JP2006182730A - New thiophene derivative and transistor element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new thiophene derivative having a higher carrier mobility and a transistor element using the same. <P>SOLUTION: The thiophene derivative is represented by formula (1) (wherein Ar<SB>1</SB>and Ar<SB>2</SB>are each an aromatic hydrocarbon group which may have a substituent or an aromatic heterocylic group which may have a substitutent and the Ar<SB>1</SB>and Ar<SB>2</SB>may be the same or different from each other; and R<SB>1</SB>and R<SB>2</SB>are each selected from an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent and a silyl group which may have a substituent). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel thiophene derivative and a transistor element using the same.

  An organic electroluminescent element, which is a typical example of an organic semiconductor device, utilizes a light emission phenomenon associated with recombination of electrons and holes in a layer made of an organic phosphor. Patent Document 1 describes that a thiophene-based compound can be used as a hole injection layer and a transport layer of the organic electroluminescence element.

JP 2004-327454 A

  By the way, as an organic semiconductor device, a transistor element using an organic phosphor other than the organic electroluminescence is also known. For this reason, it is conceivable to use the thiophene-based compound as an organic material of a transistor element. However, in order to use it as a transistor element, it is necessary to have high carrier movement performance and the like.

  Accordingly, an object of the present invention is to provide a novel thiophene derivative having higher carrier mobility and a transistor element using the same.

  This invention solved the said subject by providing the thiophene derivative shown by following formula (1), and the transistor element using the same.

(In the formula (1), Ar ₁ and Ar ₂ represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and the above Ar ₁ and Ar ₂ may be the same as or different from each other, and R ₁ and R ₂ may be an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or a substituent. An alkynyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, and a substituent Indicates a group selected from good silyl groups.)

  According to this invention, since a specific thiophene derivative is used, higher carrier mobility can be exhibited.

  The present invention relates to a thiophene derivative represented by the following formula (1) and a transistor element using the thiophene derivative.

In the above formula (1), Ar ₁ and Ar ₂ represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar ₁ and Ar ₂ may be the same as or different from each other.

  Examples of the aromatic hydrocarbon group and aromatic heterocyclic group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthranyl group.

  Examples of the substituent include substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, lower alkoxy groups, alkenyl groups, alkynyl groups, substituted or unsubstituted aryl groups, alkylsulfonyl groups, arylsulfonyl groups, alkylcyano groups, and arylcyano groups. Group, cyano group, nitro group, amino group, carboxy group, carbalkoxy group, or esters, amides and salts thereof, or halogen such as fluorine atom, chlorine atom, bromine atom and iodine atom.

R ₁ and R ₂ have an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. A group selected from an alkynyl group that may be substituted, an aryl group that may have a substituent, an alkoxy group that may have a substituent, and a silyl group that may have a substituent.

  Examples of the substituent include sulfonyl group, cyano group, nitro group, amino group, carboxy group, carbalkoxy group, ester group, amide group, halogen such as fluorine atom, chlorine atom, bromine atom and iodine atom.

Next, a method for producing the thiophene derivative represented by the above formula (1) will be described. As a thiophene derivative, a compound having R ₁ = R ₂ and Ar ₁ = Ar ₂ in formula (1) was used and synthesized according to the following reaction formulas <1> to <2>. R ₁ and Ar ₁ are the same as described above.

  As shown in Reaction Formula <1>, 2-substituted thiophene is tributyltinated and then reacted with aryl aldehyde to obtain a compound in which aryl aldehyde is substituted at the 5-position of 2-substituted thiophene.

  Next, as shown in reaction formula <2>, the above-mentioned 2,5-bis (diethoxyphosphorylmethyl) thiophene and a compound in which arylaldehyde is substituted at the 5-position of 2-substituted thiophene using a base , The compound according to formula (1) can be produced by Wittig reaction.

  A transistor element is formed by using the thiophene derivative as a constituent component of the charge transfer layer.

  In addition to the thiophene derivative, the charge transfer layer may be used in combination with other constituent components such as organic materials such as other organic phosphors and dopant materials in order to further improve the carrier mobility. . In addition to the thiophene derivative, if necessary, a layer obtained by co-depositing minor constituents such as other organic phosphors and dopant materials in the thiophene derivative layer may be used, or more in the charge transfer layer. In order to inject the carrier, a layered structure having a separated function such as a carrier injection layer may be introduced.

  Such organic materials such as other organic phosphors are not particularly limited. For example, condensed ring derivatives such as anthracene, phenanthrene, pyrene, perylene, chrysene, and quinolinol such as tris (8-quinolinolato) aluminum. Metal complexes of derivatives, benzoxazole derivatives, stilbene derivatives, benzthiazole derivatives, thiadiazole derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, oxadiazole derivatives, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, Metal complexes combining quinolinol derivatives with different ligands, oxadiazole derivative metal complexes, benzazole derivative metal complexes, coumarin derivatives, pyrrolopyridine derivatives, perinone derivatives , Thiadiazolopyridine derivatives and the like. Furthermore, examples of organic materials such as other organic phosphors based on polymers include polyphenylene vinylene derivatives, polyparaphenylene derivatives, and polythiophene derivatives.

  The dopant material is not particularly limited, and examples thereof include condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, and rubrene, benzoxazole derivatives, benzthiazole derivatives, benzines. Imidazole derivatives, benztriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, Bisstyryl derivatives such as distyrylbenzene derivatives, diazaindacene derivatives, furan derivatives, benzofuran derivatives , Phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran, etc., isobenzofuran derivatives, dibenzofuran derivatives, 7-dialkylaminocoumarins Derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzthiazolylcoumarin derivatives, 3-benzimidazolylcoumarin derivatives, 3-benzoxazolylc Coumarin derivatives such as marine derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives, oxobenzanthracene derivatives, xanthene derivatives, loaders Derivatives, fluorescein derivatives, pyrylium derivatives, carbostyryl derivatives, acridine derivatives, bis (styryl) benzene derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2,5-thia Examples thereof include diazolopyrene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, diazaflavin derivatives, and the like.

Next, a transistor element using the thiophene derivative will be described.
Examples of the transistor element include an element having a basic structure of a field effect transistor (FET) as shown in FIG.

The transistor element 10 is capable of transporting holes and electrons as carriers, and generates some light emission due to recombination of holes and electrons. The charge transfer layer 1 containing the thiophene compound as a main component, A hole injection electrode for injecting holes into this charge transfer layer 1, so-called source electrode 2, an electron injection electrode for injecting electrons into the charge transfer layer, so-called drain electrode 3, The gate electrode 4 is made of a heavy-doped silicon (denoted as “N ⁺ ” in FIG. 1) substrate that controls the carrier distribution in the charge transfer layer 1. The gate electrode 4 may be composed of a conductive layer made of an impurity diffusion layer formed in the surface layer portion of the silicon substrate, or a general metal may be used.

  Specifically, as shown in FIG. 1, an insulating film 5 made of silicon oxide or the like is provided on the gate electrode 4, and the source electrode 2 and the drain electrode 3 are provided on the insulating film 5 with a gap therebetween. The charge transfer layer 1 is provided so as to cover the source electrode 2 and the drain electrode 3 and to enter between the two electrodes.

  In order for the element to exhibit the function of a transistor, it is preferable that the carrier mobility of the organic substance constituting the charge transfer layer 1, particularly the thiophene derivative as a constituent component, satisfies a predetermined range. In addition, when the said thiophene-type compound which has said each characteristic is used, it becomes possible to make each function higher by adding subcomponents, such as the said dopant.

The higher the carrier mobility is, the higher the semiconductivity and the better. Specifically, it is preferably 1.0 × 10 ⁻⁵ cm ² / V · s or more, more preferably 1.0 × 10 ⁻⁴ cm ² / V · s or more, and 1.0 × 10 ⁻³ cm ² / V. V · s or more is more preferable. Note that the upper limit of the carrier mobility is not particularly limited, and is approximately 1 cm ² / V · s.

  The charge transfer layer 1 is formed by vapor-depositing (or co-depositing when there are a plurality of types) organic phosphors constituting the charge-transfer layer 1. The thickness of the charge transfer layer 1 may be at least about 50 nm. In some cases, the film may be formed by a coating method.

  The source electrode 2 and the drain electrode 3 are electrodes for injecting holes and electrons into the charge transfer layer 1 and are formed of gold (Au), magnesium-gold alloy (MgAu), or the like. The two are formed so as to face each other with a minute gap of 0.4 to 50 μm or the like. Specifically, for example, as shown in FIG. 2, the source electrode 2 and the drain electrode 3 are formed so as to have comb-shaped portions 2 a and 3 a each composed of a plurality of comb teeth, and the comb teeth of the source electrode 2 are formed. By arranging the comb teeth constituting the shape portion 2a and the comb teeth constituting the comb tooth shape portion 3a of the drain electrode 3 alternately with a predetermined interval, the function as the transistor element 10 is more efficiently performed. It can be demonstrated. The source electrode 2 and the drain electrode 3 may use the same type of metal, or may use electrodes that are advantageous for carrier injection so that carrier injection is easier.

  At this time, the interval between the source electrode 2 and the drain electrode 3, that is, the interval between the comb-shaped portion 2a and the comb-shaped portion 3a is preferably 50 μm or less, preferably 3 μm or less, and more preferably 1 μm or less. If it exceeds 50 μm, electrons tend to be hardly injected due to insufficient electric field strength.

  The transistor element 10 applies a voltage to the source electrode 2 and the drain electrode 3 to move both holes and electrons within the transistor element 10 and recombine them in the charge transfer layer 1. At this time, the amount of holes and electrons moving between the two electrodes through the charge transfer layer 1 depends on the voltage applied to the gate electrode 4. For this reason, by controlling the voltage applied to the gate electrode 4 and the change thereof, the conduction state between the source electrode 2 and the drain electrode 3 can be controlled. Since the transistor element 10 performs P-type driving, a negative voltage is applied to the drain electrode 3 with respect to the source electrode 2, and a negative voltage is applied to the gate electrode 4 with respect to the source electrode 2.

  Specifically, by applying a negative voltage to the gate electrode 4 with respect to the source electrode 2, holes in the charge transfer layer 1 are attracted to the gate electrode 4 side, and holes in the vicinity of the surface of the insulating film 5 are collected. The density of becomes high. When the voltage between the source electrode 2 and the drain electrode 3 is appropriately set, holes are injected from the source electrode 2 to the charge transfer layer 1 depending on the control voltage applied to the gate electrode 4, and from the drain electrode 3 to the charge transfer layer 1. In this state, electrons are injected. That is, the source electrode 2 functions as a hole injection electrode, and the drain electrode 3 functions as an electron injection electrode. Thereby, recombination of holes and electrons occurs in the charge transfer layer 1. Then, it can be turned on / off by changing the control voltage applied to the gate electrode 4.

  The transistor element 10 emits some light when recombination of holes and electrons occurs in the charge transfer layer 1. For this reason, when the degree of this light emission, that is, the light emission luminance increases, it can be expected to be used as a light emitting transistor.

Next, the present invention will be described more specifically using examples.
(Production Example 1) [Production of (E, E) -2,5-bis [4- (5-hexylthiophen-2-yl) phenyl-1-ethynyl] thiophene]
In the compound according to the above formula (1), (E, E) -2,5-bis [4- (5), which is a compound of R ₁ = R ₂ = n-hexyl group, Ar ₁ = Ar ₂ = benzene ring. -Hexylthiophen-2-yl) phenyl-1-ethynyl] thiophene was prepared.

(Production of 4- (5-hexylthiophen-2-yl) benzaldehyde)
4- (5-Hexylthiophen-2-yl) benzaldehyde was produced according to the reaction described in the above reaction formula <1>.
First, under argon atmosphere, a solution of 1.0 ml (935 mg, 5.6 mmol) of 2-hexylthiophene dissolved in 10 ml of tetrahydrofuran was cooled to −40 ° C., and this solution was added with a hexane solution of n-BuLi (1.56 M, 3 8 mL, 5.9 mmol) was added dropwise and stirred at −40 ° C. for 1 hour, and then the temperature of the reaction solution was gradually raised to 0 ° C. Tributyltin chloride was slowly added dropwise to the reaction solution, and the reaction solution was gradually warmed from 0 ° C. to room temperature and stirred for 12 hours. After completion of the reaction, the reaction solution was diluted with water and ethyl acetate and then passed through Florisil. The filtrate was extracted with ethyl acetate, the organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. After removing the desiccant and distilling off the solvent under reduced pressure, the resulting crude product was purified by distillation under reduced pressure to give 2.11 g (4.60 mmol, 83%) of 5-hexyl-2-tributylstannylthiophene. Got. This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.
-Pale yellow oil: 235-240 ° C / 2.5mmHg
MS (EI): m / z 458 (M ⁺⁺ 1).
_{^{· 1 H-NMR (CDCl 3}} , 200MHz): 0.90 (t, J = 7.2Hz, 9H), 1.07 (t, J = 7.6Hz, 3H), 1.24-1.44 ( m, 16H), 1.50-1.76 (m, 8H), 2.86 (t, J = 7.6 Hz, 2H), 6.90 (d, J = 3.0 Hz, 1H), 6. 99 (d, J = 3.0 Hz, 1H).

Next, 3.59 g (7.84 mmol) of 5-hexyl-2-tributylstannylthiophene obtained, 1.50 g (8.10 mmol) of 4-bromobenzaldehyde, tetrakis (triphenylphosphine) palladium (Pd (PPh _{3 4} ) 470 mg (5.2 mol%) and 32 ml of dry toluene as a solvent were sequentially added to a Schlenk tube, and the mixture was heated and stirred at 100 ° C. for 26 hours in an argon atmosphere. After completion of the reaction, the reaction solution was diluted with ethyl acetate and then passed through florisil to remove the catalyst. The filtrate was extracted with ethyl acetate, the organic layers were combined, washed successively with 10% aqueous potassium fluoride solution, water and saturated brine, and dried over anhydrous sodium sulfate. After removing the desiccant and distilling off the solvent under reduced pressure, the resulting crude product was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 1/1) and alumina (neutral) column chromatography ( Separation and purification with a developing solvent: hexane / ethyl acetate = 50/1) gave 2.14 g (7.85 mmol, 74%) of the desired 4- (5-hexylthiophen-2-yl) benzaldehyde. This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.
・ Pale yellow needles:
FABMS (EI): m / z 273 (M ⁺⁺ 1).
¹ H-NMR (CDCl ₃ , 200 MHz): 0.90 (t, J = 6.5 Hz, 3H), 1.23-1.43 (m, 6H), 1.58-1.78 (m, 2H), 2.84 (t, J = 7.6 Hz, 2H), 6.80 (d, J = 3.8 Hz, 1H), 7.29 (d, J = 3.8 Hz, 1H), 7. 70 (d, J = 8.4 Hz, 2H), 7.86 (d, J = 8.4 Hz, 2H), 9.98 (s, 1H).

Production of (E, E) -2,5-bis [4- (5-hexylthiophen-2-yl) phenyl-1-ethenyl] thiophene)
Next, (E, E) -2,5-bis [4- (5-hexylthiophen-2-yl) phenyl-1-ethenyl] thiophene was produced according to the reaction described in the above reaction formula <2>. .
[Production Example 1-1]
Under an argon atmosphere, a solution of 209 mg (1.86 mmol) of t-butoxypotassium in 15 mL of tetrahydrofuran was stirred at room temperature. A solution prepared by dissolving 346 mg (0.90 mmol) of 2,5-bis (diethoxyphosphorylmethyl) thiophene and 400 mg (1.47 mmol) of 4- (5-hexylthiophen-2-yl) benzaldehyde in 15 mL of tetrahydrofuran was added to this solution. The solution was slowly added dropwise at room temperature over 1 hour, stirred for 1 hour, and then heated and stirred at 50 ° C. for 22 hours. After completion of the reaction, the solvent was distilled off at room temperature under reduced pressure, 10 mL of methanol was added to the obtained brown solid, and the mixture was stirred for a while and filtered. The obtained crude product was washed with hexane, and 393 mg (0.63 mmol) of the desired (E, E) -2,5-bis [4- (5-hexylthiophen-2-yl) phenyl-1-ethenyl] thiophene. 86%). This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.
・ Yellow solid
FABMS (EI): m / z 620 (M ⁺ -1).
¹ H-NMR (CDCl ₃ , 400 MHz): 0.90 (t, J = 6.4 Hz, 6H), 1.45 to 1.80 (m, 12H), 1.70 (m, 4H), 2.82 (t, J = 7.6 Hz, 4H), 6.75 (d, J = 3.4 Hz, 2H), 6.89 (d, J = 16.0 Hz, 2H), 6.96 (s) , 2H), 7.15 (d, J = 3.4 Hz, 2H), 7.19 (d, J = 16.0 Hz, 2H), 7.44 (d, J = 8.0 Hz, 4H), 7 .54 (d, J = 8.0 Hz, 4H).

[Production Example 1-2]
Under an argon atmosphere, a solution of n-BuLi in hexane (1.60 M, 0.33 mL, 0.53 mmol) dissolved in 8 mL of tetrahydrofuran was stirred at −78 ° C. A solution prepared by dissolving 116 mg (0.26 mmol) of 2,5-bis (diethoxyphosphorylmethyl) thiophene and 142 mg (0.52 mmol) of 4- (5-hexylthiophen-2-yl) benzaldehyde in 7 mL of tetrahydrofuran was added to this solution. After slowly dropping at -78 ° C over 1 hour and stirring at -78 ° C for 1 hour, the reaction solution was gradually warmed to 0 ° C and stirred at 0 ° C for 12 hours. After completion of the reaction, the solvent was distilled off at room temperature under reduced pressure, 10 mL of methanol was added to the obtained brown solid, and the mixture was stirred for a while and filtered. The obtained crude product was washed with hexane, and 161 mg (0.26 mmol) of the desired (E, E) -2,5-bis [4- (5-hexylthiophen-2-yl) phenyl-1-ethenyl] thiophene. , 52%). This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.

(Production Example 2) [Production of (E, E) -2,5-bis [4- (5-hexylthiophen-2-yl) naphthyl-2-ethynyl] thiophene]
In the compound according to the above formula (1), (E, E) -2,5-bis [4- (5), which is a compound of R ₁ = R ₂ = n-hexyl group, Ar ₁ = Ar ₂ = naphthalene ring. -Hexylthiophen-2-yl) naphthyl-2-ethynyl] thiophene was prepared.

Under an argon atmosphere, a solution of 2,6-dibromonaphthalene (2.00 g, 7.0 mmol) in tetrahydrofuran (40 ml) was cooled to −78 ° C., and n-BuLi in hexane (1.60 M, 4.4 mL) was added to this solution. , 7.0 mmol) was added dropwise, and the mixture was stirred at −78 ° C. for 2 hours. N, N-dimethylformamide (2.0 mL, 25 mmol) was slowly added dropwise to the reaction solution, and the reaction solution was gradually warmed from −78 ° C. to room temperature and stirred for 12 hours. After completion of the reaction, the reaction solution was diluted with water and ethyl acetate. The filtrate was extracted with ethyl acetate, the organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. After removing the desiccant and distilling off the solvent under reduced pressure, the resulting crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 9/1) to give 6-bromonaphthalene-2. -Carbaldehyde (1.18 g, 5.03 mmol, 72%) was obtained. This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.
・ Chlorless needles
FAB-MS: m / z 235 (M ^<+> ).
_{^{· 1 H-NMR (CDCl 3}} , 200MHz): 7.67 (dd, J = 1.9 and 8.6Hz, 1H), 7.86 (d, J = 8.6Hz, 1H), 7.88 ( d, J = 8.6 Hz, 1H), 7.9 (dd, J = 1.9 and 8.6 Hz, 1H), 8.09 (s, 1H), 8.32 (s, 1H), 10. 16 (s, 1H).

To a Schlenk tube, 5-hexyl-2-tributylstannylthiophene (0.97 g, 2.13 mmol), 6-bromonaphthalene-2-carbaldehyde (0.5 g, 2.13 mmol), tetrakis (triphenylphosphine) palladium ( Pd (PPh ₃ ) ₄ , 123 mg, 5.0 mol%) and dry toluene (20 ml) were sequentially added as a solvent, and the mixture was heated and stirred at 100 ° C. for 63 hours under an argon atmosphere. After completion of the reaction, the reaction solution was diluted with ethyl acetate and then passed through florisil to remove the catalyst. The filtrate was extracted with ethyl acetate, the organic layers were combined, washed successively with 10% aqueous potassium fluoride solution, water and saturated brine, and dried over anhydrous sodium sulfate. After removing the desiccant and distilling off the solvent under reduced pressure, the resulting crude product was separated and purified by alumina (neutral) column chromatography (developing solvent: hexane / ethyl acetate = 20/1). Of 6- (5-hexylthiophen-2-yl) naphthalene-2-carbaldehyde (545 mg, 1.69 mmol, 80%). This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.
・ Pale yellow needles
FAB-MS: m / z 322 (M ^<+> ).
¹ H-NMR (CDCl ₃ , 200 MHz): 0.91 (t, J = 6.5 Hz, 3H), 1.26 to 1.50 (m, 6H), 1.65 to 1.82 (m, 2H), 2.86 (t, J = 7.5 Hz, 2H), 6.82 (d, J = 3.7 Hz, 1H), 7.33 (d, J = 3.7 Hz, 1H), 7. 76-8.00 (m, 4H), 8.01 (s, 1H), 8.28 (s, 1H), 10.13 (s, 1H).

Under an argon atmosphere, a solution of t-butoxypotassium (222 mg, 1.98 mmol) in tetrahydrofuran (30 mL) was stirred at room temperature. To this solution was added 2,5-bis (diethoxyphosphorylmethyl) thiophene (320 mg, 0.83 mmol) and 6- (5-hexylthiophen-2-yl) naphthalene-2-carbaldehyde (502 mg, 1.55 mmol) in tetrahydrofuran. (30 mL) The solution was slowly added dropwise at room temperature over 1 hour, stirred for 12 hours, and then heated and stirred at 50 ° C. for 48 hours. After completion of the reaction, the solvent was distilled off at room temperature under reduced pressure, methanol (10 mL) was added to the obtained brown solid, and the mixture was stirred for a while and filtered. The obtained crude product was washed successively with methanol, acetone and hexane, and the desired (E, E) -2,5-bis [4- (5-hexylthiophen-2-yl) naphthyl-2-ethenyl] thiophene was obtained. (378 mg, 0.52 mmol, 68%) was obtained. This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.
・ Pale brownish solid
FAB-MS: m / z 720 (M ^<+> ).
¹ H-NMR (CDCl ₃ , 400 MHz): 0.91 (t, J = 8.8 Hz, 6H), 1.35 to 1.50 (m, 12H), 1.67-1.78 (m, 4H), 2.85 (t, J = 7.6 Hz, 4H), 6.79 (d, J = 3.2 Hz, 2H), 7.02 (s, 2H), 7.08 (d, J = 16.0 Hz, 2H), 7.23 (m, 2H), 7.33 (d, J = 16.0 Hz, 2H), 7.66-7.85 (m, 8H), 7.79 (s, 2H), 7.94 (s, 2H).

(Production Example 3) [Production of (E, E) -2,5-bis [4- (5-hexylthiophen-2-yl) anthryl-2-ethynyl] thiophene]
In the compound according to the above formula (1), (E, E) -2,5-bis [4- (5) which is a compound of R ₁ = R ₂ = n-hexyl group and Ar ₁ = Ar ₂ = anthracene ring. -Hexylthiophen-2-yl) phenyl-1-ethynyl] thiophene was prepared.

Under an argon atmosphere, a solution of 9,10-dibromoanthracene (2.01 g, 6.0 mmol) in tetrahydrofuran (40 ml) was cooled to −78 ° C., and n-BuLi in hexane (1.60 M, 4.0 mL) was added to this solution. , 6.4 mmol) was added dropwise, and the mixture was stirred at -78 ° C for 2 hours. N, N-dimethylformamide (1.0 mL, 13 mmol) was slowly added dropwise to the reaction solution, and the reaction solution was gradually warmed from −78 ° C. to room temperature and stirred for 12 hours. After completion of the reaction, the reaction solution was diluted with water and ethyl acetate. The filtrate was extracted with ethyl acetate, the organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. After removing the desiccant and distilling off the solvent under reduced pressure, the resulting crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 9/1) to obtain 10-bromoanthracene-9. Carbaldehyde (1.17 g, 4.09 mmol, 68%) was obtained. This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.
・ Yellow Needles
FAB-MS: m / z 285 (M ⁺ ).
_{^{· 1 H-NMR (CDCl 3}} , 200MHz): 7.62-7.76 (m, 4H), 8.64-8.72 (m, 2H), 8.86-8.94 (m, 2H) 11.50 (s, 1H).

To a Schlenk tube, 5-hexyl-2-tributylstannylthiophene (208 mg, 0.46 mmol), 10-bromoanthracene-9-carbaldehyde (121 mg, 0.43 mmol), tetrakis (triphenylphosphine) palladium (Pd (PPh _{3 4} ), 29 mg, 5.9 mol%) and dry toluene (10 ml) as a solvent were sequentially added, and the mixture was heated and stirred at 100 ° C. for 42 hours under an argon atmosphere. After completion of the reaction, the reaction solution was diluted with ethyl acetate and then passed through florisil to remove the catalyst. The filtrate was extracted with ethyl acetate, the organic layers were combined, washed successively with 10% aqueous potassium fluoride solution, water and saturated brine, and dried over anhydrous sodium sulfate. After removing the desiccant and distilling off the solvent under reduced pressure, the resulting crude product was separated and purified by alumina (neutral) column chromatography (developing solvent: hexane / ethyl acetate = 17/3). Of 10- (5-hexylthiophen-2-yl) anthracene-9-carbaldehyde (156 mg, 0.42 mmol, 80%). This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.
・ Yellow Needles
-FAB-MS m / z 372 (M ^<+> ).
¹ H-NMR (CDCl ₃ , 200 MHz): 0.93 (t, J = 6.9 Hz, 3H), 1.32-1.52 (m, 6H), 1.73-1.89 (m, 2H), 2.96 (t, J = 7.5 Hz, 2H), 6.95-7.00 (m, 2H), 7.44-7.53 (m, 2H), 7.62-7. 72 (m, 2H), 8.01 (d, J = 8.8 Hz, 2H), 8.95 (d, J = 8.8 Hz, 2H), 11.57 (s, 1H).

Under a argon atmosphere, a solution of potassium t-butoxy (226 mg, 2.01 mmol) in tetrahydrofuran (40 mL) was stirred at room temperature. To this solution was added 2,5-bis (diethoxyphosphorylmethyl) thiophene (340 mg, 0.89 mmol) and 10- (5-hexylthiophen-2-yl) anthracene-9-carbaldehyde (601 mg, 1.61 mmol) in tetrahydrofuran. (20 mL) The solution was slowly added dropwise at room temperature over 1 hour, stirred for 12 hours, and then heated and stirred at 50 ° C. for 48 hours. After completion of the reaction, the solvent was distilled off at room temperature under reduced pressure, methanol (10 mL) was added to the obtained brown solid, and the mixture was stirred for a while and filtered. The obtained crude product was washed successively with methanol and hexane to give the desired (E, E) -2,5-bis [4- (5-hexylthiophen-2-yl) anthryl-2-ethenyl] thiophene (458 mg). , 0.56 mmol, 63%). This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.
・ Pale yellow solid
FAB-MS: m / z 820 (M ^<+> ).
¹ H-NMR (CDCl ₃ , 400 MHz): 0.94 (t, J = 6.8 Hz, 6H), 1.35 to 1.41 (m, 8H), 1.45 to 1.52 (m, 4H), 1.78-1.86 (m, 4H), 2.96 (t, J = 7.8 Hz, 4H), 6.96-7.00 (m, 4H), 7.12 (d, J = 3.6 Hz, 2H), 7.14 (d, J = 16.0 Hz, 2H), 7.43-7.48 (m, 4H), 7.49-7.54 (m, 4H), 7.89 (d, J = 16.0 Hz, 2H), 7.97 (d, J = 8.8 Hz, 4H), 8.44 (d, J = 8.8 Hz, 4H).

(Manufacture of transistor elements)
Next, the transistor element shown in FIGS. 1 and 2 was manufactured under the following conditions.
The source electrode 2 and the drain electrode 3 form electrodes (Cr / Au, thickness 40 nm) each having a comb-shaped portion composed of 20 comb teeth, and each comb-tooth shape is formed as shown in FIG. It arrange | positioned on the insulating film 5 so that a part may be alternately arrange | positioned. At this time, a layer (1 nm) made of chromium was provided as an adhesive layer between the insulating film 5 and both electrodes. Further, the width of the channel part (between each comb-shaped part) at this time was 10 μm or 3 μm, and the length was 4 mm.
As the insulating film 5, a silicon substrate was thermally oxidized to form a dense silicon oxide film having a thickness of 300 nm.

The charge transfer layer 1 was formed by depositing the thiophene derivative obtained in Production Example 1 alone so as to cover the periphery of the insulating film, the source electrode 2 and the drain electrode 3. .

About each obtained element, the carrier mobility was measured. As a result, the carrier mobility is 4.7 × 10 ⁻³ cm ² / V · s when the channel width is 10 μm, and the carrier mobility is 3.8 × 10 ⁻³ cm ² / V at 5 μm. V · s.

Sectional drawing which shows the example of the transistor element concerning this invention The top view which shows the structure of a source electrode and a drain electrode

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Charge transfer layer 2 Source electrode 2a Comb shape part 3 Drain electrode 3a Comb shape part 4 Gate electrode 5 Insulating film 10 Transistor element

Claims (2)

A thiophene derivative represented by the following formula (1).

(In the formula (1), Ar ₁ and Ar ₂ represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and the above Ar ₁ and Ar ₂ may be the same as or different from each other, and R ₁ and R ₂ may be an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or a substituent. An alkynyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, and a substituent Indicates a group selected from good silyl groups.)   A transistor element using the thiophene derivative according to claim 1.

Images