JP4065874B2 - Organic thin film transistor and manufacturing method thereof - Google Patents

Description

  The present invention relates to an organic thin film transistor and a method for manufacturing the same. More particularly, the present invention relates to an organic thin film transistor including an organic thin film formed on a gate insulating film via an anchor film and a method for manufacturing the same.

  In recent years, IC technology using a transistor using an organic semiconductor has been proposed. The main advantage of the above technique is a simple manufacturing method and compatibility with flexible substrates. These advantages are expected to use this transistor in low cost IC technology suitable for applications such as smart cards, electronic tags and displays.

  Here, a vacuum deposition method, a coating method, or the like is known as a film forming method used when forming a thin film transistor (TFT) with an organic semiconductor. According to these film forming methods, it is possible to increase the size of the element while suppressing an increase in cost, and the process temperature required for film formation can be made relatively low. For this reason, TFTs using organic semiconductors (hereinafter referred to as organic TFTs) have the advantage that there are few restrictions on the materials used for the substrate.

  Examples of organic TFTs are described in Japanese Patent Application Laid-Open No. 2003-258265 (Patent Document 1). The structure of the organic TFT described in this publication is shown in FIG. FIG. 3 shows a TFT having a gate electrode 2, a gate insulating film 3, source / drain electrodes (5, 7), and a semiconductor layer (organic thin film) 6 on a substrate 1. In this TFT, a gate electrode 2 is provided on a part of a substrate 1, the gate electrode 2 and the substrate 1 are covered with a gate insulating film 3, and a region on the gate insulating film 3 corresponding to the gate electrode 2 is sandwiched therebetween. Source / drain electrodes (5, 7) are provided, and the source / drain electrodes (5, 7) and the gate insulating film 3 are covered with a semiconductor layer 6.

  As the material for the semiconductor layer used here, pentacene, tetracene, thiophene, phthalocyanine and derivatives substituted at their ends as well as polythiophene, polyphenylene, polyphenylene vinylene, polyfluorene, and these as materials for the p-type semiconductor layer Examples thereof include materials selected from polymers of derivatives in which the terminal or the side chain thereof is substituted. In addition, examples of the material for the n-type semiconductor layer include materials selected from perylenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, fluorinated phthalocyanine, and derivatives substituted at these ends. It is done.

In general, the operation of the organic TFT is considered as follows.
When a voltage is applied to the gate electrode, band bending occurs in the semiconductor layer on the interface side of the gate insulating film through a change in the Fermi level of the gate electrode due to the gate voltage. This bending of the band causes injection of positive charges, which are a large number of carriers, from the source / drain electrodes, and a high surface charge density region, that is, a carrier accumulation layer is formed in the semiconductor layer on the gate insulating film interface side.

  On the other hand, by applying a reverse bias to the gate electrode, a depletion layer in which charges are eliminated is formed in the semiconductor layer on the gate insulating film interface side.

  The organic TFT is operated by changing the value of the current flowing between the source electrode and the drain electrode by controlling the channel conductance by the gate voltage.

  In addition, the movement of carriers in the semiconductor layer suppresses the movement of carriers between grains, but in the grains, the crystallinity, that is, the formation of a periodic structure, hops between adjacent molecules. Conduct quickly.

However, in an example in which an actual organic TFT is manufactured / evaluated, an inorganic oxide such as SiO ₂ is used as a gate insulating film, and an organic semiconductor material such as pentacene is deposited on the gate insulating film to form a semiconductor. In many cases, a layer is formed.

  Materials such as pentacene are strongly affected by the inorganic oxides that make up the gate insulation film and prevent stacking unique to organic matter, so the crystallinity of the semiconductor layer near the gate insulation film interface, that is, in the carrier accumulation layer There has been a problem of a significant drop.

  Further, the surface energy of the gate insulating film made of an inorganic oxide is large, which suppresses the diffusion of molecules on the substrate during the thin film growth process. Therefore, many adsorption sites were generated, and as a result, only a film having a small grain size and low crystallinity was obtained.

  The decrease in crystallinity of the semiconductor layer is a factor that greatly affects device characteristics.

  There is a report that a semiconductor layer having a large grain size was fabricated by adjusting the surface energy of the gate insulating film by treating the gate insulating film with octadecyltrichlorosilane (OTS) in order to suppress the decrease in crystallinity. (IEEE Electron Device Lett., 18, 606, 1997: Non-Patent Document 1).

JP 2003-258265 A IEEE Electron Device Lett. , 18, 606, 1997

  In the organic TFT, since the semiconductor layer is formed directly on the gate insulating film, it has been suggested to some extent that the uniformity of the semiconductor layer on the interface side of the gate insulating film has a great influence on the mobility. However, an appropriate material for a semiconductor layer and a degree of uniformity of a semiconductor layer formed using the material have not been reported.

  Further, the examples described in the above report merely suppress the influence of the insulating film, and do not control the crystallinity and electrical properties at the insulating film interface.

  Furthermore, the semiconductor layer formed on the gate insulating film by a method such as vapor deposition, coating / firing, etc., does not take into account the uniformity of the interface, so that the carrier mobility characteristics inherent to the semiconductor layer cannot be sufficiently exhibited. There was a problem.

  As a result of intensive studies, the present inventors have reached the present invention by finding a method for greatly improving the crystallinity and electrical properties of the carrier storage layer in the organic thin film that effectively affects the transistor characteristics.

  That is, an object of the present invention is to provide a structure capable of improving the carrier movement characteristics of an organic thin film in contact with a gate insulating film and maximizing the semiconductor characteristics of the organic thin film. In addition, it aims at providing the material used for this structure, and the method of controlling interface conditions.

Thus, according to the present invention, an organic thin film, a gate electrode formed on one surface of the organic thin film via a gate insulating film, and both sides of the gate electrode, on one surface or the other surface of the organic thin film and source / drain electrodes formed in contact, between the organic film and the gate insulating film, an organic thin film transistor comprising a anchor film composed of monomolecular film formed from the organic silane compound having a carrier transporting function There,
The organosilane compound has the formula (1)
R ¹ —SiZ ¹ Z ² Z ³ (1)
(R ¹ is a monovalent group in which 2 to 6 benzenes are repeated, a monovalent group in which 2 to 6 thiophenes are repeated, and a monovalent group consisting of acene condensed with 2 to 6 benzene rings, And a π-electron conjugated molecule selected from a combination thereof, and Z ^{1 to} Z ³ are the same or different and each is a halogen atom or an alkoxy group having 1 to 5 carbon atoms)
The organic thin-film transistor characterized by these is provided.

  Further, according to the present invention, a step of forming a gate insulating film on the gate electrode, and a step of forming an anchor film made of an organosilane compound and having a carrier transport function on the gate insulating film. Forming an organic thin film on the anchor film; forming a source / drain electrode on the anchor film before forming the organic thin film; or forming a source / drain electrode on the organic thin film. The manufacturing method of the organic thin-film transistor characterized by including is provided.

  The organic TFT of the present invention has an anchor film made of a monomolecular film made of an organosilane compound between the gate insulating film and the organic thin film, and carriers are transported by both the anchor film and the organic thin film. Carrier transport is made efficient and high device characteristics can be obtained.

  The organic TFT of the present invention can control the crystal growth of the organic thin film by optimizing the π electron conjugated system of the main skeleton portion of the organosilane compound constituting the anchor film. Therefore, since a large grain-sized organic thin film can be obtained, the crystallinity of the organic thin film can be improved.

  Furthermore, the TFT of the present invention can control the crystallinity of the organic thin film by the interaction with the π-electron conjugated system of the main skeleton part of the anchor film without being affected by the method for producing the organic thin film. That is, unlike the conventional organic TFT, the grain size of the organic thin film does not change due to the interaction with the substrate. Therefore, in the present invention, an organic thin film having always stable characteristics and an organic TFT having stable characteristics can be obtained.

(1) Configuration and Driving Principle The organic thin film transistor (organic TFT) of the present invention will be described with reference to the drawings.
FIG. 1 is a conceptual diagram of an example of the organic TFT of the present invention. The organic TFT of FIG. 1 has a bottom gate and bottom contact type structure. As shown in FIG. 1, it is a feature of the organic TFT of the present invention that an organic thin film 6 is formed on a gate insulating film 3 via an anchor film 4. In FIG. 1, 1 is a substrate, 2 is a gate electrode, 3 is a gate insulating film, and 5 and 7 are source / drain electrodes. FIG. 2 is an enlarged view of the gate insulating film / anchor film / organic thin film portion of FIG. FIG. 1 shows an example in which the lower surface of the organic thin film is one surface, and source / drain electrodes are formed on one surface side.

The structure of the organic TFT is not limited to the structure shown in FIG. 1 as long as the gate insulating film / anchor film / organic thin film are in contact with each other in this order. Other structures include, for example,
(1) Configuration in which an organic thin film and source / drain electrodes are provided in this order on a substrate, and an anchor film, a gate insulating film, and a gate electrode are provided in this order on the organic thin film between the source / drain electrodes. Example where source / drain electrode is formed on one surface)
(2) A configuration in which a gate electrode, a gate insulating film, an anchor film, an organic thin film, and source / drain electrodes are provided in this order on a substrate (the lower surface of the organic thin film is one surface, and the other surface is the upper surface of the organic thin film) Example of source / drain electrodes formed)
(3) A configuration in which a source / drain electrode is provided on a substrate, an organic thin film, an anchor film, and a gate insulating film are provided in this order so as to cover the source / drain electrode, and a gate electrode is provided on the gate insulating film (organic Example where the upper surface of the thin film is one surface and the source / drain electrodes are formed on the other surface side, which is the lower surface of the organic thin film)
Is mentioned.

  Here, the biggest point in these structures is a monomolecular film (having a film thickness corresponding to the size of one molecule) formed from an organosilane compound and having a carrier transport function between the gate insulating film and the organic thin film. An anchor film made of a thin film is formed. This anchor film has a function of controlling the crystallinity of the organic thin film, a function of improving device characteristics (carrier mobility, on / off ratio, etc.) of the organic thin film, and the like. The former function is a function exhibited when the gate insulating film, the anchor film, and the organic thin film are formed in this order. The latter function is achieved as long as an anchor film is provided.

  The function of controlling the crystallinity of the organic thin film is achieved because the anchor film adjusts the surface energy of the gate insulating film. In other words, by interposing the anchor film, an organic thin film having a large grain size and improved crystallinity can be formed. More specifically, the anchor film can be a film that is chemically bonded to the gate insulating film by a Si—O—Si network derived from a chemical adsorption group at the end of the organosilane compound. A film having a periodic structure can be formed on the gate insulating film by interaction between π-electron conjugated molecules, that is, intermolecular force, and can be firmly fixed to the gate insulating film. As a result, the crystallinity of the organic thin film formed on the anchor film is improved by the interaction from the π-electron conjugated system of the main skeleton constituting the organosilane monomolecular film even on the surface of the anchor film on the side where the organic thin film is formed. it can.

  The function of improving the device characteristics of the organic thin film is achieved because the anchor film itself has a carrier transport function. That is, in the organic TFT, the inventors paid attention to the fact that the region where carriers are actually accumulated is a region from the gate insulating film to about a dozen nm. That is, it has been found that if the carrier mobility can be improved in this region, the device characteristics of the entire organic TFT can be improved. Therefore, the inventors have found that in addition to improving the crystallinity of the organic thin film by the anchor film, the anchor film itself has a carrier transport function, thereby improving the carrier mobility in the region where the carriers are actually transported. I have found it.

  This carrier transport function is derived from the fact that the anchor film is formed of an organosilane compound containing a π electron conjugated molecule.

  Further, since the π-electron conjugated molecule of the anchor film itself has a carrier transport function, the carrier movement barrier at the interface between the organic thin film and the anchor film is relatively small. Therefore, the carrier can be moved across the interface indicated by the arrow 11 in FIG. Therefore, even when the carrier movement such as current movement between grains is conventionally difficult, the movement across the interface can be used.

  Further, the anchor film can adjust the crystallinity near the interface of the organic thin film. In particular, the anchor film is preferably higher in crystallinity than the organic thin film. This is because the carrier mobility can be improved and more current can flow by increasing the crystallinity of the anchor film itself, considering that the region where carriers are transported is a few dozen nm. is there.

  In addition, since the anchor film can form a Si—O—Si network derived from an organosilane compound on the gate insulating film side, an organic group derived from the organosilane compound is formed on the gate insulating film from a film without a network. Can be arranged regularly. As a result, a highly crystalline anchor film can be obtained.

  Note that the inventors of the present invention have evaluated the high crystallinity of the anchor film by X-ray diffraction and electron beam diffraction, and confirmed several diffraction peaks due to crystallinity. In addition, a highly crystalline anchor film is made of an organosilane compound having a π-electron conjugated system in the main skeleton, and due to the bond with the insulating film by the Si—O—Si network and the interaction between the π-electron conjugated systems. I think that it was obtained.

  The anchor film is formed to be a monomolecular film. The film thickness varies depending on the type of organosilane compound. Specifically, it is preferably 0.5 nm to 3 nm, and more preferably 1 nm to 2.5 nm. Here, if it is less than 0.5 nm, it is difficult to form an anchor film having high crystallinity, which is not preferable. In consideration of the structure of the compound that forms the organic thin film, the π-electron conjugated system that forms the main skeleton of the organic silane compound used for the anchor film preferably has almost the same structure. Therefore, when the thickness is larger than 3 nm, the effect described so far does not appear remarkably, and the solubility of the organosilane compound forming the anchor film is lowered. A soluble substituent such as an alkyl group must be introduced, which is not preferable because carrier movement between the anchor film and the organic thin film is suppressed and the crystallinity of the anchor film itself is lowered.

  If a film having high crystallinity is used as the anchor film, the crystallinity of the organic thin film may not be as high as that of the anchor film. That is, if an anchor film with high crystallinity is formed, even when an organic thin film with low crystallinity is used, the carrier mobility in the region where carriers move due to the presence of the anchor film can be improved. Improvements can also be expected. Therefore, the selectivity of the raw material for the organic thin film is improved, and a relatively inexpensive material and manufacturing method can be selected, which is very useful industrially. In addition, by increasing the crystallinity of the anchor film, the crystallinity of the organic thin film formed thereon is also affected by the crystallinity of the anchor film, thereby improving the anchor film.

  Hereinafter, the components of the organic TFT of the present invention will be specifically described.

(Gate, source / drain electrodes)
The gate and source / drain electrode materials are not particularly limited, and any material known in the art can be used. Specifically, metals such as gold, platinum, silver, copper and aluminum; refractory metals such as titanium, tantalum and tungsten; silicides and polycides with refractory metals; p-type or n-type highly doped silicon; ITO, Examples thereof include conductive metal oxides such as NESA; conductive polymers such as PEDOT.

The film thickness is not particularly limited, and can be appropriately adjusted to a film thickness (for example, 30 to 60 nm) usually used for a transistor.
The manufacturing method of these electrodes can be appropriately selected according to the electrode material. For example, vapor deposition, sputtering, coating, etc. can be mentioned.

(Gate insulation film)
The gate insulating film is not particularly limited, and any film known in the art can be used. Specifically, insulating films such as silicon oxide films (thermal oxide films, low-temperature oxide films: LTO films, etc., high-temperature oxide films: HTO films), silicon nitride films, SOG films, PSG films, BSG films, BPSG films; PZT , PLZT, ferroelectric or antiferroelectric film; SiOF-based film, SiOC-based film, CF-based film, HSQ (hydrosilsesquioxane) film (inorganic), MSQ (methyl silsquioxane) -based film, PAE formed by coating Examples thereof include a low dielectric film such as a (polyylene ether) film, a BCB film, a porous film, a CF film, or a porous film.

  The film thickness is not particularly limited, and can be appropriately adjusted to a film thickness (for example, 100 to 500 nm) usually used for a transistor.

  The manufacturing method of a gate insulating film can be suitably selected according to the kind. For example, vapor deposition, sputtering, coating and the like can be mentioned.

(Anchor membrane)
The anchor film material is not particularly limited as long as it is an organosilane compound having a carrier transport function after film formation. Specific examples of the organosilane compound will be described below.
As the organosilane compound, the formula (1)
R ¹ —SiZ ¹ Z ² Z ³ (1)
The compound represented by can be used.

Wherein, Z ¹ to Z ³ are the same or different, a halogen atom or an alkoxy group having 1 to 5 carbon atoms are preferred. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Preferably it is a chlorine atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group (including a structural isomer), a butoxy group (including a structural isomer), and a pentoxy group (including a structural isomer).

R ¹ is preferably an organic group containing a π-electron conjugated molecule derived from a π-electron conjugated compound. This organic group preferably includes at least one group (unit) whose conductivity can be controlled. Examples thereof include a group selected from a group derived from a monocyclic aromatic compound, a condensed aromatic compound, a monocyclic heterocyclic compound, and a condensed heterocyclic compound.

  Examples of the monocyclic aromatic compound 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. Examples of the monocyclic heterocyclic compound include furan, thiophene, pyridine, pyrimidine and the like. Examples of the condensed heterocyclic compound include indole, quinoline, acridine, benzofuran and the like.

  First, the monocyclic aromatic compound and the monocyclic heterocyclic compound are preferably compounds composed of units derived from benzene and / or thiophene. It is preferable that 2 to 8 units are combined to form a compound. When the above units are bonded, it is more preferable that 2 to 6 units are bonded in consideration of yield, economy, and mass production.

A plurality of these units may be connected in a branched manner, but are preferably connected in a linear shape. In the compound, the same unit may be bonded, all different units may be bonded, or plural types of units may be bonded regularly or in a random order. In addition, when the constituent molecule of the unit is thiophene, the bonding position may be any of 2,5-position, 3,4-position, 2,3-position, 2,4-position, etc. 2,5-positions are preferred. 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.
For example, as the non-condensed aromatic compound, the following general formula (2);

(Wherein, m is an integer of 1 to 8, preferably 1 to 6). The phenylene group may have a substituent such as an alkyl group, an aryl group, or a halogen atom.
Further, as the non-condensed aromatic heterocyclic compound, the following general formula (3);

(Wherein n is an integer of 1 to 8, preferably 1 to 6). The thiophenediyl group may have a substituent such as an alkyl group, an aryl group, or a halogen atom.

  More specifically, as specific examples of the compound in which two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds are bonded, biphenyl, bithiophenyl, terphenyl (compound of formula 1), tertenyl (formula 2) Compound), quarterphenyl, quarterthiophene, quinkephenyl, quinkethiophene, hexylphenyl, hexthiophene, thienyl-oligophenylene (see compound of formula 3), phenyl-oligooligothienylene (see compound of formula 4), Examples include groups derived from block co-oligomers (see compounds of formula 5 or 6) and bi (dithiophenylvinyl) phenyl (see compounds of formula 7).

(In the formula, n is 1 to 6, m is 1 to 3, and a + b is 2 to 6.)
Furthermore, as a condensed aromatic compound, following formula 8-10.

(N is 0-4) selected from these. Formula 8 is a compound containing an acene skeleton, Formula 9 is a compound containing an acenaphthene skeleton, and Formula 10 is a compound containing a perylene skeleton.

It is preferable that the number of the benzene rings which comprise the compound containing the acene skeleton of the said Formula 8 is 2-8. In particular, in view of the number of synthesis steps and product yield, naphthalene, anthracene, tetracene, pentacene, and hexacene having 2 to 6 benzene rings are particularly preferable. In the above formula 8, a compound in which the benzene ring is linearly condensed is shown in the form. For example, phenanthrene, chrysene, picene, pentaphen, hexaphen, heptaphene, benzoanthracene, dibenzophenanthrene, anthranaphthacene, etc. A molecule condensed in a non-linear manner is also included in the compound of formula 8.
Moreover, as a condensed heterocyclic compound, following formula 11-16

The compound selected from is mentioned.
In Formula 11, X ¹ is a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and X ² is a carbon atom or a nitrogen atom (provided that X ¹ and X ² are simultaneously a carbon atom); n1 Is an integer from 0 to 4.

In Formula 12, X ³ is a nitrogen atom, an oxygen atom or a sulfur atom; n2 and n3 are integers satisfying 0 ≦ n2 + n3 ≦ 2.

In Formula 13, X ⁴ and X ⁵ are each independently a carbon atom or a nitrogen atom (provided that X ⁴ and X ⁵ are simultaneously carbon atoms); n4 is an integer of 0 to 4.

In Formula 14, X ⁶ and X ⁷ are each independently a carbon atom or a nitrogen atom (provided that X ⁶ and X ⁷ are simultaneously carbon atoms); n5 is an integer of 0 to 4.

In formula 15, X ⁸ and X ⁹ are each independently a carbon atom, nitrogen atom, oxygen atom or sulfur atom (except when X ⁸ and X ⁹ are carbon atoms at the same time); n6 and n7 are 0 It is an integer that satisfies ≦ n6 + n7 ≦ 2.

In Formula 16, X ¹⁰ and X ¹¹ are each independently a carbon atom or a nitrogen atom (except when X ¹⁰ and X ¹¹ are simultaneously carbon atoms); n8 and n9 are 0 ≦ n8 + n9 ≦ 2 It is an integer that satisfies

Particularly preferred organic group R ¹ is a group derived from a compound containing two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds or a compound containing an acene skeleton.

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

Further, the compound for obtaining the organic group R ¹ may be a compound in which two or more units derived from a condensed aromatic compound are bonded, and a unit derived from a condensed aromatic compound and a monocyclic aromatic compound and / or Alternatively, a compound in which a unit derived from a monocyclic heterocyclic compound is bonded may be used.

  These organic groups may have a functional group at the terminal. Specific examples of the functional group include a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, Substituted or unsubstituted alkoxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Examples thereof include a substituted alkoxycarbonyl group, a carboxyl group, an ester group, a trialkoxysilyl group, and the like. Among these functional groups, a linear alkyl group having 1 to 30 carbon atoms is particularly preferable, and a linear alkyl group having 1 to 3 carbon atoms is more preferable from the viewpoint of not inhibiting crystallization of the organic thin film due to steric hindrance. .

  In addition, the functional group may be a monovalent group derived from a condensed heterocyclic compound having 2 to 8 condensed rings composed of a 5-membered ring and / or a 6-membered ring. Examples of the condensed heterocyclic compound include compounds of the following general formulas (a) to (f).

  General formula (a);

(Wherein X ¹ , X ² and n1 are the same as above)
General formula (b);

(Wherein X ³ , n2 and n3 are the same as above)
General formula (c);

(Where X ⁴ , X ⁵ and n4 are the same as above)
General formula (d);

(In the formula, X ⁶ , X ⁷ and n5 are the same as above.)
General formula (e);

(Wherein X ⁸ , X ⁹ , n6, and n7 are the same as above)
Formula (f);

(Where X ¹⁰ , X ¹¹ , n8, and n9 are the same as above)
Further, the organic group R ¹ may have a side chain. Here, the side chain may be any group as long as it does not react with an adjacent molecule. As the side chain, a substituted or unsubstituted alkyl group, halogenated alkyl group, cycloalkyl group, aryl group, diarylamino group, di- or triarylalkyl group, alkoxy group, oxyaryl group, nitrile group, nitro group, ester Group, trialkylsilyl group, triarylsilyl group, phenyl group and acene group. Among them, considering that it is used as an organic thin film material, and considering that the intermolecular interaction with adjacent molecules is greatly affected, a silyl group is formed of an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. Includes substituted trialkylsilyl groups, secondary and tertiary hydrocarbons having an alkyl group having 1 to 4 carbon atoms, phenyl groups having 1 to 4 benzene rings, naphthalene and anthracene, and alkyl groups having 1 to 4 carbon atoms A tertiary amino group and the like are preferable.

The bonding position of the silyl group (SiZ ¹ Z ² Z ³ ) with respect to the organic group R ¹ is not particularly limited, and may be any position as long as bonding is possible.
Particularly preferred examples of the organosilane compound will be described below.

以下に有機シラン化合物の合成方法を説明する。
有機シラン化合物は上記の有機基Ｒ¹を含有する分子にシリル基を導入することによって合成可能である。シリル基の導入部位は得られる単分子膜が、分子が規則的に配列される分子結晶性を確保できる限り特に制限されない。

The method for synthesizing the organosilane compound will be described below.
The organosilane compound can be synthesized by introducing a silyl group into the molecule containing the organic group R ¹ . The introduction site of the silyl group is not particularly limited as long as the obtained monomolecular film can secure molecular crystallinity in which molecules are regularly arranged.

Silylation of the organic group R ¹ -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 organosilane compound having halogen or alkoxy, (2) corresponding carbon-carbon Hydrosilation reaction by heating and stirring a compound having multiple bonds and an organic silane compound having at least one hydrogen on a silicon atom in the presence of a catalyst such as chloroplatinic acid, (3) using a palladium catalyst A reaction of synthesizing a substituted olefin by cross-coupling a vinyl boron compound and an organic halogenated silane compound can be used.

More specifically, the following method as the method (1) can be used.
(Formula) R ¹ -MgX (2)
Wherein R ¹ is the above-mentioned reference and X is a halogen atom,
^{(Formula) Y 1 -SiZ 1 Z 2 Z} 3 (3)
(Wherein Y ¹ is a halogen atom, Z ^{1 to} Z ³ are the same as above) and a compound (for example, tetrachlorosilane, triethoxyhalogenosilane) is reacted;
(Formula) R ¹ —SiZ ¹ Z ² Z ³ (4)
The method of obtaining an organosilane compound is mentioned. In the above method, 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 under anhydrous conditions. 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.

Next, an example of a method for synthesizing a compound containing an acene skeleton or a compound in which two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds are bonded as a precursor of the organic group R ¹ will be described. .

(1) A compound in which two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds are bonded. A compound composed of units derived from benzene which is a monocyclic aromatic compound or thiophene which is a heterocyclic compound. As a synthesis method, a method using a Grignard reaction after first halogenating the reaction site of benzene or thiophene is effective. If this method is used, a compound in which the number of benzene or thiophene is controlled can be synthesized. In addition to the method of applying the Grignard reagent, it can be synthesized by coupling using an appropriate metal catalyst (Cu, Al, Zn, Zr, Sn, etc.).

  Furthermore, for thiophene, in addition to the method using a Grignard reagent, the following synthesis method can be used.

That is, first, 2-position or 5-position of thiophene is halogenated (for example, bromination, chlorination). Examples of the halogenation method include treatment with 1 equivalent of N-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS), and phosphorous oxychloride (POCl ₃ ). Can be mentioned. As the solvent at this time, for example, chloroform / acetic acid (AcOH) mixed solution, DMF, and carbon tetrachloride can be used. Alternatively, by reacting halogenated thiophenes with a catalyst of tris (triphenylphosphine) nickel (triphenyl (phosphine) nickel: (PPh ₃ ) 3Ni) in a DMF solvent, the resulting thiophene in the halogenated portion. They can be joined directly.

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

Using the above reaction of thiophene, the number of thiophene rings can be increased.
In addition, the said compound can halogenate the terminal similarly to the raw material used for the synthesis | combination. Therefore, after halogenating the compound, for example, by reacting with SiCl ₄ , a silane compound having a silyl group at the terminal and having an organic residue consisting only of units derived from benzene or thiophene (simple benzene or A simple thiophene compound) can be obtained.

  Furthermore, the synthesis example of compound (A)-(C) which consists only of benzene or thiophene is shown below. In addition, in the synthesis example of the compound (A) and (B) 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 by NCS, thiophene 8 or 9-mer can be further formed.

  As a method for obtaining a block-type compound by directly bonding a unit in which a predetermined number of units derived from thiophene and benzene are bonded, there is a method using a Grignard reaction, for example. As a synthesis example in this case, the following method can be applied.

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

In this state, the unreacted bromo group and the above boronated compound are developed in, for example, a toluene solvent, and in the presence of Pd (PPh ₃ ) ₄ and Na ₂ CO ₃ at a reaction temperature of 85 ° C. If the reaction is allowed to proceed completely, coupling can occur. As a result, a block-type compound can be synthesized.
Synthesis examples of compounds (D) and (E) using such a reaction are shown below.

As a method for synthesizing a compound in which a unit derived from benzene or thiophene and a vinyl group are alternately bonded, for example, the following method can be applied. That is, after preparing a raw material having a methyl group at the reaction site of benzene or thiophene, both ends thereof are brominated using 2,2′-azobisisobutyronitrile (AIBN) and NBS. 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.
Synthesis examples of compounds (F) to (H) having different lengths using such a reaction are 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 possible group or side chain in advance at a predetermined position is used, a compound having any one of the above-mentioned (A) to (H) and having a functional group or 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. Table 1 below shows the CAS number of the raw material and the purity of the reagent when it is obtained from Kishida Chemical as a reagent manufacturer.

  In addition, according to the synthesis method of the compound in which two or more monocyclic aromatic compounds and / or monocyclic heterocyclic compounds are bonded, the condensed aromatic compound and the condensed heterocyclic compound are also monocyclic aromatic compounds, It can be combined with a monocyclic heterocyclic compound, a condensed aromatic compound and a condensed heterocyclic compound.

(2) Compound containing acene skeleton, acenaphthene skeleton, and perylene skeleton As a method for synthesizing a compound containing an acene skeleton, for example, (1) A hydrogen atom bonded to two carbon atoms at a predetermined position of a raw material compound is substituted with an ethynyl group. Later, a method of repeating a ring-closing reaction between ethynyl groups, (2) a step of replacing a hydrogen atom bonded to a carbon atom at a predetermined position of a raw material compound with a triflate group, reacting with furan or a derivative thereof, and subsequently oxidizing The method of repeating is mentioned. Synthesis examples of compounds (I) to (J) having an acene skeleton using these methods are shown below.
Method (1)

  Method (2)

  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 small reactive side chain or protecting group, the acene skeleton is similarly formed. A compound (K) containing can be synthesized. A synthesis example in this case is shown below.

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

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

  Compounds (L) to (M) having an acenaphthene skeleton and a perylene skeleton can be synthesized, for example, as follows.

  In addition, as a method of inserting a secondary amino group in which a nitrogen atom is substituted with two aromatic ring groups as a side chain into a perylene skeleton, a metal catalyst is present after halogenating the insertion part of the side chain in advance. Below, a method of coupling the secondary amino group may be mentioned. For example, in the case of the perylene molecule, a secondary amino group can be inserted by the following method, for example.

  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.

  The organosilane compound 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.

  The method for forming the anchor film is not particularly limited as long as a monomolecular film can be formed. Considering the uniformity of the anchor film surface, a highly uniform film can be formed in the order of the LB method, the dipping method, and the CVD method. Alternatively, a vapor deposition method may be used.

  For example, the organic silane compound is dissolved in an anhydrous organic solvent such as hexane, chloroform, or carbon tetrachloride. The substrate on which a thin film is to be formed is immersed in the obtained solution (for example, a concentration of about 1 mM to 100 mM) and pulled up. Alternatively, the obtained solution may be applied to the substrate surface. Thereafter, it is washed with a non-aqueous organic solvent, washed with water, left to stand or dried by heating to fix the organic thin film. This thin film may be used as an organic thin film as it is, or may be further subjected to treatment such as electrolytic polymerization.

  In order for the organic silane compound to be bonded via a silanol bond, the functional group bonded to the silyl group needs to be eliminated and replaced with a hydroxyl group or a proton. The substituted silyl group reacts with a hydroxyl group (or carboxyl group) on the surface of the gate insulating film to form a silanol bond.

  Further, when Si in the adjacent formula (1) is bridged as it is or through an oxygen atom, for example, it is controlled by a Si—O—Si network so that the distance between adjacent units is small and more highly advanced. 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 anchor film having a carrier transport function in the surface direction of the substrate can be obtained. In other words, it is possible to obtain an anchor film having electrical anisotropy having different electrical characteristics in the vertical direction and the surface direction with respect to the substrate surface.

  After the anchor film is formed, it is preferable to wash away the unreacted organosilane compound from the anchor film using a non-aqueous solvent.

(Organic thin film)
As the material for the organic thin film, a material known in the art or a compound obtained by removing a silyl group from the above organic silane compound can be used. As the organic thin film material, the following low molecular compounds and high molecular compounds are preferable in consideration of transistor driving or material supply.

  As the low molecular weight compound, a compound having a molecular weight of less than 1,000 is preferable. Specifically, acene obtained by condensing 3 to 10 benzene rings, oligothiophene obtained by repeating 3 to 10 thiophenes, and 3 to 10 benzene. Examples thereof include oligophenylenes having 1 to 10 repeating oligophenylenes, oligophenylenevinylenes having 1 to 10 repeating benzenes and vinylenes, and oligophenylenethiophenes having 1 to 10 repeating benzenes and thiophenes.

  As the polymer compound, a compound having a number average molecular weight of 1,000 or more is preferable, and a compound in which the repeating unit is a thiophene series, a phenylene vinylene series, or an acene series is exemplified. Among them, naphthacene, pentacene, perylene, rubrene, quinkethiophene (α-5T), seccithiophene (α-6T), sexual phenylene, oligophenylene vinylene having 3 units, poly (3-hexylthiophene) (P3HT), polyphenylene vinylene ( PPV) and their derivatives are particularly preferred.

  Furthermore, fullerene compounds such as fullerene (C60), C60-fused pyrrolidine-meta-C12 phenyl (C60MC12), [6,6] -phenyl C61-butanoic acid methyl ester (PCBM) can also be used.

  Further, when formed alone, an organic thin film having lower crystallinity than the anchor film can be used. If the anchor film has high crystallinity, the organic thin film is easily crystallized by the influence of the crystallinity of the anchor film, and an organic thin film transistor having high electron mobility can be obtained.

  As a method for producing an organic thin film, all general methods capable of forming an organic thin film such as a SAM method (for example, LB method, vapor deposition, dipping, dipping, casting, CVD method, etc.) can be applied. It is set as appropriate in consideration of the cost.

  The definitions of the SAM method, LB method, vapor deposition, dipping, dipping, casting, and CVD method in this specification will be given below.

  The SAM method is an abbreviation for Self-Assembled Monolayer, and refers to a method of forming a film using a material that can be self-assembled. Any of the LB method / dipping method (dip method) / cast method / CVD method is used. Is also included.

  The LB method is an abbreviation of the Langmuir-Blodgett method. An amphiphilic substance in which a hydrophobic group and a hydrophilic group are balanced on the water surface is developed on the water surface to produce a single-layer film called a monomolecular film. Furthermore, it is a method of transferring it to the substrate.

  The vapor deposition method is a method in which a raw material is heated to be vaporized and deposited in a desired region. For example, in the case of an organic semiconductor material, a vapor deposition method by resistance heating can be used.

  The dipping method (dip method) is a method of forming a film by dipping a substrate in a solution and then pulling it up. In the case of a material having crystallinity, a crystal having a specific structure can be grown. .

  The casting method means a method of forming a film by dropping and drying a solution containing a raw material in a desired region, and includes an ink jet.

  The CVD method means a method in which a solution is heated / evaporated in a sealed container or a sealed space, and vaporized molecules are adsorbed on the substrate surface in a gas phase.

In addition, as a manufacturing method of organic TFT, for example,
(1) A step of forming a gate electrode on a substrate, a step of forming a gate insulating film on the gate electrode, and a monomolecular film formed of an organosilane compound on the gate insulating film and having a carrier transport function Forming an anchor film, forming an organic thin film on the anchor film, forming a source / drain electrode on the anchor film before forming the organic thin film, or forming a source / drain on the organic thin film Forming a drain electrode.

(2) A step of forming source / drain electrodes on a substrate, a step of forming an organic thin film on the source / drain electrodes, and a monomolecular film formed from an organic silane compound on the organic thin film and having a carrier transport function (3) forming an organic thin film on the substrate, comprising: a step of forming an anchor film comprising: a step of forming a gate insulating film on the anchor film; and a step of forming a gate electrode on the gate insulating film. Forming a source / drain electrode on the organic thin film, and forming an anchor film made of an organic silane compound and having a carrier transport function on the organic thin film between the source / drain electrodes. There is a method including a step, a step of forming a gate insulating film on the anchor film, and a step of forming a gate electrode on the gate insulating film. Among the above methods, the method (1) is preferable because it is easy to adjust the crystallinity of the organic thin film with the anchor film.

Example 1
In order to produce the organic thin film transistor shown in FIG. 1, first, chromium was vapor-deposited on a substrate 1 made of silicon to form a gate electrode 2.

  Next, after depositing a gate insulating film 3 made of a silicon nitride film by a plasma CVD method, vapor deposition was performed in the order of chromium and gold, and source / drain electrodes (5, 7) were formed by a normal lithography technique.

Subsequently, the obtained substrate was immersed in a mixed solution of hydrogen peroxide and concentrated sulfuric acid (mixing ratio 3: 7) for 1 hour to hydrophilize the surface of the gate insulating film 3. Thereafter, the obtained substrate is immersed in a 20 mM solution in which pentacentriethoxysilane is dissolved in a non-aqueous solvent (for example, n-hexadecane) for 5 minutes under anaerobic conditions, slowly pulled up, washed with a solvent, and anchor film 4 Formed. Subsequently, the substrate was introduced into a vacuum, and an organic thin film 6 was formed by vapor-depositing a pentacene thin film to a thickness of 100 nm under the conditions of a vacuum degree of 1 × 10 ⁻⁶ Torr and a vapor deposition rate of 10 Å / min, thereby forming an organic TFT. .

  When the shape of the organic thin film formed above was confirmed by observation with an atomic force microscope, Φ4 μm dendritic grains due to the pentacene vapor-deposited film could be confirmed.

In addition, the organic thin film transistor obtained above had a field effect mobility of 2.2 × 10 ⁻¹ cm ² / Vs and an on / off ratio of about 6 digits, and good performance was obtained.

Comparative Example 1
As in Example 1, a gate electrode, a gate insulating film, a source and a drain electrode were formed on the substrate. Thereafter, pentacene was deposited to a thickness of 100 nm under the conditions of a vacuum degree of 1 × 10 ⁻⁶ Torr and a deposition rate of 10 Å / min to form an organic thin film, thereby forming an organic TFT.

  When the shape of the organic thin film formed above was confirmed by atomic force microscope observation, Φ1 μm dendritic grains due to the pentacene vapor-deposited film could be confirmed.

The organic thin film transistor obtained above had a field effect mobility of 1.0 × 10 ⁻¹ cm ² / Vs and an on / off ratio of about 5 digits.

Comparative Example 2
As in Example 1, a gate electrode, a gate insulating film, a source and a drain electrode were formed on the substrate. Subsequently, the obtained substrate was immersed in a mixed solution of hydrogen peroxide and concentrated sulfuric acid (mixing ratio 3: 7) for 1 hour to hydrophilize the insulating film surface. Thereafter, the obtained substrate is immersed in a 2 mM solution in which octadecyltrichlorosilane (OTS) is dissolved in a non-aqueous solvent (for example, n-hexadecane) for 5 minutes under anaerobic conditions, slowly pulled up, and solvent-washed. A film was formed. Subsequently, an organic TFT was formed by forming an organic thin film by depositing a pentacene thin film with a thickness of 100 nm under the conditions of a vacuum degree of 1 × 10 ⁻⁶ Torr and a vapor deposition rate of 10 Å / min.

  When the shape of the organic thin film formed above was confirmed by atomic force microscope observation, Φ2.5 μm dendritic grains due to the pentacene vapor deposition film could be confirmed.

The organic thin film transistor obtained above had a field effect mobility of 1.5 × 10 ⁻² cm ² / Vs and an on / off ratio of about 5 digits.

Examples 2-18 and Comparative Examples 3-9
As shown in Table 2, an organic TFT was obtained in the same manner as in Example 1 except that the material for the anchor film and the organic thin film and the method for forming both films were changed. The mobility and on / off ratio of the obtained organic TFT were measured in the same manner as in Example 1, and the results are shown in Table 2.

  The raw materials (1) to (13) for the organic thin film in Table 2 are described below. Moreover, the manufacturing method of these raw materials is described collectively as a synthesis example at the end of an Example. Et represents ethyl and Me represents methyl.

  In Table 2, in the example and comparative example which use the same organic thin film, the improvement rate of the mobility and on / off ratio of the example with respect to the comparative example which does not use an anchor film is collectively shown in Table 3. Table 3 also shows the improvement ratio of the mobility and on / off ratio of Comparative Example 2 relative to Comparative Example 1.

  In Table 2, Table 4 shows the improvement rate of mobility and on / off ratio of the examples with respect to the comparative example using the same organic thin film and not using the anchor film for each example in which the formation method of the anchor film is the same. .

  In Table 2, the improvement rate of the mobility and the on / off ratio of the example with respect to the comparative example using the same organic thin film and not using the anchor film are summarized in Table 5 for each example in which the formation method of the organic thin film is the same. (Only examples where the anchor film is formed by the dipping method).

  From Tables 2 to 5, according to Examples and Comparative Examples, when an anchor film having a carrier transport function is inserted, device characteristics (mobility, on / off ratio) are increased, and the grain size of the organic thin film can be increased. I understand.

  More specifically, from Table 2, the mobility of the organic TFT of Comparative Example 2 provided with a monomolecular film made of OTS having no carrier transport function as an anchor film is 1 of the organic TFT of Comparative Example 1 having no anchor film. It turns out that it is 5 times. On the other hand, the mobility of the organic TFT of the example is 1.9 to 6.7 times that of the organic TFT of Comparative Example 1 as an average value. Therefore, it was found that the organic TFT of the example provided with a monomolecular film having a carrier transport function as an anchor layer has a high effect of improving device characteristics in any organic thin film type.

  Furthermore, it can be seen from Table 4 that the mobility and on / off ratio of the anchor film manufacturing method improve in the order of the CVD method, the immersion method, and the LB method. In consideration of mass production, the immersion method is the most preferable method because the manufacturing process is simpler and the time required can be shortened than the LB method.

  In addition, when the organic thin film was formed by the solution coating method (average 5.1 times), a better result was obtained than when the vapor deposition method (average 2.9 times) was used. In addition, the solution coating method has an effect that an organic thin film can be obtained more easily than the vapor deposition method. Therefore, the solution coating method can be said to be the best means for forming an organic thin film.

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

  Then, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted tetrachlorosilane were stripped from the filtrate, and this solution was distilled to obtain the title compound in a yield of 55%. .

When the obtained compound was subjected to infrared absorption spectrum measurement, SiC-derived absorption was observed at 1060 cm ⁻¹ , confirming that the compound had a SiC bond.

  Moreover, when the ultraviolet-visible absorption spectrum measurement of the solution containing a compound was performed, absorption was observed by wavelength 360nm. This absorption was attributed to the π → π * transition of the terthiophene molecule contained in the molecule, and it was confirmed that the compound contained the terthiophene molecule.

  Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed. Since this compound cannot be directly measured by NMR due to the high reactivity of the compound, the compound was reacted with ethanol (hydrogen chloride generation was confirmed), and the terminal chlorine was replaced with an ethoxy group. Measurements were made later.

7.50 ppm to 7.00 ppm (m) (derived from 7H thiophene ring)
2.20 ppm (m) (derived from 3H ethoxy group)
From these results, it was confirmed that this compound was terthiophene trichlorosilane represented by the formula (2).

Synthesis Example 2: Synthesis of quarterthiophene trichlorosilane (raw material (2))
In a 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 1.0 mol of quarterthiophene was dissolved in carbon tetrachloride, then NBS and AIBN were added, and the mixture was stirred for 2.5 hours and then filtered under reduced pressure. As a result, bromoquaterthiophene was obtained. Subsequently, in a 500 ml glass flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, 0.5 mol of metal magnesium and 300 ml of THF (tetrahydrofuran) were charged, and 0.5 mol of the bromoquaterthiophene was added at 50 to 60 ° C. Was added dropwise from a dropping funnel over 2 hours, and after completion of dropping, the mixture was matured at 65 ° C. for 2 hours to prepare a Grignard reagent. A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 1.5 mol of SiCl ₄ (tetrachlorosilane) and 300 ml of toluene, cooled on ice, and at an internal temperature of 20 ° C. or lower, the Grignard reagent Was added over 2 hours, and after completion of the dropwise addition, maturation was performed at 30 ° C. for 1 hour.

  Next, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted tetrachlorosilane were stripped from the filtrate, and this solution was distilled to obtain the title compound in a yield of 45%. .

When the obtained compound was subjected to infrared absorption spectrum measurement, SiC-derived absorption was observed at 1060 cm ⁻¹ , confirming that the compound had a SiC bond.

  Moreover, when the ultraviolet-visible absorption spectrum measurement of the solution containing a compound was performed, absorption was observed by wavelength 390nm. Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed. Since this compound cannot be directly measured by NMR due to the high reactivity of the compound, the compound was reacted with ethanol (hydrogen chloride generation was confirmed), and the terminal chlorine was replaced with an ethoxy group. Measurements were made later.

7.30 ppm (m) (derived from 1H thiophene ring)
7.20 ppm to 7.00 ppm (m) (derived from 8H thiophene ring)
2.20 ppm (m) (derived from 3H ethoxy group)
From these results, it was confirmed that this compound was quarter thiophene trichlorosilane.

Synthesis Example 3: Synthesis of quinkethiophene triethoxysilane (raw material (3))
First, in a 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 1.0 mol of bithiophene was dissolved in carbon tetrachloride, then NBS and AIBN were added, and the mixture was stirred for 2.5 hours and then depressurized. Bromobithiophene was obtained by filtration.
Subsequently, 0.5 mol of bromoterthiophene, which is an intermediate of Synthesis Example 1, was synthesized, and 0.5 mol of metallic magnesium, THF (into a 500 ml glass flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel. Tetrahydrofuran) (300 ml) was charged, 0.5 mol of the bromoterthiophene was added dropwise from a dropping funnel over 2 hours at 50 to 60 ° C., and matured at 65 ° C. for 2 hours after completion of the addition to prepare a Grignard reagent. Furthermore, quinbithiophene was synthesized by adding 0.5 mol of the bromobithiophene and reacting at 50 ° C. for 4 hours. Subsequently, 0.2 mol of the quinkethiophene was reacted with NBS in the presence of AIBN to synthesize bromoquinkethiophene, then reacted with metal magnesium to synthesize a Grignard reagent, and further, a stirrer, reflux condenser , A 1 liter glass flask equipped with a thermometer and a dropping funnel was charged with 1.5 mol of triethoxychlorosilane and 300 ml of toluene, ice-cooled, and the Grignard reagent was added over 2 hours at an internal temperature of 20 ° C. or lower. After completion, maturation was performed at 30 ° C. for 1 hour.

  Then, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted materials were stripped from the filtrate, and this solution was distilled to obtain the title compound in a yield of 45%.

When the infrared absorption spectrum measurement was performed for the obtained compound, absorption derived from SiC was observed at 1050 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.

  Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.

7.3 ppm (m) (derived from 2H thiophene ring)
6.6 ppm (m) (derived from 8H thiophene ring)
3.8 ppm (m) (derived from 6H ethoxy group methylene)
1.2 ppm (m) (from 9H ethoxy group methyl group)
From these results, it was confirmed that this compound was the title compound.

Synthesis Example 4: Synthesis of 2-ethylquinkethiophene triethoxysilane (raw material (4))
First, in a 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 1.0 mol of 2-ethylbithiophene was dissolved in carbon tetrachloride, and then NBS and AIBN were added for 2.5 hours. After stirring, the mixture was filtered under reduced pressure to obtain 2-ethyl-5 ″ -bromobithiophene.

  Subsequently, 0.5 mol of bromoterthiophene, which is an intermediate of Synthesis Example 1, was synthesized, and 0.5 mol of metallic magnesium, THF (into a 500 ml glass flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel. Tetrahydrofuran) (300 ml) was charged, 0.5 mol of the bromoterthiophene was added dropwise from a dropping funnel over 2 hours at 50 to 60 ° C., and matured at 65 ° C. for 2 hours after completion of the addition to prepare a Grignard reagent. Further, 0.5 mol of 2-ethyl-5 ″ -bromobithiophene was added and reacted at 50 ° C. for 4 hours to synthesize 2-ethylquinkethiophene. Subsequently, 0.2 mol of the quinquethiophene was reacted with NBS in the presence of AIBN to synthesize 2-ethyl-5 '' '' '-bromoquinketiophene, and then reacted with magnesium metal to give a Grignard reagent. In addition, a 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 1.5 mol of triethoxychlorosilane and 300 ml of toluene, cooled on ice, and at an internal temperature of 20 ° C. or lower. The Grignard reagent was added over 2 hours, and after completion of the dropwise addition, maturation was performed at 30 ° C. for 1 hour.

  Then, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted materials were stripped from the filtrate, and this solution was distilled to obtain the title compound in a yield of 45%.

When the infrared absorption spectrum measurement was performed for the obtained compound, absorption derived from SiC was observed at 1050 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.

  Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.

7.3 ppm (m) (derived from 2H thiophene ring)
7.2 ppm (m) (derived from 8H thiophene ring)
3.8 ppm (m) (derived from 2H ethyl group methylene group)
3.5 ppm (m) (derived from 6H ethoxy group methylene)
2.6 ppm (m) (derived from 3H ethyl group methyl group)
1.2 ppm (m) (from 9H ethoxy group methyl group)
From these results, it was confirmed that this compound was the title compound.

Synthesis Example 5 Synthesis of 2-methylzexithiophenetrimethoxysilane (raw material (5))
First, 1.5 mol of bromoterthiophene, which is an intermediate of Synthesis Example 1, was synthesized. Subsequently, 1.0 mol of the bromoterthiophene was reacted with 1.0 mol of bromomethane at 60 ° C. for 3 hours to synthesize methylterthiophene. Subsequently, 2-methyl-5 ″ -bromoterthiophene was synthesized by reacting 0.7 mol of the methylterthiophene with NBS in the presence of AIBN.

  Meanwhile, a 500 ml glass flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel is charged with 0.5 mol of metal magnesium and 300 ml of THF (tetrahydrofuran), and 0.5 mol of bromoterthiophene is adjusted to 50 to 60 ° C. The mixture was added dropwise from the dropping funnel over 2 hours, and after completion of the addition, the mixture was matured at 65 ° C. for 2 hours to prepare a Grignard reagent.

  Subsequently, 2-methyl-5 ″ -bromoterthiophene was further added and reacted at 60 ° C. for 4 hours to synthesize 2-methylzexithiophene. Furthermore, after reacting 0.2 mol of 2-methylzexithiophene with NBS in the presence of AIBN to synthesize 2-methyl-5 '' '' ''-bromozexithiophene, it was reacted with metallic magnesium to give Grignard. A reagent was synthesized, and 1.5 mol of triethoxychlorosilane and 300 ml of toluene were charged into a 1 liter glass flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, and cooled with ice at an internal temperature of 20 ° C. or less. The Grignard reagent was added over 2 hours, and after completion of the dropwise addition, maturation was performed at 30 ° C. for 1 hour.

  Next, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted materials were stripped from the filtrate, and this solution was distilled to obtain the title compound.

When the infrared absorption spectrum measurement was performed for the obtained compound, absorption derived from SiC was observed at 1050 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.

Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
7.3 ppm (m) (derived from 2H thiophene ring)
7.1 ppm (m) (derived from 10H thiophene ring)
3.8 ppm (m) (derived from 6H ethoxy group methylene)
2.6 ppm (m) (derived from 3H methyl group)
1.2 ppm (m) (from 9H ethoxy group methyl group)
From these results, it was confirmed that this compound was the title compound.

Synthesis Example 6: Synthesis of quinkephenyltrichlorosilane (raw material (6))
A 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel is charged with 0.5 mol of metal magnesium and 300 ml of THF (tetrahydrofuran), and 0.5 mol of quinkephenyl is added dropwise at 50-60 ° C. It dropped over 2 hours from the funnel, and after completion of dropping, the mixture was matured at 65 ° C. for 2 hours to prepare a Grignard reagent.

A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel is charged with 1.0 mol of SiCl ₄ (tetrachlorosilane) and 300 ml of toluene, cooled on ice, and at an internal temperature of 20 ° C. or less, a Grignard reagent Was added over 2 hours, and after completion of the dropwise addition, maturation was performed at 30 ° C. for 1 hour (Grignard reaction).

  Next, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted tetrachlorosilane were stripped from the filtrate, and this solution was distilled to obtain the title compound in a yield of 50%. .

When the infrared absorption spectrum measurement was performed for the obtained compound, absorption derived from SiC was observed at 1080 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.

  Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed. Direct NMR measurement of the resulting compound is impossible due to the high reactivity of the compound, so the compound was reacted with ethanol (hydrogen chloride generation was confirmed), and the terminal chlorine was converted to an ethoxy group. Then, measurement was performed.

7.95 ppm to 7.35 ppm (m) (from 21H aromatics)
3.6 ppm (m) (derived from 6H ethoxy group methylene group)
1.4ppm (m) (derived from 9H ethoxy group methyl group)
From these results, it was confirmed that the obtained compound was the title compound.

Synthesis Example 7: Synthesis of zexiphenyltrichlorosilane (raw material (7))
A 500 ml glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel is charged with 0.5 mol of metallic magnesium and 300 ml of THF (tetrahydrofuran), and 0.5 mol of zexiphenyl is added from the dropping funnel at 50 to 60 ° C. The solution was added dropwise over 2 hours, and after completion of the addition, matured at 65 ° C. for 2 hours to prepare a Grignard reagent.

A 1 liter glass flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel is charged with 1.0 mol of SiCl ₄ (tetrachlorosilane) and 300 ml of toluene, cooled on ice, and at an internal temperature of 20 ° C. or less, a Grignard reagent Was added over 2 hours, and after completion of the dropwise addition, maturation was performed at 30 ° C. for 1 hour (Grignard reaction).

  Next, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted tetrachlorosilane were stripped from the filtrate, and this solution was distilled to obtain the title compound in a yield of 45%. .

When the obtained compound was subjected to infrared absorption spectrum measurement, SiC-derived absorption was observed at 1070 cm ⁻¹ , confirming that the compound had a SiC bond.

  Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed. Direct NMR measurement of the resulting compound is impossible due to the high reactivity of the compound, so the compound was reacted with ethanol (hydrogen chloride generation was confirmed), and the terminal chlorine was converted to an ethoxy group. Then, measurement was performed.

7.95 ppm to 7.35 ppm (m) (derived from 25H aromatics)
3.6 ppm (m) (derived from 6H ethoxy group methylene group)
1.4ppm (m) (derived from 9H ethoxy group methyl group)
From these results, it was confirmed that the obtained compound was the title compound.

Synthesis Example 8: Synthesis of triethoxysilanylanthracene (raw material (8))
Triethoxysilanyl anthracene was synthesized by the following method. First, 1 mM of anthracene dissolved in 50 mL of carbon tetrachloride and NBS were added to a 100 ml eggplant flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, and reacted for 1.5 hours in the presence of AIBN. After removing unreacted substances and HBr by filtration, 9-bromoanthracene was obtained by taking out a reservoir brominated at only one position using a column chromatograph. Subsequently, after reacting with metal magnesium to form a Grignard reagent, it was dissolved in a carbon tetrachloride solution of chlorotriethoxysilane and reacted at 60 ° C. for 2 hours to synthesize the title compound (yield 15%).

  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. Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.

7.80 ppm to 7.60 ppm (m)
(From 9H aromatics)
3.8 ppm (m) (derived from 6H ethoxy group methylene group)
1.5 ppm (m) (derived from 9H ethoxy group methyl group)
From these results, it was confirmed that this compound was the title compound.

Synthesis Example 9 Synthesis of triethoxysilanyltetracene (raw material (9))
Triethoxysilanyltetracene was synthesized by the following method. First, 1 mM tetracene dissolved in 50 mL carbon tetrachloride and NBS were added to a 100 ml eggplant flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, and reacted for 1.5 hours in the presence of AIBN. After removing unreacted substances and HBr by filtration, 9-bromotetracene was obtained by taking out a reservoir brominated at only one position using a column chromatograph. Subsequently, after reacting with metal magnesium to form a Grignard reagent, it was dissolved in a chloroform solution of H-Si (OC ₂ H ₅ ) ₃ and reacted at 60 ° C. for 2 hours to synthesize the title compound (yield) 10%).

  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 481 nm. This absorption was attributed to the π → π * transition of the tetracene skeleton contained in the molecule, and it was confirmed that the compound contained the tetracene skeleton.

Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
7.80 ppm to 7.30 ppm (m)
(11H aromatic origin)
3.6 ppm (m) (derived from 6H ethoxy group methylene group)
1.4ppm (m) (derived from 9H ethoxy group methyl group)
From these results, it was confirmed that this compound was the title compound.

Synthesis Example 10 Synthesis of triethoxysilanylpentacene (raw material (10))
Triethoxysilanylpentacene was synthesized by the following method. First, 1 mM pentacene dissolved in 50 mL carbon tetrachloride and NBS were added to a 100 ml eggplant flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, and reacted for 1.5 hours in the presence of AIBN. After removing unreacted substances and HBr by filtration, 9-bromopentacene was obtained by taking out a reservoir brominated at only one position using a column chromatograph. Subsequently, after reacting with metal magnesium to form a Grignard reagent, it was dissolved in a chloroform solution of H-Si (OC ₂ H ₅ ) ₃ and reacted at 60 ° C. for 2 hours to synthesize the title compound (yield) 10%).

  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.

Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
7.80 ppm to 7.30 ppm (m) (derived from 13H aromatics)
3.6 ppm (m) (derived from 6H ethoxy group methylene group)
1.4ppm (m) (derived from 9H ethoxy group methyl group)
From these results, it was confirmed that this compound was the title compound.

Synthesis Example 11 Synthesis of 2-methyl 10-triethoxysilanylpentacene (raw material (11))
2-Methyl 10-triethoxysilanylpentacene was synthesized by the following method.

First, a Grignard reagent was formed by adding magnesium in, for example, a chloroform solution containing bromomethane. Subsequently, 10-methylpentacene was formed by slowly adding the chloroform solution of 10-bromopentacene of Synthesis Example 1 above. Subsequently, after bromination of the intermediate using, for example, NBS, a compound brominated at other than the 2-position was removed by extraction to obtain 2-bromo-10-methylpentacene. Further, H-Si (OC ₂ H ₅ ) ₃ was dissolved in chloroform, and the solution was reacted by adding it to the chloroform solution containing 3-bromo-9-octadecyltetracene to synthesize the title compound ( Yield 12%).

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.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.

7.80 ppm to 7.30 ppm (m) (derived from 13H aromatics)
3.6 ppm (m) (derived from 6H ethoxy group methylene group)
2.8 ppm (m) (derived from 3H methyl group)
1.4ppm (m) (derived from 9H ethoxy group methyl group)
From these results, it was confirmed that this compound was the title compound.

Synthesis Example 12 Synthesis of trichloro- (4- {2- [4- (2-p-tolyl-ethyl) -phenyl] -ethyl} -phenyl) silane (raw material (12))
About the said compound, it synthesize | combined with the following methods.

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

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

When an infrared absorption spectrum measurement was performed on the formed target compound, absorption derived from SiC was confirmed at 1070 cm ⁻¹ , and it was confirmed that the compound contained SiC bonds. Furthermore, the nuclear magnetic resonance measurement of the compound was performed. Since this compound is highly reactive and cannot be directly measured by NMR, it was measured after reacting with ethanol and replacing the terminal chlorine with an ethoxy group.

7.4 ppm to 7.2 ppm (m) (derived from 12H phenyl skeleton)
7.1 ppm to 7.0 ppm (m) (derived from 4H vinyl group skeleton)
3.8 ppm to 3.7 ppm (m) (derived from 6H ethoxy group methylene)
2.5 ppm to 2.4 ppm (m) (derived from 3H methyl group)
1.4 ppm to 1.2 ppm (m) (from 9H ethoxy group methyl group)
From these results, it was confirmed that this compound was a compound represented by the above structural formula.

Synthesis Example 13: Synthesis of triethoxy- [2,2 ′; 6 ′, 2 ″] ternaphthalen-6-yl-silane (raw material (13))
First, 100 mM NBS and AIBN were added to a carbon tetrachloride solution containing 50 mM of 2-bromonaphthalene (CASno.90-11-9), and reacted at 60 ° C. for 2 hours in an N ₂ atmosphere, whereby 2,6-dibromo was obtained. Naphthalene was synthesized. Subsequently, after synthesizing Grignard reagent by dissolving 2-bromonaphthalene 40 mM in THF, adding metal magnesium and reacting at 60 ° C. for 1 hour in an N 2 atmosphere, the THF solution containing 2,6-dibromonaphthalene 20 mM Grignard reagent was added and reacted at 20 ° C. for 9 hours to synthesize [2,2 ′; 6 ′, 2 ″] ternaphthalene. Thereafter, 20 mM NBS and AIBN are added to a carbon tetrachloride solution containing 10 mM of [2,2 ′; 6 ′, 2 ″] ternaphthalene, and reacted at 60 ° C. for 2 hours in an N ₂ atmosphere. Bromo- [2,2 ′; 6 ′, 2 ″] ternaphthalene was formed, then magnesium metal was added and reacted at 60 ° C. for 1 hour in an N 2 atmosphere to synthesize a Grignard reagent. Further, chlorotriethoxysilane 10 mM Was added and reacted at 60 ° C. for 2 hours to obtain the title compound in 40% yield.

When the obtained compound was subjected to infrared absorption spectrum measurement, SiC-derived absorption was observed at 1090 cm ⁻¹ , confirming that the compound had a SiC bond.

Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
7.9 ppm (m) (4H aromatic)
7.6 ppm (m) (8H aromatic)
7.5ppm (m) (4H aromatic)
7.3 ppm (m) (3H aromatic)
3.6 ppm (m) (6H ethoxy group methylene group)
1.5 ppm (m) (9H ethoxy group methyl group)
From this result, it was confirmed that the obtained compound was triethoxy- [2,2 ′; 6 ′, 2 ″] ternaphthalen-6-yl-silane.

It is a schematic block diagram of the organic thin-film transistor of this invention. It is an enlarged view of the gate insulating film of the organic thin-film transistor of FIG. 1, an anchor film, and an organic thin film part. It is a schematic block diagram of the conventional organic thin-film transistor.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Gate electrode 3 Gate insulating film 4 Anchor film 5, 7 Source / drain electrode 6 Organic thin film 10 Arrow indicating carrier movement direction 11 Arrow indicating carrier movement across the anchor film / organic thin film interface

Claims (8)

An organic thin film, a gate electrode formed on one surface of the organic thin film via a gate insulating film, and a source formed on both sides of the gate electrode and in contact with one surface or the other surface of the organic thin film / An organic thin film transistor comprising a drain electrode and an anchor film formed of an organic silane compound and having a carrier transport function between the organic thin film and the gate insulating film,
The organosilane compound has the formula (1)
R ¹ —SiZ ¹ Z ² Z ³ (1)
(R ¹ is a monovalent group consisting of 2-6 repeating benzenes, a monovalent group repeating 2-6 thiophenes, a monovalent group consisting of acene condensed with 2-6 benzene rings, And a π-electron conjugated molecule selected from a combination thereof, and Z ^{1 to} Z ³ are the same or different and each is a halogen atom or an alkoxy group having 1 to 5 carbon atoms)
The organic thin-film transistor characterized by these. The organosilane compound has the formula (1)
R ¹ —SiZ ¹ Z ² Z ³ (1)
(R ¹ includes a π-electron conjugated molecule composed of a monovalent group in which 2 to 6 thiophenes are repeated, and Z ^{1 to} Z ³ are the same or different and are a halogen atom or an alkoxy group having 1 to 5 carbon atoms. Is)
The organic thin film transistor according to claim 1, wherein The organosilane compound has the formula (1)
R ¹ —SiZ ¹ Z ² Z ³ (1)
(R ¹ includes a π-electron conjugated molecule composed of a monovalent group composed of acene condensed with 2 to 6 benzene rings, and Z ^{1 to} Z ³ are the same or different and each represents a halogen atom or a carbon number. 1 to 5 alkoxy groups)
The organic thin film transistor according to claim 1, wherein The organosilane compound has the formula (1)
R ¹ —SiZ ¹ Z ² Z ³ (1)
(R ¹ is a monovalent group consisting of 2-6 benzene repeats, a monovalent group repeated 2-6 thiophenes, and a monovalent group consisting of acene condensed with 2-6 benzene rings. A π-electron conjugated molecule containing at least two selected groups, wherein Z ^{1 to} Z ³ are the same or different and are a halogen atom or an alkoxy group having 1 to 5 carbon atoms)
The organic thin film transistor according to claim 1, wherein   The organic thin film transistor according to claim 1, wherein the organic thin film is a film formed by depositing a low molecular compound or a high molecular compound.   Forming a gate insulating film on the gate electrode; forming an anchor film made of an organic silane compound having a carrier transport function on the gate insulating film; and an organic thin film on the anchor film And forming a source / drain electrode on the anchor film before forming the organic thin film, or forming a source / drain electrode on the organic thin film. A method for manufacturing a thin film transistor. The method of manufacturing an organic thin film transistor according to claim 6 , wherein the anchor film is formed by an immersion method or an LB method. The method of manufacturing an organic thin film transistor according to claim 6 , wherein the organic thin film is formed by a solution coating method.

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