bonded, the following general formula (i):

(Wherein m is an integer of 2 to 30, preferably 2 to 8). The phenylenes may have a substituent such as an alkyl group, an aryl group, or a halogen atom. In the present specification, the compound of the general formula (i) where m = 1 is included and referred to as a phenylene compound.

（式中、ｎは２〜３０、好ましくは２〜８の整数である）で表されるチオフェン類が挙げられる。チオフェン類は、アルキル基、アリール基、ハロゲン原子などの置換基を有していてもよい。本明細書中、ｎ＝１の上記一般式（ｉｉ）の化合物を包含してチオフェン系化合物と称するものとする。 As a specific example of a compound in which two or more monocyclic heterocyclic compounds are bonded, the following general formula (ii);

(Wherein n is an integer of 2 to 30, preferably 2 to 8). Thiophenes may have a substituent such as an alkyl group, an aryl group, or a halogen atom. In the present specification, the compound of the general formula (ii) where n = 1 is included and referred to as a thiophene compound.

  More specifically, as specific examples of a compound in which two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds are bonded, biphenyl (compound of formula i and m = 2), bithiophenyl (compound of formula ii) n = 2 compound), terphenyl (compound of formula iii), tertienyl (compound of formula iv), quaterphenyl (compound of formula i, m = 4), quaterthiophene (compound of formula ii, n = 4), Quinkephenyl (compound of formula i, m = 5), Quinkethiophene (compound of formula ii, n = 5), Hexiphenyl (compound of formula i, m = 6), Hexithiophene (formula ii, n = 6 Compound), thienyl-oligophenylene (see compound of formula v), phenyl-oligo-oligothienylene (see compound of formula vi), block co-oligomer (compound of formula vii or viii) ) Include groups derived from a.

(In the formulas (v) and (vi), n is an integer of 1 to 8; in the formula (vii), a + b is an integer of 2 to 10; in the formula (viii), m is an integer of 1 to 8 .)

  From the viewpoint of the molecular crystallinity of the organic thin film, the organic group B is a monocyclic aromatic compound (particularly benzene), monocyclic, among the π-electron conjugated skeleton-containing molecules and non-π-electron conjugated skeleton-containing molecules. Heterocyclic compounds (especially thiophene), condensed aromatic compounds (especially naphthalene, acene, pyrene, perylene), saturated aliphatic compounds (especially alkanes), or compounds in which two or more of these compounds are bonded, particularly 2-8 It is preferably a group derived from

  From the viewpoint of the conductivity of the organic thin film, the organic group B is a monocyclic aromatic compound, a condensed aromatic compound, a monocyclic heterocyclic compound, a condensed heterocyclic compound, or two or more of these compounds, In particular, a group derived from a compound having 2 to 8 bonds is preferred.

  From the viewpoint of the conductivity of the organic thin film, more preferable organic groups B are monocyclic aromatic compounds (particularly benzene), monocyclic heterocyclic compounds (particularly thiophene), condensed aromatic compounds (particularly naphthalene, acene, pyrene). , Perylene), or a group derived from a compound in which two or more, particularly 2 to 8, of these compounds are bonded.

  From the viewpoint of the conductivity of the organic thin film, the most preferred organic group B is a monocyclic aromatic compound (especially benzene), a monocyclic heterocyclic compound (especially thiophene), or two or more thereof, particularly 2-8. It is a group derived from a single-bonded compound or a condensed aromatic compound (especially acene, pyrene, perylene). Particularly preferred organic groups B are groups derived from thiophene compound derivatives, phenylene compound derivatives, naphthalene derivatives, anthracene derivatives, tetracene derivatives, pyrene derivatives, and perylene derivatives.

The most preferable organic group B will be described in detail from the viewpoint of molecular crystallinity for obtaining an organic thin film in which the organic compound (I) molecule, particularly, the organic group B constituting the molecule is highly aligned.
Such an organic group B is a group derived from a compound molecule (hereinafter simply referred to as compound β) having a distance between adjacent molecules in the crystalline state of about 0.5 nm or less. That is, for example, in an organic thin film obtained by reacting a trichlorosilyl group with a hydroxyl group on the substrate surface in octadecyltrichlorosilane (OTCS), which is a typical organic silane compound that forms a self-assembled film, a siloxane network Si at the substrate interface The distance between adjacent carbon atoms of the carbon atom directly bonded to the Si atom of —O—Si is 0.425 to 0.435 nm in the axial coordination, and 0.49 to 0.50 nm in the equatorial coordination (An Introduction to ULTRATHIN ORGANIC FILMS From Langmuir-Blodgett to Self-Assembly, p256, Abraham Ulman). Therefore, if the organic group B is derived from the compound β whose distance between adjacent molecules in the crystalline state is within the above range, the organic group B is combined with the intermolecular interaction of the organic group B without disturbing the siloxane network. It is possible to form a molecular film that is highly aligned and very stable.

  As the compound β, for example, among the above-mentioned compounds, a linear monocyclic aromatic compound, a linear condensed aromatic compound, a linear monocyclic heterocyclic compound, a linear condensed heterocyclic compound, Examples thereof include linear saturated aliphatic compounds, or linked compounds in which 2 to 30, preferably 2 to 8 of these compounds are bonded. The organic group B is preferably a group derived from such a compound β from the viewpoint of molecular crystallinity.

  Particularly preferred organic group B is a linear monocyclic aromatic compound, a linear monocyclic heterocyclic compound, a linear saturated aliphatic compound, or 2 to 30 of these compounds among the aforementioned compounds. , Preferably a group derived from a linked compound in which 2 to 8 are bonded, or a linear condensed aromatic compound.

Specific examples of linear monocyclic aromatic compounds include, for example, p-biphenyl (2P), p-terphenyl (3P), p-quarterphenyl (4P), p-quinkephenyl (5P), p- Examples include sexiphenyl (6P).
Specific examples of the linear condensed aromatic compound include naphthalene, anthracene, naphthacene, pentacene, and perylene.
Specific examples of the linear monocyclic heterocyclic compound include, for example, α-bithiophene (2T), α-terthiophene (3T), α-quarterthiophene (4T), α-quinkethiophene (5T), α- Examples include sexithiophene (6T) and α-octithiophene (8T).

Specific examples of the linear condensed heterocyclic compound include carbazole, thiochromene, thioxanthene and the like.
Specific examples of the linear saturated aliphatic compound include H— (CH ₂ ) _n —H (n is an integer of 1 to 30).
Specific examples of those linking compounds include 2-methyl-α-quarterthiophene, 2-octyl-α-quarterthiophene, and the like.

  The crystal characteristic value of an example of the compound β in which the distance between adjacent molecules in the crystalline state is within the above range is shown below.

In the table, a, b and c are crystal lattice constants, respectively, and Z is the number of molecules contained in the unit lattice.
The data in the table is based on the following documents.
J.Am.Chem.Soc., 125, 6323 (2003)
J.Mater.Chem., 10, 571 (2000)
Proc. Indian Acad. Sci., 115, Nos5 & 6, 637 (2003)
J. Phys. Chem. B., 108, 8614 (2004)
Cryst.Res.Technol., 36 (1), 47 (2001)
J.Phys.Condens.Matter., 15, 3375 (2003)

  Some of the values in the table exceed the distance range between adjacent molecules described above, but this is only a crystal lattice constant, and the unit cell includes the number of molecules described as Z. Therefore, the distance between adjacent molecules of the compound molecule is within the above range.

  The organic group B may have a functional group at an arbitrary position. 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, and therefore, among these functional groups, an alkyl group having 1 carbon atom is particularly preferable.

  From the viewpoint of achieving a high degree of sequence control of the organic group B, the organic group B preferably has no substituent, and may have a substituent so that the distance between adjacent molecules does not exceed the above range. Examples of such a substituent include a methyl group, an ethyl group, a methoxy group, an ethoxy group, an amino group, and a sulfo group.

  The organic group B is a group as described above, and a siloxane network is formed at both ends as described later, but the organic group B itself does not form a bond between adjacent molecules. Therefore, in the present invention, since the arrangement of the organic group B depends only on the siloxane network at both ends thereof, it is controlled without distortion and the stability is remarkably high. On the other hand, when the organic group B has, for example, an acetylene group and a polyacetylene bond or the like is generated between adjacent molecules, a network of polyacetylene bonds is formed in addition to the siloxane network. As a result, a stable film cannot be formed.

Preferred specific examples of the compound of the present invention are shown below.

(Synthesis method)
The organic compound represented by the general formula (I) (hereinafter sometimes referred to as the organic compound (I)) is a π-electron conjugated skeleton-containing molecule or a non-π conjugated skeleton-containing molecule (hereinafter, these molecules). Can be synthesized by introducing a silyl group into the “organic group B-containing molecule”. The introduction site of the silyl group is not particularly limited as long as the obtained single monomolecular film or monomolecular cumulative film can ensure molecular crystallinity in which molecules are regularly arranged, but is usually at both ends of the molecule. In particular, when the organic group B-containing molecule has a linear shape, silyl groups are introduced at both ends of the molecule. When the organic group B-containing molecule has point symmetry, it is preferable to introduce the silyl group so that the intermediate point of the silyl group introduction site in the general structural formula is the center point of the molecule.

  Silylation of the organic group B-containing molecule can be achieved by various known techniques. For example, (1) reaction of Grignard reagent or lithium reagent obtained from a compound having a halogen atom such as corresponding bromine, chlorine, or iodine with an organosilicon compound having halogen or alkoxy, (2) corresponding carbon-carbon Hydrosilation reaction by heating and stirring a compound having multiple bonds and an organosilicon compound having at least one hydrogen on a silicon atom in the presence of a catalyst such as chloroplatinic acid, and (3) using a palladium catalyst. A reaction in which a vinylboron compound and an organic silicon halide compound are cross-coupled to synthesize a substituted olefin can be used.

More specifically, the following method can be used.
First, as the first method,
(Formula) H-B-MgX (2)
Wherein B is the same as B in the formula (I), and X is a halogen atom;
^{(Formula) Y 1 -Si (A 1)} (A 2) (A 3) (3)
(Wherein Y ¹ is a halogen atom, and A ^{1 to} A ³ are the same as those in formula (I)), and a compound (for example, tetrachlorosilane, tetraethoxysilane) is reacted;
^{(Formula) H-B-Si (A} 1) (A 2) (A 3) (4)
Synthesize
In formula (4), a halogen atom is bonded to B, and reacted with magnesium or lithium metal in the presence of ethoxyethane or tetrahydrofuran (THF) (formula) MgX-B-Si (A ¹ ) (A ² ) ^{(A 3)} or ^{LiX-B-Si (A 1} ) (A 2) (A 3) (5)
After synthesizing the compound represented by
^{(Formula) Y 2 -Si (A 4)} (A 5) (A 6) (6)
(Wherein Y ² is a halogen atom, and A ^{4 to} A ⁶ are the same as those in the above formula (I)), and reacted with a compound (for example, tetraethoxysilane, tetrabutoxysilane, tetramethoxysilane). And a method of obtaining the organic compound (I).

As a second method,
^{(Formula) X 1 -B-X 2 (} 8)
(Wherein B is the same as B in the formula (I), X ¹ and X ² are different from each other and are a halogen atom), and a metal catalyst comprising magnesium or lithium is used. After making the Grignard reactant,
^{(Formula) Y 1 -Si (A 1)} (A 2) (A 3) (3)
(Wherein Y ¹ is a halogen atom, and A ^{1 to} A ³ are the same as those in formula (I)), and a Grignard reactant represented by the following formula (formula) Si (A ¹ ) ^{(A 2) (A 3)} -B-MgX 2 (9)
And then
^{(Formula) Y 2 -Si (A 4)} (A 5) (A 6) (6)
(Wherein Y ² is a halogen atom, and A ^{4 to} A ⁶ are the same as those in the formula (I)) and a compound represented by the formula (9) are reacted to form an organic compound (I ). In the first and second methods, examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

  The reaction temperature during the synthesis is preferably, for example, −100 to 150 ° C., more preferably −20 to 100 ° C. The reaction time is, for example, about 0.1 to 48 hours for each step. The reaction is usually carried out in an organic solvent that does not affect the reaction. Examples of organic solvents that do not adversely affect the reaction include, for example, aliphatic or aromatic hydrocarbons such as hexane, pentane, benzene, and toluene, ether solvents such as diethyl ether, dipropyl ether, dioxane, and tetrahydrofuran (THF), methylene chloride, Chlorinated hydrocarbons such as chloroform and carbon tetrachloride can be used, and these can be used alone or as a mixed solution. 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.

In the first and second methods, Y ¹ preferably has higher elimination reactivity than A ^{1 to} A ³ , and Y ² preferably has higher elimination reactivity than A ^{4 to} A ⁶ . In particular, Y ¹ and Y ² are preferably iodine atoms.

The silyl group can also be introduced by the following method.
For example, first, a Grignard reagent containing the above-mentioned π-electron conjugated skeleton or non-π-electron conjugated skeleton is prepared. A silane compound containing a silyl group having a group (A ^{4 to} A ⁶ ) having relatively low elimination reactivity (eg, tetraethoxysilane, tetrabutoxysilane, tetramethoxysilane, and organic solvent) The silyl group is introduced into one end of the organic group B-containing molecule by reacting at −200 to −60 ° C. for 10 to 30 hours. Subsequently, the obtained compound is converted into a silane compound containing a silyl group having relatively high elimination reactivity (A ^{1 to} A ³ ), for example, tetrachlorosilane, tetraethoxysilane, and -200 in an organic solvent. The silyl group is introduced into the other end of the organic group B-containing molecule by reacting at ~ -60 ° C for 10 to 30 hours. Even if any silyl group is introduced, the organic solvent is not particularly limited as long as it does not inhibit the silylation reaction. For example, aliphatic hydrocarbons such as hexane and pentane, diethyl ether, dipropyl ether, and the like. , Ethers such as dioxane and tetrahydrofuran (THF), aromatic hydrocarbons such as benzene, toluene and nitrobenzene, and chlorinated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride. These can be used alone or as a mixed solution.

A silyl group may be introduced into the organic group B-containing molecule without preparing a Grignard reagent. For example, an organic group B-containing molecule is converted into a silane compound containing a silyl group having a group with relatively low elimination reactivity (A ^{4 to} A ⁶ ), for example, tetraethoxysilane, tetrabutoxysilane, tetramethoxysilane, The silyl group is introduced into one end of the organic group B-containing molecule by reacting in an organic solvent at −200 to −60 ° C. for 10 to 30 hours. Subsequently, the obtained compound is converted into a silane compound containing a silyl group having relatively high elimination reactivity (A ^{1 to} A ³ ), for example, tetrachlorosilane, tetraethoxysilane, and -200 in an organic solvent. The silyl group is introduced into the other end of the organic group B-containing molecule by reacting at ~ -60 ° C for 10 to 30 hours. The same organic solvent as described above is used.

  The organic compound of the present invention synthesized by such a method 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. Can do.

  Next, an example of a method for synthesizing a compound containing two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds or an acene skeleton suitable as a precursor of the organic group B will be described.

(1) Compound in which two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds are bonded An example of a method for synthesizing a compound consisting only of benzene or thiophene is shown in the following (A) to (C). In addition, in the synthesis example of the compound which consists only of the following thiophene, only the reaction from the trimer of thiophene to 6 or 7-mer was shown. However, by reacting with thiophene having a different number of units, compounds 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 for obtaining a block-type compound 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. As a synthesis example in this case, the following method can be applied.

First, after a predetermined position of simple benzene or simple thiophene compound is halogenated (for example, brominated), it can be debrominated and boronated by adding 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 halogen groups (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 block-type compound can be synthesized.
An example of a synthetic route for the compounds (D) and (E) using such a reaction is shown below.

As a synthesis method of a compound in which a unit derived from benzene or thiophene and a vinyl group (unsaturated aliphatic compound) 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 compound 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 compound has a methyl group at the terminal, for example, if this methyl group is further brominated and the above synthetic route is applied again, a compound having a larger number of units can be formed.
An example of a synthesis route for compounds (F) to (H) 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, if 2-octadecyl terthiophene is used as a raw material, 2-octadecyl sexual thiophene can be obtained as compound (A) by the above synthesis route. 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 (H) 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.

(2) Compound containing acene skeleton As a method for synthesizing a compound containing an acene skeleton, for example, (1) after substituting a hydrogen atom bonded to two carbon atoms at a predetermined position of a raw material compound with an ethynyl group, Examples include a method of repeating a ring-closing reaction and (2) a method in which a hydrogen atom bonded to a carbon atom at a predetermined position of a raw material compound is substituted with a triflate group, reacted with furan or a derivative thereof, and subsequently oxidized. It is done. An example of a method for synthesizing an acene skeleton using these methods is shown below.
Method (1)

Method (2)

  Further, in the above method (2), since the benzene rings of the acene skeleton are increased one by one, for example, even if a predetermined part of the raw material compound contains a low-reactivity functional group or protective group, the acene skeleton is similarly applied. Can be synthesized. An example of this case is shown below.

  Ra and Rb are preferably a functional group having a low reactivity such as a hydrocarbon group or an ether group, or a protective group.

  Further, in the reaction formula of the above method (2), the starting compound having two acetonitrile groups and a trimethylsilyl group may be changed to a compound in which these groups are all trimethylsilyl groups. Further, in the above reaction formula, after the reaction using the furan derivative, the reaction product is refluxed under lithium iodide and DBU (1,8-diazabicyclo [5.4.0] undec-7-ene). A compound having one more benzene ring than the starting compound and two hydroxyl groups substituted 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. For example, tetracene is available from Tokyo Kasei with a purity of 97% or more.

(Organic thin film and method for forming the same)
The organic thin film of the present invention is formed using the organic compound (I), and is a siloxane-based molecular film (hereinafter sometimes simply referred to as an organic thin film) characterized by having a siloxane network on the film surface. is there. Specifically, as shown in FIG. 2, the monomolecular film formed from the organic compound (I) has not only the two-dimensional siloxane network 2a on the substrate side but also the two-dimensional siloxane network 2b on the film surface side. . Both the two-dimensional siloxane network 2a and the two-dimensional siloxane network 2b are formed in a substantially parallel direction with respect to the substrate 1 as a whole. Therefore, the intermolecular interaction necessary for ordering the film in a highly efficient manner works efficiently, so that it has very high stability, and the organic compound (I) molecule, particularly its organic group B, is highly sequence controlled. Is done. That is, since the same siloxane network is formed at both ends of the organic group B, the alignment is effectively controlled and oriented. Moreover, the orientation is less distorted compared to a film in which a siloxane network is not formed on the film surface or a film in which polyacetylene or the like is formed on the film surface. In addition, since the organic thin film of the present invention is immobilized on the substrate by chemical bonding, for example, compared with a film produced by physical adsorption on the substrate, it effectively prevents physical peeling and the physical strength of the film. Can be improved. In addition, a dense film having excellent surface smoothness and strength can be formed as compared with a film in which a siloxane network is not formed on the film surface.

The organic thin film of the present invention may have a structure of a single monomolecular film or a monomolecular cumulative film. In the case of a monomolecular cumulative film, at least the most substrate side of the monomolecular films constituting the film. These monomolecular films and the monomolecular film closest to the film surface, preferably all monomolecular films may be formed from the organic compound (I). As described above, all monomolecular films formed from the organic compound (I) have a two-dimensional siloxane network on both the substrate side and the film surface side. For example, when the bilayer monomolecular film is a bilayer cumulative film formed from the organic compound (I), as shown in FIG. 3, each monomolecular film is also provided on the substrate side (2a, 3a). The film surface side (2b, 3b) also has a two-dimensional siloxane network. The two-dimensional siloxane network on the substrate side is based on the silyl group of organic compound (I); -Si (A ¹ ) (A ² ) (A ³ ), and the two-dimensional siloxane network on the film surface side is an organic compound. silyl group ^(I); is based on ^{-Si (a 4) (a 5} ) (a 6).

Hereinafter, preferred embodiments of the organic thin film will be described.
When a preferable organic thin film has a structure of a single monomolecular film having one monomolecular film on the substrate, the monomolecular film is formed using the organic compound (I). In the case of having a monomolecular cumulative film structure having n (n is an integer of 2 or more) monomolecular films sequentially, all monomolecular films are formed using the organic compound (I). In the case where the organic thin film has a monomolecular cumulative film structure, the numbers of the monomolecular films are given in order from the substrate side.

  The organic compound (I) that forms the first to nth monomolecular films in the case where the organic thin film has a monomolecular cumulative film structure may be selected independently within the above range for each film. For example, the organic compound (I) used may be the same for some or all of the films, or may be different for all of the films.

  The substrate can be appropriately selected depending on the use of the organic thin film. For example, elemental semiconductors such as silicon and germanium, semiconductors such as compound semiconductors such as GaAs, InGaAs, and ZnSe; glass, quartz glass; polyimide, polyethylene, polyethylene terephthalate (PET), polytetrafluoroethylene, PEN, PES, and Teflon (registered) Insulating polymer film such as trademark); stainless steel (SUS); metal such as gold, platinum, silver, copper and aluminum; refractory metal such as titanium, tantalum and tungsten; silicide with refractory metal, polycide, etc. Insulators such as silicon oxide (thermal silicon oxide, low temperature silicon oxide: LTO, high temperature silicon oxide: HTO), silicon nitride, SOG, PSG, BSG, BPSG; PZT, PLZT, ferroelectric or antiferroelectric; SiOF material, SiOC material or CF material Is an HSQ (hydrosilsesquioxane) material (inorganic), MSQ (methyl silsesquioxane) material, PAE (polyylene ether) material, BCB material, porous material or CF material or porous material formed by coating Examples thereof include a substrate made of a material such as a low dielectric material. Furthermore, so-called SOI substrates, multilayer SOI substrates, SOS substrates, and the like can also be used. These substrates may be used alone or in a plurality of layers. For example, the substrate may be made of an inorganic substance used as an electrode of a semiconductor device, and a film made of an organic substance may be formed on the surface thereof. In the present invention, it is preferable that the substrate surface has a hydrophilic group such as a hydroxyl group or a carboxyl group, particularly a hydroxyl group, and if it does not, a hydrophilic group may be imparted to the substrate surface by subjecting the substrate to a hydrophilic treatment. . The hydrophilic treatment of the substrate can be performed by immersion in a hydrogen peroxide solution-sulfuric acid mixed solution, irradiation with ultraviolet light, or the like.

Even when the organic thin film has a structure of a single monomolecular film or a monomolecular cumulative film, in the monomolecular film formed using the organic compound (I), the organic compound molecules are A ^{1 to} A ^3. A silyl group having an A ⁴ (hereinafter sometimes referred to as a highly reactive silyl group) is oriented toward the substrate side, and a silyl group having an A ^{4 to} A ⁶ (hereinafter sometimes referred to as a low reactive silyl group) is on the film surface side. Are aligned so as to be oriented.

  Therefore, for example, in the case of having a structure of a single monomolecular film, at the monomolecular film-substrate interface, highly reactive silyl groups are chemically bonded (particularly silanol bonds (-Si-O--) by reaction with hydrophilic groups on the substrate surface. )) And simultaneously form siloxane bonds between adjacent molecules to form a siloxane network 2a (eg, FIG. 1). On the other hand, a low-reactivity silyl group exists on the film surface side, and a siloxane network 2b is formed by forming a siloxane bond between adjacent molecules by subsequent pH treatment described in detail later (for example, FIG. 2).

  Further, for example, when the substrate has a monomolecular cumulative film structure having the first and second monomolecular films sequentially, formation of a siloxane bond is formed in the siloxane network 2b on the film surface side of the single monomolecular film. Therefore, the second monomolecular film is formed with the hydroxyl group as a reaction site. That is, at the first monomolecular film-second monomolecular film interface, the highly reactive silyl group of the second monomolecular film reacts with a hydroxyl group on the surface of the first monomolecular film to form a chemical bond (particularly a silanol bond (-Si-O -)) And simultaneously form siloxane bonds between adjacent molecules to form the siloxane network 3a (eg, FIGS. 3 and 5A and 5B). On the other hand, the low-reactivity silyl group of the second monomolecular film is present on the film surface side, and a siloxane bond is formed between adjacent molecules to form a siloxane network 3b by subsequent pH treatment described in detail later ( For example, FIG. 3 and FIG. 5 (A) and (B)).

  In addition, for example, when the substrate has a monomolecular cumulative film structure having first to n-th (n is an integer of 3 or more) monomolecular films in sequence, the siloxane on the film surface side of the above two-layer monomolecular cumulative film Since the network 3b has a hydroxyl group that has not contributed to the formation of the siloxane bond, the third to nth monomolecular films are formed using the hydroxyl group as a reaction site. The arrangement structure of the third to nth monomolecular films is the same as that of the second monomolecular film of the two-layer monomolecular cumulative film.

  In particular, when the organic thin film has a monomolecular cumulative film structure and all the monomolecular films are formed of the organic compound (I), the lowermost monomolecular film is bonded to the substrate through a chemical bond, particularly a silanol bond. The other monomolecular films are sequentially formed through chemical bonds, particularly siloxane bonds, with the monomolecular film immediately below.

In the monomolecular film formed using the organic compound (I), the arrangement of the organic compound (I) molecules as described above indicates the elimination reactivity of the two silyl groups possessed by the organic compound (I) at both ends. This is achieved by controlling. As a result, a single monomolecular film having a uniform film thickness and molecular crystallinity in which molecules are arranged in an orderly manner and its accumulated film can be manufactured with good reproducibility. That is, in order for the silylated organic compound to be bonded via a silanol bond or a siloxane bond, the functional group bonded to the silyl group needs to be eliminated and replaced with a hydroxyl group or a proton. In the present invention, by utilizing the difference in elimination reactivity of two silyl groups, a group having relatively high elimination reactivity (A ^{1 to} A ³ ) in ^one silyl group is selectively replaced with a hydroxyl group or proton. And is reacted with a hydroxyl group (or carboxyl group) on the surface of the substrate or the monomolecular film immediately below. As a result, the silyl group having A ^{1 to} A ³ groups is oriented to the substrate side, and a silanol bond or a siloxane bond is formed. The other silyl group has only a group (A ^{4 to} A ⁶ ) having relatively low elimination reactivity, and such a group is not substituted with a hydroxyl group or a proton, so that it reacts with a substrate or a monomolecular film immediately below. Not oriented to the film surface side. In addition, the silyl group having such A ^{4 to} A ⁶ groups is activated by ph treatment described in detail later, and a siloxane network on the film surface side is formed. At this time, hydroxyl groups that have not contributed to the formation of siloxane bonds exist in the siloxane network on the film surface side, and are thus used as reaction sites. As a result, since the compound molecules are arranged in the same direction in each monomolecular film, it is possible to form single monomolecular films having a more uniform film thickness and better molecular crystallinity and their accumulated films. If each of the silyl groups at both ends has a group having a relatively high elimination reactivity, each monomolecular film is partially bi- and tri-molecularly formed in the thickness direction. Therefore, the desired molecular crystallinity cannot be achieved.

  When the organic thin film is a single monomolecular film, the film thickness can be appropriately adjusted depending on the type of the organic group B. For example, about 1 nm to 12 nm, and further considering economy and mass production, 1 nm to About 3.5 nm is preferable. The film thickness in the case of the monomolecular film is approximately c × d when the film thickness of the monomolecular film is c and the cumulative number is d layers. When preparing thin films with different functions for each monomolecular film, the molecular structure and film thickness of the monomolecular film may vary depending on the function. It can be appropriately adjusted according to the above.

  In such a monomolecular film or a cumulative monomolecular film, the organic compound (I) is easily self-assembled, and a siloxane network is formed on the substrate side and the film surface side of each monomolecular film. A thin film in which units (molecules) are oriented in the direction of That is, a highly crystallized organic thin film can be obtained by minimizing the distance between adjacent units, and as a result, an organic thin film exhibiting conductivity in a direction perpendicular to the substrate surface can be obtained.

  In addition, since Si in the adjacent organic compound (I) molecule is crosslinked as it is or through an oxygen atom, for example, a Si—O—Si network is formed, and the distance between adjacent units is small and more advanced. Is crystallized. In particular, when the units are arranged in a straight line, adjacent units do not interfere with each other, and the distance between adjacent units can be minimized to obtain a highly crystallized material. it can. By such unit orientation, an organic thin film exhibiting semiconductor characteristics in the surface direction of the substrate can be obtained.

  As described above, a thin film having electrical anisotropy having different electrical characteristics in the vertical direction and the surface direction with respect to the substrate surface can be obtained.

A method for forming an organic thin film using the organic compound (I) will be briefly described with reference to the drawings.
In forming the organic thin film, first, using the organic compound (I), the silyl group having A ^{1 to} A ³ in the compound is reacted with the substrate surface by a method such as LB method, dipping method, coating method or the like. 1 monomolecular film is formed. The organic compound (I) has two silyl groups having different elimination reactivity of contained groups (A ^{1 to} A ³ and A ^{4 to} A ⁶ ) at both ends. The silyl group having (A ^{1 to} A ³ ) is selectively bonded to the substrate surface, and at the same time, a siloxane bond is formed between adjacent molecules to form a siloxane network. For example, FIG. 1 is a conceptual diagram of a single monomolecular film when the compound of the general formula (a1) is used, in which a chlorine atom having a relatively high elimination reactivity is substituted with a hydroxyl group and has the group. Siloxane groups are selectively bonded to the substrate surface to form the siloxane network 2a. In FIG. 1, the functional group bonded to the terminal silyl group on the film surface (air interface) side is not easily desorbed, so that no adsorption reaction with other molecules or the substrate occurs.

In the present invention, in order to selectively bond a silyl group having a relatively high elimination reactivity group (A ^{1 to} A ³ ) to the substrate, the high elimination reactivity group is selectively hydroxyl group or Replace with proton. To do so, by utilizing a difference in reactivity of each group ^(A 1 ^{~A 6)} by the reaction conditions, it may be changed solvent atmosphere and the reaction temperature and the like at the time of film formation. For example, the proton concentration in the solvent can be adjusted and the reactivity can be controlled by changing the pH when the solvent is water, or by using a hydroxylated solvent when the solvent is an organic solvent.
For example, when a monomolecular film is formed by an LB method described later using an organic compound in which A ^{1 to} A ³ are halogen atoms and A ^{4 to} A ⁶ are alkoxy groups, the pH of water is set to 7. By adjusting, only A ^{1 to} A ³ can be substituted with hydroxyl groups. When a monomolecular film is formed by the dipping method described later using the organic compound, A ^{1 to} A ³ can easily be converted into a hydroxyl group due to the presence of a small amount of water in the organic solvent in which the organic compound is dissolved. Since it is substituted, it is not always necessary to adjust pH and the like.
For example, when a monomolecular film is formed by an LB method described later using an organic compound in which A ^{1 to} A ³ are ethoxy groups and A ^{4 to} A ⁶ are butoxy groups, the pH of water is 4 By adjusting to ^1, only A ^{1 to} A ³ can be substituted with hydroxyl groups.

In the LB method (Langmuir Brodget method), the organic compound (I) is dissolved in an organic solvent, and the obtained solution is dropped on the water surface whose pH is adjusted to form a thin film on the water surface. At this time, the group (A ^{1 to} A ³ ) having relatively high elimination reactivity in the silyl group at one end of the organic compound is converted into a hydroxyl group by hydrolysis. Next, silyl having a group (A ^{1 to} A ³ ) having relatively high elimination reactivity in an organic compound by applying pressure on the water surface in this state and pulling up the substrate having a hydrophilic group (particularly a hydroxyl group) on the surface. A siloxane network is formed between adjacent molecules while bonding the group to the substrate, and a monomolecular film as shown in FIG. 1 is obtained.

In the dipping method and the coating method, first, the organic compound (I) is dissolved in an organic solvent. For example, the organic compound (I) is dissolved in a non-aqueous organic solvent such as hexane, chloroform or carbon tetrachloride to obtain a solution having a concentration of about 1 mM to 100 mM. A substrate having a hydrophilic group (especially a hydroxyl group) on the surface is immersed in the obtained solution and pulled up. Alternatively, the resulting solution is coated on the substrate surface. At this time, the group (A ^{1 to} A ³ ) having relatively high elimination reactivity in the silyl group at one end of the organic compound is hydrolyzed and converted into a hydroxyl group by a small amount of water in the organic solvent. Next, by holding for a predetermined time, a siloxane group having relatively high elimination reactivity (A ^{1 to} A ³ ) in the organic compound is bonded to the substrate, and a siloxane network is formed between adjacent molecules. A monomolecular film as shown in FIG. 1 is obtained.

  After forming a monomolecular film having a low-reactive silyl group on the film surface side, for example, as shown in FIG. 1, the unreacted organic compound is usually washed away from the monomolecular film using a non-aqueous solvent. .

Next, the monomolecular film having a low-reactivity silyl group on the film surface side is subjected to pH treatment to cause hydrolysis reaction and dehydration condensation reaction of the unreacted silyl group (low-reactivity silyl group) present on the film surface side. A siloxane network is formed (eg, FIG. 2). In the pH treatment, for example, the substrate on which the monomolecular film is formed is immersed in water having a relatively low pH. By this, the group (A ^{4 to} A ⁶ ) having a relatively low elimination reactivity that the low-reactive silyl group present on the film surface side in the monomolecular film has a hydrolysis reaction and a dehydration condensation reaction associated therewith, A siloxane network is formed on the film surface side. At this time, for example, as shown in FIG. 2, since the siloxane network on the film surface side has a hydroxyl group, it is used as a reaction site for forming the next monomolecular film. The details of the mechanism by which the siloxane network on the film surface side has a hydroxyl group are not clear, but are thought to be based on the following mechanism. That is, before the pH treatment, a siloxane network is already formed on the substrate side of the monomolecular film, and the organic groups B are oriented with a certain degree of order, so that the behavior of the silyl groups on the film surface side is restricted. When pH treatment is performed in such a state, two hydroxyl groups out of the hydroxyl groups converted from the A ^{4 to} A ⁶ groups have a relatively high contact probability with the hydroxyl group of the silyl group of the adjacent molecule. Although a bond is formed, the remaining one hydroxyl group is considered to remain as it is because the probability of contact with the other hydroxyl group is relatively low. For example, in FIGS. 2 and 3, etc., the siloxane network on the film surface side has one hydroxyl group per silicon atom, but these are schematic views only, that is, not all silicon atoms are necessarily 1 It does not have to have two hydroxyl groups. As long as the object of the present invention is achieved, for example, all three hydroxyl groups that one silicon atom may have contribute to the formation of a siloxane network, and there may be silicon atoms that do not have a hydroxyl group.

The conditions for the pH treatment are not particularly limited as long as the low-reactive silyl group of the organic compound (I) molecule forming the monomolecular film can be hydrolyzed to convert A ^{4 to} A ⁶ into a hydroxyl group. The hydrolysis reaction may be accelerated by raising the water temperature.
For example, when the low-reactive silyl group is a trimethoxysilyl group, the pH of the treated water is suitably about pH 3-4 and a temperature of 20-40 ° C.
Further, for example, when the low-reactive silyl group is a triethoxysilyl group, pH 2 to 3 and a temperature of 25 to 40 ° C. are suitable for the pH-treated water.
Further, for example, when the low-reactive silyl group is a tripropoxysilyl group, the pH-treated water is suitably pH 1-2 and temperature 25-40 ° C.
In addition, for example, when the low-reactive silyl group is a tributoxysilyl group, pH 1 and a temperature of 40 to 60 ° C. are appropriate for the pH-treated water.
Further, for example, when the low-reactive silyl group is a trimethylsilyl group, the pH-treated water is suitably pH 2-3 and temperature 25-40 ° C.
Further, for example, when the low-reactivity silyl group is a triethylsilyl group, the pH of the treated water is suitably pH 1-2 and the temperature 25-40 ° C.
Further, for example, when the low-reactivity silyl group is a tripropylsilyl group, pH 1 and a temperature of 40 to 60 ° C. are suitable for the pH-treated water.

  After obtaining a single monomolecular film in which a siloxane network is formed on the film surface side, an unreacted organic compound is usually washed away from the monomolecular film using a non-aqueous solvent. After removal, the organic thin film is fixed by washing with water and leaving it to dry by heating. This thin film may be used as an organic thin film as it is, or may be further subjected to treatment such as electrolytic polymerization.

  When forming a monomolecular accumulation film, the monomolecular film made of organic compound (I) is accumulated using the unreacted hydroxyl group present on the film surface side of the previously formed single monomolecular film as the site of the adsorption reaction. Let The organic compound used here may be the same as or different from that used for the already formed monomolecular film among the organic compounds (I).

  The accumulated monomolecular film is formed according to the same method as the LB method, dipping method, and coating method.

  FIG. 3 is an example of a two-layer cumulative film composed of two monomolecular films. In FIG. 3, the monomolecular film is accumulated on the monomolecular film of FIG. 2 using the same organic compound as that constituting the film, but the accumulated monomolecular film is used in the film immediately below. It may be made of a different material from the organic compound.

When the accumulated monomolecular film is made of the organic compound (I), the above process is repeated to sequentially and uniformly prepare monomolecular films of the same or different organic compound (I) on the substrate. be able to. In any monomolecular film, the organic compound (I) has a silyl group having a group (A ^{1 to} A ³ ) having a relatively high elimination reactivity and the surface of the monomolecular film or the surface of the monomolecular film directly below the substrate. Since they are bonded, the resulting thin film has a uniform film thickness and excellent molecular crystallinity. In the present invention, the effect of the present invention can be obtained even when a cumulative film is formed by laminating 2 to 20 monomolecular films, particularly 2 to 10 layers. The total film thickness at that time depends on the length of the compound molecule to be used and thus cannot be defined unconditionally, but is usually 4 to 300 nm, particularly 4 to 100 nm.

  In the organic thin film as described above, the monomolecular film made of the organic compound (I) is a self-assembled film that aggregates by non-covalent bonds such as van der Waals, electrostatic and π-π stacking interactions. A highly oriented film can be easily adjusted by utilizing the self-organizing property of molecules.

(Use)
The organic compound (I) of the present invention is useful for applications that can make use of film thickness uniformity and / or excellent molecular crystallinity (alignment), such as organic devices, optical elements, and coating agents. In particular, as an organic layer (thin film) constituent material in organic devices such as organic thin film transistors, organic photoelectric conversion elements, and organic electroluminescence elements, by selecting the organic group B of the organic compound (I) to be one that exhibits π electron conjugation Useful.

For example, the organic thin film using the organic compound (I) of the present invention can be selected by selecting the type of the organic group B (particularly the presence or absence of heteroatoms) and the type of functional group (electron withdrawing type or electron donating type group). For example, it is used as a thin film constituting an organic thin film transistor such as a TFT, a conductive material constituting a light emitting element, a solar cell, a fuel cell, a sensor, a photoconductive material (photoconductor), a nonlinear optical material, an insulating material, etc. Can do. In addition, since an enzyme or the like can be bound as a ligand by holding a functional group at the terminal, it can also be used as a biosensor. Below, the more specific application example of the organic thin film of this invention is described.
・ TFT semiconductor layer and insulating layer (region between source and drain)
-Films between electrodes of organic EL elements and organic phosphorescent light emitting elements (light emitting layer, electron injection layer, hole injection layer, hole transport layer, electron transport layer, etc.)
-A film between electrodes of an organic semiconductor laser (for example, a current injection laser such as a diode) (holes and electrons injected from each electrode are recombined on the organic thin film to emit light, and the resulting light is emitted. (It can be taken out from a certain direction)
-P-type semiconductor layer and n-type semiconductor layer of a solar cell (Since an organic thin film has photoexcitation characteristics, a p-n junction can be formed by stacking p-type and n-type materials as thin films. Can be formed) as well as exciton block layer, fuel cell separator, gas sensor gas molecule or odor sensor odor component adsorption film (if organic thin film is placed on comb electrode, organic film conductivity by gas molecule adsorption) A gas sensor that evaluates the concentration of gas molecules can be formed by changing
・ Ion sensitive membranes of ion sensors ・ Sensitive membranes of biosensors (for example, immunosensors) (utilizing enzyme selectivity in organic thin films)

(Organic device)
The organic device of the present invention may be any type of device as long as it has an organic thin film formed using the organic compound (I). For example, organic semiconductors such as organic thin film transistors, organic photoelectric conversion elements, and organic EL elements Device. Since such an organic semiconductor device has an organic thin film excellent in film thickness uniformity and molecular crystallinity, a device with few carrier traps between domains can be manufactured.

(Organic thin film transistor)
The organic thin film transistor includes at least a substrate, a gate electrode formed on the substrate, a gate insulating film formed on the gate electrode, and a source electrode provided in contact with or without contact with the gate insulating film, It has a drain electrode and a semiconductor layer.
In the present invention, the transistor may have various configurations such as a bottom contact type, a top-and-bottom contact type, and a top contact type depending on the arrangement of the source electrode, the drain electrode, and the semiconductor layer.

  A schematic cross-sectional configuration diagram of an example of the top contact transistor is illustrated in FIG. The transistor in FIG. 6A includes a substrate 25, a gate electrode 24 formed on the substrate 25, a gate insulating film 23 formed on the gate electrode 24, and a semiconductor layer formed on the gate insulating film 23. 20 and a source electrode 21 and a drain electrode 22 formed on the semiconductor layer 20 so as to be separated from each other.

  A schematic cross-sectional configuration diagram of an example of a top-and-bottom contact transistor is shown in FIG. 6B, the source electrode 21 is formed on a part of the surface of the gate insulating film 23, and the semiconductor layer 20 is formed on the surface of the source electrode 21 and the remaining part of the gate insulating film 23. The drain electrode 22 is formed on a part of the surface of the semiconductor layer 20 and the surface of the drain electrode 22 and the remaining surface of the semiconductor layer 20 form one plane. It has the same structure.

  A schematic cross-sectional configuration diagram of an example of the bottom contact transistor is illustrated in FIG. In the transistor of FIG. 6C, the source electrode 21 and the drain electrode 22 are formed on the gate insulating film 23 with a space therebetween, and the source electrode and the drain electrode 22 are formed on the gate insulating film 23 between the source electrode 21 and the drain electrode 22. The transistor has the same structure as the transistor in FIG. 6A except that the semiconductor layer 20 is formed in contact with the drain electrode.

In FIGS. 6A to 6C, the same reference numerals indicate common members.
In the present invention, the semiconductor layer 20 and / or the gate insulating film 23 is an organic thin film formed using the organic compound (I), and has a structure of a single monomolecular film or a monomolecular cumulative film. Specifically, the semiconductor layers in FIGS. 6A, 6B, and 6C may have a single monomolecular film structure or a monomolecular cumulative film structure, and preferably have a monomolecular cumulative film structure.

When the semiconductor layer has a single monomolecular film structure, the monomolecular film is formed using the organic compound (I). The monomolecular film is not particularly limited as long as it is formed from the organic compound (I) within the above range. Among them, the organic group B is a monocyclic aromatic compound, a monocyclic heterocyclic compound, a condensed system. An organic group which is a group derived from an aromatic compound, a condensed heterocyclic compound or a compound in which two or more of these compounds are bonded, particularly a group derived from a phenylene compound derivative, a thiophene compound derivative, a perylene derivative or a pentacene derivative It is preferably formed from compound (I). At this time, A ^{1 to} A ⁶ are not particularly limited and may be the same as described above. Such a monomolecular film is bonded to the gate insulating film directly below via a chemical bond.

When the semiconductor layer has a monomolecular cumulative film structure, the cumulative number of monomolecular films is not particularly limited, but is usually 2 to 20 layers, preferably 2 to 10. The monomolecular cumulative film as the semiconductor layer is formed of at least one monomolecular film, preferably all monomolecular films, using the organic compound (I).
For example, the lowermost monolayer of the two-layer cumulative film is a compound in which the organic group B is a monocyclic heterocyclic compound, a condensed aromatic compound or a compound in which two or more of these compounds are bonded, particularly a thiophene compound derivative or a perylene derivative. , Formed from the organic compound (I) which is a group derived from a pentacene derivative (A ^{1 to} A ⁶ are not particularly limited, and may be the same as described above). Is formed from the organic compound (I) which is a group derived from a monocyclic heterocyclic compound, a condensed aromatic compound or a compound in which two or more of these compounds are bonded, particularly a thiophene compound derivative, a perylene derivative or a pentacene derivative. It is preferable.
Further, for example, the lowermost monolayer of the three-layer cumulative film is a compound in which the organic group B is a monocyclic heterocyclic compound, a condensed aromatic compound or a compound in which two or more of these compounds are bonded, particularly a thiophene compound derivative or a perylene derivative. , Formed from the organic compound (I) which is a group derived from a pentacene derivative (A ^{1 to} A ⁶ are not particularly limited and may be the same as described above), and the monolayer of the second layer has an organic group B Monocyclic heterocyclic compounds, condensed aromatic compounds or compounds in which two or more of these compounds are bonded, in particular organic compounds (I) (A ¹ to (A ¹ ) which are groups derived from thiophene compound derivatives, perylene derivatives, pentacene derivatives) A ⁶ is not particularly limited, and may be the same as described above. In the third monolayer, the organic group B is a monocyclic heterocyclic compound, a condensed aromatic compound or a compound thereof. Pieces Compounds above bound, formed in particular thiophene compound derivative, perylene derivative, an organic compound is a group derived from pentacene derivative (I) (A ¹ ~A ⁶ is not particularly limited, and may be the same as above) It is preferable.

For example, when the semiconductor layer is a cumulative film of 2 to 20 layers, all monomolecular films may be formed of the same organic compound (I). In this case, the same organic compound (I) constituting all monomolecular films is a compound in which the organic group B is a monocyclic heterocyclic compound, a condensed aromatic compound or a compound in which two or more of these compounds are bonded, particularly a thiophene type. It is preferably a group derived from a compound derivative, a perylene derivative, or a pentacene derivative (A ^{1 to} A ⁶ are not particularly limited and may be the same as described above).

  Whether the semiconductor layer has a single monomolecular film or a monomolecular cumulative film, a dopant may be added to each monomolecular film. As the dopant, those known in the field of organic thin film transistors can be used, and examples thereof include halogen, iodine, and alkali metal.

  The monomolecular film formed using the organic compound (I) in the semiconductor layer of the transistor of the present invention is bonded to the film immediately below through a chemical bond. In particular, when all the monomolecular films of the monomolecular cumulative film are formed using the organic compound (I), all the monomolecular films are bonded to the film immediately below through a chemical bond.

  The monomolecular film not containing the organic compound (I) in the semiconductor layer of the transistor may be made of any organic compound, for example, a π-electron conjugate capable of inducing the organic group B exemplified in the description of the organic compound (I). It may consist of sex skeleton-containing molecules.

  As a method for producing the semiconductor layer, the monomolecular film made of the organic compound (I) may be formed by employing a method similar to the method for forming the organic thin film. The monomolecular film not containing the organic compound (I) may be formed by employing a method such as spin coating, casting, dip coating, or LB. Although the thickness of each monomolecular film constituting the semiconductor layer depends on the molecular length and cannot be defined unconditionally, it is suitably 4 to 300 nm, particularly 4 to 100 nm.

When the gate insulating film has a single monomolecular film structure, the monomolecular film is formed using the organic compound (I). The single monomolecular film is not particularly limited as long as it is formed from the organic compound (I) within the above range, but among the above, it is formed from the organic compound (I) in which the organic group B is a linear saturated aliphatic compound. It is preferable that At this time, A ^{1 to} A ⁶ are not particularly limited and may be the same as described above. Such a monomolecular film is bonded to the substrate through a chemical bond.
When the gate insulating film has a monomolecular cumulative film structure, the cumulative number of monomolecular films is not particularly limited, but is usually 2 to 20 layers, preferably 2 to 10.
For example, when the gate insulating film is a cumulative film of 2 to 20 layers, all the monomolecular films may be formed of the same organic compound (I).
The monomolecular film formed using the organic compound (I) in the gate insulating film in the transistor of the present invention is bonded to the film immediately below through a chemical bond. In particular, when all the monomolecular films of the monomolecular cumulative film are formed using the organic compound (I), all the monomolecular films are bonded to the film immediately below through a chemical bond.
As a manufacturing method of the gate insulating film, the monomolecular film made of the organic compound (I) may be formed by adopting the same method as the organic thin film forming method. The monomolecular film not containing the organic compound (I) may be formed by employing a method such as spin coating, casting, dip coating, or LB. Although the thickness of each monomolecular film constituting the gate insulating film depends on the molecular length and cannot be specified unconditionally, it is suitably 4 to 300 nm, particularly 4 to 100 nm.

For the substrate 25, the gate electrode 24, the gate insulating film 23, the source electrode 21 and the drain electrode 22, well-known materials conventionally used in the field of organic transistors can be used.
Specifically, the substrate is made of, for example, a Si wafer or glass.
The gate insulating film is made of, for example, silicon oxide, silicon nitride, aluminum oxide, or the like, and can be formed by a method such as vapor deposition or CVD. The thickness of the gate insulating film is not particularly limited, but is usually selected from 50 to 1000 nm.
The gate electrode, the source electrode, and the drain electrode are each independently, for example, conductive metal oxide such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), gold, silver, aluminum, chromium, nickel, etc. It is made of metal and can be formed by methods such as vapor deposition, CVD, and sputtering. The film thickness of these electrodes is not particularly limited, but is usually selected independently from 10 to 100 nm.

(Organic photoelectric conversion element)
As shown in FIG. 7, the organic photoelectric conversion element has an organic layer 35 between the transparent electrode 31 and the counter electrode 32. In the present invention, the organic layer 35 uses the organic compound (I). It is the formed organic thin film.

That is, the organic layer 35 is composed of at least the photoconductive layers 33 and 34. From the viewpoint of improving the conversion efficiency, the photoconductive layer 35 is composed of an electron acceptor layer 33 and p that function as an n-type photoconductive layer as shown in FIG. It is preferably composed of an electron donor layer 34 that functions as a type photoconductive layer.
The n-type photoconductive layer 33 and the p-type photoconductive layer 34 that can constitute the organic layer 35 in the photoelectric conversion element of the present invention may each have a structure of a single monomolecular film or a monomolecular cumulative film, The organic layer 35 as a whole has a monomolecular cumulative film structure. In the present invention, at least one monomolecular film constituting the organic layer, preferably all monomolecular films are formed using the organic compound (I).

Specifically, the n-type photoconductive layer 33 has a single monomolecular structure, and the organic group B is a perylene derivative, a perinone derivative, a naphthalene derivative, a fluorine-substituted monocyclic heterocyclic compound, or a condensed aromatic compound. Or a compound in which two or more of these compounds are bonded, particularly a perylene derivative, a group derived from a fluorine-substituted oligothiophene derivative (I) (A ^{1 to} A ⁶ are not particularly limited, and are the same as above. It is preferable that it is formed from the above. When the n-type photoconductive layer 33 has a monomolecular cumulative film structure, all the monomolecular films constituting the cumulative film are formed from the preferred organic compound (I) in the case of having a single monomolecular film structure. It is preferable that all the monomolecular films may be formed from the same organic compound (I). The thickness of the n-type photoconductive layer is not particularly limited, but is suitably 4 to 300 nm, particularly 4 to 100 nm.

The p-type photoconductive layer 34 has a structure of a single monomolecular film, and the organic group B includes two or more monocyclic aromatic compounds, monocyclic heterocyclic compounds, condensed aromatic compounds, or compounds thereof. It is formed from organic compounds (I) (A ^{1 to} A ⁶ are not particularly limited and may be the same as described above) which is a group derived from a bonded compound, particularly a phenylene compound derivative or a thiophene compound derivative. It is preferable. When the p-type photoconductive layer 34 has a monomolecular cumulative film structure, all the monomolecular films constituting the cumulative film are formed from the preferred organic compound (I) in the case of having a single monomolecular film structure. It is preferable that all the monomolecular films may be formed from the same organic compound (I). The thickness of the p-type photoconductive layer is not particularly limited, but 4 to 300 nm, particularly 4 to 100 nm is suitable.

  The monomolecular film formed using the organic compound (I) in the organic layer 35 in the photoelectric conversion element of the present invention is bonded to the film or electrode directly below via a chemical bond. In particular, when all the monomolecular films in all the layers are formed using the organic compound (I), all the monomolecular films are bonded to the film or electrode directly below through a chemical bond.

  The monomolecular film not containing the organic compound (I) in the organic layer of the photoelectric conversion element may be composed of any organic compound, for example, π capable of inducing the organic group B exemplified in the description of the organic compound (I). It may consist of an electron conjugated skeleton-containing molecule.

  As a method for producing a photoelectric conversion element, a monomolecular film made of the organic compound (I) among monomolecular films constituting the organic layer 35 may be formed by employing a method similar to the method for forming the organic thin film. The monomolecular film not containing the organic compound (I) may be formed by employing a method such as spin coating, casting, dip coating, or LB.

For the transparent electrode 31 and the counter electrode 32, a known material conventionally used in the field of photoelectric conversion elements can be used.
The transparent electrode is preferably made of, for example, glass or plastic coated with a conductive metal oxide such as ITO.
The counter electrode is preferably, for example, (metal such as platinum, gold, or aluminum, or conductive metal oxide such as ITO).
Although the thickness of a transparent electrode and a counter electrode is not specifically limited, Usually, it is 50-1000 nm each independently.

(Organic EL device)
As shown in FIG. 8, the organic EL element has an organic layer 48 between an anode 41 and a cathode 42. In the present invention, the organic layer 48 is formed using the organic compound (I). Organic thin film.

That is, the organic layer 48 is composed of at least the light emitting layer 43 and may have an electron transport layer 45 and a hole transport layer 44 formed adjacent to the light emitting layer 43 as desired. Further, the organic layer 48 has a hole injection layer (not shown) between the anode 41 and the hole transport layer 44 and an electron injection layer (shown between the cathode 42 and the electron transport layer 45) from the viewpoint of improving the light emission efficiency. (Not shown).
In the EL device of the present invention, the light emitting layer 43, the electron transport layer 45, the hole transport layer 44, the hole injection layer, and the electron injection layer that can constitute the organic layer 48 are each a single monomolecular film or a monomolecular cumulative film. The organic layer 48 as a whole has a monomolecular cumulative film structure. In the present invention, at least one monomolecular film constituting the organic layer, preferably all monomolecular films are formed using the organic compound (I).

Specifically, the light emitting layer 43 is a layer having a function of emitting light in which holes injected from the hole transport layer 44 and electrons injected from the electron transport layer 45 move and the holes and electrons recombine. Such a light-emitting layer 43 has a single monomolecular film structure, and the organic group B is a group derived from a condensed aromatic compound, an oligothiophene derivative, particularly a condensed aromatic compound (I) ( A ^{1 to} A ⁶ are not particularly limited and may be the same as described above. In the case where the light emitting layer has a monomolecular cumulative film structure, all the monomolecular films constituting the cumulative film are formed of the preferred organic compound (I) in the case of having a single monomolecular film structure. It is preferable that all the monomolecular films may be formed from the same organic compound (I). The thickness of the light emitting layer is not particularly limited, but is suitably 4 to 300 nm, particularly 4 to 100 nm.

The hole transport layer 44 and the hole injection layer are layers having a function of increasing the efficiency of hole injection from the anode 41 to the light emitting layer 43 and preventing electrons from escaping to the anode 41. Each of the hole transport layer 44 and the hole injection layer has a single monomolecular film structure, and the organic group B is a monocyclic heterocyclic compound, a condensed aromatic compound, or two of these compounds. It is formed from organic compounds (I) (A ^{1 to} A ⁶ are not particularly limited and may be the same as described above), which is a group derived from the above bonded compounds, particularly phenylene compound derivatives and thiophene compound derivatives. Preferably it is. In the case where the hole transport layer 44 and the hole injection layer have a monomolecular cumulative film structure, all the monomolecular films constituting the cumulative film have the structure of a single monomolecular film. Preferably, it is formed from I), and all monomolecular films may be formed from the same organic compound (I). The thicknesses of the hole transport layer and the hole injection layer are not particularly limited, but are independently 4 to 300 nm, particularly 4 to 100 nm.

The electron transport layer 45 and the electron injection layer are layers having a function of increasing the efficiency of electron injection from the cathode 42 to the light emitting layer 43. Each of the electron transport layer 45 and the electron injection layer has a single monomolecular structure, and the organic group B is a perylene derivative, a perinone derivative, a naphthalene derivative, a fluorine-substituted monocyclic heterocyclic compound, a condensed Group aromatic compounds or compounds in which two or more of these compounds are bonded, particularly perylene derivatives, organic compounds (I) which are groups derived from fluorine-substituted oligothiophene derivatives (A ^{1 to} A ⁶ are not particularly limited, It may be the same as described above. When the electron transport layer 45 and the electron injection layer have a monomolecular cumulative film structure, the preferable organic compound (I) when all the monomolecular films constituting the cumulative film have a single monomolecular film structure. Preferably, all monomolecular films may be formed from the same organic compound (I). The thicknesses of the electron transport layer and the electron injection layer are not particularly limited, but are independently 4 to 300 nm, particularly 4 to 100 nm.

  The monomolecular film formed using the organic compound (I) in the organic layer 48 in the EL element of the present invention is bonded to the film or electrode directly below via a chemical bond. In particular, when all the monomolecular films in all the layers are formed using the organic compound (I), all the monomolecular films are bonded to the film or electrode directly below through a chemical bond.

  The monomolecular film not containing the organic compound (I) in the organic layer of the EL element may be composed of any organic compound, for example, π electrons capable of inducing the organic group B exemplified in the description of the organic compound (I). It may consist of a conjugated skeleton-containing molecule.

  As a method for manufacturing an EL element, a monomolecular film made of the organic compound (I) among monomolecular films constituting the organic layer 48 may be formed by employing a method similar to the method for forming the organic thin film. The monomolecular film not containing the organic compound (I) may be formed by employing a method such as spin coating, casting, dip coating, or LB.

For the anode 41, an electrically conductive compound of metal or alloy having a high hole injection capability and a relatively large work function is used. Examples of such compounds include gold, copper iodide, tin oxide, ITO and the like. Among these, a substance having a high transmittance in the visible light region is preferable, and ITO is most preferable.
For the cathode 42, a metal or an alloy (for example, 4 eV or less) having a relatively small work function is used. Examples of such compounds include alkali metals, alkaline earth metals and Group III metals such as gallium and indium, but magnesium that is inexpensive and relatively chemically stable is most widely used. Since magnesium is easily oxidized, a mixture with an antioxidant is more preferable.
The thicknesses of the anode and the cathode are not particularly limited, but are preferably independently 10 nm to 5 μm.

Experimental example 1
<Synthesis Example 1: Synthesis of disilylated quarterthiophene (hereinafter referred to as thiophene (a1)) represented by the general formula (a1)>

In order to chlorinate 2,2′-bithiophene (492-97-7), it was treated with NBS and chloroform in acetic acid to carry out chlorination (intermediate 1). By directly reacting chlorinated bithiophenes with tris (triphenylphosphine) nickel (tris (triphenylphosphine) nickel: (PPh ₃ ) 3Ni) in a DMF solvent, the bithiophenes are directly bonded to each other at the chlorinated portion. Then, quarterthiophene was synthesized.

A 1 liter glass flask is charged with 1 equivalent of quarterthiophene, 1 equivalent of triethoxybromosilane, (hexane / diethyl ether) mixed solution (300 ml) under a dry nitrogen stream, and 1 equivalent of t-butyllithium is brought to -78 ° C. After dropping from the dropping funnel over 12 hours, the mixture was warmed to room temperature once the dropping was completed, and then cooled again to -196 ° C. The reaction solution was distilled to obtain a triethoxysilylated quarterthiophene colorless liquid as a fraction.
The obtained triethoxysilylated quarterthiophene was dissolved in a toluene solvent, and 1 equivalent of t-butyllithium was added dropwise at 0 ° C. over 10 hours. After completion of dropping, the mixture was stirred at room temperature for 12 hours to obtain a suspension. The suspension was dropped into a toluene solution mixed with 1 equivalent of tetrachlorosilane at −78 ° C. over 10 hours. After completion of dropping, the flask was removed from the cooling bath, and stirring was further performed for 6 hours.
After removing lithium chloride as a precipitate by filtration, (a1) was obtained by filtration under reduced pressure.

The result of the instrumental analysis of the obtained thiophene (a1) is shown.
¹ H NMR (δ CDCl ₃ ):
7.00 ppm (m, 8H, C ₄ H ₂ S)
3.83 ppm (m, 6H, C ₂ H ₅ )
1.22 ppm (m, 9H, C ₂ H ₅ )
_{UV-Vis: 400nm (C 4} H 2 S)
From the above measurement results, it was confirmed that this compound had the structure of the general formula (a1).

<Synthesis Example 2: Synthesis of disilylated hexythiophene (hereinafter referred to as thiophene (a3)) represented by the general formula (a3)>
Using the method shown in Synthesis Example 1, hexthiophene was synthesized by two-step coupling of bithiophene.

A 1 liter glass flask was charged with 1 equivalent of hexythiophene, 1 equivalent of triethoxybromosilane, (hexane / diethyl ether) mixed solution (300 ml) under a dry nitrogen stream, and 1 equivalent of t-butyllithium at −80 ° C. Was added dropwise over 12 hours from the dropping funnel, and after the completion of dropping, the mixture was once warmed to room temperature and then cooled again to -180 ° C. The reaction solution was distilled to obtain a triethoxysilylated colorless liquid of hexthiophene as a fraction.
The obtained triethoxysilylated hexthiophene was dissolved in a toluene solvent, and 1 equivalent of t-butyllithium was added dropwise at 0 ° C. over 10 hours. After completion of the dropping, stirring was performed at room temperature for 20 hours to obtain a suspension. The suspension was dropped into a toluene solution mixed with 1 equivalent of tetrachlorosilane at −80 ° C. over 10 hours. After completion of dropping, the flask was removed from the cooling bath, and stirring was further performed for 6 hours.
After removing lithium chloride as a precipitate by filtration, (a3) was obtained by vacuum filtration.

The result of the instrumental analysis of the obtained thiophene (a3) is shown.
¹ H NMR (δ CDCl ₃ ):
7.00 ppm (m, 12H, C ₄ H ₂ S)
3.83 ppm (m, 6H, OC ₂ H ₅ )
1.22 ppm (m, 9H, OC ₂ H ₅ )
_{UV-Vis: 439nm (C 4} H 2 S)
From the above measurement results, it was confirmed that this compound had the structure of the general formula (a3).

<Example 1: A single film consisting only of a monomolecular film of thiophene (a1), a single film consisting only of a monomolecular film of thiophene (a3), and a monomolecular film of thiophene (a1) and thiophene (a3) Manufacture of bilayer cumulative film consisting of monomolecular film>
Production Method A substrate obtained by immersing a Si wafer and a quartz glass substrate in a (hydrogen peroxide / sulfuric acid) mixed solution and subjecting it to hydrophilic treatment by irradiation with ultraviolet light and thoroughly washing with pure water was used as the substrate. Film formation was performed using the prepared substrate. Subsequently, the following steps (1) to (4) were performed to form the title monomolecular film and the two-layer cumulative film.

Step (1);
First, a 0.2 mM toluene solution of thiophene (a1) is developed on the water surface at pH = 7, and an adsorption reaction on the substrate accompanying the elimination of the chlorine atom in the trichlorosilyl group is performed using the LB method. A monomolecular film (a1) was prepared. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.
Step (2) (pH treatment);
Next, the thiophene (a1) monomolecular film is immersed in water at pH = 2 and a water temperature of 25 ° C. to cause hydrolysis reaction and condensation reaction of the triethoxysilyl group of thiophene (a1). A thiophene (a1) monomolecular film having a siloxane network was formed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Step (3);
Separately, a monomolecular film of thiophene (a3) was obtained by the same method as in the above step (1), except that thiophene (a3) was used and the hydrolysis reaction of trichlorosilyl group was carried out under conditions of pH = 7 and water temperature of 25 ° C. Was prepared. Next, thiophene (a3) in which a siloxane network is formed on the film surface by the same method as in the above step (2) except that the hydrolysis and condensation reaction of the triethoxysilyl group was performed under conditions of pH = 2 and water temperature of 25 ° C. ) Monomolecular film was prepared. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Step (4);
Next, a 0.2 mM toluene solution of thiophene (a3) is spread on the water surface at pH = 5, and is deposited on the monomolecular film of thiophene (a1) prepared by the above process by the LB method. Formed. By carrying out under the condition of pH = 5, the adsorption reaction proceeds by hydrolysis reaction and condensation reaction of silanol group (hydroxyl group) and trichlorosilyl group of thiophene (a3) which were not provided to the siloxane network of thiophene (a1). . Furthermore, a cumulative film having a siloxane network formed on the film surface was formed by the same method as in the above step (2) except that the hydrolysis reaction of the triethoxysilyl group was carried out under the conditions of pH = 2 and water temperature of 25 ° C. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Film evaluation [film thickness confirmation]
Using the monomolecular bilayer film of thiophene (a1) and (a3) as a sample, the surface morphology of the accumulated film was observed at 50 μm size with an atomic force microscope (AFM) (SPA400; manufactured by Seiko Instruments Inc.). The film was uniformly formed. Since the mean square roughness of the film is 0.39 nm, which is not significantly different from the value of 0.26 nm for only Si as the substrate, it can be said that the film has high uniformity. When the film was cut by mechanical treatment, the film thickness was about 6 nm corresponding to the sum of the molecular lengths of quarterthiophene and hexythiophene. From this, it was found that a monomolecular bilayer film having a uniform film thickness was prepared.

[Main skeleton confirmation]
In order to evaluate the accumulated state of the film in detail, a single film consisting only of a monomolecular film of thiophene (a1), a single film consisting only of a monomolecular film of thiophene (a3), and thiophenes (a1) and (a3) The UV-visible absorption spectrum was measured using (UV-3000; manufactured by Shimadzu Corp.) as a sample of the monomolecular bilayer film. As a result, the monomolecular film of thiophene (a1) has a peak at around 400 nm, the monomolecular film of thiophene (a3) has a peak at around 440 nm, and the monomolecular bilayer films of thiophene (a1) and (a3) have peaks at around 400 and 440 nm, respectively. Absorption with position was observed.

[Confirmation of crystallinity]
The crystal arrangement was evaluated based on electron diffraction (ED) measurement by “H-7500; manufactured by Hitachi, Ltd.”. As a sample, a single film consisting only of a monomolecular film of thiophene (a1), a single film consisting only of a monomolecular film of thiophene (a3), and a monomolecular bilayer film of thiophene (a1) and (a3) are used. It was. As a substrate for performing ED measurement, a substrate obtained by adhering a form bar film as a support film to a copper mesh sheet and having SiO ₂ deposited for surface hydrophilization treatment was used. As a result, the monomolecular film of thiophene (a1) corresponds to a diffraction spot corresponding to a plane spacing of 0.40 and 0.34 nm, and the monomolecular film of thiophene (a3) corresponds to a plane spacing of 0.42 and 0.36 nm. In the diffraction spot and the monomolecular bilayer film of thiophene (a1) and (a3), diffraction spots corresponding to the plane spacings of 0.40 and 0.34 nm, 0.42 and 0.36 nm were observed, respectively. From this, it was found that not only each single film but also a monomolecular bilayer cumulative film, a film having a high order of crystal arrangement could be prepared.

[Confirmation of siloxane network formation on film surface]
In order to confirm whether or not a siloxane network on the film surface was formed by the pH treatment, infrared absorption spectrum measurement before and after the pH treatment was performed. Note that before and after the pH treatment in the monomolecular bilayer film of thiophene (a1) and (a3) is before and after the last pH treatment.
First, as a result of performing an infrared absorption spectrum measurement of a thiophene (a1) monomolecular film, a thiophene (a3) monomolecular film, and a bilayer cumulative film composed of thiophene (a1) and thiophene (a3) before pH treatment, each ^{1290cm -1, 1280cm -1,} absorption derived from stretching vibration of C-O was observed at 1290cm ^-1.
On the other hand, after pH treatment, infrared of a thiophene (a1) monomolecular film having a siloxane network formed on the film surface, a thiophene (a3) monomolecular film, and a two-layer cumulative film composed of thiophene (a1) and thiophene (a3) As a result of the absorption spectrum measurement, the absorption derived from the above-mentioned CO disappeared, and broad absorption centered on 3300 cm ⁻¹ was confirmed. This absorption is derived from the stretching vibration of OH.

  Static water of a thiophene (a1) monomolecular film, a thiophene (a3) monomolecular film, and a bilayer cumulative film composed of thiophene (a1) and thiophene (a3) having a siloxane network formed on the film surface after pH treatment When the contact angles were measured, they were 22 °, 23 °, and 25 °, respectively.

From these facts, it can be said that the alkoxy group on the film surface is converted to a hydroxyl group by the pH treatment.
Furthermore, by the above crystallinity confirmation, a single film consisting only of the monomolecular film of thiophene (a1), a single film consisting only of the monomolecular film of thiophene (a3), and thiophenes (a1) and (a3) The interplanar spacing of each monomolecular bilayer film was 0.5 nm or less. Si (OH) ₃ is very reactive, and at the above intermolecular distance, a siloxane bond can be easily formed by a dehydration reaction between hydroxyl groups between adjacent molecules.
That is, in the above, in both the monomolecular film and the two-layered cumulative film, it was confirmed that absorption derived from C—O disappeared due to pH treatment, and absorption of OH occurred. It can be said that a functional siloxane network is formed.

<Example 2: Production of a monomolecular film of thiophene (a1) and a cumulative film of 2 to 5 layers>
Step (1);
First, the hydrophilic substrate prepared by the method shown in Example 1 was immersed in a 0.01 mM toluene solution of thiophene (a1) at room temperature for 12 hours. A monomolecular film of thiophene (a1) was prepared by the reaction between the hydroxyl group present on the substrate surface and the trichlorosilyl group. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.
Step (2) (pH treatment);
Next, the thiophene (a1) monomolecular film is immersed in water at pH = 2 and a water temperature of 25 ° C. to cause hydrolysis reaction and condensation reaction of the triethoxysilyl group of thiophene (a1). A thiophene (a1) monomolecular film having a siloxane network was formed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Step (3);
Next, the substrate on which the thiophene (a1) monomolecular film was formed in the step (2) was immersed in a 0.01 mM toluene solution of thiophene (a1) at 50 ° C. for 12 hours. The hydroxyl group present on the substrate surface and the trichlorosilyl group reacted to prepare a second thiophene (a1) monomolecular film on the lowermost monomolecular film. Furthermore, a siloxane network was formed on the film surface by the same method as in the above step (2) except that the hydrolysis reaction of the triethoxysilyl group was carried out under conditions of pH = 2 and a water temperature of 25 ° C. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Step (4);
Further, by repeating the step (3) for forming the second monomolecular film described above three times, a five-layer cumulative film in which five monomolecular films of thiophene (a1) are laminated is prepared. did.

Film evaluation [film thickness confirmation]
Using a 2-5 layer cumulative film of thiophene (a1) as a sample, the surface morphology of the cumulative film was observed at 50 μm size with an atomic force microscope (AFM) (SPA400; manufactured by Seiko Instruments Inc.). It was formed uniformly.
Since the mean square roughness of the film is 0.42 nm, which is not significantly different from the value of 0.26 nm of only Si as the substrate, it can be said that the uniformity of the film is high. When the film was cut by mechanical treatment, the film thickness was 5 nm for the two-layer film, 7.5 nm for the three-layer film, 10 nm for the four-layer film, and 12.5 nm for the five-layer film. It was equivalent to the cumulative number of lengths. From this, it was found that a monomolecular bilayer film having a uniform film thickness was prepared.

[Main skeleton confirmation]
In order to evaluate the accumulated state of the film in detail, a single monomolecular film of thiophene (a1) and a 2 to 5 layer accumulated film were used as samples, and UV-visible absorption spectrum was obtained by (UV-3000; manufactured by Shimadzu Corporation). Measurements were made. As a result, absorption having a peak position near 350 nm was observed in all the films.

[Confirmation of crystallinity]
The crystal arrangement was evaluated based on electron diffraction (ED) measurement by “H-7500; manufactured by Hitachi, Ltd.”. As a sample, a single monomolecular film of thiophene (a1) and a two- to five-layer cumulative film were used. As a substrate for performing ED measurement, a substrate obtained by adhering a form bar film as a support film to a copper mesh sheet and having SiO ₂ deposited for surface hydrophilization treatment was used. As a result, diffraction spots corresponding to plane spacings of 0.40 and 0.34 nm were observed in all films. From this, it was found that not only a single film but also a 2-5 layer cumulative film, a film having a high order of crystal arrangement could be prepared.

[Confirmation of siloxane network formation on film surface]
In order to confirm whether or not a siloxane network on the film surface was formed by the pH treatment, infrared absorption spectrum measurement before and after the pH treatment was performed. Note that before and after the pH treatment in the two- to five-layer cumulative film of thiophene (a1) is before and after the last pH treatment.
First, as a result of measuring the infrared absorption spectrum of each film before pH treatment, absorption derived from stretching vibration of C—O was confirmed at 1290 cm ⁻¹ .
On the other hand, after the pH treatment, the infrared absorption spectrum of each film was measured. As a result, the absorption derived from the C—O disappeared and broad absorption centered on 3300 cm ⁻¹ was confirmed. This absorption is derived from the stretching vibration of OH.

  When the static contact angles of pure water of the monomolecular film of thiophene (a1) having a siloxane network formed on the film surface after pH treatment and the accumulated film of two to five layers were measured, they were 22 °, 22 °, and 23 °, respectively. 23 ° and 25 °.

From these facts, it can be said that the alkoxy group on the film surface is converted to a hydroxyl group by the pH treatment.
Furthermore, according to the above crystallinity confirmation, the interplanar spacing of the monomolecular film of thiophene (a1) and the two-layer to five-layer cumulative film was 0.5 nm or less. Si (OH) ₃ is very reactive, and at the above intermolecular distance, a siloxane bond can be easily formed by a dehydration reaction between hydroxyl groups between adjacent molecules.
That is, in the above, in both the monomolecular film of thiophene (a1) and the two-layer to five-layer cumulative film, it can be confirmed that absorption due to C—O disappeared by pH treatment and absorption of OH occurred. From this, it can be said that a hydrophilic siloxane network is formed on the film surface.

[Electrical characteristics confirmation]
Based on the in-plane electrical AFM measurement, the electrical characteristics of the single film and the 2-5 layers cumulative film were evaluated. FIG. 4 is a schematic diagram of the measurement system. Electrical characteristics were evaluated using a mica having a comb-shaped electrode produced by depositing several tens of nanometers of gold / chrome as a substrate. In the figure, 10 is an SPM device piezo element, 11 is a cantilever, 12 is a single or cumulative film, 13 is a gold / chrome electrode, 14 is a mica substrate, and 15 is an ammeter measuring means.
The current characteristics from the electrode interface in the in-plane direction showed a good tendency as the cumulative number increased, and was about 10 ⁻⁴ S · cm ⁻¹ for the single film, whereas for the five-layer cumulative film A large value of about 40 ⁻³ S · cm ⁻¹ was exhibited. From this, it is possible to improve the electrical characteristics by preparing a highly oriented cumulative film, and the accumulation of monomolecular films using the compounds of the present invention can be used to control the film thickness for higher performance of organic devices. Useful knowledge can be given.

Experimental Example 2;
<Synthesis Example 3: Synthesis of disilylated terphenyl represented by general formula (b2) (hereinafter referred to as terphenyl (b2))>
A 1 liter glass flask was charged with 1 equivalent of terphenyl, 1 equivalent of triethoxybromosilane, and 300 ml of a chloroform solution under a dry nitrogen stream, and 1 equivalent of t-butyllithium was added from a dropping funnel at -78 ° C. for 12 hours. The mixture was added dropwise, and after the completion of the addition, the mixture was once warmed to room temperature and then cooled again to -196 ° C. The reaction solution was distilled to obtain a triethoxysilylated terphenyl colorless liquid as a fraction.

The obtained triethoxysilylated terphenyl was dissolved in a toluene solvent, and 1 equivalent of t-butyllithium was added dropwise at 0 ° C. over 10 hours. After completion of dropping, the mixture was stirred at room temperature for 12 hours to obtain a suspension. The suspension was dropped into a toluene solution mixed with 1 equivalent of tetrachlorosilane at −78 ° C. over 10 hours. After completion of dropping, the flask was removed from the cooling bath, and stirring was further performed for 6 hours.
After removing lithium chloride as a precipitate by filtration, terphenyl (b2) was obtained by vacuum filtration.

The result of the instrumental analysis of the obtained terphenyl (b2) is shown.
¹ H NMR (δ CDCl ₃ ):
_{7.30~7.54ppm (m, 12H, C 6} H 4)
1.49 ppm (m, 6H, C ₂ H ₅ )
0.90 ppm (m, 9H, C ₂ H ₅ )
UV-Vis: 261 nm (Ph)
From the above measurement results, it was confirmed that this compound had the structure of the general formula (b2).

<Synthesis Example 4: Synthesis of disilylated terphenyl represented by general formula (b8) (hereinafter referred to as terphenyl (b8))>

  A 1-liter glass flask was charged with 1 equivalent of terphenyl, 1 equivalent of tri-t-butoxybromosilane, and 300 ml of chloroform mixed solution under a dry nitrogen stream, and 1 equivalent of t-butyllithium was added dropwise at -78 ° C. The solution was dropped from the funnel over 12 hours, and after completion of the dropping, the mixture was once warmed to room temperature and then cooled again to -190 ° C. The reaction solution was distilled to obtain a tri-t-butoxysilylated terphenyl colorless liquid as a fraction.

The obtained tri-t-butoxysilylated terphenyl was dissolved in a toluene solvent, and 1 equivalent of t-butyllithium was added dropwise at 0 ° C. over 10 hours. After completion of dropping, the mixture was stirred at room temperature for 12 hours to obtain a suspension. The suspension was dropped into a toluene solution mixed with 1 equivalent of tetrachlorosilane at −80 ° C. over 10 hours. After completion of dropping, the flask was removed from the cooling bath, and stirring was further performed for 6 hours.
After removing lithium chloride as a precipitate by filtration, terphenyl (b8) was obtained by filtration under reduced pressure.

The result of the instrumental analysis of the obtained terphenyl (b8) is shown.
¹ H NMR (δ CDCl ₃ ):
_{7.30~7.54ppm (m, 12H, C 6} H 6)
3.83 ppm (m, 6H, C ₂ H ₅ )
1.32 ppm (m, 6H, OC ₄ H ₉ )
1.22 ppm (m, 9H, C ₂ H ₅ )
UV-Vis: 259 nm (Ph)
From the above measurement results, it was confirmed that this compound had the structure of the general formula (b8).

<Example 3: A single film consisting only of a monomolecular film of terphenyl (b2), a single film consisting only of a monomolecular film of terphenyl (b8), and a monomolecular film and terphenyl of terphenyl (b2) Production of Bilayer Accumulated Film Consisting of Monomolecular Film of (b8)>
Production Method A substrate obtained by immersing a Si wafer and a quartz glass substrate in a (hydrogen peroxide / sulfuric acid) mixed solution and subjecting it to hydrophilic treatment by irradiation with ultraviolet light and thoroughly washing with pure water was used as the substrate. Film formation was performed using the prepared substrate. Subsequently, the following steps (1) to (4) were performed to form the title monomolecular film and the two-layer cumulative film.

Step (1);
First, a 0.2 mM toluene solution of terphenyl (b2) is developed on the water surface of pH = 7, and an adsorption reaction on the substrate accompanying desorption of chlorine atoms in the trichlorosilyl group is performed using the LB method. A monomolecular film of terphenyl (b2) was prepared. The obtained substrate was washed with an organic solvent to remove the remaining unreacted terphenyl.
Step (2) (pH treatment);
Next, the terphenyl (b2) monomolecular film is immersed in water at pH = 2 and a water temperature of 25 ° C. to cause hydrolysis reaction and condensation reaction of the triethoxysilyl group of terphenyl (b2). A terphenyl (b2) monomolecular film having a siloxane network formed on the surface was formed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted terphenyl.

Step (3);
Separately, terphenyl (b8) was used in the same manner as in the above step (1), except that terphenyl (b8) was used and the triethoxysilyl group hydrolysis reaction was carried out under conditions of pH = 2 and water temperature of 25 ° C. A molecular film was prepared. Next, terphenyl having a siloxane network formed on the film surface by the same method as in the above step (2), except that the hydrolysis and condensation reaction of the tributoxysilyl group was carried out under the conditions of pH = 1 and water temperature of 50 ° C. A monomolecular film of b8) was prepared. The obtained substrate was washed with an organic solvent to remove the remaining unreacted terphenyl.

Step (4);
Next, a 0.2 mM toluene solution of terphenyl (b8) is developed on the water surface at pH = 2, and is deposited on the monomolecular film of terphenyl (b2) prepared by the above process by the LB method. A film was formed. By carrying out the reaction under the condition of pH = 2, the adsorption reaction is a hydrolysis reaction and condensation reaction of silanol group (hydroxyl group) and triethoxysilyl group of terphenyl (b8) that have not been supplied to the siloxane network of terphenyl (b2). To proceed. Furthermore, a cumulative film having a siloxane network formed on the film surface was formed by the same method as in the above step (2) except that the hydrolysis reaction of the tributoxysilyl group was performed under the conditions of pH = 1 and water temperature of 50 ° C. The obtained substrate was washed with an organic solvent to remove the remaining unreacted terphenyl.

Film evaluation [film thickness confirmation]
Using the monomolecular bilayer film of terphenyl (b2) and (b8) as a sample, the surface morphology of the accumulated film was observed at 50 μm size with an atomic force microscope (AFM) (SPA400; manufactured by Seiko Instruments Inc.). The film was uniformly formed. Since the mean square roughness of the film is 0.35 nm, which is not significantly different from the value of 0.26 nm for only Si as the substrate, it can be said that the film has high uniformity. When the film was cut by mechanical treatment, the film thickness was about 2.8 nm corresponding to the molecular length of two terphenyl molecules. From this, it was found that a monomolecular bilayer film having a uniform film thickness was prepared.

[Main skeleton confirmation]
In order to evaluate in detail the cumulative state of the film, a single film consisting only of a monomolecular film of terphenyl (b2), a single film consisting only of a monomolecular film of terphenyl (b8), and terphenyl (b2) and Using the monomolecular bilayer film of (b8) as a sample, UV-visible absorption spectrum measurement was performed using (UV-3000; manufactured by Shimadzu Corporation). As a result, the monomolecular film of terphenyl (b2) is around 260 nm, the monomolecular film of terphenyl (b8) is around 260 nm, and the monomolecular bilayer film of terphenyl (b2) and (b8) is around 260 nm. Absorption with a peak position was observed.

[Confirmation of crystallinity]
The crystal arrangement was evaluated based on electron diffraction (ED) measurement by “H-7500; manufactured by Hitachi, Ltd.”. As a sample, a single film consisting only of a monomolecular film of terphenyl (b2), a single film consisting only of a monomolecular film of terphenyl (b8), and a monomolecular bilayer of terphenyl (b2) and (b8) A membrane was used. As a substrate for performing ED measurement, a substrate obtained by adhering a form bar film as a support film to a copper mesh sheet and having SiO ₂ deposited for surface hydrophilization treatment was used. As a result, a diffraction spot corresponding to a surface spacing of 0.41 and 0.35 nm is obtained for the monomolecular film of terphenyl (b2), and a surface spacing of 0.41 and 0.35 nm is also obtained for the monomolecular film of terphenyl (b8). In the corresponding diffraction spot and the monomolecular bilayer film of terphenyl (b2) and (b8), diffraction spots corresponding to a plane spacing of 0.41 and 0.35 nm were observed, respectively. From this, it was found that not only each single film but also a monomolecular bilayer cumulative film, a film having a high order of crystal arrangement could be prepared.

[Confirmation of siloxane network formation on film surface]
In order to confirm whether or not a siloxane network on the film surface was formed by the pH treatment, infrared absorption spectrum measurement before and after the pH treatment was performed. In addition, before and after the pH treatment in the monomolecular bilayer film of terphenyl (b2) and (b8) is before and after the last pH treatment.
First, before the pH treatment, infrared absorption spectrum measurement of a terphenyl (b2) monomolecular film, a terphenyl (b8) monomolecular film, and a bilayer cumulative film composed of terphenyl (b2) and terphenyl (b8) was performed. results went, respectively ^{1285 -1,} 1285 -1, absorption derived from stretching vibration of C-O was observed at 1290cm ^-1.
On the other hand, after the pH treatment, a terphenyl (b2) monomolecular film having a siloxane network formed on the film surface, a terphenyl (b8) monomolecular film, and a two-layer accumulation comprising terphenyl (b2) and terphenyl (b8) As a result of measuring the infrared absorption spectrum of the film, the absorption derived from C—O disappeared, and broad absorption centered on 3300 cm ⁻¹ was confirmed. This absorption is derived from the stretching vibration of OH.

  Pure terphenyl (b2) monomolecular film, terphenyl (b8) monomolecular film having a siloxane network formed on the film surface after pH treatment, and a bilayer cumulative film composed of terphenyl (b2) and terphenyl (b8) When the static contact angles of water were measured, they were 24 °, 26 °, and 28 °, respectively.

From these facts, it can be said that the alkoxy group on the film surface is converted to a hydroxyl group by the pH treatment.
Furthermore, by the above crystallinity confirmation, a single film consisting only of the monomolecular film of terphenyl (b2), a single film consisting only of the monomolecular film of terphenyl (b8), and terphenyl (b2) and The interplanar spacing of the monomolecular bilayer film of (b8) was 0.5 nm or less. Si (OH) ₃ is very reactive, and at the above intermolecular distance, a siloxane bond can be easily formed by a dehydration reaction between hydroxyl groups between adjacent molecules.
That is, in the above, in both the monomolecular film and the two-layered cumulative film, it was confirmed that absorption derived from C—O disappeared due to pH treatment, and absorption of OH occurred. It can be said that a functional siloxane network is formed.

<Example 4: Preparation of organic thin film transistor and evaluation of electrical characteristics>
An organic thin film transistor of the type shown in FIG. 9 was produced.
First, chromium / gold was vapor-deposited on the silicon substrate 25 to produce the gate electrode 24. Next, a gate insulating film 23 made of a silicon oxide film was deposited by chemical vapor deposition. Further, chromium / gold was vapor-deposited using a mask, and the source electrode 21 and the drain electrode 22 were produced.
The produced substrate with electrodes was irradiated with ultraviolet light, and the surface of the gate insulating film 23 was hydrophilized. A two-layer cumulative film composed of monomolecular films of terphenyl (b5) and (b8) was prepared in the same manner as in Example 3 except that the obtained substrate was used. A thin film transistor was obtained.
In order to evaluate the electrical characteristics of the transistor, field effect mobility and on / off ratio were measured. The amount of current flowing by changing the voltage between the source / drain while applying various negative gate voltages (4155A; manufactured by HP) was measured. As a result, it was found that the field effect mobility was about 4 × 10 ⁻² cm ² V ⁻¹ s ⁻¹ and the on / off ratio was about 5 digits. From the above results, it was confirmed that the monomolecular cumulative film using different types of π-electron conjugated organic compounds has the effect of improving the uniformity, orientation, crystallinity, and electrical characteristics of the film.

<Comparative Example 1>
A transistor was produced in the same manner as in Example 4 except that terphenylyltriethoxysilane was used in place of terphenyl (b5) and terphenyl (b8).
The electrical characteristics of the obtained transistor were evaluated in the same manner as in Example 4. As a result, the field effect mobility is about ¹ × 10 ⁻² cm ² V ⁻¹ s ⁻¹ , the on / off ratio is about 4 digits, and the transistor of Example 4 is remarkably excellent in electrical characteristics. understood.

Experimental example 3
<Synthesis Example 5: Synthesis of disilylated anthracene represented by general formula (c1) (hereinafter referred to as anthracene (c1))>

  Anthracene (120-12-7) was obtained from Tokyo Kasei.

Silane coupling reaction Under a nitrogen atmosphere, 1 equivalent of anthracene and NBS dissolved in 50 mL of carbon tetrachloride was added to a 100 ml eggplant flask and allowed to react for 1.5 hours in the presence of AIBN. After removing unreacted substances and HBr by filtration, the column 1-bromoanthracene was obtained by using a column chromatograph to take out a reservoir brominated at only one site and purifying the column chromatograph. .
1 equivalent of 1-bromoanthracene was dissolved in 30 ml of THF solution, and 1 equivalent of n-BuLi was slowly added dropwise at 0 ° C. over 10 hours. The mixed solution was stirred for 4 hours and then warmed to room temperature. The dark green solution produced by the reaction was dropped into 1 equivalent of tetraethoxysilane in THF at room temperature and refluxed and mixed for 15 hours. Next, the reaction solution was filtered under reduced pressure to remove unreacted tetraethoxysilane and n-BuLi, and then 1-triethoxysilylanthracene was obtained.
1 equivalent of 1-triethoxysilylanthracene was dissolved in 30 ml of THF solution, and 1 equivalent of n-BuLi was slowly added dropwise at 0 ° C. over 10 hours. The mixed solution was stirred for 4 hours and then warmed to room temperature. The dark green solution produced by the reaction was dropped into 1 equivalent of a tetrachlorosilane solution in THF at room temperature, and the mixture was refluxed for 15 hours and mixed. Next, the reaction solution was filtered under reduced pressure to remove unreacted tetraethoxysilane and n-BuLi, and then purified by column chromatography to obtain anthracene (c1).

The result of the instrumental analysis of the obtained anthracene (c1) is shown.
¹ H NMR (δ CDCl ₃ ):
_{8.30~7.40ppm (m, 8H, C 14} H 8)
3.83 ppm (m, 6H, OC ₂ H ₅ )
1.22 ppm (m, 9H, OC ₂ H ₅ )
UV-Vis: 375 nm (C ₁₄ H ₈ )
From the above measurement results, it was confirmed that this compound had the structure of the general formula (c1).

<Synthesis Example 6: Synthesis of fluorinated terthiophene represented by general formula (f1) (hereinafter referred to as fluoroterthiophene (f1))>

All reactions were performed under a nitrogen atmosphere. 2,3,4,5-tetrabromothiophene was prepared by mixing with bromine in an acetic acid solution mixed with zinc using 1 equivalent of thiophene as a catalyst while refluxing. Next, magnesium and trimethoxychlorosilane are mixed in a THF solution in an amount that gives a molar ratio of (2,3,4,5-tetrabromothiophene: magnesium: trimethoxychlorosilane = 1: 2.5: 2.5). And subjected to ultrasonic cleaning for 4 days. The obtained 2,5-ditrimethoxysilyl-3,4-dibromothiophene was mixed in phenylsulfonyl nitrogen fluoride ((PhSO ₂ ) ₂ NF) and n-butyllithium in THF solution at −78 ° C. Reacted to difluorinate dibromo. The product after the reaction was treated with NBS in acetic acid at 80 ° C. to perform bromination of the trimethoxysilyl group (intermediate 1). In addition, 2,5-ditrimethoxysilyl-3,4-difluorothiophene was treated with n-butyllithium, (PhSO ₂ ) ₂ NF, tributyltin chloride (Bu ₃ SnCl) at −78 ° C. Fluorination reaction of the trimethoxysilyl group was performed to obtain 2,3,4-trifluoro-5-trimethoxysilyl-thiophene (intermediate 2). Intermediates 1 and 2 are reacted at 80 ° C. in a mixture consisting of PdCl ₂ (PPh ₃ ) ₂ and DMF to obtain 2-trimethoxysilyl-3,4,7,8,9-pentafluoro-bithiophene. It was. The resulting product and intermediate 1 were reacted by the same reaction mechanism as described above, thereby synthesizing terthiophene in which both ends were trimethoxysilyl groups. This terthiophene was mixed in a THF solution and cooled to −78 ° C. with a dry ice / acetone bath, and then 2 equivalents of silver trifluoroacetate was added dropwise and stirred for 5 minutes to dissolve. Next, a THF solution in which 2 equivalents of iodine were dissolved was dropped, and the mixture was stirred for 8 hours at −78 ° C., warmed to room temperature, and 2-trimethoxysilyl-3,4,7,8,11, 12-Sexiffluoro-13-iodo-terthiophene was obtained. 1 equivalent of the obtained product was dissolved in 30 ml of THF solution, and 1 equivalent of n-BuLi was slowly added dropwise at 0 ° C. over 10 hours. The mixed solution was stirred for 4 hours and then warmed to room temperature. The resulting solution was dropped into 1 equivalent of tetrachlorosilane in THF at room temperature, and the mixture was refluxed for 15 hours and mixed. Next, the reaction solution was filtered under reduced pressure to remove unreacted 2-trimethoxysilyl-3,4,7,8,11,12-seciffluoro-13-iodo-terthiophene and n-BuLi, and then the column By purifying by chromatography, fluoroterthiophene (f1) was obtained.

The result of the instrumental analysis of the obtained fluoroterthiophene (f1) is shown.
¹ H NMR (δ CDCl ₃ ):
1.49 ppm (m, 9H, CH ₃ )
_{UV-Vis: 365nm (C 4} H 2 S)
From the above measurement results, it was confirmed that this compound had the structure of the general formula (f1).

<Example 5: A single film consisting only of a monomolecular film of anthracene (c1), a single film consisting only of a monomolecular film of fluoroterthiophene (f1), and a monomolecular film and fluoroterthiophene of anthracene (c1) Production of 2-layer cumulative film consisting of monomolecular film of (f1)>
Production Method A substrate obtained by immersing a Si wafer and a quartz glass substrate in a (hydrogen peroxide / sulfuric acid) mixed solution and subjecting it to hydrophilic treatment by irradiation with ultraviolet light and thoroughly washing with pure water was used as the substrate. Film formation was performed using the prepared substrate. Subsequently, the following steps (1) to (4) were performed to form the title monomolecular film and the two-layer cumulative film.

Step (1);
First, a 0.2 mM toluene solution of anthracene (c1) is developed on the water surface at pH = 7, and an adsorption reaction on the substrate accompanying the elimination of the chlorine atom in the trichlorosilyl group is performed using the LB method. A monomolecular film of (c1) was prepared. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.
Step (2) (pH treatment);
Next, the anthracene (c1) monomolecular film is immersed in water at pH = 2 and a water temperature of 25 ° C. to cause hydrolysis reaction and condensation reaction of the triethoxysilyl group of anthracene (c1). An anthracene (c1) monomolecular film having a siloxane network was formed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Step (3);
Separately, fluoroterthiophene (f1) was used in the same manner as in the above step (1) except that the hydrolysis reaction of trichlorosilyl group was pH = 7 and the water temperature was 25 ° C. A monomolecular film was prepared. Next, fluoroterthiophene having a siloxane network formed on the film surface by the same method as in the above step (2) except that the hydrolysis and condensation reaction of the trimethoxysilyl group was carried out under the conditions of pH = 3 and water temperature of 25 ° C. A monomolecular film of (f1) was prepared. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Step (4);
Next, a 0.2 mM toluene solution of fluoroterthiophene (f1) is developed on the water surface at pH = 4, and is deposited on the monomolecular film of anthracene (c1) prepared by the above process by the LB method. A film was formed. By carrying out under the condition of pH = 4, the adsorption reaction is carried out by hydrolysis reaction and condensation reaction of silanol group (hydroxyl group) and trichlorosilyl group of fluoroterthiophene (f1) which have not been supplied to the siloxane network of anthracene (c1). proceed. Furthermore, a cumulative film having a siloxane network formed on the film surface was formed by the same method as in the above step (2) except that the hydrolysis reaction of the trimethoxysilyl group was carried out under conditions of pH = 3 and water temperature of 25 ° C. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Film evaluation [film thickness confirmation]
Using a monomolecular bilayer film of anthracene (c1) and fluoroterthiophene (f1) as a sample, the surface morphology of the accumulated film was observed with an atomic force microscope (AFM) (SPA400; manufactured by Seiko Instruments Inc.) at a size of 50 μm. The film was uniformly formed with a size of 50 μm. Since the root mean square roughness of the film is 0.36 nm, which is not significantly different from the value of 0.26 nm for only Si as the substrate, it can be said that the uniformity of the film is high. When the film was cut by mechanical treatment, the film thickness was about 3.2 nm corresponding to the sum of the molecular lengths of anthracene and terthiophene. From this, it was found that a monomolecular bilayer film having a uniform film thickness was prepared.

[Main skeleton confirmation]
In order to evaluate the accumulated state of the film in detail, a single film consisting only of a monomolecular film of anthracene (c1), a single film consisting only of a monomolecular film of fluoroterthiophene (f1), and anthracene (c1) and fluoro Using a monomolecular bilayer film of terthiophene (f1) as a sample, UV-visible absorption spectrum measurement was performed using (UV-3000; manufactured by Shimadzu Corporation). As a result, the monomolecular film of anthracene (c1) is around 365 nm, the monomolecular film of fluoroterthiophene (f1) is around 375 nm, the monomolecular bilayer film of anthracene (c1) and fluoroterthiophene (f1) is 365 and Absorption having a peak position in the vicinity of 375 nm was observed.

[Confirmation of crystallinity]
The crystal arrangement was evaluated based on electron diffraction (ED) measurement by “H-7500; manufactured by Hitachi, Ltd.”. As a sample, a single film consisting only of a monomolecular film of anthracene (c1), a single film consisting only of a monomolecular film of fluoroterthiophene (f1), and a single molecule of anthracene (c1) and fluoroterthiophene (f1) A two-layer film was used. As a substrate for performing ED measurement, a substrate obtained by adhering a form bar film as a support film to a copper mesh sheet and having SiO ₂ deposited for surface hydrophilization treatment was used. As a result, the diffraction spots corresponding to the interplanar spacing of 0.42 and 0.32 nm are obtained for the monomolecular film of anthracene (c1), and the interplanar spacing of 0.45 and 0.37 nm for the monomolecular film of fluoroterthiophene (f1). Corresponding diffraction spots, diffraction spots corresponding to plane spacings of 0.42 and 0.32 nm, 0.45 and 0.37 nm were observed in the monolayer bilayer films of anthracene (c1) and fluoroterthiophene (f1), respectively. It was. From this, it was found that not only each single film but also a monomolecular bilayer cumulative film, a film having a high order of crystal arrangement could be prepared.

[Confirmation of siloxane network formation on film surface]
In order to confirm whether or not a siloxane network on the film surface was formed by the pH treatment, infrared absorption spectrum measurement before and after the pH treatment was performed. Note that before and after the pH treatment in the monomolecular bilayer film of anthracene (c1) and fluoroterthiophene (f1) is before and after the last pH treatment.
First, before the pH treatment, an infrared absorption spectrum measurement of an anthracene (c1) monomolecular film, a fluoroterthiophene (f1) monomolecular film, and a bilayer cumulative film composed of anthracene (c1) and fluoroterthiophene (f1) is performed. results went, respectively ^{1288cm -1, 1280cm -1,} absorption derived from stretching vibration of C-O was observed at 1285 ^-1.
On the other hand, after pH treatment, an anthracene (c1) monomolecular film in which a siloxane network is formed on the film surface, a fluoroterthiophene (f1) monomolecular film, and a two-layer accumulation composed of anthracene (c1) and fluoroterthiophene (f1) As a result of measuring the infrared absorption spectrum of the film, the absorption derived from the C—O disappeared and broad absorption centered on 3300 cm ⁻¹ was confirmed. This absorption is derived from the stretching vibration of OH.

  Pure anthracene (c1) monomolecular film, fluoroterthiophene (f1) monomolecular film, and bilayer cumulative film composed of anthracene (c1) and fluoroterthiophene (f1) having a siloxane network formed on the film surface after pH treatment When the static contact angles of water were measured, they were 21 °, 23 °, and 22 °, respectively.

From these facts, it can be said that the alkoxy group on the film surface is converted to a hydroxyl group by the pH treatment.
Furthermore, by the above crystallinity confirmation, a single film consisting only of the monomolecular film of the anthracene (c1), a single film consisting only of the monomolecular film of the fluoroterthiophene (f1), and anthracene (c1) and fluoro The interplanar spacing of the monomolecular bilayer film of terthiophene (f1) was 0.5 nm or less. Si (OH) ₃ is very reactive, and at the above intermolecular distance, a siloxane bond can be easily formed by a dehydration reaction between hydroxyl groups between adjacent molecules.
That is, in the above, in both the monomolecular film and the two-layered cumulative film, it was confirmed that absorption derived from C—O disappeared due to pH treatment, and absorption of OH occurred. It can be said that a functional siloxane network is formed.

<Example 6: Preparation of organic photoelectric conversion element and evaluation of electrical characteristics>
Using an ITO substrate as an anode and hydrophilizing the surface of the substrate by ultraviolet light irradiation, the monolayer cumulative film of anthracene (c1) and fluoroterthiophene (f1) shown in Example 5 is applied to the ITO substrate. Type anthracene (c1) and an n-type fluoroterthiophene (f1) film were adsorbed on the film by the LB method. On this ITO glass / (c1) / (f1) film, gold was deposited to a thickness of 40 nm at a vacuum degree of 10 ⁻³ to obtain a photoelectric conversion element cell having an effective area of 20 × 10 mm ² . The photoelectric conversion element cell was irradiated with light of a 500 W xenon lamp from the ITO electrode side, and the open circuit voltage Vo, the short circuit current Io, the fill factor FF, and the photoelectric conversion efficiency μ were measured. As a result, the respective values were 80 mV, 44 μA / cm ² , 0.45, and 4.3%.

<Comparative example 2>
The same as Example 6 except that anthracene having no terminal silyl group was used instead of anthracene (c1), and fluoroterthiophene having no terminal silyl group was used instead of fluoroterthiophene (f1). The photoelectric conversion element was produced by the method.
The electrical characteristics of the obtained photoelectric conversion element were evaluated in the same manner as in Example 6. As a result, the values of Voc, Io, FF and μ are 45 mV, 13 μA / cm ² , 0.13 and 1.1%, respectively, and the photoelectric conversion element of Example 6 is remarkably excellent in electrical specification. understood.

Experimental Example 4
<Synthesis Example 7: Synthesis of disilylated alkane represented by general formula (d1) (hereinafter referred to as alkane (d1))>

Octadecyltriethoxysilane (OTES, CAS No. 7399-00-0) was purchased from Tokyo Chemical Industry. Alkane (d1) was synthesized using the purchased OTES.
OTES was dissolved in a toluene solvent, and 1 equivalent of t-butyllithium was added dropwise at 0 ° C. over 10 hours. After completion of dropping, the mixture was stirred at room temperature for 12 hours to obtain a suspension. The suspension was dropped into a toluene solution mixed with 1 equivalent of tetrachlorosilane at −78 ° C. over 10 hours. After completion of dropping, the flask was removed from the cooling bath, and stirring was further performed for 6 hours.
After removing lithium chloride as a precipitate by filtration, alkane (d1) was obtained by filtration under reduced pressure.

The result of the instrumental analysis of the obtained alkane (d1) is shown.
¹ H NMR (δ CDCl ₃ ):
3.83 ppm (m, 6H, C ₂ H ₅ )
1.3 ppm (m, 4H, C ₁₈ H ₃₆ )
1.29 ppm (m, 30 H, C ₁₈ H ₃₆ )
1.22 ppm (m, 9H, C ₂ H ₅ )
0.58 ppm (m, 2H, C ₁₈ H ₃₆ )
From the above measurement results, it was confirmed that this compound had the structure of the general formula (d1).
It was confirmed that disilylation of a 19-36 long-chain alkane can be performed using the same method.

<Example 7: A single film consisting only of a monomolecular film of alkane (d1), a single film consisting only of a monomolecular film of fluoroterthiophene (f1), and a monomolecular film and fluoroterthiophene of alkane (d1) Production of 2-layer cumulative film consisting of monomolecular film of (f1)>
Production Method A substrate obtained by immersing a Si wafer and a quartz glass substrate in a (hydrogen peroxide / sulfuric acid) mixed solution and subjecting it to hydrophilic treatment by irradiation with ultraviolet light and thoroughly washing with pure water was used as the substrate. Film formation was performed using the prepared substrate. Subsequently, the following steps (1) to (4) were performed to form the title monomolecular film and the two-layer cumulative film.

Step (1);
First, a 0.2 mM toluene solution of alkane (d1) is developed on the water surface at pH = 7, and an adsorption reaction on the substrate accompanying the desorption of chlorine atoms in the trichlorosilyl group is performed using the LB method. A monomolecular film of (d1) was prepared. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.
Step (2) (pH treatment);
Next, the alkane (d1) monomolecular film is immersed in water at pH = 2 and a water temperature of 25 ° C. to cause hydrolysis reaction and condensation reaction of the triethoxysilyl group of the alkane (d1), and on the film surface. An alkane (d1) monomolecular film having a siloxane network was formed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Step (3);
Separately, fluoroterthiophene (f1) was used in the same manner as in the above step (1) except that the hydrolysis reaction of trichlorosilyl group was pH = 7 and the water temperature was 25 ° C. A monomolecular film was prepared. Next, fluoroterthiophene having a siloxane network formed on the film surface by the same method as in the above step (2) except that the hydrolysis and condensation reaction of the trimethoxysilyl group was carried out under the conditions of pH = 3 and water temperature of 25 ° C. A monomolecular film of (f1) was prepared. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Step (4);
Next, a 0.2 mM toluene solution of fluoroterthiophene (f1) is developed on the water surface at pH = 4, and deposited on the monomolecular film of alkane (d1) prepared by the above process by the LB method. A film was formed. By carrying out under the condition of pH = 4, the adsorption reaction is carried out by hydrolysis reaction and condensation reaction of silanol group (hydroxyl group) and trichlorosilyl group of fluoroterthiophene (f1) that have not been supplied to the siloxane network of alkane (d1). proceed. Furthermore, a cumulative film having a siloxane network formed on the film surface was formed by the same method as in the above step (2) except that the hydrolysis reaction of the trimethoxysilyl group was carried out under conditions of pH = 3 and water temperature of 25 ° C. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Film evaluation [film thickness confirmation]
Using a monomolecular bilayer film of alkane (d1) and fluoroterthiophene (f1) as a sample, the surface morphology of the accumulated film was observed at 50 μm size with an atomic force microscope (AFM) (SPA400; manufactured by Seiko Instruments Inc.). The film was uniformly formed with a size of 50 μm. Since the mean square roughness of the film is 0.40 nm, which is not significantly different from the value of 0.26 nm for only Si as the substrate, it can be said that the film has high uniformity. When the film was cut by mechanical treatment, the film thickness was about 3.6 nm corresponding to the sum of the molecular lengths of alkane and terthiophene. From this, it was found that a monomolecular bilayer film having a uniform film thickness was prepared.

[Main skeleton confirmation]
In order to evaluate the accumulated state of the film in detail, a single film consisting only of a monomolecular film of alkane (d1), a single film consisting only of a monomolecular film of fluoroterthiophene (f1), and alkane (d1) and fluoro Using a monomolecular bilayer film of terthiophene (f1) as a sample, UV-visible absorption spectrum measurement was performed using (UV-3000; manufactured by Shimadzu Corporation). As a result, no absorption was observed in the monomolecular film of alkane (d1), in the vicinity of 375 nm in the monomolecular film of fluoroterthiophene (f1), and in the monomolecular bilayer film of alkane (d1) and fluoroterthiophene (f1). Absorption having a peak position in the vicinity of 375 nm was observed.

[Confirmation of crystallinity]
The crystal arrangement was evaluated based on electron diffraction (ED) measurement by “H-7500; manufactured by Hitachi, Ltd.”. As a sample, a single film consisting only of a monomolecular film of alkane (d1), a single film consisting only of a monomolecular film of fluoroterthiophene (f1), and a single molecule of alkane (d1) and fluoroterthiophene (f1) A two-layer film was used. As a substrate for performing ED measurement, a substrate obtained by adhering a form bar film as a support film to a copper mesh sheet and having SiO ₂ deposited for surface hydrophilization treatment was used. As a result, in the monomolecular film of alkane (d1), diffraction spots corresponding to 0.42 and 0.35 nm interplanar spacing were obtained, and in the monomolecular film of fluoroterthiophene (f1), 0.45 and 0.37 nm interplanar spacing were obtained. Corresponding diffraction spots, diffraction spots corresponding to plane spacings of 0.42 and 0.35 nm, 0.45 and 0.37 nm were observed in the monomolecular bilayer film of alkane (d1) and fluoroterthiophene (f1), respectively. It was. From this, it was found that not only each single film but also a monomolecular bilayer cumulative film, a film having a high order of crystal arrangement could be prepared.

[Confirmation of siloxane network formation on film surface]
In order to confirm whether or not a siloxane network on the film surface was formed by the pH treatment, infrared absorption spectrum measurement before and after the pH treatment was performed. Note that before and after the pH treatment in the monomolecular bilayer film of alkane (d1) and fluoroterthiophene (f1) is before and after the final pH treatment.
First, before the pH treatment, an infrared absorption spectrum measurement of an alkane (d1) monomolecular film, a fluoroterthiophene (f1) monomolecular film, and a two-layer cumulative film composed of alkane (d1) and fluoroterthiophene (f1) is performed. results went, respectively ^{1295cm -1, 1290cm -1,} absorption derived from stretching vibration of C-O was observed at 1285 ^-1.
On the other hand, after pH treatment, a two-layer accumulation consisting of an alkane (d1) monomolecular film having a siloxane network formed on the film surface, a fluoroterthiophene (f1) monomolecular film, and alkane (d1) and fluoroterthiophene (f1) As a result of measuring the infrared absorption spectrum of the film, the absorption derived from the C—O disappeared and broad absorption centered on 3300 cm ⁻¹ was confirmed. This absorption is derived from the stretching vibration of OH.

  Pure alkane (d1) monomolecular film, fluoroterthiophene (f1) monomolecular film, and bilayer cumulative film composed of alkane (d1) and fluoroterthiophene (f1) having a siloxane network formed on the film surface after pH treatment When the static contact angles of water were measured, they were 24 °, 24 °, and 26 °, respectively.

From these facts, it can be said that the alkoxy group on the film surface is converted to a hydroxyl group by the pH treatment.
Further, by the above crystallinity confirmation, a single film consisting only of the monomolecular film of the alkane (d1), a single film consisting only of the monomolecular film of the fluoroterthiophene (f1), and alkane (d1) and fluoro The interplanar spacing of the monomolecular bilayer film of terthiophene (f1) was 0.5 nm or less. Si (OH) ₃ is very reactive, and at the above intermolecular distance, a siloxane bond can be easily formed by a dehydration reaction between hydroxyl groups between adjacent molecules.
That is, in the above, in both the monomolecular film and the two-layered cumulative film, it was confirmed that absorption derived from C—O disappeared due to pH treatment, and absorption of OH occurred. It can be said that a functional siloxane network is formed.

Experimental Example 5
<Synthesis Example 8; Synthesis of alkane (x1)>
Octadecyltriethoxysilane (OTES, CAS No. 7399-00-0) was purchased from Tokyo Chemical Industry. Let alkane (x1).

<Example 8: Manufacture of a single film consisting only of a monomolecular film of alkane (d1) and a single film consisting only of a monomolecular film of alkane (x1)>
Production Method A substrate obtained by immersing a Si wafer and a quartz glass substrate in a (hydrogen peroxide / sulfuric acid) mixed solution and subjecting it to hydrophilic treatment by irradiation with ultraviolet light and thoroughly washing with pure water was used as the substrate. Film formation was performed using the prepared substrate. Subsequently, the following steps (1) to (3) were performed to form the title monomolecular film.

Step (1);
First, a 0.2 mM toluene solution of alkane (d1) is developed on the water surface at pH = 7, and an adsorption reaction on the substrate accompanying the desorption of chlorine atoms in the trichlorosilyl group is performed using the LB method. A monomolecular film of (d1) was prepared. The obtained substrate was washed with an organic solvent to remove the remaining unreacted alkane.
Step (2) (pH treatment);
Next, the alkane (d1) monomolecular film is immersed in water at pH = 2 and a water temperature of 25 ° C. to cause hydrolysis reaction and condensation reaction of the triethoxysilyl group of the alkane (d1), and on the film surface. An alkane (d1) monomolecular film having a siloxane network was formed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted alkane, and washed with pure water.

Step (3);
Separately, alkane (x1) is a single molecule of alkane (x1) by the same method as in the above step (1), except that the hydrolysis reaction of triethoxysilyl group is pH = 7 and water temperature is 25 ° C. A membrane was prepared. The operation by the method similar to the said process (2) was not performed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted alkane.

Film evaluation [film thickness confirmation]
Using the monomolecular film of alkane (d1) and the monomolecular film of alkane (x1) as samples, the surface morphology of the film was observed at a size of 50 μm with an atomic force microscope (AFM) (SPA400; manufactured by Seiko Instruments Inc.). The film was uniformly formed with a size of 50 μm. When the film was cut by mechanical treatment, the film thickness was about 2.4 nm corresponding to the molecular length of alkane. From this, it was found that a film having a uniform film thickness was prepared.
Further, when the surface shapes of the alkane (d1) monomolecular film and the alkane (x1) monomolecular film were observed with a size of 10 μm by an atomic force microscope (AFM) (SPA400: manufactured by Seiko Instruments Inc.), the surface irregularities 2 The root mean square roughness (RMS) is 0.33 nm for the alkane (d1) monomolecular film and 0.46 nm for the alkane (x1) monomolecular film, and the alkane (d1) monomolecular film has higher smoothness. Was found to be obtained.

[Confirmation of crystallinity]
The crystal arrangement was evaluated based on electron diffraction (ED) measurement by “H-7500; manufactured by Hitachi, Ltd.”. As a sample, a single film consisting only of a monomolecular film of alkane (d1) and a single film consisting only of a monomolecular film of alkane (x1) were used. As a substrate for performing ED measurement, a substrate obtained by adhering a form bar film as a support film to a copper mesh sheet and having SiO ₂ deposited for surface hydrophilization treatment was used. As a result, diffraction spots corresponding to 0.42 and 0.35 nm spacing were observed in both films. From this, it was found that a film with high order of crystal arrangement could be prepared for any film.
The stability of the film was evaluated by the disappearance of the diffraction spot by electron beam irradiation. The alkane (x1) monomolecular film disappeared by irradiation with an electron beam for about 1 minute, and the structure of the film was destroyed, whereas the alkane (d1) monomolecular film was irradiated with an electron beam for 5 minutes or more. Even a diffraction spot was observed. This indicates that the strength of the alkane (d1) monomolecular film is improved, and it can be said that this is an effect that a siloxane network is formed on the substrate side and the surface side of the film.

[Confirmation of siloxane network formation on film surface]
In order to confirm whether or not a siloxane network on the film surface was formed by the pH treatment, infrared absorption spectrum measurement before and after the pH treatment was performed.
First, as a result of infrared absorption spectrum measurement before pH treatment of the alkane (d1) monomolecular film, absorption derived from stretching vibration of C—O was confirmed at 1290 cm ⁻¹ .
In addition, as a result of the infrared absorption spectrum measurement after the pH treatment of the alkane (d1) monomolecular film, the absorption derived from the above-mentioned CO disappeared, and broad absorption centering on 3300 cm ⁻¹ was confirmed. It was done. This absorption is derived from the stretching vibration of OH.
On the other hand, as a result of measuring the infrared absorption spectrum of the alkane (x1) monomolecular film, the absorption derived from the C—O was not measured.

  When static contact angle measurement was performed with pure water, the alkane (d1) monomolecular film was 24 ° and the alkane (x1) monomolecular film was 90 °. The alkane (d1) monomolecular film surface was found to be hydrophilic due to the formation of a siloxane network.

From these facts, it can be said that the alkane (d1) monomolecular film has the alkoxy group on the film surface converted into a hydroxyl group by the above pH treatment.
Furthermore, according to the above crystallinity confirmation, the interplanar spacings of the alkane (d1) monomolecular film and the alkane (x1) monomolecular film were both 0.5 nm or less. In the alkane (d1) monomolecular film before pH treatment, Si (OH) ₃ is very reactive, and at the above intermolecular distance, a siloxane bond is easily formed by dehydration reaction between hydroxyl groups between adjacent molecules. be able to.
That is, in the alkane (d1) monomolecular film, it was confirmed that absorption due to C—O disappeared due to pH treatment and absorption of OH was generated, so that a hydrophilic siloxane network was formed on the film surface. It can be said that.

Experimental Example 6
<Synthesis Example 9: Production of terthiophene (a2) (trichlorosilane-terthiophene-triethoxysilane) by Grignard method>
A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 2 mol of metallic magnesium and 300 ml of toluene solution in a dry argon stream, and 0.5 mol of terthiophene was added at about 10 degrees. The mixture was added dropwise over 12 hours, and after completion of the addition, the mixture was aged at 15 ° C. for 4 hours to prepare a Grignard reagent.

  In a flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel, 2 mol of metal magnesium, 300 ml of toluene solution, and 2.0 mol of tetraethoxysilane were charged in a dry argon stream, and the obtained Grignard reagent was added at 0 ° C. The mixture was dropped from the dropping funnel over 12 hours while cooling, and aged at room temperature for 2 hours after completion of the dropping. The reaction solution was filtered under reduced pressure to remove magnesium, and then triethoxysilane-terthiophene was obtained.

  A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 2.0 mol of tetrachlorosilane and 300 ml of tetrahydrofuran (THF) under a dry argon stream, and the internal temperature was 25 ° C. or lower. Triethoxysilane-terthiophene was added dropwise over 2 hours, and aging was performed at 30 ° C. for 1 hour after completion of the addition. Next, the reaction solution is filtered under reduced pressure to remove magnesium chloride, and then THF and unreacted tetrachlorosilane are stripped from the filtrate, and the solution is distilled to obtain the compound represented by the formula (a2). It was.

The result of the instrumental analysis of the obtained compound is shown.
¹ H NMR (δ CDCl ₃ ): 7.63-7.78 ppm (m, C ₄ H ₂ S)
2.20 ppm (m, C ₂ H ₅ )
From the above measurement results, it was confirmed that this compound was trichlorosilane-terthiophene-triethoxysilane represented by the formula (a2).
In this synthesis example, synthesis was performed by the first method.

Experimental Example 7
<Synthesis Example 10: Production of trichlorosilane-biphenyl-trimethoxysilane (formula (b10))>
In a 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 1 mol of 1-iodo-4-chlorobiphenyl was charged with 2 mol of metallic lithium and 300 ml of THF under a dry argon stream, The mixture was added dropwise at a temperature of −10 ° C. over 12 hours. After completion of the addition, the mixture was aged at room temperature for 4 hours to obtain 4-chloro-biphenyllithium.

  A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 3.0 mol of tetrachlorosilane and 300 ml of THF under a dry argon stream, cooled on ice, and obtained at an internal temperature of 20 ° C. or lower. 4-Chloro-biphenyllithium was added dropwise over 2 hours and reacted at 20 ° C. after completion of the dropwise addition. Next, the reaction solution was filtered under reduced pressure to remove unreacted lithium, and then THF and unreacted tetrachlorosilane were removed from the filtrate to obtain 1-trichlorosilane-4-chlorobiphenyl.

  In order to use the obtained 1-trichlorosilane-4-chlorobiphenyl again as a Grignard reagent, metal magnesium was similarly reacted at an internal temperature of 10 ° C. to synthesize 1-trichlorosilane-4-biphenylmagnesium, By reacting with tetrachlorosilane, a compound represented by the formula (b10) was obtained.

The result of the instrumental analysis of the obtained compound is shown.
IR: 1590 (m), 1490 (m), 1430 (m), 1120 (m), 700 (s) cm ⁻¹ (Si—Ph)
UV-Vis: 261 nm (Ph)
From the above measurement results, it was confirmed that this compound was trichlorosilane-biphenyl-trimethoxysilane represented by the formula (b10).
In this synthesis example, the synthesis was performed by the second method.

Experimental Example 8
<Synthesis Example 11: Synthesis of triethoxysilane-tetracene-tributoxysilane (formula (c6))>
A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 2 mol of metallic magnesium and 300 ml of chloroform solution under a dry argon stream, and 0.5 mol of tetracene was added from the dropping funnel at about 10 ° C. The solution was added dropwise over 12 hours, and after completion of the addition, the mixture was aged at 15 ° C. for 4 hours to prepare a Grignard reagent.

  A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 2.0 mol of tetrabutoxysilane and 300 ml of THF under a dry argon stream, and the resulting Grignard reagent was obtained at an internal temperature of 25 ° C. or less. Was dropped over 2 hours, and after completion of the dropping, aging was performed at 30 ° C. for 1 hour. Subsequently, after filtering the reaction liquid under reduced pressure and removing magnesium chloride, tributoxysilane-tetracene was obtained from THF and unreacted tetrabutoxysilane from the filtrate.

  A flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel was charged with 2 mol of metallic magnesium and 300 ml of a toluene solution under a dry argon stream, and the dropping funnel was cooled while cooling the resulting tributoxysilane-tetracene to 0 ° C. To 12 hours, and after completion of the dropwise addition, the mixture was aged at room temperature for 2 hours to obtain an intermediate. 2.0 mol of tetraethoxysilane and 300 ml of THF were charged, and the intermediate was added dropwise over 8 hours while cooling to 10 ° C. The mixture was stirred for 4 hours at 10 ° C., then warmed to room temperature, and further stirred for 2 hours. After stirring, the mixture was hydrolyzed, and the organic layer was separated, washed with water, and dried over magnesium sulfate. The compound shown by Formula (c6) was obtained by distilling a solvent off and isolate | separating the remainder with a silica gel column.

The result of the instrumental analysis of the obtained compound is shown.
¹ H NMR (δ CDCl ₃ ): 2.20 ppm (m, C ₂ H ₅ )
UV-Vis: 400-500 nm (tetracene p band), 265 nm (tetracene β band)
From the above measurement results, it was confirmed that this compound was triethoxysilane-tetracene-tributoxysilane represented by the formula (c6). In addition to tetracene, other acene compounds such as anthracene and pentacene were confirmed to be capable of producing silicon compounds by the same method.
In this synthesis example, synthesis was performed by the first method.

Experimental Example 9
<Synthesis Example 12: Production of n-trioctylsilane-quarterthiophene-triethoxysilane (formula (a13))>
A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 300 ml of THF and tetraethoxysilane under a dry argon stream, and the Grignard reagent obtained in the same manner as in Experimental Example 1 had an internal temperature of 0 ° C. The solution was added dropwise over 12 hours, and after completion of the addition, the mixture was aged at room temperature for 4 hours to obtain triethoxysilane-quarterthiophene.

  A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 2.0 mol of tetraoctylsilane and 300 ml of THF under a dry argon stream, cooled on ice, and at an internal temperature of 25 ° C. or less, Grignard The reagent was added dropwise over 2 hours, and after completion of the addition, aging was performed at 30 ° C. for 1 hour. Next, the reaction solution was filtered under reduced pressure to remove unreacted magnesium, and then THF and unreacted tetraoctylsilane were removed from the filtrate, and this solution was removed to obtain a compound represented by the formula (a13).

The result of the instrumental analysis of the obtained compound is shown.
¹ H NMR (δ CDCl ₃ ): 7.63-7.78 (m, C ₄ H ₂ S)
IR: 2966, 2893 cm ⁻¹ (s, C ₂ H ₅ )
UV-Vis: 410 nm (toluene solution) (thiophene ring)
From the above results, it was found that this compound was n-trioctylsilane-quarterthiophene-triethoxysilane represented by the formula (a13).

Experimental Example 10
<Synthesis Example 13>
According to Synthesis Examples 9 and 10, trichlorosilane-quinkethiophene-triethoxysilane, trichlorosilane-hexithiophene-triethoxysilane, trichlorosilane-triphenyl-triethoxysilane, trioctadecylsilane-terphenyl-tri It was confirmed that chlorosilane could also be produced. Furthermore, it was confirmed that a silicon compound containing octathiophene and octaphenylene in which benzene and thiophene having both different functional groups at both ends were similarly bonded up to 8 was confirmed. It was confirmed that a compound in which 9 or more of benzene and thiophene were bonded made it difficult to obtain raw materials and the synthesis yield was reduced.

Experimental Example 11
<Synthesis Example 14: Production of tributoxysilane-dibenzoperylene-triethoxysilane (formula (c13))>
Naphthalene was synthesized binaphthyl (Aldrich) naphthalene by reaction with _{NaNO 2 -TfOH (Tf = CF 3} SO 2) solution. Binaphthyl was reacted with LiTHF under oxygen bubbling to obtain perylene. SbF ₅ purchased from Aldrich was diluted twice in a dry argon atmosphere. SO ₂ ClF was synthesized from SO ₂ Cl ₂ produced by halogen exchange reaction of NH ₄ F and TFA. Perylene reacted with _SbF 5 _-SO 2 ClF, to obtain a dibenzoperylene was purified by HPLC. Chlorination was performed by reacting 1 equivalent of NCS with dibenzoperylene in AcOH in the presence of CHCl ₃ with respect to dibenzoperylene. Then, it reacted with n-BuLi and tetrabutoxysilane in a THF solution to obtain tributoxysilane-dibenzoperylene (yield 8%).

  A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 2.0 mol of tetraethoxysilane and 300 ml of THF under a dry argon stream, cooled on ice, and at an internal temperature of 25 ° C. or less, Grignard The reagent was added dropwise over 2 hours, and after completion of the addition, aging was performed at 30 ° C. for 1 hour. Next, the reaction solution was filtered under reduced pressure to remove unreacted magnesium, and then THF and unreacted tetraethoxysilane were removed from the filtrate, and this solution was removed to obtain a compound represented by the formula (c13).

When the obtained compound was subjected to infrared absorption measurement, Si—O—C absorption was observed at a wavelength of 1050 nm. From this, it was confirmed that the obtained compound contains a silyl group.
When the ultraviolet-visible absorption spectrum of the chloroform solution containing the compound was measured, absorption was observed at a wavelength of 378 nm. This absorption was attributed to the π → π ^* transition of the dibenzoperylene skeleton contained in the molecule, and it was confirmed that the compound contained the dibenzoperylene skeleton.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
8.9 ppm (m) (from 1H aromatics)
8.0 ppm (m) (from 1H aromatics)
7.8 ppm (m) (from 4H aromatics)
7.4 ppm (m) (derived from 2H aromatics)
6.6 ppm (m) (from 1H aromatics)
6.1 ppm (m) (from 1H aromatics)
3.7 ppm (m) (from 1H aromatics)
3.4 ppm (m) (derived from 12H butoxy group and ethoxy group methylene group)
2.6 ppm (m) (from 1H aromatics)
1.4 ppm (m) (derived from methylene group of 12H butoxy group)
1.1 ppm (m) (derived from methyl group of 9H ethoxy group)
1.0 ppm (m) (derived from the methyl group of 9H butoxy group)
From these results, it was confirmed that this compound was tributoxysilane-dibenzoperylene-triethoxysilane. This compound is referred to as dibenzoperylene (c13).

<Example 9: Manufacture of a monomolecular film of dibenzoperylene (c13) and a 2-layer to 5-layer cumulative film>
Step (1);
First, a hydrophilic substrate prepared by the method shown in Example 1 was immersed in a 0.01 mM toluene solution of dibenzoperylene (c13) at room temperature for 12 hours. A monomolecular film of dibenzoperylene (c13) was prepared by a reaction between a hydroxyl group present on the substrate surface and a triethoxysilyl group. The obtained substrate was washed with an organic solvent to remove the remaining unreacted dibenzoperylene.
Step (2) (pH treatment);
Next, the dibenzoperylene (c13) monomolecular film is immersed in water having a pH = 1 and a water temperature of 50 ° C., thereby causing hydrolysis and condensation reaction of the tributoxysilyl group of dibenzoperylene (c13), and the film A dibenzoperylene (c13) monomolecular film having a siloxane network formed on the surface was formed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted dibenzoperylene.

Step (3);
Next, the substrate on which the dibenzoperylene (c13) monomolecular film was formed in the step (2) was immersed in a 0.01 mM toluene solution of dibenzoperylene (c13) at 50 ° C. for 12 hours. A hydroxyl group present on the substrate surface and a triethoxysilyl group reacted to prepare a second-layer dibenzoperylene (c13) monomolecular film on the lowermost monomolecular film. Furthermore, a siloxane network was formed on the film surface by the same method as in the above step (2) except that the hydrolysis reaction of the tributoxysilyl group was carried out under the conditions of pH = 1 and water temperature of 50 ° C. The obtained substrate was washed with an organic solvent to remove the remaining unreacted dibenzoperylene.

Step (4);
Further, by repeating the step (3) for forming the second monomolecular film described above three times, a five-layer cumulative film in which five monomolecular films of dibenzoperylene (c13) are laminated is obtained. Prepared.

Film evaluation [film thickness confirmation]
Using a 2-5 layer cumulative film of dibenzoperylene (c13) as a sample, the surface morphology of the cumulative film was observed at 50 μm size with an atomic force microscope (AFM) (SPA400; manufactured by Seiko Instruments Inc.). Was uniformly formed. Since the mean square roughness of the film is 0.42 nm, which is not significantly different from the value of 0.26 nm of only Si as the substrate, it can be said that the uniformity of the film is high. When the film was cut by mechanical treatment, the film thickness was 3.4 nm for the two-layer film, 5.2 nm for the three-layer film, 7.0 nm for the four-layer film, and 8.5 nm for the five-layer film. This corresponds to a cumulative number of times the molecular length of dibenzoperylene. From this, it was found that a film having a uniform film thickness was prepared.

[Main skeleton confirmation]
In order to evaluate the accumulated state of the film in detail, a single monomolecular film of dibenzoperylene (c13) and a laminated film of 2 to 5 layers were used as samples, and UV-visible absorption was performed (UV-3000; manufactured by Shimadzu Corporation). Spectrum measurement was performed. As a result, absorption having a peak position near 380 nm was observed in all the films.

[Confirmation of crystallinity]
The crystal arrangement was evaluated based on electron diffraction (ED) measurement by “H-7500; manufactured by Hitachi, Ltd.”. As a sample, a single monomolecular film of dibenzoperylene (c13) and a 2-layer to 5-layer cumulative film were used. As a substrate for performing ED measurement, a substrate obtained by adhering a form bar film as a support film to a copper mesh sheet and having SiO ₂ deposited for surface hydrophilization treatment was used. As a result, diffraction spots corresponding to plane spacings of 0.48 and 0.41 nm were observed in all films. From this, it was found that not only a single film but also a 2-5 layer cumulative film, a film having a high order of crystal arrangement could be prepared.

[Confirmation of siloxane network formation on film surface]
In order to confirm whether or not a siloxane network on the film surface was formed by the pH treatment, infrared absorption spectrum measurement before and after the pH treatment was performed. In addition, before and after the pH treatment in the bilayer to five-layer cumulative film of dibenzoperylene (c13) is before and after the final pH treatment.
First, as a result of measuring the infrared absorption spectrum of each film before pH treatment, absorption derived from stretching vibration of C—O was confirmed at 1290 cm ⁻¹ .
On the other hand, after the pH treatment, the infrared absorption spectrum of each film was measured. As a result, the absorption derived from the C—O disappeared and broad absorption centered on 3300 cm ⁻¹ was confirmed. This absorption is derived from the stretching vibration of OH.

  When the static contact angles of pure water of the monomolecular film of dibenzoperylene (c13) having a siloxane network formed on the film surface after pH treatment and the accumulated film of two to five layers were measured, 26 °, 27 °, and 28 °, respectively. °, 29 °, 29 °.

From these facts, it can be said that the alkoxy group on the film surface is converted to a hydroxyl group by the pH treatment.
Furthermore, according to the above-mentioned crystallinity confirmation, the interplanar spacing of the monomolecular film of dibenzoperylene (c13) and the two- to five-layer cumulative film was 0.5 nm or less. Si (OH) ₃ is very reactive, and at the above intermolecular distance, a siloxane bond can be easily formed by a dehydration reaction between hydroxyl groups between adjacent molecules.
That is, in the above, it was confirmed that absorption from C—O disappeared by pH treatment and absorption of OH occurred in both the monomolecular film of dibenzoperylene (c13) and the two to five-layer cumulative film. As a result, it can be said that a hydrophilic siloxane network is formed on the film surface.

<Example 10: Preparation of organic thin film transistor and evaluation of electrical characteristics>
An organic thin film transistor of the type shown in FIG. 9 was produced.
First, chromium / gold was vapor-deposited on the silicon substrate 25 to produce the gate electrode 24. Next, a gate insulating film 23 made of a silicon oxide film was deposited by chemical vapor deposition. Further, chromium / gold was vapor-deposited using a mask, and the source electrode 21 and the drain electrode 22 were produced.
The produced substrate with electrodes was irradiated with ultraviolet light, and the surface of the gate insulating film 23 was hydrophilized. A 5-layer cumulative film of dibenzoperylene (c13) was prepared in the same manner as in Example 9 except that the obtained substrate was used, and an organic thin film transistor of the type shown in FIG. 9 was obtained.
In order to evaluate the electrical characteristics of the transistor, field effect mobility and on / off ratio were measured. The amount of current flowing by changing the voltage between the source / drain while applying various negative gate voltages (4155A; manufactured by HP) was measured. As a result, it was found that the field effect mobility was about 8 × 10 ⁻² cm ² V ⁻¹ s ⁻¹ and the on / off ratio was about 5 digits.

Experimental Example 12
<Synthesis Example 15: Synthesis of disilylated benzene (hereinafter referred to as benzene (b11))>
In a 1 liter glass flask, 1 equivalent of benzene [cas. no: 71-43-2], 1 equivalent of triethoxybromosilane, (hexane / diethyl ether) mixed solution (300 ml) was added, and 1 equivalent of t-butyllithium was added dropwise from a dropping funnel over 12 hours at -78 ° C. After the completion of the dropwise addition, the mixture was once warmed to room temperature and then cooled again to -196 ° C. The reaction solution was distilled to obtain a triethoxysilylated benzene colorless liquid as a fraction.
The obtained triethoxysilylated benzene was dissolved in a toluene solvent, and 1 equivalent of t-butyllithium was added dropwise at 0 ° C. over 10 hours. After completion of dropping, the mixture was stirred at room temperature for 12 hours to obtain a suspension. The suspension was dropped into a toluene solution mixed with 1 equivalent of tetrachlorosilane at −78 ° C. over 10 hours. After completion of dropping, the flask was removed from the cooling bath, and stirring was further performed for 6 hours.
After removing lithium chloride as a precipitate by filtration, benzene (b11) was obtained by filtration under reduced pressure.
The result of the instrumental analysis of the obtained benzene (b11) is shown.
¹ H NMR (δ CDCl ₃ ):
7.3 ppm (m, 4H, C ₆ H ₄ )
3.83 ppm (m, 6H, C ₂ H ₅ )
1.22 ppm (m, 9H, C ₂ H ₅ )
UV-Vis: 208 nm (C ₆ H ₄ )
From the above measurement results, it was confirmed that this compound had the structure of the general formula (b11).

<Synthesis Example 16; Synthesis of Silylated Benzene Silylated with Triethoxysilyl Group on One Side (hereinafter referred to as Benzene (x2))>
As a comparative example, silylated benzene (x2) silylated with a triethoxysilyl group only on one side was prepared in the same manner as in Synthesis Example 15.

<Example 11: Production of a single film consisting only of a monomolecular film of benzene (b11) and a single film consisting only of a monomolecular film of benzene (x2)>
Production Method A substrate obtained by immersing a Si wafer and a quartz glass substrate in a (hydrogen peroxide / sulfuric acid) mixed solution and subjecting it to hydrophilic treatment by irradiation with ultraviolet light and thoroughly washing with pure water was used as the substrate. Film formation was performed using the prepared substrate. Subsequently, the following steps (1) to (3) were performed to form the title monomolecular film.

Step (1);
First, a 0.2 mM toluene solution of benzene (b11) is developed on the water surface at pH = 7, and an adsorption reaction on the substrate accompanying the elimination of chlorine atoms in the trichlorosilyl group is performed using the LB method. A monomolecular film of (b11) was prepared on a Si wafer. The obtained substrate was washed with an organic solvent to remove the remaining unreacted benzene.
Step (2) (pH treatment);
Next, the benzene (b11) monomolecular film is immersed in water at pH = 2 and a water temperature of 25 ° C. to cause hydrolysis reaction and condensation reaction of the triethoxysilyl group of benzene (b11). A benzene (b11) monomolecular film having a siloxane network was formed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted benzene.

Step (3);
Separately, a monomolecular film of benzene (x2) was obtained by the same method as in the above step (1), except that benzene (x2) was used and the hydrolysis reaction of triethoxysilyl group was adjusted to pH = 2 and water temperature of 25 ° C. Was prepared. The operation by the method similar to the said process (2) was not performed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted benzene.

Film evaluation [film thickness confirmation]
Using a monomolecular film of benzene (b11) and a monomolecular film of benzene (x2) as samples, the surface morphology of the film was observed at 50 μm size with an atomic force microscope (AFM) (SPA400; manufactured by Seiko Instruments Inc.). The film was uniformly formed with a size of 50 μm. The root-mean-square roughness of the film is 0.33 nm for the benzene (b11) monomolecular film, which is not significantly different from the value of 0.26 nm for only Si as the substrate. On the other hand, it was 0.39 nm in the benzene (x2) monomolecular film. When the film was cut by mechanical treatment, the film thickness was about 0.4 nm corresponding to the molecular length of benzene. From this, it was found that a film having a uniform film thickness was prepared.
In addition, when the surface shapes of the benzene (b11) monomolecular film and the benzene (x2) monomolecular film were observed at a size of 10 μm by an atomic force microscope (AFM) (SPA400: manufactured by Seiko Instruments Inc.), the surface irregularities 2 The root mean square roughness (RMS) is 0.33 nm for the benzene (b11) monomolecular film and 0.39 nm for the benzene (x2) monomolecular film, and the benzene (b11) monomolecular film has higher smoothness. Was found to be obtained.

[Main skeleton confirmation]
In order to evaluate the accumulated state of the film in detail, UV-visible absorption spectrum measurement was performed by using a monomolecular film of benzene (b11) and a monomolecular film of benzene (x2) as a sample (UV-3000; manufactured by Shimadzu Corporation). Went. As a result, absorption having a peak position near 220 nm was observed in all the films.

[Confirmation of crystallinity]
The crystal arrangement was evaluated based on electron diffraction (ED) measurement by “H-7500; manufactured by Hitachi, Ltd.”. As a sample, a single film consisting only of a monomolecular film of benzene (b11) and a single film consisting only of a monomolecular film of benzene (x2) were used. As a substrate for performing ED measurement, a substrate obtained by adhering a form bar film as a support film to a copper mesh sheet and having SiO ₂ deposited for surface hydrophilization treatment was used. As a result, diffraction spots corresponding to plane spacings of 0.41 and 0.33 nm were observed in both films. From this, it was found that a film with high order of crystal arrangement could be prepared for any film.
The stability of the film was evaluated by the disappearance of the diffraction spot by electron beam irradiation. The benzene (x2) monomolecular film disappeared by the electron beam irradiation for about 1 minute and the structure of the film was destroyed, whereas the benzene (d11) monomolecular film was irradiated with the electron beam for 5 minutes or more. Even a diffraction spot was observed. This indicates that the strength of the film is improved in the benzene (d11) monomolecular film, and it can be said that this is an effect that a siloxane network is formed on the substrate side and the surface side of the film.

[Confirmation of siloxane network formation on film surface]
In order to confirm whether or not a siloxane network on the film surface was formed by the pH treatment, infrared absorption spectrum measurement before and after the pH treatment was performed.
First, as a result of measuring the infrared absorption spectrum before pH treatment of the benzene (d11) monomolecular film, absorption derived from stretching vibration of C—O was confirmed at 1290 cm ⁻¹ .
Moreover, as a result of measuring the infrared absorption spectrum after the pH treatment of the benzene (d11) monomolecular film, the absorption derived from the CO disappeared and broad absorption centering on 3300 cm ⁻¹ was confirmed. It was done. This absorption is derived from the stretching vibration of OH.
On the other hand, as a result of measuring the infrared absorption spectrum of the benzene (x2) monomolecular film, the absorption derived from the C—O was not measured.

  When the static contact angle was measured with pure water, the benzene (d11) monomolecular film was 24 ° and the benzene (x2) monomolecular film was 88 °. The benzene (d11) monomolecular film surface was found to be hydrophilic due to the formation of a siloxane network.

From these facts, it can be said that in the benzene (d11) monomolecular film, the alkoxy group on the film surface is converted to a hydroxyl group by the above pH treatment.
Furthermore, according to the above crystallinity confirmation, the interplanar spacing of the benzene (d11) monomolecular film and the benzene (x2) monomolecular film was both 0.5 nm or less. In the benzene (d11) monomolecular film before pH treatment, Si (OH) ₃ is very reactive, and at the above intermolecular distance, a siloxane bond is easily formed by dehydration reaction between hydroxyl groups between adjacent molecules. be able to.
That is, in the benzene (d11) monomolecular film, it was confirmed that absorption due to C—O disappeared due to pH treatment and absorption of OH was generated, so that a hydrophilic siloxane network was formed on the film surface. It can be said that. In addition, a monomolecular film of benzene (d11) was prepared by the same method except that an aluminum substrate forcedly oxidized by vacuum ultraviolet irradiation was used instead of the Si wafer in the step (1). In the infrared absorption spectrum measurement of the monomolecular film before the pH treatment in the step (2), absorption attributed to Si—O—Si vibration was observed at 1100 cm ⁻¹ . Thus, it can be said that a siloxane network is formed also on the substrate side, and the film is fixed to the substrate by a chemical bond (-Si-O-).

Experimental Example 13
<Synthesis Example 17: Synthesis of disilylated thiophene (hereinafter referred to as thiophene (a14))>
In a 100 ml glass flask, 1 equivalent of thiophene [cas. no: 110-02-1] and NBS were added and reacted in the presence of AIBN for 2 hours. After removing unreacted substances and HBr by filtration, a stored product brominated at only one place was taken out using a column chromatograph and purified by column chromatography to obtain 1-bromothiophene.
1 equivalent of 1-bromothiophene was dissolved in 20 ml of THF solution, and 1 equivalent of n-BuLi was slowly added dropwise at 0 ° C. over 10 hours. The mixed solution was stirred for 4 hours and then warmed to room temperature. The dark green solution produced by the reaction was dropped into 1 equivalent of tetraethoxysilane in THF at room temperature and refluxed and mixed for 15 hours. Next, the reaction solution was filtered under reduced pressure to remove unreacted tetraethoxysilane and n-BuLi, and then 1-triethoxysilylthiophene was obtained.
1 equivalent of 1-triethoxysilylthiophene was dissolved in 30 ml of THF solution, and 1 equivalent of n-BuLi was slowly added dropwise at 0 ° C. over 10 hours. The mixed solution was stirred for 4 hours and then warmed to room temperature. The dark green solution produced by the reaction was dropped into 1 equivalent of a tetrachlorosilane solution in THF at room temperature, and the mixture was refluxed for 15 hours and mixed. Next, the reaction solution was filtered under reduced pressure to remove unreacted tetrachlorosilane and n-BuLi, and then purified by column chromatography to obtain thiophene (a14).
The result of the instrumental analysis of the obtained thiophene (a14) is shown.
¹ H NMR (δ CDCl ₃ ):
6.5 ppm (m, 2H, C ₄ H ₂ S)
3.41 ppm (m, 6H, C ₂ H ₅ )
1.11 ppm (m, 9H, C ₂ H ₅ )
_{UV-Vis: 218nm (C 4} H 2 S)
From the above measurement results, it was confirmed that this compound had the structure of the general formula (a14).

<Synthesis Example 18: Synthesis of silylated thiophene (hereinafter referred to as thiophene (x3)) silylated with a triethoxysilyl group only on one side>
As a comparative example, silylated benzene (x3) silylated with a triethoxysilyl group only on one side was prepared in the same manner as in Synthesis Example 17.

<Example 12: Production of a single film consisting only of a monomolecular film of thiophene (a14) and a single film consisting only of a monomolecular film of thiophene (x3)>
Production Method A substrate obtained by immersing a Si wafer and a quartz glass substrate in a (hydrogen peroxide / sulfuric acid) mixed solution and subjecting it to hydrophilic treatment by irradiation with ultraviolet light and thoroughly washing with pure water was used as the substrate. Film formation was performed using the prepared substrate. Subsequently, the following steps (1) to (3) were performed to form the title monomolecular film.

Step (1);
First, a 0.2 mM toluene solution of thiophene (a14) is developed on the water surface at pH = 7, and an adsorption reaction on the substrate accompanying the elimination of the chlorine atom in the trichlorosilyl group is performed using the LB method. A monomolecular film (a14) was prepared. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.
Step (2) (pH treatment);
Next, the thiophene (a14) monomolecular film is immersed in water at pH = 2 and a water temperature of 25 ° C. to cause hydrolysis reaction and condensation reaction of the triethoxysilyl group of thiophene (a14). A thiophene (a14) monomolecular film having a siloxane network was formed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Step (3);
Separately, a monomolecular film of thiophene (x3) was obtained by the same method as in the above step (1) except that thiophene (x3) was used and the hydrolysis reaction of triethoxysilyl group was adjusted to pH = 2 and water temperature of 25 ° C. Was prepared. The operation by the method similar to the said process (2) was not performed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene.

Film evaluation [film thickness confirmation]
Using the monomolecular film of thiophene (a14) and the monomolecular film of thiophene (x3) as a sample, the surface morphology of the film was observed at 50 μm size with an atomic force microscope (AFM) (SPA400; manufactured by Seiko Instruments Inc.). The film was uniformly formed with a size of 50 μm. The root mean square roughness of the film is 0.34 nm for the thiophene (a14) monomolecular film, and there is no significant difference compared with the value of 0.26 nm for only Si as the substrate. On the other hand, it was 0.40 nm in the thiophene (x3) monomolecular film. When the film was cut by mechanical treatment, the film thickness was about 0.4 nm corresponding to the molecular length of thiophene. From this, it was found that a film having a uniform film thickness was prepared.
Further, when the surface shapes of the thiophene (a14) monomolecular film and the thiophene (x3) monomolecular film were observed with an atomic force microscope (AFM) (SPA400: manufactured by Seiko Instruments Inc.) at a size of 10 μm, the surface irregularities 2 The root mean square roughness (RMS) is 0.34 nm for the thiophene (a14) monomolecular film and 0.40 nm for the thiophene (x3) monomolecular film, and the thiophene (a14) monomolecular film has higher smoothness. Was found to be obtained.

[Main skeleton confirmation]
In order to evaluate the accumulated state of the film in detail, UV-visible absorption spectrum measurement was performed by using a monomolecular film of thiophene (a14) and a monomolecular film of thiophene (x3) as a sample (UV-3000; manufactured by Shimadzu Corporation). Went. As a result, absorption having a peak position near 190 nm was observed in all the films.

[Confirmation of crystallinity]
The crystal arrangement was evaluated based on electron diffraction (ED) measurement by “H-7500; manufactured by Hitachi, Ltd.”. As a sample, a single film consisting only of a monomolecular film of thiophene (a14) and a single film consisting only of a monomolecular film of thiophene (x3) were used. As a substrate for performing ED measurement, a substrate obtained by adhering a form bar film as a support film to a copper mesh sheet and having SiO ₂ deposited for surface hydrophilization treatment was used. As a result, diffraction spots corresponding to plane spacings of 0.42 and 0.33 nm were observed in both films. From this, it was found that a film with high order of crystal arrangement could be prepared for any film.
The stability of the film was evaluated by the disappearance of the diffraction spot by electron beam irradiation. The thiophene (x3) monomolecular film disappeared by the electron beam irradiation for about 1 minute, and the structure of the film was destroyed, whereas the thiophene (a14) monomolecular film was irradiated with an electron beam for 5 minutes or more. Even a diffraction spot was observed. This indicates that the strength of the thiophene (a14) monomolecular film is improved, and it can be said that this is an effect that a siloxane network is formed on the substrate side and the surface side of the film.

[Confirmation of siloxane network formation on film surface]
In order to confirm whether or not a siloxane network on the film surface was formed by the pH treatment, infrared absorption spectrum measurement before and after the pH treatment was performed.
First, infrared absorption spectrum measurement was performed before pH treatment of the thiophene (a14) monomolecular film, and as a result, absorption derived from stretching vibration of C—O was confirmed at 1285 cm ⁻¹ .
In addition, as a result of infrared absorption spectrum measurement after pH treatment of the thiophene (a14) monomolecular film, absorption derived from the above-mentioned CO disappeared, and broad absorption centering on 3300 cm ⁻¹ was confirmed. It was done. This absorption is derived from the stretching vibration of OH.
On the other hand, as a result of measuring the infrared absorption spectrum of the thiophene (x3) monomolecular film, the absorption derived from the C—O was not measured.

  When the static contact angle was measured with pure water, the thiophene (a14) monolayer was 27 ° and the thiophene (x3) monolayer was 82 °. The thiophene (a14) monomolecular film surface was found to be hydrophilic due to the formation of a siloxane network.

From these facts, it can be said that in the thiophene (a14) monomolecular film, the alkoxy group on the film surface is converted to a hydroxyl group by the pH treatment.
Furthermore, according to the above crystallinity confirmation, the interplanar spacing of the thiophene (a14) monomolecular film and the thiophene (x3) monomolecular film was 0.5 nm or less. In the thiophene (a14) monomolecular film before pH treatment, Si (OH) ₃ is very reactive, and at the above intermolecular distance, a siloxane bond is easily formed by dehydration reaction between hydroxyl groups between adjacent molecules. be able to.
That is, in the thiophene (a14) monomolecular film, it was confirmed that absorption due to C—O disappeared due to pH treatment, and absorption of OH was generated, so that a hydrophilic siloxane network was formed on the film surface. It can be said that. A monomolecular film of thiophene (a14) was prepared by the same method except that an aluminum substrate forcedly oxidized by irradiation with vacuum ultraviolet rays was used instead of the Si wafer in the step (1). In the infrared absorption spectrum measurement of the monomolecular film before the pH treatment in the step (2), absorption attributed to Si—O—Si vibration was observed at 1100 cm ⁻¹ . Thus, it can be said that a siloxane network is formed also on the substrate side, and the film is fixed to the substrate by a chemical bond (-Si-O-).

Experimental Example 14
<Synthesis Example 19: Production of Tributoxysilane-Perylene-Triethoxysilane (Formula (c12))>
Naphthalene was synthesized binaphthyl (Aldrich) naphthalene by reaction with _{NaNO 2 -TfOH (Tf = CF 3} SO 2) solution. Binaphthyl was reacted with LiTHF under oxygen bubbling to obtain perylene. Chlorination was performed by reacting NCS equivalent to perylene with perylene in AcOH in the presence of CHCl ₃ . Then, it reacted with n-BuLi and tetrabutoxysilane in a THF solution to obtain tributoxysilane-perylene (yield 8%).

A 1-liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with tributoxysilane-perylene, 1 equivalent of tetraethoxysilane, and 300 ml of THF under a dry argon stream, cooled on ice, and an internal temperature of 25 ° C. Below, a Grignard reagent was dripped over 2 hours, and it age | cure | ripened at 30 degreeC after completion | finish of dripping for 1 hour. Next, the reaction solution was filtered under reduced pressure to remove unreacted magnesium, and then THF and unreacted tetraethoxysilane were removed from the filtrate. This solution was removed to obtain a compound represented by the formula (c12).
When the obtained compound was subjected to infrared absorption measurement, Si—O—C absorption was observed at a wavelength of 1050 nm. From this, it was confirmed that the obtained compound contains a silyl group.
When the ultraviolet-visible absorption spectrum of the chloroform solution containing the compound was measured, absorption was observed at a wavelength of 378 nm. This absorption was attributed to the π → π ^* transition of the perylene skeleton contained in the molecule, and it was confirmed that the compound contained a perylene skeleton.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
8.8 ppm (m) (derived from 2H aromatics)
7.8 ppm (m) (from 3H aromatics)
6.6 ppm (m) (derived from 2H aromatics)
6.4 ppm (m) (derived from 2H aromatics)
3.7 ppm (m) (from 1H aromatics)
3.4 ppm (m) (derived from 12H butoxy group and ethoxy group methylene group)
1.4 ppm (m) (derived from methylene group of 12H butoxy group)
1.1 ppm (m) (derived from methyl group of 9H ethoxy group)
1.0 ppm (m) (derived from the methyl group of 9H butoxy group)
From these results, it was confirmed that this compound was n-tributoxysilane-perylene-triethoxysilane. This compound is referred to as perylene (c12).

<Example 13: Production of single monomolecular film of perylene (c12) and 2-layer to 5-layer cumulative film>
Step (1);
First, a hydrophilic substrate prepared by the method shown in Example 1 was immersed in a 0.01 mM toluene solution of perylene (c12) at 50 ° C. for 12 hours. A hydroxyl group present on the substrate surface and a triethoxysilyl group reacted to prepare a monomolecular film of perylene (c12). The obtained substrate was washed with an organic solvent to remove the remaining unreacted perylene.
Step (2) (pH treatment);
Next, the perylene (c12) monomolecular film is immersed in water at pH = 1 and a water temperature of 50 ° C. to cause hydrolysis and condensation reaction of the tributoxysilyl group of perylene (c12). A perylene (c12) monomolecular film having a siloxane network was formed. The obtained substrate was washed with an organic solvent to remove the remaining unreacted perylene.

Step (3);
Next, the substrate on which the perylene (c12) monomolecular film was formed in the step (2) was immersed in a 0.01 mM toluene solution of perylene (c12) at 50 ° C. for 12 hours. A hydroxyl group present on the substrate surface and a triethoxysilyl group reacted to prepare a second layer of perylene (c12) monomolecular film on the lowermost monomolecular film. Furthermore, a siloxane network was formed on the film surface by the same method as in the above step (2) except that the hydrolysis reaction of the tributoxysilyl group was carried out under the conditions of pH = 1 and water temperature of 50 ° C. The obtained substrate was washed with an organic solvent to remove the remaining unreacted perylene.

Step (4);
Further, by repeating the step (3) for forming the second monomolecular film described above three times, a five-layer cumulative film in which five monolayers of perylene (c12) are laminated is prepared. did.

Film evaluation [film thickness confirmation]
Using a 2-5 layer film of perylene (c12) as a sample, the surface morphology of the film was observed with an atomic force microscope (AFM) (SPA400; manufactured by Seiko Instruments Inc.) at a size of 50 μm. It was formed uniformly. The root mean square roughness of the film is 0.31, 0.33, 0.36, and 0.39 nm, respectively, and there is no significant difference compared to the value of 0.26 nm for the substrate Si alone. Can be said to be expensive.
When the film was cut by mechanical treatment, the film thickness was 2.8 nm for the two-layer film, 4.2 nm for the three-layer film, 5.6 nm for the four-layer film, and 7 nm for the five-layer film. This corresponds to a cumulative number of times the molecular length. From this, it was found that a film having a uniform film thickness was prepared.

[Main skeleton confirmation]
In order to evaluate the accumulated state of the film in detail, a single monomolecular film of perylene (c12) and a 2 to 5 layer accumulated film were used as samples, and UV-visible absorption spectrum was obtained by (UV-3000; manufactured by Shimadzu Corporation). Measurements were made. As a result, absorption having a peak position near 360 nm was observed in all the films.

[Confirmation of crystallinity]
The crystal arrangement was evaluated based on electron diffraction (ED) measurement by “H-7500; manufactured by Hitachi, Ltd.”. As a sample, a monolayer of perylene (c12) and a 2- to 5-layer cumulative film were used. As a substrate for performing ED measurement, a substrate obtained by adhering a form bar film as a support film to a copper mesh sheet and having SiO ₂ deposited for surface hydrophilization treatment was used. As a result, diffraction spots corresponding to plane spacings of 0.46 and 0.34 nm were observed in all films. From this, it was found that not only a single film but also a 2-5 layer cumulative film, a film having a high order of crystal arrangement could be prepared.

[Confirmation of siloxane network formation on film surface]
In order to confirm whether or not a siloxane network on the film surface was formed by the pH treatment, infrared absorption spectrum measurement before and after the pH treatment was performed. In addition, before and after the pH treatment in the two- to five-layer cumulative film of perylene (c12) is before and after the last pH treatment.
First, as a result of measuring the infrared absorption spectrum of each film before pH treatment, absorption derived from stretching vibration of C—O was confirmed at 1290 cm ⁻¹ .
On the other hand, after the pH treatment, the infrared absorption spectrum of each film was measured. As a result, the absorption derived from the C—O disappeared and broad absorption centered on 3300 cm ⁻¹ was confirmed. This absorption is derived from the stretching vibration of OH.

  When the static contact angles of pure water of the monomolecular film of perylene (c12) having a siloxane network formed on the film surface after the pH treatment and the two-layer to five-layer cumulative film were measured, 27 °, 27 °, and 28 °, respectively. 29 ° and 30 °.

From these facts, it can be said that the alkoxy group on the film surface is converted to a hydroxyl group by the pH treatment.
Furthermore, according to the above crystallinity confirmation, the interplanar spacing of the monomolecular film of perylene (c12) and the two-layer to five-layer cumulative film was 0.5 nm or less. Si (OH) ₃ is very reactive, and at the above intermolecular distance, a siloxane bond can be easily formed by a dehydration reaction between hydroxyl groups between adjacent molecules.
That is, in the above, it can be confirmed that absorption derived from C—O disappeared due to pH treatment and absorption of OH occurred in both the monomolecular film of perylene (c12) and the accumulated film of 2 to 5 layers. Thus, it can be said that a hydrophilic siloxane network is formed on the film surface.

<Example 14: Preparation of organic thin film transistor and evaluation of electrical characteristics>
An organic thin film transistor of the type shown in FIG. 9 was produced.
First, chromium / gold was vapor-deposited on the silicon substrate 25 to produce the gate electrode 24. Next, a gate insulating film 23 made of a silicon oxide film was deposited by chemical vapor deposition. Further, chromium / gold was vapor-deposited using a mask, and the source electrode 21 and the drain electrode 22 were produced.
The produced substrate with electrodes was irradiated with ultraviolet light, and the surface of the gate insulating film 23 was hydrophilized. A five-layer cumulative film of perylene (c12) was prepared in the same manner as in Example 12 except that the obtained substrate was used, and an organic thin film transistor of the type shown in FIG. 9 was obtained.
In order to evaluate the electrical characteristics of the transistor, field effect mobility and on / off ratio were measured. The amount of current flowing by changing the voltage between the source / drain while applying various negative gate voltages (4155A; manufactured by HP) was measured. As a result, it was found that the field effect mobility was about 6.4 × 10 ⁻² cm ² V ⁻¹ s ⁻¹ and the on / off ratio was about 5 digits.

It is a conceptual diagram which shows the molecular arrangement | sequence of an example of the monomolecular film formed in the board | substrate in this invention. It is a conceptual diagram which shows the molecular arrangement | sequence of an example of the monomolecular film which has a siloxane network on the film | membrane surface. FIG. 3 is a conceptual diagram showing a molecular arrangement of a two-layer monomolecular cumulative film formed by further forming a monomolecular film on the monomolecular film of FIG. 2. It is the schematic for demonstrating the electrical conductivity measurement by an in-plane electric AFM measurement. (A) is a schematic diagram of a two-layer cumulative film using one type of organic compound (I), and (B) is a schematic diagram of a two-layer cumulative film using two types of organic compound (I). (A)-(C) show the schematic block diagram of an example of the organic thin-film transistor of this invention. The schematic block diagram of an example of the organic photoelectric conversion element of this invention is shown. BRIEF DESCRIPTION OF THE DRAWINGS The schematic block diagram of an example of the organic EL element of this invention is shown. The schematic sectional drawing of the organic thin-film transistor manufactured in the Example is shown. It is a figure for demonstrating the relationship between intermolecular distance and intermolecular force.

Explanation of symbols

1: hydrophilized substrate, 10: SPM device type piezo element, 11: cantilever, 12: monomolecular film or monomolecular cumulative film, 13: gold / chromium electrode, 14: mica substrate, 15: ammeter measuring means, 20: semiconductor layer, 21: source electrode, 22: drain electrode, 23: gate insulating film, 24: gate electrode, 25: silicon substrate, 31: transparent electrode, 32: counter electrode, 33: n-type photoconductive layer, 34 : P-type photoconductive layer, 35 :: organic layer, 41: anode, 42: cathode, 43: light emitting layer, 44: hole transport layer, 45: electron transport layer, 48: organic layer.

Claims (15)

General formula (I);

(In the formula, A ^{1 to} A ⁶ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, and A ^{1 to} A ⁶ are elimination reactivity. Satisfying the relationship of A ^{1 to} A ³ > A ^{4 to} A ⁶ ; B is a divalent organic group), and has a siloxane network on the film surface A characteristic siloxane-based molecular film.   The siloxane-based molecular film according to claim 1, which is immobilized on a substrate by a chemical bond.   The siloxane-based molecular film according to claim 1 or 2, wherein the molecular film has a structure of a single monomolecular film or a monomolecular cumulative film.   The siloxane-based molecular film according to any one of claims 1 to 3, wherein the organic group B is oriented.   The organic group B is a linear monocyclic aromatic compound, a linear condensed aromatic compound, a linear monocyclic heterocyclic compound, a linear condensed heterocyclic compound, or a linear saturated aliphatic compound. Or a siloxane-based molecular film according to any one of claims 1 to 4, which is a group derived from a compound in which 2 to 30 of these compounds are bonded.   Organic group B is a linear monocyclic aromatic compound, a linear monocyclic heterocyclic compound, a linear saturated aliphatic compound, a compound in which 2 to 30 of these compounds are bonded, or a linear The siloxane molecular film according to any one of claims 1 to 5, which is a group derived from a condensed aromatic compound. A combination of A ^{1 to} A ³ and A ^{4 to} A ⁶ is one of the following (1) to (4): The siloxane-based molecular film according to any one of claims 1 to 6;
(1) A ^{1 to} A ³ are each independently a halogen atom, and A ^{4 to} A ⁶ are each independently an alkoxy group;
(2) A ^{1 to} A ³ are each independently a halogen atom, and A ^{4 to} A ⁶ are each independently an alkyl group;
(3) A ^{1 to} A ³ are each independently an alkoxy group having 1 to 2 carbon atoms, A ^{4 to} A ⁶ are each independently an alkoxy group having 3 to 4 carbon atoms; and (4) A ^{1 to} A ³ are each independently an alkoxy group having 1 to 2 carbon atoms, and A ^{4 to} A ⁶ are each independently an alkyl group having 3 to 8 carbon atoms. (Formula) H-B-MgX (2)
(Wherein B is a divalent organic group and X is a halogen atom);
^{(Formula) Y 1 -Si (A 1)} (A 2) (A 3) (3)
(Wherein Y ¹ is a halogen atom, and A ^{1 to} A ³ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 18 carbon atoms). Reaction with the compound
^{(Formula) H-B-Si (A} 1) (A 2) (A 3) (4)
Synthesize
In the formula (4), a halogen atom is bonded to B and reacted with magnesium or lithium metal in the presence of ethoxyethane or tetrahydrofuran (THF) (formula) MgX-B-Si (A ¹ ) (A ² ) ^{(A 3)} or ^{LiX-B-Si (A 1} ) (A 2) (A 3) (5)
After synthesizing the compound represented by
^{(Formula) Y 2 -Si (A 4)} (A 5) (A 6) (6)
(Wherein Y ² is a halogen atom, and A ^{4 to} A ⁶ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 18 carbon atoms, and is eliminated. The organic compound of the general formula (I) is obtained by reacting with a compound represented by the formula (I satisfies A ^{1 to} A ³ > A ^{4 to} A ⁶ ). A method for producing the siloxane molecular film according to claim 1. ^{(Formula) X 1 -B-X 2 (} 8)
(Wherein B is a divalent organic group, X ¹ and X ² are different from each other and are a halogen atom), and a Grignard reactant using a metal catalyst comprising magnesium or lithium. And then
^{(Formula) Y 1 -Si (A 1)} (A 2) (A 3) (3)
(Wherein Y ¹ is a halogen atom, and A ^{1 to} A ³ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 18 carbon atoms). Grignard reactant represented by the following formula (formula) Si (A ¹ ) (A ² ) (A ³ ) -B-MgX ² (9)
And then
^{(Formula) Y 2 -Si (A 4)} (A 5) (A 6) (6)
(Wherein Y ² is a halogen atom, and A ^{4 to} A ⁶ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 18 carbon atoms, and is eliminated. A compound represented by (formula 9) and a compound represented by (formula 9) are reacted with each other to obtain an organic compound of the general formula (I), which satisfies the relationship of A ^{1 to} A ³ > A ^{4 to} A ⁶ A method for producing a siloxane-based molecular film according to any one of claims 1 to 7. (1) A step of reacting a silyl group having A ^{1 to} A ³ in the organic compound described in the general formula (I) with a substrate surface to form a monomolecular film composed of a monomolecular layer directly adsorbed on the substrate. ,
(2) a step of washing and removing unreacted organic compounds using a non-aqueous solvent;
(3) a step of forming a siloxane network by hydrolysis reaction and condensation reaction of unreacted silyl groups existing on the film surface side of the obtained monomolecular film, and (4) unreacted on the film surface on which the siloxane network is formed. A method for producing a siloxane-based molecular film according to claim 8 or 9, comprising the step of accumulating monomolecular films composed of the organic compound of the general formula (I) using the hydroxyl group of the compound as an adsorption reaction site. .   The method for producing a siloxane-based molecular film according to any one of claims 8 to 10, wherein the substrate has a hydroxyl group on the surface.   The organic device which has a siloxane type molecular film in any one of Claims 1-7.   The organic device includes at least a substrate, a gate electrode formed on the substrate, a gate insulating film formed on the gate electrode, and a source electrode and a drain provided in contact with or non-contact with the gate insulating film The organic device according to claim 12, wherein the organic device is an organic thin film transistor having an electrode and a semiconductor layer, and the semiconductor layer and / or the gate insulating film is a siloxane-based molecular film.   The organic device according to claim 12, wherein the organic device is an organic photoelectric conversion element having at least an organic layer between a transparent electrode and a counter electrode, and the organic layer is a siloxane-based molecular film. . The organic device according to claim 12, wherein the organic device is an organic EL element having an organic layer between at least an anode and a cathode, and the organic layer is a siloxane-based molecular film.

Images