JP2011057638A - Phenylenevinylene compound, and field-effect transistor containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phenylenevinylene compound useful for an organic semiconductor material, and an n-type transistor containing the same. <P>SOLUTION: The phenylenevinylene compound is represented by chemical formula (I), (wherein two of X<SP>1</SP>-X<SP>4</SP>or X<SP>5</SP>-X<SP>8</SP>are each a cyano group and the remainders and X<SP>1</SP>-X<SP>8</SP>are each a hydrogen atom or a hydrocarbon group; and at least one of R<SP>1</SP>-R<SP>10</SP>is a perfluoroalkyl group and the remainders are each a hydrogen atom or a hydrocarbon group). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a phenylene vinylene compound useful for an organic semiconductor material, and an n-type organic field effect transistor using the compound as an electron transfer layer.

  A field effect transistor is one of unipolar transistors using one kind of carrier, and is widely used as an important switching element or amplifying element. The structure consists of a semiconductor layer that forms a current path between the source electrode and the drain electrode, and an insulator layer that isolates the semiconductor layer from a gate voltage that controls the flow of current by applying a voltage. It is configured.

  The characteristics of a field effect transistor are important for the mobility and on / off value of the semiconductor, and are determined by the characteristics of the semiconductor used, especially the semiconductor material.

  Conventionally, inorganic semiconductor materials such as amorphous silicon and polysilicon have been used for semiconductor materials. Since inorganic semiconductors represented by silicon are processed at a high temperature during production, there is a drawback that it is difficult to use a plastic substrate or a plastic film as a substrate. In addition, since the device manufacturing process is performed in a vacuum, an expensive manufacturing facility is required, resulting in a high cost.

  In recent years, it has been used in organic field effect transistors, organic light-emitting diodes, photovoltaic cells, etc. from the viewpoint of basic optoelectronic engineering of organic semiconductors, and research on organic semiconductors and organic semiconductor materials has been promoted from this viewpoint.

  An organic field effect transistor using an organic semiconductor material instead of an inorganic semiconductor material can be reduced in weight and area, and the manufacturing process can be simplified. For this reason, there is an advantage that the cost can be reduced and the disposal process can be simplified. In addition, by using an organic compound soluble in a solvent, there is an advantage that an organic field effect transistor can be manufactured by forming an organic semiconductor film using a printing method such as application of a solution or inkjet. Yes.

  A large number of organic semiconductor materials have been developed as p-type organic semiconductors, which are semiconductors in which positively charged holes play a role of transmitting current. There are few variations as an n-type organic semiconductor, which is a semiconductor in which a free electron having a negative charge plays a role of transmitting a current.

  For example, Patent Document 1 discloses an organic thin film transistor including polyparaphenylene vinylene in a p-type organic semiconductor layer. The p-type organic semiconductor layer is a hole transport layer that moves holes between the source electrode and the drain electrode. Non-Patent Document 1 and Non-Patent Document 2 disclose organic semiconductors that exhibit n-type characteristics. Although it can be said that the organic semiconductors disclosed in these non-patent documents exhibit n-type characteristics to some extent, they cannot be formed by a coating method or a printing method.

JP 2006-253675 A

A. A.Facchetti et al., Advanced Materials, 2003, Vol. 15, No. 1, p.33-38. Sea. R. Newman et al., Chemistry of Materials, 2004, Vol. 16, p.4436-4451.

  The present invention has been made to solve the above-mentioned problems, and a phenylene vinylene compound useful for an organic semiconductor material, and an organic semiconductor layer easily formed from an organic semiconductor material containing the compound by a coating method or a printing method. An object of the present invention is to provide an n-type organic field effect transistor which is formed into a film and exhibits high electron mobility and on / off value.

  The phenylene vinylene compound according to claim 1, which has been made to achieve the above object, has the following chemical formula (I):

(In the formula, two of X ^{1 to} X ⁴ are cyano groups, and the remainder and X ^{5 to} X ⁸ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or X ^{5 to} X ⁸ are cyano groups, the remainder and X ^{1 to} X ⁴ are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent, and R ^{1 to} R ^5. And at least one of R ^{6 to} R ¹⁰ is a perfluoroalkyl group represented by C _n F _{2n + 1} (n is a positive number of 1 to 20), and the remainder has a hydrogen atom or a substituent. It is a hydrocarbon group having 1 to 20 carbon atoms which may be present).

  The phenylene vinylene compound according to claim 2 is the compound according to claim 1, wherein the chemical formula (I) is represented by the following chemical formula (II):

（式中、Ｘ^１〜Ｘ^４、Ｘ^５〜Ｘ^８およびｎは前記と同じ）で表されることを特徴とする。

(Wherein, X ^{1 to} X ⁴ , X ^{5 to} X ⁸ and n are the same as described above).

  The phenylene vinylene compound according to claim 3 is the phenylene vinylene compound according to claim 1, wherein the chemical formula (II) is represented by the following chemical formula (III):

下記化学式（IV）

The following chemical formula (IV)

または下記化学式（Ｖ）

Or the following chemical formula (V)

で表されることを特徴とする。

It is represented by.

  An organic semiconductor material described in claim 4 contains the phenylene vinylene compound according to any one of claims 1 to 3.

  An n-type organic field effect transistor according to claim 5 is an organic semiconductor layer forming a current path between a source electrode and a drain electrode on a substrate, and a gate for controlling a current in the current path. The electrode is isolated by an insulator layer, and the organic semiconductor material according to claim 4 is contained in the organic semiconductor layer.

  The phenylene vinylene compound of the present invention has an electron-withdrawing substituent in its phenylene vinylene skeleton, and is useful as an organic semiconductor material. This organic semiconductor material can be easily formed not only by a vapor deposition method but also by a printing method such as a coating method or an ink jet method using a highly soluble phenylene vinylene compound, unlike a condensed ring compound found in a π-conjugated system. .

  An n-type organic field effect transistor made of this organic semiconductor material exhibits high electron mobility, can eliminate a carrier barrier, and can have a higher on / off value.

  In addition, this n-type organic field effect transistor can have a light emitting property due to the high light emission quantum efficiency of the phenylene vinylene compound.

It is sectional drawing of the n-type field effect transistor which contains the phenylene vinylene compound to which this invention is applied in the organic-semiconductor layer. It is sectional drawing of another n-type field effect transistor which contains the phenylene vinylene compound to which this invention is applied in the organic-semiconductor layer. It is sectional drawing of another n-type field effect transistor which contains the phenylene vinylene compound to which this invention is applied in the organic-semiconductor layer.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

In an example of the phenylene vinylene compound of the present invention, X ² and X ^{3 in} the chemical formula (I) are cyano groups, X ¹ and X ^{4 to} X ⁸ are hydrogen atoms, and R ³ and R ⁸ are —CF _3. And R ¹ , R ² , R ^{4 to} R ⁷ , R ⁹ and R ¹⁰ are each a hydrogen atom and represented by the following chemical formula (III).

When two of X ^{1 to} X ⁴ which are substituents of the vinylene moiety are cyano groups and the remaining two are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent, an aromatic ring X < ⁵ > -X < ⁸ > which is a substituent of is a C1-C20 hydrocarbon group which may have a hydrogen atom or a substituent.

Conversely, when X ^{5 to} X ⁸ which are substituents of the aromatic ring are two, a cyano group and the remaining two are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. X ^{1 to} X ⁴ which are substituents of the vinylene moiety are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent.

  The hydrocarbon group having 1 to 20 carbon atoms which may have these substituents has, for example, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An alkynyl group which may be substituted, an aryl group which may have a substituent, and the like.

  The alkyl group may be a linear or branched alkyl group or a cyclic cycloalkyl group. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and other linear or branched alkyl groups; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group And cycloalkyl groups such as cyclononanyl group, cyclodecanyl group, cycloundecanyl group, and cyclododecanyl group.

  The alkyl group may have a substituent. Examples of the substituent include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group; a pyridyl group, a thienyl group, a furyl group, a pyrrolyl group, and an imidazolyl group. Group, pyrazinyl group, oxazolyl group, thiazolyl group, pyrazolyl group, benzothiazolyl group, benzoimidazolyl group and other heteroaromatic ring groups; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, alkoxy groups such as tert-butoxy group, pentyloxy group, isopentyloxy group, neopentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group; Group, ethi Alkylthio groups such as thio group, propylthio group and butylthio group; arylthio groups such as phenylthio group and naphthylthio group; trisubstituted silyloxy groups such as tert-butyldimethylsilyloxy group and tert-butyldiphenylsilyloxy group; methylsulfinyl group and ethyl Alkylsulfinyl groups such as sulfinyl groups; arylsulfinyl groups such as phenylsulfinyl groups; sulfonic acid ester groups such as methylsulfonyloxy groups, ethylsulfonyloxy groups, phenylsulfonyloxy groups, methoxysulfonyl groups, ethoxysulfonyl groups, and phenyloxysulfonyl groups Cyano group; nitro group; and the like.

  The alkenyl group may be linear or branched. Examples of the alkenyl group include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group. These alkenyl groups may have a substituent, and as the substituent, those similar to the substituents exemplified in the description of the alkyl group can be used.

  The alkynyl group may be linear or branched. Examples of the alkynyl group include ethynyl group, propynyl group, propargyl group, butynyl group, pentynyl group, hexynyl group, and phenylethynyl group. These alkynyl groups may have a substituent, and as the substituent, those similar to the substituents exemplified in the description of the alkyl group can be used.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. These aryl groups may have a substituent, and as such a substituent, a substituent other than the aryl group exemplified in the description of the alkyl group, the above-described alkyl group, alkenyl group, alkynyl group, or the like is used. be able to.

  A method for producing a phenylene vinylene compound is shown below.

In the case where X ^{1 to} X ⁴ have a cyano group as shown in the above chemical formulas (III) and (IV), a Knoevenagel condensation reaction between an aldehyde compound or a ketone compound and a phenylacetonitrile compound is preferably used. It is done.

The chemical reaction when X ¹ and X ⁴ are cyano groups is shown in the following reaction formula (VI), and the chemical reaction when X ² and X ³ are cyano groups is shown in the following reaction formula (VII).

On the other hand, when X ^{5 to} X ⁸ have a cyano group as represented by the chemical formula (V), a Wittig-Horner reaction between an aldehyde compound or a ketone compound and a phenylmethyl phosphate compound is preferable. Used.

For example, the chemical reaction when X ⁵ and X ⁸ are cyano groups is shown in the following reaction formula (VIII).

  The phenylene vinylene compound obtained by these reactions can be isolated and purified by a method usually performed in the isolation and purification of organic compounds. For example, when the target product is precipitated as a solid in the reaction mixture, it can be filtered as it is. When the target product is not precipitated, the reaction mixture can be concentrated as it is to precipitate a solid, and the target product can be obtained by filtration. By purifying the target product thus obtained by sublimation, recrystallization, distillation, silica gel column chromatography, or the like, a highly pure phenylene vinylene compound can be obtained.

In these reaction formulas (VI), (VII) and (VIII), R ^{1 to} R ¹⁰ may use the above-described substituents, but R ^{1 to} R ⁵ and R may be used from the viewpoint of the convenience of the reaction operation. ^{6 to} R ¹⁰ are preferably the same substituents in this order.

  These reactions are preferably performed in the presence of a base.

  Examples of the base include metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide and potassium t-butoxide; metals such as sodium hydride, potassium hydride and calcium hydride Hydrides; hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide, aluminum hydroxide; alkali metals such as sodium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or Examples include alkaline earth metal carbonates and hydrogen carbonates; tertiary amines such as trimethylamine, triethylamine, tributylamine, trioctylamine, triethanolamine, pyridine, and quinoline. Among the above, it is preferable to use metal alkoxide, metal hydride, alkali metal or alkaline earth metal hydroxide.

In the case of (VI), the amount of the base used is preferably 1.5 to 10 mol and more preferably 2 to 5 mol with respect to 1 mol of the phenylacetonitrile compound. Moreover, in the case of (VII), it is preferable in it being 1.5-10 mol with respect to 1 mol of aldehyde compounds or ketone compounds, and it is more preferable in it being the range of 2-5 mol. In the case of (VIII), it is preferably 1.5 to 10 moles, more preferably 2 to 5 moles per mole of the phenylmethyl phosphate ester compound. Furthermore, these reactions are carried out in the presence of a solvent. Is preferable.

  The solvent is preferably a solvent that dissolves to the extent that each compound as a raw material does not hinder the reaction rate. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and mesitylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, and decane; and alicyclic carbons such as cyclohexane and cyclooctane. Hydrogen; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, tetrahydrofuran and 1,4-dioxane; alcohols such as methanol, ethanol, 2-propanol and t-butanol; non-dimethylsulfoxide, N-methylpyrrolidone and the like A protic polar solvent; and a mixed solvent thereof. Among these, aromatic hydrocarbons typified by toluene or ethers typified by tetrahydrofuran are preferably used. Moreover, when using a metal alkoxide as a base, alcohol is used suitably.

  It is preferable that the usage-amount of a solvent is 1-500 mass parts with respect to 1 mass part of an aldehyde compound or a ketone compound, and it is more preferable that it is 3-100 mass parts.

  The reaction temperature is preferably in the range of −80 ° C. to 200 ° C., and more preferably in the range of −20 ° C. to 100 ° C. from the viewpoint of the reaction rate and the stability of the target product.

  The reaction time varies depending on the amount ratio of each compound used as a raw material and the reaction temperature in each reaction, but is preferably in the range of 0.5 to 100 hours.

  These phenylene vinylene compounds can be used as organic semiconductor materials with n-type characteristics having high electron transfer and on / off values.

  Furthermore, an n-type organic field effect transistor can be manufactured by using the organic-semiconductor material containing the phenylene vinylene compound of this invention for an organic-semiconductor layer.

  In an n-type organic field effect transistor, a gate electrode layer to which a voltage is applied, an insulator layer, an organic semiconductor layer, and a source / drain electrode layer serving as a current path are stacked on a substrate. is there. There are a bottom gate / top contact type, a bottom gate / bottom contact type, a top gate / bottom contact type, and a top gate / top contact type, depending on the stacking arrangement of these layers.

  A preferred embodiment of the n-type organic field effect transistor will be described in detail with reference to FIG.

  As shown in FIG. 1, the n-type organic field effect transistor 1 is an organic semiconductor containing a gate electrode layer composed of a gate electrode 6, an insulator layer 7, and a phenylene vinylene compound on an insulating support substrate which is a substrate 5. The bottom gate / top contact type in which the layer 8 and the source / drain electrode layer composed of the source electrode 9 and the drain electrode 10 are sequentially stacked. The gate electrode 6 controls the current flowing in the current path, and is isolated from the organic semiconductor layer 8 and the source / drain electrode layer by the insulator layer 7. The source / drain electrode layer is deposited on the organic semiconductor layer 8, and forms a channel region that becomes a current path between the source electrode 9 and the drain electrode 10.

  The n-type organic field effect transistor 1 generates an electric field when a voltage is applied to the gate electrode 6, and forms a channel region serving as a current path between the source electrode 9 and the drain electrode 10 in the source / drain electrode layer. In the source / drain electrode layer and the organic semiconductor layer 8, electrons are supplied from the source electrode 9 to the organic semiconductor layer 8, electrons are discharged from the organic semiconductor layer 8 to the drain electrode 10, and a current flows. . The transistor operation is performed by changing the carrier density of the organic semiconductor layer 8 and the insulator layer 7 and changing the amount of current flowing between the source electrode 9 and the drain electrode 10.

  Specific examples of the raw material for forming the insulating support substrate 5 include polyethylene terephthalate (PET), glass, quartz, silicon, ceramic, and plastic.

  The thickness of the insulating support substrate 5 is preferably about 0.05 to 2 mm, and more preferably about 0.1 to 1 mm.

The insulator layer 7 preferably has an electric conductivity at room temperature of 10 ⁻² A / cm ² or less under a field strength of 1.0 MV / cm. Further, the relative dielectric constant is usually about 4.0, and it is preferable that the relative dielectric constant shows a high value.

  Specific examples of the raw material for the insulator layer 7 include silicon oxide, silicon nitride, amorphous silicon, aluminum oxide, and tantalum oxide. In addition, the group consisting of polystyrene, polyvinylphenol, polycarbonate, polyester, polyvinyl acetate, polyurethane, polysulfone, (meth) acrylic resin, epoxy resin, hydrocarbon resin and phenol resin having cyano group, polyimide resin and polyparaxylylene resin You may form from the resin or resin composition which has 1 type, or 2 or more types of resin selected from these as a main component.

  The film thickness of the insulator layer 7 is preferably about 50 nm to 2 μm, more preferably about 100 nm to 1 μm.

  The raw material to be the gate electrode 6, the source electrode 9, and the drain electrode 10 is not particularly limited as long as it exhibits conductivity. Specifically, platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, Indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, silicon, carbon, graphite, classy carbon, silver paste and carbon paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, Gallium, niobium, sodium-potassium alloy, magnesium / silver mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide Mixture, lithium / aluminum mixture, amorphous silicon, and the like. In addition, a known conductive polymer whose conductivity is improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, a complex of polyethylenedioxythiophene and polystyrenesulfonic acid, or the like is also preferably used.

  The film thicknesses of the gate electrode 6, the source electrode 9, and the drain electrode 10 are preferably 0.01 to 2 μm, and more preferably 0.2 to 1 μm.

  Further, the channel length L, which is the distance between the source electrode 9 and the drain electrode 10, is usually 100 μm or less and preferably 50 μm or less. On the other hand, the channel width W is usually 2000 μm or less and preferably 500 μm or less. L / W is usually 0.1 or less and preferably 0.05 or less.

  The organic semiconductor layer 8 uses the phenylene vinylene compound of the present invention or an organic semiconductor material containing it. The organic semiconductor layer 8 is an electron transfer layer for transferring electrons from one electrode to the other electrode.

  The film thickness of the organic semiconductor layer 8 is preferably about 1 nm to 10 μm, and more preferably about 10 to 500 nm.

  The method for forming the n-type organic field effect transistor 1 is not particularly limited, and a conventionally known method can be used.

  The insulator layer 7 can be formed by, for example, a coating method such as spin coating or blade coating, a vapor deposition method, a sputtering method, a printing method such as screen printing, ink jetting, or an electrostatic charge image developing method. Alternatively, a photo-curing resin that forms an insulator by applying a monomer as a precursor of the insulator and then curing it by irradiation with light may be used.

  The gate electrode 6, the source electrode 9, and the drain electrode 10 can be formed by, for example, a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method, or the like. Furthermore, as these patterning methods, there are a photolithography method, a printing method such as ink jet printing, screen printing, offset printing, letterpress printing, a soft lithography method such as a micro contact printing method, and a method combining a plurality of these methods. Can be mentioned. Moreover, it can also form by the method of irradiating energy rays, such as a laser and an electron beam, and removing a material.

  The organic semiconductor layer 8 can be formed by dissolving a phenylene vinylene compound in a solvent and applying it by casting, dipping, spin coating, or the like, or vacuum deposition.

  Next, FIG. 2 shows an embodiment of another n-type organic field effect transistor 1a.

  As shown in FIG. 2, the n-type organic field effect transistor 1 a includes a gate electrode 6, an insulator layer 7, a source / drain electrode layer that is a source electrode 9 and a drain electrode 10, and an organic substrate on an insulating substrate 5. The semiconductor layer 8 is a bottom gate / bottom contact type in which the semiconductor layers 8 are sequentially stacked. Except for the difference in the channel region due to the difference in the arrangement of the source / drain electrode layers and the organic semiconductor layer 8, it is the same as that shown in FIG.

  FIG. 3 shows another embodiment of another n-type organic field effect transistor 1b.

  In the n-type organic field effect transistor 1b, as shown in FIG. 3, a source / drain electrode layer, an organic semiconductor layer 8, an insulator layer 7, and a gate electrode 6 are sequentially formed on an insulating substrate 5. Gate / bottom contact type.

  The structure of the n-type organic field effect transistor is not particularly limited. When the organic semiconductor layer 8 is exposed as shown in FIGS. 1 and 2, a protective film is formed on the organic semiconductor layer 8. It may be what you are doing. This protective film can minimize the influence of outside air on the organic semiconductor layer 8. Examples of the raw material of the protective film include polymers such as epoxy resin, acrylic resin, polyurethane, polyimide, and polyvinyl alcohol, and inorganic oxides and nitrides such as silicon oxide, silicon nitride, and aluminum oxide. The protective film can be formed by a coating method, a vacuum deposition method, or the like.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

Example 1
The chemical reaction of Example 1 is shown in the following reaction formula (IX).

  P-Phenylenediacetonitrile (313 mg, 2 mmol), 4-trifluoromethylbenzaldehyde (870 mg, 5 mmol) and ethanol (25 ml) were added to a three-necked flask with an internal volume of 100 ml equipped with a thermometer and a dropping funnel, and purged with argon. An ethanol (EtOH) solution (5 ml) of potassium t-butoxide (110 mg, 1.0 mmol) was added dropwise so that the internal temperature was kept at 30 ° C. or lower, and after completion of the addition, the mixture was heated and stirred for 2 hours under reflux conditions. After cooling the reaction solution, 30 ml of methylene chloride was added to the concentrate obtained by distilling off ethanol under reduced pressure. After washing with 20 ml of water using a separatory funnel, the organic layer was separated and dried over anhydrous magnesium sulfate. Magnesium sulfate is removed by filtration, and the concentrate obtained by distilling off the low-boiling components from the obtained filtrate under reduced pressure is purified by silica gel column chromatography (developing solvent: methylene chloride) to be a yellow solid. The compound was obtained (yield: 740 mg, yield: 79%).

The nuclear magnetic resonance (NMR) spectrum data of the compound is shown below.
¹ H-NMR (270 MHz, CDCl ₃ ) δ: 8.03 (d, 4H), 7.81 (s, 4H), 7.76 (d, 4H), 7.65 (s, 2H).

Example 2
The chemical reaction of Example 2 is shown in the following reaction formula (X).

  To a 200-ml three-necked flask equipped with a thermometer and a dropping funnel was added terephthalaldehyde (518 mg, 3.88 mmol), 4-trifluoromethylphenylacetonitrile (1440 mg, 7.75 mmol), t-butanol (55 ml) and tetrahydrofuran ( 20 ml) and added with argon. After heating to an internal temperature of 50 ° C., a solution of potassium t-butoxide (100 mg, 0.89 mmol) in tetrahydrofuran (THF) (25 ml) was added dropwise so that the internal temperature was kept in the range of 50 to 55 ° C. After the completion of the dropwise addition, the mixture was heated and stirred at 50 ° C. for 30 minutes. After cooling the reaction solution, the precipitated solid was collected by filtration, and this solid was purified by silica gel column chromatography (developing solvent: methylene chloride) to obtain a compound as a yellow solid (yield: 1030 mg, yield: 57%). ).

The NMR spectrum data of the compound is shown below.
¹ H-NMR (270 MHz, CDCl ₃ ) δ: 8.05 (s, 4H), 7.79 (dd, 8H), 7.64 (s, 2H)

Example 3
The chemical reaction of Example 3 is shown in the following reaction formula (XI).

  To a 100 ml three-necked flask equipped with a thermometer and a dropping funnel was added (2,5-dicyano-1,4-phenylenebismethylene) bis (diethylphosphonate) (300 mg, 0.7 mmol) (Synthesis 1988). Year, page 386 and Organic Reactions 1977, volume 25, page 73), 4-trifluoromethylphenylacetonitrile (292 mg, 1.7 mmol) and tetrahydrofuran (10 ml) were added, Argon substitution was performed. After cooling the reaction solution at 0 ° C., a tetrahydrofuran solution (10 ml) of potassium t-butoxide (165 mg, 1.5 mmol) was added dropwise so that the internal temperature was kept in the range of 0 to 5 ° C. The mixture was stirred at 0 ° C. for 1 hour and then at room temperature for 12 hours. 10 ml of water was added to the reaction mixture, and tetrahydrofuran was distilled off under reduced pressure, and 30 ml of methylene chloride was added to the concentrate obtained. After washing with 20 ml of water using a separatory funnel, the organic layer was separated and dried over anhydrous magnesium sulfate. Magnesium sulfate is removed by filtration, and the concentrate obtained by distilling off the low-boiling components from the obtained filtrate under reduced pressure is purified by silica gel column chromatography (developing solvent: methylene chloride) to be a yellow solid. The compound was obtained (yield: 156 mg, yield: 48%).

The NMR spectrum data of the compound is shown below.
¹ H-NMR (270 MHz, CDCl ₃ ) δ: 8.11 (s, 2H), 7.70 (s, 8H), 7.42 (d, J = 14.7 Hz, 4H)

Example 4 Top Contact Type-n Type Organic Field Effect Transistor A silicon wafer having a thickness of 500 μm was cut into a size of 3.5 × 2.5 cm, and this film was used as an insulating support substrate. This substrate was treated with ozone, or with hexamethyldisilazane (HMDS) or octyltrichlorosilane (OTs) after ozone treatment. An n-type silicon wafer was formed on this processing substrate and used as a gate electrode. A 200 nm silicon oxide (SiO ₂ ) insulator layer was formed on the gate electrode by thermal oxidation. Then, using a vacuum deposition method on SiO _2, the compound of Examples 1 to 3 and 30nm deposited to form an organic semiconductor layer. Further, gold was vapor-deposited with a thickness of 50 nm on the organic semiconductor layer using a vacuum vapor deposition method to obtain a top contact type n-type organic field effect transistor shown in FIG. The deposition was performed so that the channel length (L) was 50, 75 and 100 μm, and the channel width (W) was 1000 μm.

  About the obtained n-type organic field effect transistor, the voltage of 10-60V is applied between a source electrode and a drain electrode using an electrometer, a gate voltage is changed in the range of -20-100V, voltage-current A curve was obtained at a temperature of 25 ° C., and the transistor characteristics were evaluated. Transistor characteristics were observed only for positive bias. This means that the obtained field effect transistor is an n-type organic field effect transistor.

The field effect mobility (μ) was calculated using the following formula (A) representing the drain current Id.
Id = (W / 2L) μCi (Vg−Vt) ² (A)
In the above formula (A), L is the gate length and W is the gate width. Ci is a capacitance per unit area of the insulating layer, Vg is a gate voltage, and Vt is a threshold voltage.

  The on / off ratio was calculated from the ratio between the maximum and minimum drain current values (Id).

  The obtained transistor characteristic evaluation results are shown in Table 1.

Example 5 Bottom Contact Type-n Type Organic Field Effect Transistor A comb-shaped electrode was formed on a silicon oxide insulator layer (thickness 300 nm) formed in the same manner as in Example 4 using a photolithography method. As for the electrode layer structure, chromium (Cr) was vapor-deposited on silicon oxide to a film thickness of 10 nm, and gold was vapor-deposited thereon to a film thickness of 20 nm. The comb pattern was such that the electrode channel length was 25 μm and the channel width was 294 μm (6 μm × 49).

50 nm of the compounds of Examples 1 to 3 were deposited on the silicon oxide on which this electrode was formed under an ultra-vacuum pressure of 10 ⁻⁵ Pa at a substrate temperature of room temperature or 50 ° C. and a deposition rate of 0.1 to 0.3%. A layer was formed. In the case of the coating method, a chloroform solution was dropped on a substrate to form a film.

  For the obtained n-type organic field effect transistor, the transistor characteristics were evaluated in the same manner as in Example 4. Table 1 shows the results of transistor characteristic evaluation.

  In Table 1, the notation of the element manufacturing method, “top” indicates the top contact type, “bottom” indicates the bottom contact type, and “notation” indicates the surface treatment, indicating that only ozone treatment is performed.

  The phenylene vinylene compound of the present invention is used as an organic semiconductor material for organic field effect transistors, organic light emitting diodes, and photovoltaic cells.

  1. 1a, 1b are n-type organic field effect transistors, 5 is a substrate, 6 is a gate electrode, 7 is an insulator layer, 8 is an organic semiconductor layer, 9 is a source electrode, 10 is a drain electrode, and L is a channel length. .

Claims (5)

The following chemical formula (I)

(In the formula, two of X ^{1 to} X ⁴ are cyano groups, and the remainder and X ^{5 to} X ⁸ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or X ^{5 to} X ⁸ are cyano groups and the remainder and X ^{1 to} X ⁴ are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent,
At least one of R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ is a perfluoroalkyl group represented by C _n F _{2n + 1} (n is a positive number of 1 to 20), and the remainder is a hydrogen atom or (It is a hydrocarbon group having 1 to 20 carbon atoms that may have a substituent)
The phenylene vinylene compound characterized by these. The chemical formula (I) is represented by the following chemical formula (II)

(Wherein, X ^{1 to} X ⁴ , X ^{5 to} X ⁸ and n are the same as above)
The phenylene vinylene compound according to claim 1, which is represented by: The chemical formula (II) is represented by the following chemical formula (III)

The following chemical formula (IV)

Or the following chemical formula (V)

The phenylene vinylene compound according to claim 2, wherein   An organic semiconductor material comprising the phenylene vinylene compound according to claim 1.   On the substrate, an organic semiconductor layer forming a current path between the source electrode and the drain electrode and a gate electrode controlling the current in the current path are separated by an insulator layer, and the organic An n-type organic field effect transistor, wherein the semiconductor layer contains the organic semiconductor material according to claim 4.

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