JP3955872B2 - Organic device using organic compound having different functional groups with different elimination reactivity at both ends - Google Patents

Description

  The present invention relates to an organic device using an organic compound having different functional groups with different elimination reactivity at both ends and a method for producing the same.

  Conventionally, an inorganic material such as a silicon crystal has been used in many semiconductor devices. However, in the inorganic material, crystal defects are generated with the miniaturization of the device, which affects the device performance and limits the fine processing.

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

  The organic compound exhibits crystallinity or amorphousness depending on the chemical structure and processing conditions. When using an organic compound in a semiconductor device, it is necessary to select a material suitable for the intended characteristics. In a device such as a transistor that requires high carrier mobility, crystallinity is generally required for a film made of an organic compound. Of the organic compounds, a high molecular weight material having a distribution in molecular weight makes it very difficult to realize 100% perfect crystal, and thus low molecular organic compounds are usually used for devices. In addition, it is desired that a film made of an organic compound is highly crystallized in order to reduce the size of the device and to develop the quantum effect.

  When the organic semiconductor device does not perform processing such as doping on the organic material, carriers are obtained by carrier injection from the interface of the contact electrode material to be used. In order to increase the carrier injection efficiency, the organic compound in direct contact with the electrode is required to have the same ionization potential as that of the metal electrode to be used, so that the type of the organic compound is limited. That is, an organic thin film formed of a laminated film including a buffer layer such as a carrier injection layer is optimally formed on and between the electrodes.

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

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

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

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

  However, the conductivity of the self-assembled film is determined by the organic functional group in the silicon-based compound contained in the film, but commercially available silane coupling agents contain π-electron conjugated molecules in the organic functional group. There are no compounds, so it is difficult to impart conductivity to the self-assembled film. Accordingly, there is a need for a silicon-based compound suitable for devices such as TFTs and containing a π-electron conjugated molecule as an organic functional group.

  As such a silicon-based compound, a compound having one thiophene ring as a functional group at the end of a molecule, and the thiophene ring being bonded to Si via a linear hydrocarbon group has been proposed (for example, Patent Document 1). ). Furthermore, as a polyacetylene film, a film in which a —Si—O— network is formed on a substrate by a chemical adsorption method and a portion of an acetylene group is polymerized has been proposed (for example, Patent Document 2). 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. Further, 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 the conductive thin film is used as a semiconductor layer (for example, Patent Document 3). Furthermore, a field effect transistor using a semiconductor thin film mainly composed of a silicon compound having a silanol group in a thiophene ring contained in polythiophene has been proposed (for example, Patent Document 4).

  However, although the compounds proposed above can produce a self-assembled film that can be chemically adsorbed to a substrate, the film has high order, crystallinity, and electrical conductivity that can be used in electronic devices such as TFTs. Could not always be produced. Furthermore, when the compound proposed above is used for the semiconductor layer of the organic TFT, there is a problem that the off-current becomes large. This is thought to be because all of the proposed compounds have bonds in the direction of the molecule and in the direction perpendicular to the molecule.

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

  On the other hand, the above compound may be chemically adsorbed to the substrate by forming a two-dimensional network of Si-O-Si, and there is a possibility that ordering due to intermolecular interaction between specific long-chain alkyls may be obtained. However, since one thiophene molecule as a functional group only contributes to the π-electron conjugated system, there is a problem that the interaction between molecules is weak and the spread of the π-electron conjugated system essential for electrical conductivity is very small. there were. Even if the number of thiophene molecules, which are the above functional groups, can be increased, the factor that forms the order of the film matches the intermolecular interaction between the long-chain alkyl part and the thiophene part. It is difficult to make it.

  Furthermore, as an electrical conduction characteristic, a single thiophene molecule that is a functional group has a large HOMO-LUMO energy gap, and there is a problem that sufficient carrier mobility cannot be obtained even when used as an organic semiconductor layer in a TFT or the like. Existed.

  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 the cumulative film using the chemical adsorption method reported so far, there is, for example, Patent Document 5. 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 having a uniform film thickness and a high order of crystal arrangement with high reproducibility. In a device using a monomolecular cumulative film having a non-uniform film thickness and a low order of crystal arrangement, carriers are trapped between the cumulative films, resulting in performance degradation.
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

  Another object of the present invention is to provide an organic device excellent in electric conduction characteristics that can be easily manufactured by a simple method, and a manufacturing method thereof.

（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、特に、有機基Ｂがπ電子共役を示す２価の有機基である上記一般式（Ｉ）の有機化合物を用いてなる有機デバイスに関する。 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), in particular, a divalent organic group in which the organic group B exhibits π-electron conjugation The present invention relates to an organic device using the organic compound of the general formula (I).

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 ) (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 reactivity is reacted with a ¹ ~A ^3> a ⁴ satisfy the relationship to a ⁶⁾ compounds represented by a process for the preparation of an organic device, characterized in that to obtain the organic compound.
The present invention also relates to an organic device formed using the organic compound.

The present invention also provides: (Formula) X ¹ -BX 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. An organic device characterized in that the organic compound is obtained by reacting a compound represented by (Formula 9) with a compound represented by (Formula 9), wherein the reactivity is A ^{1 to} A ³ > A ^{4 to} A ⁶ are satisfied It relates to the manufacturing method.
The present invention also relates to an organic device formed using the organic compound.

The present invention also includes (1) a step of reacting a silyl group having A ^{1 to} A ³ in the organic compound 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, and (3) the unreacted silyl group present on the film surface side of the obtained monomolecular film as an adsorption reaction site, The present invention relates to a method for manufacturing an organic device comprising a step of accumulating monomolecular films made of an organic compound.

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 organic compound of the present invention is chemically adsorbed to a substrate by forming a two-dimensional network of Si-O-Si formed between compound molecules, and acts on molecules, which is a short distance force necessary for crystallization of a film. Since the intermolecular interaction that works works efficiently, it is possible to construct a highly crystallized film having very high stability. Therefore, compared to a film produced by physical adsorption on the substrate, the obtained film can be strongly adsorbed on the surface of the substrate and physical peeling can be prevented.

In addition, the organic compound-derived network and the organic group that compose the organic thin film are directly bonded, and the organic compound-derived network and the organic compound having high ordering (crystallinity) due to the intermolecular interaction between the π-conjugated molecules. A thin film can be formed. Thereby, carriers are smoothly moved by hopping conduction in a direction perpendicular to the molecular plane. In addition, since high conductivity is obtained in the molecular axis direction, the conductive material can be widely applied not only to organic thin film transistor materials but also to solar cells, fuel cells, sensors, and the like.
Moreover, it becomes possible to easily produce the above compounds.

  Further, as shown in the formula (I), in an organic compound having silyl groups at both ends, the elimination reactivity of the group bonded to silicon is different between the silyl groups at both ends, thereby adsorbing on the substrate and The adsorption reaction on the film surface can be sequentially and selectively performed 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 an organic thin film having high molecular orientation in which molecules are arranged not only in the in-plane direction but also in a film thickness direction with high order.

  When such an organic thin film is produced as a monomolecular cumulative film, the organic thin film has different electrical characteristics in the film thickness direction corresponding to the electrical characteristics of a monomolecular layer having a thickness of several nanometers as a structural unit. As a result, 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 of the present invention has a self-organizing property, it is not necessary to produce an organic thin film having high crystallinity and orientation in a vacuum, and can be carried out in the air. . This means that the production is simple and inexpensive, and therefore has great merit as an industrial process.

  Further, if the hydrophilic treatment, which is a pretreatment of the substrate, is performed by patterning, 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.

  Monomolecular accumulation film can arrange materials with different conductivity, heat sensitivity, and light sensitivity in the vertical direction from the substrate in the order of several nanometers, so high density recording, high speed response switch, fine region conductivity, etc. Field, electron and hole injection, electron and hole transport, organic electroluminescence (EL) elements having a heterostructure with a thickness on the order of nm, such as a light emitting layer, photoelectric conversion elements used in solar cells, etc. Can do.

で表される。 (Organic compounds)
The organic compound 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 viewpoints 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 viewpoints of 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, the 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 within the alkoxy group or the order within 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 4 carbon atoms, preferably 2-propyl group, sec- or tert-butyl group, particularly tert-butyl group at the same time.

  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).

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, an unsaturated aliphatic skeleton, and a composite skeleton thereof.

  Examples of the π-electron conjugated skeleton-containing molecule (π-electron conjugated compound) capable of deriving the organic group b1 include a monocyclic aromatic compound, a condensed aromatic compound, a monocyclic heterocyclic compound, and a condensed heterocyclic ring. Examples thereof include compounds, unsaturated aliphatic compounds, and linked compounds in which two or more of these compounds are bonded.

Examples of monocyclic aromatic compounds include benzene, toluene, xylene, mesitylene, cumene and the like.
Examples of the condensed aromatic compound include naphthalene, anthracene, naphthacene, pentacene, hexacene, heptacene, octacene, nonacene, azulene, fluorene, pyrene, acenaphthene, perylene, anthraquinone and the like. 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. In the above formula (α1), a compound in which a benzene ring is linearly condensed is shown in the form. Molecules that are condensed non-linearly, such as sen, are also included in the compound of formula (α1).

Examples of the monocyclic heterocyclic compound include furan, thiophene, pyridine, pyrimidine, oxazole and the like.
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.

  Examples of unsaturated aliphatic compounds include alkenes such as ethylene, propylene, butylene, butene and pentene, alkadienes such as propadiene, butadiene, pentadiene and hexadiene, and butatriene, pentatriene, hexatriene, heptatriene and octatriene. Examples include alkatrienes.

  The linking compound is at least two selected from the group consisting of the above-mentioned monocyclic aromatic compounds, condensed aromatic compounds, monocyclic heterocyclic compounds, condensed heterocyclic compounds and unsaturated aliphatic compounds, A compound in which 2 to 8 compounds are bonded by a single bond. A compound in which two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds are bonded, particularly 2 to 8 is preferable.

  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 in 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, when the constituent compound molecule is thiophene, the bonding position of the compound constituting the linking compound is any of 2,5-position, 3,4-position, 2,3-position, 2,4-position, etc. However, the 2,5-position is preferable among them. In the case of benzene, any of 1,4-position, 1,2-position, 1,3-position and the like may be used, and among them, 1,4-position is preferable.

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 compounds in which two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds are bonded, biphenyl, bithiophenyl, terphenyl (compound of formula iii), tertenyl (formula iv) Compound), quarterphenyl, quarterthiophene, quinkephenyl, quinkethiophene, hexylphenyl, hexythiophene, thienyl-oligophenylene (see compound of formula v), phenyl-oligooligothienylene (see compound of formula vi), And groups derived from block co-oligomers (see compounds of formula vii or viii).

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

  The organic group b1 derived from the π-electron conjugated compound 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. Therefore, among the above functional groups, a linear alkyl group having 1 to 30 carbon atoms is particularly preferable.

  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. And may be substituted with a halogen atom. 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 alkane include linear alkanes having 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Examples of the halogen atom that may be substituted when these non-π electron conjugated skeleton-containing molecules constitute the organic group b2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  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, an unsaturated aliphatic compound, or their A group derived from a compound in which two or more, particularly 2 to 8, compounds are bonded is preferable.

  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), an unsaturated aliphatic compound (especially alkene, alkadiene, alkatriene), 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, ethylene derivatives, naphthalene derivatives, anthracene derivatives, tetracene derivatives, pyrene derivatives, and perylene derivatives.

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 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 ^{Li-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 a 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, 2,2′-azobisisobutyronitrile (AIBN) and N-bromosuccinimide (NBS) are used at both ends. 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. In addition, after the reaction using the furan derivative in the above reaction formula, the reaction product is refluxed under lithium iodide and DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) to obtain the starting compound. A compound having one more benzene ring and two substituted hydroxyl groups 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 formed using the organic compound (I) may have either a single monomolecular film or a monomolecular cumulative film, and in the case of a monomolecular cumulative film, at least the constituent of the film One, particularly at least two monomolecular films may be formed from the organic compound (I).

Hereinafter, preferred embodiments of the organic thin film will be described.
A preferable organic thin film has a structure of a single monomolecular film having one monomolecular film on the substrate, and 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, at least first to (n-1) monomolecular films, more preferably all monomolecular films Is 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 that can form the nth monomolecular film (outermost surface film) when the organic thin film has a monomolecular cumulative film structure is the organic compound (I) A that forms the (n-1) th monomolecular film. It is not particularly limited as long as it has a reactive group capable of reacting with a silyl group having ^{4 to} A ⁶ to form a chemical bond. For example, a silyl group having the same A ^{1 to} A ³ as described above, a halogen atom , Organic compounds having a reactive group such as a hydroxyl group or a carboxyl group. Preferably, the organic compound (I) is used.

  In addition, when the organic thin film has a monomolecular cumulative film structure, the first to (n-1) th monomolecular film, and the organic compound (I) forming the first to nth monomolecular film as required is for each film. It may be selected independently within the above range. 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 (hydrogen silsesquioxane) material (inorganic), MSQ (methyl silsesquioxane) material, PAE (polyarylene 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, a chemical bond (particularly a silanol bond) is formed at the monomolecular film-substrate interface by a reaction between a highly reactive silyl group and a hydrophilic group on the substrate surface, A low-reactive silyl group is present on the film surface side. As a result, the monomolecular film is bonded (adsorbed) to the substrate by the highly reactive silyl group.

  Further, for example, in the case where the substrate has a monomolecular cumulative film structure having the first and second monomolecular films sequentially, the highly reactive silyl group of the first monomolecular film is present at the first monomolecular film-substrate interface. A chemical bond (particularly silanol bond (—Si—O—)) is formed by a reaction between the substrate and the hydrophilic group on the substrate surface. Further, at the interface between the first monomolecular film and the second monomolecular film, a chemical bond (for example, siloxane) is generated by a reaction between the low-reactivity silyl group of the first monomolecular film and the reactive group (for example, silyl group) of the second monomolecular film. A bond (-Si-O-Si-)) is formed. As a result, the first monomolecular film is bonded (adsorbed) to the substrate by a highly reactive silyl group, and is bonded (adsorbed) to the second monomolecular film by a low reactive silyl group.

  Further, for example, in the case where the substrate has a monomolecular cumulative film structure having first to nth (n is an integer of 3 or more) monomolecular films sequentially, the first monomolecular film-substrate interface has the first monomolecular film structure. A chemical bond (particularly silanol bond (—Si—O—)) is formed by the reaction between the highly reactive silyl group of the molecular film and the hydrophilic group of the substrate surface. The k-th monomolecular film (k is an integer of 2 or more and (n-1) or less)-(k-1) monomolecular film interface and the highly reactive silyl group of the k-th monomolecular film and the (k-1) ) A chemical bond (particularly a siloxane bond) is formed by reaction with the low-reactivity silyl group of the monomolecular film. Further, at the k-th monomolecular film- (k + 1) monomolecular film interface when k is an integer of 2 or more and (n-2) or less, the low-reactive silyl group and the (k + 1) -th monomolecule of the k-th monomolecular film are used. Chemical bonds (particularly siloxane bonds) are formed by reaction with the highly reactive silyl groups of the film. At the k-th monomolecular film- (k + 1) monomolecular film (outermost surface film) interface when k is (n-1), the low-reactive silyl group of the k-th monomolecular film and the (k + 1) -th monomolecule Chemical bonds (eg siloxane bonds) are formed by reaction with reactive groups (eg silyl groups) on the membrane. As a result, the kth monomolecular film is bonded to the (k−1) th monomolecular film by the highly reactive silyl group, and is bonded to the (k + 1) th monomolecular film by the low reactive silyl group. That is, the second to (n-1) monomolecular films are bonded (adsorbed) to the monomolecular film immediately below by the highly reactive silyl group, and bonded (adsorbed) to the monomolecular film immediately above by the low reactive silyl group. To do.

  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. Incidentally, a silyl group having such A ⁴ to A ⁶ group is activated during the formation of the monomolecular film immediately above, it is used as a reaction site. As a result, since compound molecules are arranged in the same direction in each monomolecular film, single monomolecular films having a uniform film thickness and molecular crystallinity and their accumulated films can be formed. 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.

  Such a single monomolecular film or a cumulative monomolecular film can be a thin film in which the organic compound (I) is easily self-assembled and units (molecules) are oriented in a certain direction. 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 chain, the adjacent units are not coupled to each other, and the distance between the adjacent units can be minimized to obtain a highly crystallized material. 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. A silyl group having (A ^{1 to} A ³ ) selectively binds to the substrate surface. 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 Silyl groups are selectively bonded to the substrate surface. 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 Blodget 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 a relatively high elimination reactivity in an organic compound by applying pressure on the water surface in this state and pulling up a substrate having a hydrophilic group (particularly a hydroxyl group) on the surface. The group is bonded to the substrate to obtain a single monomolecular film as shown in FIG.

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 silyl group having a group (A ^{1 to} A ³ ) having relatively high elimination reactivity in an organic compound is bonded to the substrate, and a single monomolecular film as shown in FIG. Is obtained.

  After the single monomolecular film is formed, the 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 cumulative film, an unreacted silyl group present on the film surface side of the previously formed single monomolecular film is used as an adsorption reaction site, and a monomolecular film made of the organic compound (I) is used. Accumulate. The organic compound used here may be the same as or different from that used in the monomolecular film already formed in the organic compound (I), or the “n-th”. It may be an “organic compound capable of forming a monomolecular film (outermost surface film)”. Prior to newly accumulating the monomolecular film, usually, A ^{4 to} A ⁶ groups (in FIG. 1, an ethoxy group) of the unreacted silyl group existing on the film surface side of the already formed monomolecular film. ) Is substituted with a hydroxyl group by adjusting (activation) the solvent atmosphere and reaction temperature as described above. For example, the surface of the previously formed monomolecular film may be brought into contact with water adjusted to a predetermined pH. Specifically, the previously formed monomolecular film may be immersed in water having a predetermined pH, or water having a predetermined pH may be dropped on the surface of the monomolecular film. This makes it possible to accumulate the monomolecular film more effectively using the unreacted silyl group as an adsorption reaction site.

The accumulated monomolecular film is formed according to the same method as the LB method, dipping method, and coating method. In particular, when employing an LB method, (in FIG. 1, an ethoxy group) already A ⁴ to A ⁶ groups of the monomolecular film surface formed by adjusting the water to be used for a given pH, a hydroxyl group Can be substituted. In addition, when the A ^{4 to} A ⁶ group before substitution itself has a certain degree of reactivity with a newly formed monomolecular organic compound, it does not necessarily have to be substituted with a hydroxyl group. FIG. 2 shows a conceptual diagram when an ethoxy group of an unreacted silyl group existing on the film surface side in FIG. 1 is substituted with a hydroxyl group.

  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, among all the monomolecular films constituting the thin film, the monomolecular film made of the organic compound (I) is a van der Waals, electrostatic, or π-π stacking interaction. It is a self-assembled film that aggregates by non-covalent bonds. 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 can be used as a thin film constituting a conductive material, a photoconductive material (photoconductor), a nonlinear optical material, or the like constituting an organic thin film transistor such as a TFT, a light emitting element, a solar cell, a fuel cell, or a sensor. 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 (region between source and drain)
-Films between electrodes of organic EL devices and organic phosphorescent light emitting devices (light emitting layer, electron injection layer, hole injection 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 and n-type materials for solar cells (Since organic thin films have photoexcitation properties, p-n junctions can be formed by stacking p-type and n-type materials as thin films, so solar cells can be formed.)
・ Separator of fuel cell ・ Adsorption film of gas molecule of gas sensor or smell component of odor sensor A gas sensor to be evaluated can be formed)
・ 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 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.

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 (a12)) represented by the general formula (a12)>

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 triisopropylbromosilane, and 300 ml of a chloroform solution under a dry nitrogen stream. The solution was added dropwise over a period of time, and after the completion of the addition, the mixture was once warmed to room temperature and then cooled again to -180 ° C. The reaction solution was distilled to obtain a triisopropylsilylated hexthiophene colorless liquid as a fraction.

The obtained triisopropylsilylated hexthiophene was dissolved in a chloroform 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 chloroform solution mixed with 1 equivalent of tetraethoxysilane 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, (a12) was obtained by filtration under reduced pressure.

The result of the instrumental analysis of the obtained thiophene (a12) 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 )
1.80 ppm (m, 3H, C ₃ H ₇ )
1.22 ppm (m, 9H, OC ₂ H ₅ )
0.90 ppm (m, 18H, C ₃ H ₇ )
_{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 (a12).

<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 (a12), and a monomolecular film of thiophene (a1) and thiophene (a12) Manufacture of bilayer cumulative film consisting of monomolecular film>
A substrate obtained by immersing a Si wafer and a quartz glass substrate in a (hydrogen peroxide solution / sulfuric acid) mixed solution and applying a 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.
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.
Separately, a monomolecular film of thiophene (a12) was prepared by the same method as described above except that thiophene (a12) was used and the pH of the lower layer water was adjusted to 2.

  Next, a 0.2 mM toluene solution of thiophene (a12) is spread on the water surface at pH = 2, 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 = 2, the adsorption reaction proceeds by hydrolysis of the triethoxysilyl group of thiophene (a1) and (a12).

  When 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 at 50 μm size. Further, 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.

  In order to evaluate the accumulated state of the film in detail, a single film consisting only of a monomolecular film of thiophene (a1) and a monomolecular bilayer film of thiophene (a1) and (a12) were used as samples (UV-3000; UV-visible absorption spectrum measurement was performed by Shimadzu Corporation. As a result, absorption having peak positions was observed in the vicinity of 350 nm for the monomolecular film of thiophene (a1), and in the vicinity of 350 and 410 nm for the monomolecular bilayer films of thiophene (a1) and (a12). From the above, it was found that two layers of films can be accumulated.

Based on the electron diffraction (ED) measurement by "H-7500; manufactured by Hitachi, Ltd.", the crystal arrangement of the monomolecular bilayer cumulative film was evaluated. 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 (a2), and a monomolecular bilayer film of thiophene (a1) and (a2) 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 diffraction spots corresponding to the plane spacing of 0.40 and 0.34 nm are obtained for the monomolecular film of thiophene (a1), and 0.40 and 0.34 nm for the monomolecular bilayer films of thiophene (a1) and (a12). , 0.42 and 0.36 nm are observed, respectively. From this, it was found that not only each single film but also a monomolecular bilayer cumulative film, a cumulative film having a high order of crystal arrangement could be prepared.

<Example 2: Formation of a single film composed of a monomolecular film of thiophene (a1) and a stacked film of two to five layers>
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. The lowermost monomolecular film was formed by the reaction between the hydroxyl group present on the substrate surface and the trichlorosilyl group, and the adsorption of thiophene (a1) molecules. The obtained substrate was washed with an organic solvent to remove the remaining unreacted thiophene (a1). The cleaned substrate was immersed in pure water having pH = 4 to hydrolyze the triethoxysilyl group to obtain a trihydroxysilyl group. Then, the monomolecular film-formed substrate terminated at the hydroxysilyl group end was immersed in a 0.01 mM toluene solution of thiophene (a1) at room temperature for 12 hours. A second monomolecular film was prepared on the lowermost monomolecular film by an adsorption reaction between the hydroxysilyl group present on the film surface of the lowermost monomolecular film and the trichlorosilyl group in the solution. Further, the above-described accumulation process of the second monomolecular film was repeated three times to prepare a five-layer accumulation film in which five monolayers of thiophene (a1) were laminated.

In the following, AFM observation, ultraviolet-visible absorption spectrum measurement, and ED measurement were performed in the same manner as in Example 1 in order to evaluate the film thickness, absorption characteristics, and periodicity of crystal arrangement according to the cumulative number of films. . As a result, from AFM observation, as the cumulative number increases by one, the film thickness increases by about 3 nm, and from the UV-Vis absorption spectrum measurement, the absorbance corresponding to the π-π ^* transition varies with the film thickness. On the other hand, since it increased linearly, it was found that the film could be uniformly accumulated. When ED measurement was performed on each of the five-layer cumulative films from a single monomolecular film, diffraction spots with an interplanar spacing of 0.40 and 0.34 nm were observed. It was found that the formation of a highly oriented cumulative film was not caused by a decrease in film accumulation.

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 the general formula (b5) (hereinafter referred to as terphenyl (b5))>

  A 1-liter glass flask was charged with 1 equivalent of terphenyl, 1 equivalent of triethylbromosilane, and 300 ml of a chloroform solution under a dry nitrogen stream, and 1 equivalent of t-butyllithium was added at −78 ° C. from a dropping funnel over 12 hours. 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 triethylsilylated terphenyl colorless liquid as a fraction.

The obtained triethylsilylated 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 (b5) was obtained by filtration under reduced pressure.

The result of the instrumental analysis of the obtained terphenyl (b5) is shown.
¹ H NMR (δ CDCl ₃ ):
_{7.30~7.54ppm (m, 12H, C 6} H 6)
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 (b5).

<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: Production of two-layer cumulative film comprising a monomolecular film of terphenyl (b5) and a monomolecular film of terphenyl (b8)>
Films were formed using a substrate that had been subjected to hydrophilization treatment by immersion in a mixed solution of Si wafer and quartz glass (hydrogen peroxide solution / sulfuric acid) and irradiation with ultraviolet light, and thoroughly washed with pure water.
A 0.2 mM toluene solution of terphenyl (b5) was developed on the water surface at pH = 7 and water temperature of 40 ° C., and the adsorption reaction to the silanol group on the substrate surface accompanying the elimination of the chlorine atom in the trichlorosilyl group was determined by the LB method. Then, a monomolecular film of terphenyl (b5) was prepared. The prepared membrane was washed with an organic solvent and dried. Observation of terphenyl (b5) monomolecular film by atomic force microscope (AFM), confirmation of surface shape, substrate / film height difference by mechanical cutting of film, terphenyl (b5) monomolecular film Was found to be made. Further, in the UV-visible absorption spectrum measurement, absorption attributed to the π-π ^* transition of terphenyl was observed at 290 nm, and it was confirmed that the monomolecular film was formed of terphenyl (b5).

  Next, a 0.2 mM toluene solution of terphenyl (b8) was developed on the water surface at pH = 4 and water temperature of 40 ° C., and formed on the monomolecular film of terphenyl (b5) prepared in the above process by the LB method. Then, a cumulative film was formed through silanol bonds as shown in FIG.

  When film surface morphology observation by atomic force microscope (AFM) observation was performed at 50 μm size in the same manner as in Example 1, the film was uniformly formed at 50 μm size. Further, when the film was cut by mechanical treatment, the film thickness was about 4 nm corresponding to the sum of the respective molecular lengths. From this, it was found that a two-layer film having a uniform film thickness was prepared.

Based on the electron diffraction (ED) measurement by the same method as in Example 1, the crystal structure of the two-layer cumulative film was evaluated. The sample for ED measurement was performed using a form bar film on which SiO ₂ was deposited as a substrate. As a result, a diffraction spot due to the crystal structure of the phenylene portion was observed in the two-layer cumulative film. This indicates that both monolayers of terphenyls (b5) and (b8) independently form crystal sequences having high order.

<Example 4: Preparation of organic thin film transistor and evaluation of electrical characteristics>
FIG. 9 An organic thin film transistor 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, and the organic thin film transistor shown in FIG. 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 trimethylchlorosilane are mixed in a THF solution in an amount that gives a molar ratio of (2,3,4,5-tetrabromothiophene: magnesium: trimethylchlorosilane = 1: 2.5: 2.5), Ultrasonic cleaning was applied for 4 days. The obtained 2,5-ditrimethylsilyl-3,4-dibromothiophene was mixed in phenylsulfonyl nitrogen fluoride ((PhSO ₂ ) ₂ NF) and n-butyllithium in THF and reacted at −78 ° C. And dibromo was difluorinated. The product after the reaction was treated with NBS in acetic acid at 80 ° C. to perform bromination of the trimethylsilyl group (intermediate 1). In addition, 2,5-ditrimethylsilyl-3,4-difluorothiophene was treated with n-butyllithium, (PhSO ₂ ) ₂ NF, and tributyltin chloride (Bu ₃ SnCl) at −78 ° C. to give trimethylsilyl at the 2-position. A group fluorination reaction was performed to obtain 2,3,4-trifluoro-5-trimethylsilyl-thiophene (intermediate 2). Intermediates 1 and 2 were reacted at 80 ° C. in a mixed solution consisting of PdCl ₂ (PPh ₃ ) ₂ and DMF to obtain 2-trimethylsilyl-3,4,7,8,9-pentafluoro-bithiophene. The resulting product and intermediate 1 were reacted by the same reaction mechanism as described above, thereby synthesizing terthiophene in which both ends were trimethylsilyl 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 was dissolved was dropped, and the mixture was stirred for 8 hours at −78 ° C., warmed to room temperature, and 2-trimethylsilyl-3,4,7,8,11,12- Sexifluoro-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-trimethylsilyl-3,4,7,8,11,12-sexualfluoro-13-iodo-terthiophene and n-BuLi, and then column chromatography. To obtain fluoroterthiophene (f1).

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: Manufacture of a bilayer cumulative film composed of a monomolecular film of anthracene (c1) and a monomolecular film of fluoroterthiophene (f1)>
Films were formed using a substrate that had been subjected to hydrophilization treatment by immersion in a mixed solution of Si wafer and quartz glass (hydrogen peroxide solution / sulfuric acid) and irradiation with ultraviolet light, and thoroughly washed with pure water.
A 0.2 mM toluene solution of anthracene (c1) is developed on the water surface at pH = 7 and water temperature of 40 ° C., and the adsorption reaction to the silanol group on the substrate surface accompanying the elimination of the chlorine atom in the trichlorosilyl group is performed by the LB method A monomolecular film of anthracene (c1) was prepared. The prepared membrane was washed with an organic solvent and dried. Observation of anthracene (c1) monomolecular film by atomic force microscope (AFM), confirmation of surface shape, confirmation of substrate / film height difference by mechanical cutting of film, and production of anthracene (c1) monomolecular film It turned out that it was made. Further, in the UV-visible absorption spectrum measurement, absorption attributed to the π-π ^* transition of anthracene was observed at 370 nm, and it was confirmed that the monomolecular film was formed of anthracene (c1).

  Next, a 0.2 mM toluene solution of fluoroterthiophene (f1) was developed on the water surface at pH = 4 and water temperature of 40 ° C., and formed on the monomolecular film of anthracene (c1) prepared in the above process by the LB method. A cumulative film was formed through silanol bonds as shown in FIG.

  When film surface morphology observation by atomic force microscope (AFM) observation was performed at 50 μm size in the same manner as in Example 1, the film was uniformly formed at 50 μm size. Further, when the film was cut by mechanical treatment, the film thickness was about 3.5 nm corresponding to the sum of the respective molecular lengths. From this, it was found that a two-layer film having a uniform film thickness was prepared.

Based on the electron diffraction (ED) measurement by the same method as in Example 1, the crystal structure of the two-layer cumulative film was evaluated. The sample for ED measurement was performed using a form bar film on which SiO ₂ was deposited as a substrate. As a result, diffraction spots due to the crystal structures of the anthracene part and the terthiophene part were observed in the two-layer cumulative film. This indicates that each monomolecular film of anthracene (c1) and fluoroterthiophene (f1) independently forms a highly ordered crystal arrangement.

<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: Formation of monomolecular film of alkane (d1)>
Films were formed using a substrate that had been subjected to hydrophilization treatment by immersion in a mixed solution of Si wafer and quartz glass (hydrogen peroxide solution / sulfuric acid) and irradiation with ultraviolet light, and thoroughly washed with pure water.
A 0.2 mM toluene solution of alkane (d1) is developed on the water surface at pH = 2 and a water temperature of 24 ° C., and the adsorption reaction to the silanol group on the substrate surface accompanying the elimination of the chlorine atom in the trichlorosilyl group is performed by the LB method. A monomolecular film of alkane (d1) was prepared. The prepared membrane was washed with an organic solvent and dried. Atomic force microscope (AFM) observation of alkane (d1) monomolecular film, confirmation of surface shape, confirmation of substrate / film height difference by mechanical cutting of film, and preparation of alkane (d1) monomolecular film It turned out that it was made. Further, in the infrared absorption spectrum measurement, absorptions attributed to the CH ₂ symmetric / reverse symmetric stretching vibrations of alkane (d1) are observed at 2890 and 2920 cm ⁻¹ , respectively, and the monomolecular film is formed of alkane (d1). Confirmed that.

  Next, a 0.2 mM toluene solution of fluoroterthiophene (f1) was developed on the water surface at pH = 4 and water temperature of 40 ° C., and formed on the monomolecular film of alkane (d1) prepared in the above process by the LB method. A cumulative film was formed through silanol bonds as shown in FIG.

  When film surface morphology observation by atomic force microscope (AFM) observation was performed at 50 μm size in the same manner as in Example 1, the film was uniformly formed at 50 μm size. Further, when the film was cut by mechanical treatment, the film thickness was about 4.8 nm corresponding to the sum of the respective molecular lengths. From this, it was found that a two-layer film having a uniform film thickness was prepared.

Based on the electron diffraction (ED) measurement by the same method as in Example 1, the crystal structure of the two-layer cumulative film was evaluated. The sample for ED measurement was performed using a form bar film on which SiO ₂ was deposited as a substrate. As a result, diffraction spots due to the crystal structures of the alkane part and the terthiophene part were observed in the two-layer cumulative film. This indicates that each monolayer of alkane (d1) and fluoroterthiophene (f1) independently forms a highly ordered crystal arrangement.

Experimental Example 5
<Synthesis Example 8: Production of trichlorosilane-terthiophene-triethoxysilane formula (a2) 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 was filtered under reduced pressure to remove magnesium chloride, and then THF and unreacted tetrachlorosilane were stripped from the filtrate, and this solution was distilled to obtain a compound represented by the formula (a2). .

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 6
<Synthesis Example 9: 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 7
<Synthesis Example 10: 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 8
<Synthesis Example 11: 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 9
<Synthesis Example 12>
In accordance with Synthesis Examples 8 and 9, 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 10
<Synthesis Example 13: Production of n-trioctylsilane-dibenzoperylene-triethoxysilane formula (a14)>
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. Thereafter, it was reacted with n-BuLi and trioctylsilane in a THF solution to obtain trioctylsilane-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 (a14).

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.
7.8 ppm (m) (derived from 5H aromatics)
7.4 ppm (m) (derived from 2H aromatics)
7.1 ppm (m) (derived from 2H aromatics)
6.3 ppm (m) (derived from 2H aromatics)
3.8 ppm (m) (derived from methylene group of 6H ethoxy group)
3.6 ppm (m) (derived from 2H aromatics)
1.3 ppm (m) (derived from methyl group of 9H ethoxy group)
From these results, it was confirmed that this compound was n-trioctylsilane-dibenzoperylene-triethoxysilane.

  Next, a 0.2 mM chloroform solution of n-trioctylsilane-dibenzoperylene-triethoxysilane formula (a14) is developed on the water surface at pH = 4 and water temperature of 40 ° C. A five-layer cumulative film through silanol bonds as shown was prepared.

  When film surface morphology observation by atomic force microscope (AFM) observation was performed at 50 μm size in the same manner as in Example 1, the film was uniformly formed at 50 μm size. Moreover, when the film was cut by mechanical treatment, the film thickness was about 20 nm corresponding to the sum of the respective molecular lengths. From this, it was found that a five-layer film having a uniform film thickness was prepared.

Based on the electron diffraction (ED) measurement by the same method as in Example 1, the crystal structure of the five-layer cumulative film was evaluated. The sample for ED measurement was performed using a form bar film on which SiO ₂ was deposited as a substrate. As a result, diffraction spots attributable to the crystal structure of the dibenzoperylene portion were observed in the five-layer cumulative film.

<Example 8: Production of organic thin film transistor and evaluation of electrical characteristics>
FIG. 9 An organic thin film transistor 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 composed of a monomolecular film of n-trioctylsilane-dibenzoperylene-triethoxysilane formula (a14) was prepared in the same manner as in Example 3 except that the obtained substrate was used. 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 11
<Synthesis Example 14: Production of n-trichlorosilane-coronene-triethoxysilane formula (a15)>
Perylene synthesized in Synthesis Example 13 is mixed with an electrophile in bromoacetaldehyde diethyl acetal to anionize perylene, and treated with molecular iodine to give 1-peryleneacetaldehyde diethyl acetal and an isotope substituted at the 3-position Got. 1 and 3-peryleneacetaldehyde diethyl acetal was dissolved in concentrated sulfuric acid and methanol mixed solvent, and subjected to ultrasonic treatment for 1 hour to obtain benzoperylene. Similarly, the obtained benzoperylene was anionized and treated with molecular iodine to obtain 5 and 7-benzoperyleneacetaldehyde diethyl acetal. These benzoperylene derivatives were sonicated and recrystallized from a toluene solvent. Coronene was synthesized by purification by the method. Chlorination was performed by reacting 1 equivalent of NCS with coronene in AcOH in the presence of CHCl ₃ with respect to coronene. Thereafter, it was reacted with n-BuLi and triethoxysilane in a THF solution to obtain triethoxysilane-coronene (yield 46%).

  A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 2 mol of metallic magnesium, 2.0 mol of tetrachlorosilane, and 300 ml of tetrahydrofuran (THF) under a dry argon stream, and the internal temperature was 25 ° C. or less. Then, the obtained triethoxysilane-coronene was dropped over 2 hours, and after completion of the dropping, aging was performed at 30 degrees for 1 hour. Next, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then THF and unreacted tetrachlorosilane were stripped from the filtrate, and this solution was distilled to obtain a compound represented by the formula (a14). .

When the obtained compound was subjected to infrared absorption measurement, Si—C absorption was observed at a wavelength of 700 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 wavelengths of 338 and 300 nm. This absorption was attributed to the π → π ^* transition of the coronene skeleton contained in the molecule, and it was confirmed that the compound contained the coronene skeleton.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
7.4 ppm (m) (from 11H aromatics)
From these results, it was confirmed that this compound was trichlorosilane-coronene-triethoxysilane.

  Next, a 0.2 mM chloroform solution of n-trichlorosilane-coronene-triethoxysilane formula (a15) is developed on the water surface at pH = 2 and a water temperature of 23 ° C., and as shown in FIG. A five-layer cumulative film via a silanol bond was prepared.

  When film surface morphology observation by atomic force microscope (AFM) observation was performed at 50 μm size in the same manner as in Example 1, the film was uniformly formed at 50 μm size. Moreover, when the film was cut by mechanical treatment, the film thickness was about 22 nm corresponding to the sum of the respective molecular lengths. From this, it was found that a seven-layer film having a uniform film thickness was prepared.

Based on the electron diffraction (ED) measurement by the same method as in Example 1, the crystal structure of the seven-layer cumulative film was evaluated. The sample for ED measurement was performed using a form bar film on which SiO ₂ was deposited as a substrate. As a result, diffraction spots attributable to the crystal structure of the dibenzoperylene portion were observed in the five-layer cumulative film.

<Example 9: Preparation of organic thin film transistor and evaluation of electrical characteristics>
FIG. 9 An organic thin film transistor 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 seven-layer cumulative film composed of a monomolecular film of n-trichlorosilane-coronene-triethoxysilane formula (a15) was prepared in the same manner as in Example 3 except that the obtained substrate was used, and FIG. The organic thin film transistor shown 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 7 × 10 ⁻² cm ² V ⁻¹ s ⁻¹ and the on / off ratio was about 6 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. FIG. 2 is a conceptual diagram when an ethoxy group of an unreacted silyl group existing on the film surface side in FIG. 1 is substituted with a hydroxyl group when forming a monomolecular cumulative film. 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) And (B) is a schematic diagram of a monomolecular cumulative film using two types of organic compounds (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 (9)

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. A ^{1 to} A ³ > A ^{4 to} A ⁶ are satisfied, and B is a monocyclic aromatic compound, a condensed aromatic compound, a monocyclic heterocyclic compound, a condensed heterocyclic compound, or a compound thereof. An organic device having an organic thin film formed using an organic compound represented by ( 2 to 8 bonded divalent organic groups derived from a bonded compound ). Organic group B is a monocyclic aromatic compounds, organic according to claim 1 is a monocyclic heterocyclic compounds or radicals which compounds thereof from 2 to 8 bound compound or a condensed aromatic compound, Machine device. Organic device according to claim 1 in combination with A ¹ to A ³ and ^A 4 to A ⁶ are of one of the following (1) to (4);
(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 4 carbon atoms. (Formula) H-B-MgX (2)
(In the formula, B represents a divalent aromatic compound, a condensed aromatic compound, a monocyclic heterocyclic compound, a condensed heterocyclic compound, or a divalent derivative derived from a compound in which 2 to 8 of these compounds are bonded . An 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 ) (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 according to claim 1, wherein 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 ). Device manufacturing method. ^{(Formula) X 1 -B-X 2 (} 8)
(In the formula, B is a divalent aromatic compound, a condensed aromatic compound, a monocyclic heterocyclic compound, a condensed heterocyclic compound, or a divalent derivative derived from a compound in which 2 to 8 of these compounds are bonded . An organic group, and X ¹ and X ² are different from each other and are halogen atoms.) After using a metal catalyst made of magnesium or lithium as a 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 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 The manufacturing method of the organic device of Claim 1 characterized by the above-mentioned . 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 an organic thin film transistor comprising an electrode and a semiconductor layer, an organic according to claim 1, wherein the semiconductor layer is an organic thin film formed by using the organic compound represented by the general formula (I) device. An organic thin film in which an organic device is an organic photoelectric conversion element having an organic layer between at least a transparent electrode and a counter electrode, and the organic layer is formed using an organic compound represented by the general formula (I) The organic device according to claim 1 , wherein: The organic device is an organic EL element having an organic layer at least between an anode and a cathode, and the organic layer is an organic thin film formed using an organic compound represented by the general formula (I) The organic device according to claim 1 . (1) A step of reacting a silyl group having A ^{1 to} A ³ in the organic compound of the general formula (I) with a substrate surface to form a monomolecular film composed of a monomolecular layer directly adsorbed on the substrate,
(2) an organic compound unreacted step removed by washing with a non-aqueous solvent, and (3) as an unreacted sites silyl group adsorption reactions present in the membrane surface of the obtained monomolecular film, generally The method for producing an organic device according to claim 1, further comprising a step of accumulating monomolecular films made of the organic compound of formula (I) .

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