JP5009716B2 - Field-effect transistor using hexabenzocoronene nanotubes - Google Patents

Description

  The present invention relates to an organic semiconductor material comprising a hexaperihexabenzocoronene derivative represented by the general formula [1], a method for producing the same, and a semiconductor device and a field effect transistor using the organic semiconductor material.

Transistors are indispensable as electronic components for constructing and operating electronic circuits. Currently, the mainstream transistor is a transistor based on silicon, which is manufactured using amorphous silicon or polycrystalline silicon. The process of forming these silicon films is performed at a very high temperature of about 350 ° C. or higher, so the types of substrate materials that can be used are limited, and lightweight resin substrates are used because their heat-resistant temperature is low. There is a problem that you can not.
On the other hand, there is an increasing expectation for manufacturing transistors using organic molecules or polymers for the purpose of reducing costs, manufacturing electronic circuits on plastic films, and driving elements. Advantages of using an organic compound as an electronic device include reduction in the weight and flexibility of the element and simplification of the process. In order to produce such an organic transistor, it is necessary to produce an organic thin film having as good crystallinity as possible, and the crystallinity of the thin film is closely related to the characteristics of the transistor, that is, the carrier mobility. At present, two types of methods for producing an organic thin film are mainly used: a vacuum deposition method and a solution process (coating method). A dry process such as a vacuum deposition method is not preferable from an industrial point of view because productivity is reduced and cost is high. In order to take advantage of using an organic semiconductor material, a spin coating method or a printing method is used. It is desirable to use a simple and low-cost solution process such as an inkjet method. However, conventionally, when the solution process is used, a process of spontaneous crystallization of organic molecules on the substrate or improvement of crystallinity by performing, for example, annealing treatment after thin film preparation is necessary. .

For example, Mori et al. Disclosed a hexabenzocoronene thin film substituted with an alkyl group as an organic semiconductor material. However, a vacuum deposition method is required for the thin film preparation, and an annealing treatment is also required, which is practical. (Patent Document 1 and Non-Patent Document 1). Nanbu et al. Have proposed an unsubstituted hexabenzocoronene thin film as an organic semiconductor material. However, this material is poor in solubility, so that the film forming method is limited to the vacuum deposition method, which is not practical (patents). Reference 2). Mullen et al. Have proposed a thin film prepared by a solution process using a hexabenzocoronene derivative substituted with an alkyl group. In order to treat the substrate surface on which the thin film is formed with polytetrafluoroethylene (PTFE), 300 is proposed. It requires a high temperature process at ℃ (Non-Patent Document 2), requires an alignment method using a special device called a zone casting method (Non-Patent Document 3), or requires a strong magnetic field (Non-Patent Document 4) Productivity was also poor and it was not a practical method.
On the other hand, the present inventors have focused on hexaperihexabenzocoronene (HBC) as a basic element for constructing a nanostructure, and introduced a hydrophilic substituent and a hydrophobic substituent into the HBC skeleton to obtain a diameter of about 20 nm, It has been reported that supramolecular nanotubes having an aspect ratio of 5000 or more can be easily and quantitatively obtained by a solution process (see Patent Documents 3 and 4). In this HBC nanotube, the HBC plane is helically arranged by π-stacking interaction, and charge carriers (holes) are easily formed by chemical doping to exhibit conductivity (resistivity: 10 Ωcm).

JP 2006-100592 A JP 2004-158709 A Japanese Patent Laid-Open No. 2005-220046 JP-A-2005-220047 T. Mori, H. Takeuchi, H. Fujikawa, J. Appl. Phys. 2005, 97, 066102 K. Mullen et.al.Advanced Materials 2003, 15, 495 K. Mullen et.al.Advanced Materials 2005, 17, 684 K. Mullen et. Al. J. Am. Chem. Soc. 2005, 127, 16233

  The present invention provides an organic semiconductor material which is easy to form a thin film as a semiconductor material and has excellent characteristics, an organic semiconductor device using the same, and an organic semiconductor element such as an organic field effect transistor using the organic semiconductor device.

The inventors of the present invention focused on a supramolecular structure formed by molecules assembled in a self-organized manner. A supramolecular structure forms a specific nanostructure by spontaneously assembling molecules in a solution, but takes various structural forms such as dots, wires, tubes, and coils depending on the type of molecule. Since the molecules are regularly arranged in the structure, these structures can be considered as crystals on the nanometer scale. By using such a supermolecular structure, crystallization on the substrate surface is called. It is expected that a thin film element can be manufactured without a process.
The present inventors have reported that amphiphilic hexabenzocoronene derivatives having both hydrophilic groups and hydrophobic groups, which we have already reported, have a diameter of about 20 nanometers by self-assembly in a solvent. Focusing on the formation of a meter-like tubular structure, a thin film element was fabricated using supramolecular nanotubes formed by self-assembled assembly of the amphiphilic hexabenzocoronene. As a result, even in the case of a thin film element manufactured by applying amphiphilic hexabenzocoronene to the surface of the substrate by an appropriate method, the characteristics of the transistor are exhibited without any special crystallization treatment, and the amphiphilic hexabenzocoronene Using the supramolecular nanotubes formed by self-organized assembly, it was found that the manufactured thin film device exhibited significantly good transistor characteristics, and the present invention was achieved.
That is, the present invention provides the following general formula [1]

[Wherein, each R ¹ independently represents an alkyl group,
R ² is independently —C ₆ H ₄ O (—R ⁴ —O—) nR ³ (where R ³ represents an alkyl group, R ⁴ represents an alkylene group, and n represents 0 or a positive integer) Represent)
X represents each independently a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an ethynyl group, a cyano group, a pyridyl group, a terpyridyl group, and a porphyrinyl group. ]
The organic-semiconductor material consisting of the hexaperihexabenzocoronene derivative represented by these, and its manufacturing method.
The present invention also provides an organic material comprising a nanosized self-assembled body formed in a solution comprising the hexaperihexabenzocoronene derivative represented by the general formula [1] and one or more solvents. It relates to semiconductor materials.
Furthermore, this invention relates to the semiconductor device which has an organic-semiconductor layer containing the organic-semiconductor material containing the hexaperihexabenzocoronene derivative represented by above-mentioned general formula [1].
Moreover, this invention relates to the field effect transistor which has an organic-semiconductor layer containing the organic-semiconductor material containing the hexaperihexabenzocoronene derivative represented by general formula [1] mentioned above.

The present invention will be described in detail as follows.
(1) An organic semiconductor material comprising a hexaperihexabenzocoronene derivative represented by the general formula [1].
(2) The organic semiconductor material according to (1), wherein R ^{3 of the} hexaperihexabenzocoronene derivative represented by the general formula [1] is a methyl group.
(3) The organic semiconductor material according to (1) or (2), wherein R ^{1 of the} hexaperihexabenzocoronene derivative represented by the general formula [1] is an alkyl group having 8 to 30 carbon atoms.
(4) The organic semiconductor material according to (3), wherein R ^{1 of the} hexaperihexabenzocoronene derivative represented by the general formula [1] is an alkyl group having 8 to 20 carbon atoms.
(5) The organic semiconductor material according to any one of (1) to (4), wherein R ^{1 of the} hexaperihexabenzocoronene derivative represented by the general formula [1] is a bulky alkyl group.
(6) The organic semiconductor material according to any one of (1) to (5), wherein X of the hexaperihexabenzocoronene derivative represented by the general formula [1] is a hydrogen atom or a halogen atom.
(7) The organic semiconductor material according to any one of (1) to (5), wherein X of the hexaperihexabenzocoronene derivative represented by the general formula [1] is a hydrogen atom.
(8) An organic material comprising a nano-sized self-assembled body formed in a solution comprising the hexaperihexabenzocoronene derivative according to any one of (1) to (7) above and one or more solvents. Semiconductor material.
(9) An organic semiconductor material containing the self-assembled body according to (8), which is in a tube shape.
(10) The hexaperihexabenzocoronene derivative represented by the above general formula [1] is dissolved in a solvent, and after heating this, the suspension obtained by returning to room temperature is applied on the substrate, A method for producing an organic semiconductor material comprising a hexaperihexabenzocoronene derivative represented by the general formula [1], comprising forming a thin film.
(11) The manufacturing method according to (10), wherein the surface of the substrate is pretreated with a silyl compound.
(12) The production method according to (11), wherein the silyl compound is 1,1,1,3,3,3-hexamethyldisilazane (HMDS).
(13) A semiconductor device comprising an organic semiconductor layer containing the organic semiconductor material according to any one of (1) to (9).
(14) A field effect transistor having an organic semiconductor layer containing the organic semiconductor material according to any one of (1) to (9).
(15) The field effect transistor according to (14), wherein the field effect transistor is a p-type field effect transistor.

The hexaperihexabenzocoronene derivative represented by the general formula [1] in the present invention has two hydrophobic side chains such as an alkyl group on one side of hexabenzocoronene (HBC) and an oxyalkylene chain on the other side. There are two such hydrophilic side chains and it has an amphiphilic double-headed structure. By heating and allowing to cool in a solution of this molecule in a solvent such as tetrahydrofuran or dichloromethane, the molecules spontaneously assemble to form self-assembled nanotubes with a diameter of about 20 nanometers and a length of several microns. To do. Within this nanotube, hexabenzocoronene has a regularly aligned structure inside the wall of the nanotube. That is, a one-dimensional channel that can serve as an electrical path is formed.
The present invention provides an organic semiconductor material using self-organized nanotubes formed in this way, and can form a thin film as an organic semiconductor material by an extremely simple method of concentration and coating, Provided is a novel organic semiconductor material that has high productivity and can be used in a practical manner. The organic semiconductor material of the present invention uses self-organized nanotubes having a diameter of about 20 nanometers and a length of several microns, and is an organic semiconductor material having high performance and excellent stability.
The organic semiconductor material of the present invention can be applied to nanodevices such as organic thin film transistors and molecular conductors, and in particular, it has been revealed that p-type transistor characteristics are exhibited by using field effect transistor elements.

The compound represented by the general formula [1] of the present invention will be described in more detail.
In the hexaperihexabenzocoronene derivative represented by the general formula [1] of the present invention, the alkyl group represented by R ¹ has, for example, 1 to 30 carbon atoms, preferably 8 to 30 carbon atoms, and more preferably 8 carbon atoms. -20 linear, branched or cyclic (however, in the case of cyclic, the number of carbon atoms is 3 to 30) alkyl group. Specific examples of preferred alkyl groups include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and the like. . These alkyl groups may be linear, branched or cyclic, but are preferably linear alkyl groups having 8 or more carbon atoms, for example, a dodecyl group is most preferable. In the case of an alkyl group having 10 or less carbon atoms, a bulky group such as a t-butyl group is preferable.

—C ₆ H ₄ O (—R ⁴ —O—) nR ³ represented by R ² in the hexaperihexabenzocoronene derivative represented by the general formula [1] of the present invention (where R ³ is an alkyl group) R ⁴ represents an alkylene group, and n represents 0 or a positive integer.) R ^{4 in the} group is a straight chain having 1 to 10, preferably 1 to 5, more preferably 2 to 5 carbon atoms. A chain or branched alkylene group may be mentioned. Specific examples of preferred alkylene groups include methylene group, ethylene group, propylene group and the like. Particularly preferred alkylene groups include an ethylene group (—CH ₂ CH ₂ —).
—C ₆ H ₄ — in R ² represents a phenylene group, which may be an o-phenylene group, an m-phenylene group, or a p-phenylene group. A preferred phenylene group is a p-phenylene group. Is mentioned.
The alkyl group represented by R ³ in R ² is, for example, linear, branched or cyclic (provided that the number of carbon atoms is 1 to 20, preferably 1 to 10, more preferably 1 to 6). In this case, the alkyl group has 3 to 10 carbon atoms.), And specific examples thereof include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and secondary butyl. Group, tertiary butyl group, pentyl group, hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. Such an alkyl group indicates that the end of the polyalkyleneoxy chain is a group other than a hydrogen atom, and there is no particular problem as long as it is a group other than a hydrogen atom capable of hydrogen bonding. A preferred terminal group is a methyl group.
N in R ² is 0 or an arbitrary positive integer, but 0 or an integer of 1 to 6 is preferable, and an integer of 0 or 1 to 4 is more preferable.
Specific examples of preferred groups of ^{_{-C 6 H 4 O (-R 4}} -O-) nR 3 represented by R ^2, for _{example, -p-C 6 H 4 O} (CH 2 CH 2 O) nCH 3 . Among _{them, -p-C 6 H 4 OCH} 3, -p-C 6 H 4 OCH 2 CH 2 OCH 3, -p-C 6 H 4 O (CH 2 CH 2 O) 2 CH 3, - _{p-C 6 H 4 O (} CH 2 CH 2 O) 3 CH 3, although _{-p-C 6 H 4 O (} CH 2 CH 2 O) 4 CH 3 and the like as a preferable example, of course, limited to It is not something.

In the above general formula [1], the substituent represented by X is any group that does not interfere with the production and use of the organic semiconductor material comprising the amphiphilic hexaperihexabenzocoronene derivative of the present invention. Examples of such a group include, but are not limited to, a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an ethynyl group, a cyano group, a pyridyl group, a terpyridyl group, and a porphyrinyl group. is not. In addition, as a pyridyl group, any of 2-pyridyl group, 3-pyridyl group, or 4-pyridyl group may be sufficient. Preferable X includes a hydrogen atom or a halogen atom, and more preferable X includes a hydrogen atom.
As the most preferable specific example of the hexaperihexabenzocoronene derivative represented by the general formula [1] of the present invention, for example, the following general formula [2]

(In the formula, n represents an integer of 0 to 4.)
However, the present invention is not limited to these.

The compound represented by the general formula [1] of the present invention can be produced according to any known method. For example, it can be produced by ring closure according to the method described in Patent Document 3 or Patent Document 4.
For example, among the compounds represented by the formula [2], the compound 9 in which n is 1 can also be produced according to a known method. The example of the specific manufacturing method of this compound is shown with the following reaction pathway.

First, acetylene protected with a trimethylsilyl group (TMS) is reacted with compound 1 to obtain compound 2. On the other hand, the bromobenzene derivative of compound 3 is reacted with 1,4-dimethylpiperazine-2,3-dione to give diketone derivative 4, and then this is reacted with dibenzyl ketone to give cyclopentanone derivative 5. This compound 5 is reacted with the previously prepared compound 2 to give a hexaphenylbenzene derivative 6, the -OMe group of this compound 6 is hydrolyzed and then etherified with a methoxyethyl group to obtain a compound 8. The target compound 9 can be produced by cyclizing the obtained compound 8 in the presence of a Lewis acid according to a known method.
FIG. 1 shows a compound 9 which is a typical example of the hexaperihexabenzocoronene derivative represented by the general formula [1] of the present invention. As shown in FIG. 1, hexa peri hexabenzocoronene derivative of the present invention, the hydrophobic group of the alkyl group moiety (shown as C ₁₂ in Figure 1.), Hexabenzocoronene portion having a π orbital ( HBC) and a hydrophilic group (shown as EG in FIG. 1) of the alkyleneoxy group portion.

Hereinafter, a self-assembled body formed in a solution comprising the amphiphilic hexaperihexabenzocoronene derivative of the present invention and one or more solvents will be described.
The hexaperihexabenzocoronene derivative represented by the general formula [1] of the present invention is dissolved in tetrahydrofuran or dichloromethane, heated in a sealed container with a drier, and then allowed to stand at room temperature, whereby a yellow suspension is obtained. Got. From an electron microscope, X-ray diffraction measurement, etc., it was confirmed that nanotubes having a diameter of about 20 nanometers were formed (FIG. 2). FIG. 2 schematically shows the structure of the nanotube of the present invention. The nanotube structure of the present invention is a tube in which the hexabenzocoronene part (HBC) of the hexaperihexabenzocoronene derivative is laminated, forming a helical structure with the hydrophobic group part on the inside, and the hydrophilic group is exposed on the surface. ing. In FIG. 2, an enlarged view of a part of the helical structure is shown on the right side.
It is a ribbon-like aggregate having a width of ˜20 nm composed of two layers formed by the amphipathic property and the π-π stacking effect of the hexaperihexabenzocoronene derivative of the present invention. The ribbon is then spirally wound, the strength of which is adjusted by the degree of hydration of the triethylene glycol chain. Therefore, when the degree of hydration is reduced, this helical ribbon structure is folded into a nanotube-like structure. The origin of helicity is also thought to be related to the hydration of triethylene glycol. In this case, it should be noted that a chiral structure was obtained from the non-chiral molecule.

Next, a thin film was formed on the substrate using the yellow suspension thus obtained, and a metal electrode was attached to produce a device.
Specifically, a silicon substrate surface covered with a silicon oxide insulating film (200 nm) is treated with 1,1,1,3,3,3-hexamethyldisilazane (HMDS) to form a hydrophobic monomolecular film. did. On top of this, a thin film of HBC nanotubes was prepared using the yellow suspension described above. A gold electrode having a channel length of 50 microns and a channel width of 1 mm was fabricated on the sample by vacuum deposition, and a top contact and bottom gate type device was fabricated. A schematic representation of this structure is shown in FIG.

The FET characteristics were examined using the FET element thus manufactured.
In FIG. 4, the FET characteristics (output characteristics) of the HBC nanotube thin film were measured when the source-drain voltage was swept from 0V to -50V and the gate voltage was changed from 0V to -50V every 5V. The current value was amplified as the gate voltage increased, and a linear current was observed in the region where the source-drain voltage was small, and a saturated current value was observed in the region where the source-drain voltage was large, indicating typical FET characteristics. FIG. 5 shows the FET characteristics (transfer characteristics) of the HBC nanotube thin film when the source-drain voltage is fixed at −50 V and the gate voltage is swept from 0 V to −50 V. From this analysis, it was revealed that the ON / OFF ratio was 1.4 × 10 ⁴ , the mobility was 4.3 × 10 ⁻⁴ cm ² / Vs, and the threshold voltage was + 3V.

The organic semiconductor material of the present invention can form a thin film by a simple operation, has a stable nanotube structure, and has excellent electrical characteristics.
The organic semiconductor layer containing the organic semiconductor material of the present invention is coated with a solution or dispersion liquid on a substrate by a method such as coating, for example, a spin coating method, a dip method, a printing method such as inkjet printing or screen printing, and the like. A thin film can be formed by removing the dispersion medium.
Examples of the semiconductor element having an organic semiconductor layer containing the organic semiconductor material of the present invention include a diode, a thin film transistor, and a field effect transistor. A memory or an IC tag using these semiconductor elements; or a photodiode or a light emitting diode A semiconductor device such as a light-emitting transistor, a gas sensor, a biosensor, a blood sensor, an immune sensor, an artificial retina, or a taste sensor can be used. A preferred semiconductor element using the organic semiconductor material of the present invention is a field effect transistor.
The field effect transistor (FET) having an organic semiconductor layer containing the organic semiconductor material of the present invention is suitable as, for example, a switching transistor, a signal driver circuit element, a memory circuit element, a signal processing circuit element or the like of a pixel constituting a display. Can be used. Examples of the display include a liquid crystal display, a dispersive liquid crystal display, an electrophoretic display, a particle rotating display element, an electrochromic display, an organic electroluminescence display, and electronic paper. Moreover, if a plastic substrate is used, it can be suitably applied to a display, a sensor or the like that can be bent.

  In the semiconductor device of the present invention, various materials can be used as a substrate material for forming a thin film. For example, ceramic substrates such as glass, quartz, aluminum oxide, sapphire, silicon nitride, silicon carbide, silicon, germanium, gallium Semiconductor substrates such as arsenic, gallium phosphide and gallium nitrogen, polyesters such as polyethylene terephthalate and polynaphthalene terephthalate, polyethylene, polypropylene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, resin substrates such as cyclic polyolefin, polyimide, polyamide and polystyrene, paper Moreover, a nonwoven fabric etc. can also be used.

As a semiconductor element having an organic semiconductor layer containing the organic semiconductor material of the present invention, a field effect transistor (FET) will be described in more detail as an example, but the present invention can be similarly applied to other semiconductor devices. For example, an example of a structure of a field effect transistor using the organic semiconductor material of the present invention includes a substrate, a gate electrode, a gate insulating layer, an organic semiconductor film, a source electrode and a drain electrode.
As the substrate, a material such as silicon, glass, quartz, or ceramic, or a plastic material can be used. If necessary, the surface of the substrate can be surface-treated with a silyl compound in advance. Examples of the silyl compound used include silyl compounds such as 1,1,1,3,3,3-hexamethyldisilazane.
Gate electrodes include metals such as aluminum, gold, platinum, chromium, tungsten, tantalum, nickel, copper, silver, magnesium, and calcium, or alloys thereof, and polysilicon, amorphous silicon, graphite, tin-doped indium oxide, oxidation Using a material such as zinc or a conductive polymer, the film is formed by a well-known film forming method such as a vacuum evaporation method, an electron beam evaporation method, an RF sputtering method, or a printing method. The gate electrode is preferably gold, platinum, or chromium because holes can be easily injected. The thickness of the gate electrode 12 is usually in the range of 5 nm to 3 μm, and preferably in the range of 30 nm to 1 μm.

After film formation, patterning is performed as necessary to obtain a desired shape. As the patterning method, for example, a well-known patterning method such as a photolithography method or a printing method can be used. Alternatively, the pattern may be directly formed by irradiating with an energy beam such as a laser or an electron beam.
As the gate insulating layer, materials such as SiO ₂ , Si ₃ N ₄ , SiON, Al ₂ O ₃ , Ta ₂ O ₅ , amorphous silicon, polyimide resin, polyvinyl phenol resin, polyparaxylylene resin, polymethyl methacrylate resin, and the like are used. It is formed by a known film formation method and patterning method similar to those used for the gate electrode. Moreover, the film thickness of a gate insulating layer is the range of 10 nm-3 micrometers normally, for example, and it is preferable that it is the range of 50 nm-1 micrometer.
The thickness of the organic semiconductor film is, for example, usually in the range of 5 nm to 300 nm and preferably in the range of 10 nm to 60 nm.
As source and drain electrodes, gold, platinum, chromium, tungsten, tantalum, nickel, copper, aluminum, silver, magnesium, calcium, or an alloy thereof, or polysilicon, amorphous silicon, graphite, tin-added indium oxide It is formed by a well-known film formation method and patterning method similar to those for the gate electrode, using a material such as zinc oxide or a conductive polymer. Moreover, the film thickness of a source electrode and a drain electrode is the range of 5 nm-3 micrometers normally, for example, and it is preferable that it is the range of 30 nm-1 micrometer.
Since the organic semiconductor material of the present invention has high stability, various materials can be used as materials for the gate electrode, the gate insulating layer, the source electrode, and the drain electrode.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples.
In the following examples, commercially available reagents and solvents were used as they were unless otherwise specified.
¹ H-NMR and ¹³ C-NMR spectra were measured at 500 and 125 MHz, respectively, using a JEOL NM-Excalibur500 type spectrometer with the non-deuterated solvent remaining in the deuterated solvent as an internal standard.
The infrared absorption spectrum was measured using JASCO-FT / IR-660.
The ultraviolet absorption spectrum was measured using an ultraviolet-visible near-infrared spectrophotometer JASCO-V560DS.
Mass spectrometry was performed using an Applied Biosystems BioSpectrometry Workstation model Voyager-DE STR spectrometer and dithranol as a matrix.
Scanning electron micrographs were taken at 5 kV using a JEOL JSM-6700F FE-SEM.
Transmission electron micrographs were taken at 120 kV using a Philips model Tecnai F20 electron microscope.

Compound 9 was prepared by the reaction route described above.
(1) Production of 1,2-bis (4′-methoxy-4-biphenylyl) ethyne (2) 4-Bromo-4-methoxybiphenyl (1) (2.7 g, 10.12 mmol), 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) (9.2 g, 60.43 mmol), PdCl ₂ (PPh ₃ ) ₂ (425 mg, 0.61 mmol), and cuprous iodide (CuI) (191 mg , 1.00 mmol) was dissolved in benzene (20 ml), and trimethylsilylacetylene (0.71 ml, 496 mg, 5.05 mmol) and water (70 μl) were added successively. This mixed solution was heated to 60 ° C. and kept for 24 hours. The formed precipitate was separated by filtration, washed with ice-cooled dichloromethane, and then recrystallized from toluene to give 1,2-bis (4′-methoxy-). 4-Biphenylyl) ethyne (2) was obtained as light brown crystals.
Yield: 1.4 g (3.51 mmol), yield: 69%.
¹ H-NMR (500 MHz, THF-d ₈ ): δ
7.56 (t, J = 8.5 Hz, 8H), 7.50 (d, J = 8.5 Hz, 4H),
6.93 (d, J = 8.5 Hz, 4H), 3.76 (s, 6H).
MALDI-TOF-MS: As C ₂₈ H ₂₂ O ₂ :
Calculated value [M + H] ⁺ : m / z = 390.47;
Measurement value: 390.13.

(2) Production of 3,4-di (4-dodecylphenyl) -2,5-diphenylcyclopentadien-1-one (5) 1,2-bis- (4-dodecylphenyl) -1,2-diketone ( 4) was prepared by the method described in the literature (S. Ito et al., Chem. Eur. J. 6, 4327 (2000)).
1,2-bis- (4-dodecylphenyl) -1,2-diketone (4) (1.5 g, 2.75 mmol) and dibenzyl ketone (0.58 g, 2.76 mmol) were dissolved in dioxane and 100 ° C. To the mixture, tetrabutylammonium hydroxide (1.0 M in methanol) (1 eq, 2.76 ml) was added in one portion and heated for an additional 15 minutes. The reaction mixture was poured into water and extracted with dichloromethane. The extract was evaporated to dryness and purified by silica gel column chromatography [eluent: dichloromethane / hexane (concentration gradient: 10-50% dichloromethane)]. Further purification by preparative HPLC, eluting with dichloromethane / hexane (1: 3), evaporated to dryness to remove the solvent and 2,5-diphenyl-3,4-bis (4-dodecylphenyl) cyclopentadienone (5) was obtained as a purple powder.
Yield: 0.88 g, yield: 44%.
¹ H-NMR (500 MHz, CDCl ₃ ): δ
7.24 (m), 6.96 (d, J = 7.94Hz, 4H), 6.80 (d, J = 7.94Hz, 4H),
2.55 (t, J = 7.63Hz, 4H), 1.56 (br., 4H), 1.26 (br., 36H),
0.88 (t, J = 6.71Hz, 6H).
MALDI-TOF (dithranol): m / z = 720 (M ⁺ ).

(3) Production of 2,3-bis (4′-methoxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (6) 3,4-di (4- Dodecylphenyl) -2,5-diphenylcyclopentadien-1-one (5) (6.7 g, 9.22 mmol) and 1,2-bis (4′-methoxy-4-biphenylyl) ethyne (2) (3. 6 g, 9.22 mmol) was suspended in diphenyl ether (10 ml) in Schlenk, refluxed (˜300 ° C.) for 24 hours, and then cooled to room temperature. Ethanol (300 ml) was added to the reaction mixture, and the resulting brown precipitate was separated by filtration and purified by silica gel column chromatography (eluent: ethyl acetate / hexane (7/1)). Bis (4′-methoxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (6) was obtained as a colorless solid.
Yield: 8.0 g (7.38 mmol), yield: 80%.
¹ H-NMR (500 MHz, CDCl ₃ ): δ
7.34 (d, J = 8.5 Hz, 4H), 7.06 (d, J = 7.5 Hz, 4H),
6.89-6.80 (m, 18H), 6.68 (d, J = 8.0 Hz, 4H),
6.62 (d, J = 8.0 Hz, 4H), 3.77 (s, 6H), 2.33 (t, J = 7.5 Hz, 4H),
1.41-1.35 (m, 4H), 1.31-1.20 (m, 32H), 1.09 (br., 4H),
0.87 (t, J = 7.5 Hz, 6H).
¹³ C-NMR (125 MHz, CDCl ₃ ): δ
158.69, 140.77, 140.59, 140.34, 139.68, 139.19, 137.82, 136.83,
133.31, 131.83, 131.46, 131.18, 127.60, 126.50, 126.48, 124.91,
124.59, 113.90, 55.34, 35.38, 32.01, 32.00, 31.23, 29.81, 29.76,
29.60, 29.46, 28.88, 22.79, 14.21.
_{MALDI-TOF-MS:} as _{C 80 H} 90 _{O 2:}
Calculated value [M + H] ⁺ : m / z = 1083.57;
Measurement value: 1083.81.

(4) Production of 2,3-bis (4′-hydroxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (7) 2,3-bis (4 ′ -Methoxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (6) (8.0 g, 7.38 mmol) in dichloromethane solution at 0 ° C. BBr ₃ ) (2.6 ml, 27.5 mmol) was added and stirred at 0 ° C. for 45 minutes and then at room temperature overnight. The reaction mixture was poured into a mixture of ice water / tetrahydrofuran (10/9) and extracted with dichloromethane. The extract was washed with brine, dried over anhydrous magnesium sulfate, and then evaporated to dryness on a rotary evaporator. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / hexane (7/1)) to give 2,3-bis (4′-hydroxy-4-biphenylyl) -5,6-di (4-dodecylphenyl). ) -1,4-diphenylbenzene (7) was obtained as a colorless solid.
Yield: 7.0 g (6.63 mmol), yield: 90%.
¹ H-NMR (500 MHz, CDCl ₃ ): δ
7.28 (d, J = 8.5 Hz, 4H), 7.04 (d, J = 8.5 Hz, 4H),
6.89-6.79 (m, 14H), 6.75 (d, J = 8.5 Hz, 4H),
6.67 (d, J = 8.5 Hz, 4H), 6.61 (d, J = 8.0 Hz, 4H),
2.33 (t, J = 7.5Hz, 4H), 1.40-1.35 (m, 4H), 1.30-1.19 (m, 34H),
1.08 (br., 4H), 0.87 (t, J = 7.5 Hz, 6H).
¹³ C-NMR (125 MHz, CDCl ₃ ): δ
154.58, 140.75, 140.60, 140.33, 139.64, 139.24, 139.20, 137.80,
136.77, 133.53, 131.82, 131.44, 131.16, 127.84, 126.49, 126.47,
124.91, 124.57, 115.30, 35.37, 32.00, 31.22, 29.80, 29.75, 29.59,
29.45, 28.87, 22.77, 14.20.
_{MALDI-TOF-MS:} as _{C 78 H} 86 _{O 2:}
Calculated value [M + H] ⁺ : m / z = 1054.66;
Measurement value: 1054.89.

(5) Production of 2,3-bis [4 ′-(2-methoxyethoxy) -4-biphenylyl] -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (8) -Bis (4'-hydroxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (7) (200 mg, 0.19 mmol) and excess para-toluenesulfonic acid 2- Methoxyethyl ester (131 mg, 0.57 mmol) was dissolved in dry tetrahydrofuran (20 ml), potassium hydroxide (66 mg, 1.17 mmol) was added, and the mixture was refluxed (˜90 ° C.) for 24 hours under an argon atmosphere. The reaction was evaporated to dryness and the residue was extracted with dichloromethane / water. The organic layer was washed with water, then washed with 0.2N hydrochloric acid, and further washed with water. The extract was dried over magnesium sulfate and filtered, and the filtrate was evaporated to dryness. The residue was purified by silica gel column chromatography (eluent: dichloromethane / acetone (10 / 0-9 / 1)), and 2,3-bis [4 ′-(2-methoxyethoxy) -4-biphenylyl] -5, 6-di (4-dodecylphenyl) -1,4-diphenylbenzene (8) was obtained.
Yield: 210 mg, Yield: 94%.

(6) Production of 2,5-bis [4 ′-(2-methoxyethoxy) phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (9) 2,3-bis [4 ′-( 2-methoxyethoxy) -4-biphenylyl] -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (8) (150 mg, 0.13 mmol) in a solution of dry dichloromethane (40 ml) A solution of iron (FeCl ₃ ) (620 mg, 3.84 mmol) in nitromethane (MeNO ₂ ) (3.0 ml) was added slowly under an argon atmosphere. The mixture was reacted for 1 hour at 25 ° C. with stirring, and the reaction solution was poured into 200 ml of methanol. The produced precipitate was separated by filtration and subjected to silica gel column chromatography (eluent: hot tetrahydrofuran) to collect a yellow fraction. The residue obtained by evaporating this fraction to dryness was recrystallized from tetrahydrofuran to give 2,5-bis [4 ′-(2-methoxyethoxy) phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene. (9) was obtained as yellow crystals.
Yield: 88 mg, yield: 59%.
¹ H-NMR (500 MHz, THF-d ₈ , 55 ° C.): δ (ppm)
8.57 (s, 2H), 8.48 (s, 2H), 8.33 (br, 2H), 8.27 (br, 2H), 8.20 (s, 2H),
8.15 (s, 2H), 7.77 (d, J = 8.0Hz, 4H), 7.46 (br, 2H),
7.16 (d, J = 8.0Hz, 4H), 4.30 (br, 4H), 3.86 (br, 4H), 3.50 (s, 6H),
2.95 (br, 4H), 2.26 (br, 4H), 1.61-1.25 (m, 36H),
0.84 (t, J = 7.0Hz, 6H).
_{MALDI-TOF-MS:} as _{C 84 H} 86 _{O 4:}
Calculated value [M + H] ⁺ : m / z = 1159.66;
Measurement value: 1159.43.

Production of 2,5-bis [4 ′-{2- (2-methoxyethoxy) ethoxy} phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (11) According to the following reaction formula, compound 11 Manufactured.

2,3-bis [4] in the same manner as in (5) of Example 1 except that p-toluenesulfonic acid 2- (2-methoxyethyl) ethyl ester was used instead of p-toluenesulfonic acid 2-methoxyethyl ester. '-{2- (2-methoxyethoxy) ethoxy} -4-biphenylyl] -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (10) was synthesized. Subsequently, the obtained 2,3-bis [4 ′-{2- (2-methoxyethoxy) ethoxy} -4-biphenylyl] -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene ( 10) is reacted in the same manner as (6) of Example 1 to give 2,5-bis [4 ′-[2- (2-methoxyethoxy) ethoxy] phenyl] -11,14-didodecyl-hexa-peri- Hexabenzocoronene (11) was obtained.
MALDI-TOF-MS: as C ₈₈ H ₉₄ O ₆ ;
Calculated value [M + H] ⁺ : m / z = 1247.68;
Measurement value: 1246.71

Production of 2,5-bis [4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy} phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (13) Compound 13 was prepared according to the formula.

Except that p-toluenesulfonic acid 2- [2- (2-methoxyethoxy) ethoxy] ethyl ester was used instead of p-toluenesulfonic acid 2-methoxyethyl ester, 2, 3-bis [4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy} -4-biphenylyl] -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (12) And then the obtained 2,3-bis [4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy} -4-biphenylyl] -5,6-di (4-dodecylphenyl) ) -1,4-diphenylbenzene (12) is reacted in the same manner as (6) of Example 1 to give 2,5-bis [4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy. } Phenyl]- 1,14 didodecyl - hexa - peri - give hexabenzocoronene (13).
_{MALDI-TOF-MS:} as _{C 92 H} 102 _{O 8:}
Calculated value [M + H] ⁺ : m / z = 1335.79;
Measured value: 1334.76

Production of 2,5-bis [4′-2-methoxyphenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (14) Compound 14 was produced according to the following reaction formula.

2,3-bis (4′-methoxy-4-biphenylyl) -5,6-di (4-dodecylphenyl) -1,4-diphenylbenzene (6) synthesized in Example 1 was replaced with (6 ) To synthesize 2,5-bis [4′-2-methoxyphenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (14).
_{MALDI-TOF-MS:} as _{C 80 H} 78 _{O 2:}
Calculated value [M + H] ⁺ : m / z = 1071.47;
Measurement value: 1070.60

Preparation of self-assembled nanotube of compound (9) 2,5-bis [4 ′-(2-methoxyethoxy) phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (9) synthesized in Example 1 ) Was dissolved in dichloromethane to a concentration of 1 mg / ml, heated in a sealed container with a dryer, and then allowed to stand at room temperature to obtain a yellow suspension. From an electron microscope, X-ray diffraction measurement, etc., it was confirmed that nanotubes having a diameter of about 20 nanometers were formed.
FIG. 6 shows an FE-SEM image of the self-assembly of the compound (9) in a dichloromethane solution (1 mg / 1 ml). FIG. 7 shows a TEM photograph of the self-assembled body of the compound (9) in a dichloromethane solution (1 mg / 1 ml).

Preparation of self-assembled nanotube of compound (11) 2,5-bis [4 ′-{2- (2-methoxyethoxy) ethoxy} phenyl] -11,14-didodecyl-hexa-peri- synthesized in Example 2 Self-assembled nanotubes having a diameter of about 20 nanometers of the compound (11) were prepared in the same manner as in Example 5 except that hexabenzocoronene (11) was used, and were confirmed with an electron microscope.
FIG. 8 shows a TEM photograph of the self-assembled body of the compound (11) in a dichloromethane solution (1 mg / 1 ml).

Preparation of self-assembled nanotubes of compound (11) Self-assembled nanotubes having a diameter of about 20 nanometers of compound (11) were prepared in the same manner as in Example 6 except that tetrahydrofuran (THF) was used instead of dichloromethane. This was confirmed with an electron microscope.
FIG. 9 shows a TEM photograph of the self-assembled body of the compound (11) in a THF solution (1 mg / 1 ml).

Preparation of self-assembled nanotube of compound (14) 2,5-bis [4′-2-methoxyphenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (14) synthesized in Example 4 was used A self-assembled nanotube having a diameter of about 20 nanometers of the compound (14) was produced in the same manner as in Example 5 except that it was confirmed by an electron microscope.
FIG. 10 shows a TEM photograph of the self-assembled body of the compound (14) in a dichloromethane solution (1 mg / 1 ml).

Preparation of self-assembled nanotubes of compound (14) Self-assembled nanotubes having a diameter of about 20 nanometers of compound (11) were prepared in the same manner as in Example 8 except that THF was used instead of dichloromethane. Confirmed with.
FIG. 11 shows a TEM photograph of the self-assembled product of the compound (14) in a THF solution (1 mg / 1 ml).

Preparation of amorphous film of compound (9) The surface of a silicon substrate covered with a silicon oxide insulating film (200 nm) was treated with 1,1,1,3,3,3-hexamethyldisilazane (HMDS) to form a hydrophobic single layer. A molecular film was formed. 2,5-bis [4 ′-(2-methoxyethoxy) phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (9) synthesized in Example 1 was adjusted to a concentration of 1 mg / ml. The product was dissolved in dichloromethane, heated with a dryer in a sealed container, and immediately coated on the substrate to prepare a film of compound (9). When confirmed with an electron microscope, the nanotubes were not formed and were amorphous.
The FE-SEM image of the amorphous film of compound (9) is shown in FIG.

Fabrication of device using nanotube thin film of compound (9) The surface of a silicon substrate covered with a silicon oxide insulating film (200 nm) was treated with 1,1,1,3,3,3-hexamethyldisilazane (HMDS). A hydrophobic monomolecular film was formed. On top of that, the suspension obtained in Example 5 was applied and 2,5-bis [4 ′-(2-methoxyethoxy) phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (9) A nanotube thin film was prepared. A gold electrode having a channel length of 50 microns and a channel width of 1 mm was fabricated on the sample by vacuum deposition, and a top contact and bottom gate type device was fabricated.
The structure of the fabricated FET element is schematically shown in FIG.

FET Characteristics of Nanotube Thin Film of Compound (9) FIG. 4 shows the results of Example 11 when sweeping the source-drain voltage from 0 V to −50 V and changing the gate voltage from 0 V to −50 V every 5 V. The FET characteristic (output characteristic) of the nanotube thin film of 5-bis [4 '-(2-methoxyethoxy) phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (9) is shown. The current value was amplified as the gate voltage increased, and a linear current was observed in the region where the source-drain voltage was small, and a saturated current value was observed in the region where the source-drain voltage was large, indicating typical FET characteristics. FIG. 5 shows the FET characteristics (transfer characteristics) of the HBC nanotube thin film when the source-drain voltage is fixed at −50 V and the gate voltage is swept from 0 V to −50 V. From this analysis, it was revealed that the ON / OFF ratio was 1.4 × 10 ⁴ , the mobility was 4.3 × 10 ⁻⁴ cm ² / Vs, and the threshold voltage was + 3V.

FET characteristics of nanotube thin film of compound (11) A device using a nanotube thin film of compound (11) was produced in the same manner as in Example 11 except that the suspension obtained in Example 7 was used. Subsequently, the FET characteristics of the nanotube thin film of the compound (11) were measured using the device in the same manner as in Example 12 to obtain FIG. FIG. 13 shows the FET characteristics (left) output characteristics and (right) transfer characteristics of the nanotube thin film of compound (11).
The ON-OFF ratio was 1.1 × 10 ⁴ , the mobility was 1.5 × 10 ⁻⁴ cm ² / Vs, and the threshold voltage was + 13V.

FET characteristics of nanotube thin film of compound (14) A device using a nanotube thin film of compound (14) was prepared in the same manner as in Example 11 except that the suspension obtained in Example 8 was used. Then, the FET characteristics of the nanotube thin film of the compound (14) were measured in the same manner as in Example 12 to obtain FIG. FIG. 14 shows the FET characteristic (left) output characteristic and (right) transfer characteristic of the nanotube thin film of compound (14).
The ON-OFF ratio was 2.0 × 10 ³ , the mobility was 1.9 × 10 ⁻⁴ cm ² / Vs, and the threshold voltage was −17V.

FET Properties of Nanotube Thin Film of Compound (13) 2,5-bis [4 ′-{2- [2- (2-methoxyethoxy) ethoxy] ethoxy} phenyl] -11,14-didodecyl- synthesized in Example 3 Self-assembled nanotubes having a diameter of about 20 nanometers of compound (13) were prepared in the same manner as in Example 5 except that hexa-peri-hexabenzocoronene (13) was used and THF was used instead of dichloromethane. In the same manner as in Example 11, a device using a nanotube thin film of the compound (13) was produced. Next, using the device, the FET characteristics of the nanotube thin film of the compound (13) were measured in the same manner as in Example 12 to obtain FIG. FIG. 15 shows the FET characteristics (left) output characteristics and (right) transfer characteristics of the nanotube thin film of compound (13).
The ON-OFF ratio was 1.0 × 10 ³ and the mobility was 1.8 × 10 ⁻⁵ cm ² / Vs.

FET characteristics of amorphous film of compound (9) The silicon substrate surface covered with silicon oxide insulating film (200 nm) is treated with 1,1,1,3,3,3-hexamethyldisilazane (HMDS) to make it hydrophobic A monomolecular film was formed. 2,5-bis [4 ′-(2-methoxyethoxy) phenyl] -11,14-didodecyl-hexa-peri-hexabenzocoronene (9) synthesized in Example 1 was adjusted to a concentration of 1 mg / ml. The product was dissolved in dichloromethane, heated in a sealed container with a dryer, and immediately applied to the substrate to prepare an amorphous film of compound (9). A gold electrode having a channel length of 50 microns and a channel width of 1 mm was formed on the top of the sample by vacuum vapor deposition to produce a top contact and bottom gate type device (see FIG. 3). Using this element, the FET characteristics of the amorphous film of the compound (9) were measured in the same manner as in Example 12 to obtain FIG. FIG. 13 shows the FET characteristics (left) output characteristics and (right) transfer characteristics of the nanotube thin film of the amorphous film of compound (9).
The ON-OFF ratio was 2.3 × 10 ² , the mobility was 5.5 × 10 ⁻⁵ cm ² / Vs, and the threshold voltage was −14V.

The organic semiconductor material of the present invention can be formed into a thin film by a simple method, and has an advantage that a large-area thin film can be easily formed with relatively inexpensive equipment. As an industrial and practical organic semiconductor material, Application to nanodevices such as organic thin film transistors and molecular wires is easy.
Therefore, the organic semiconductor material of the present invention is useful in the semiconductor material field and the electronic material field, and has industrial applicability.

FIG. 1 shows the compound (9) as an example of the amphiphilic hexaperihexabenzocoronene derivative of the present invention, and schematically shows the structural features thereof. FIG. 2 schematically shows the structure of the self-assembled nanotube of the amphiphilic hexaperihexabenzocoronene derivative of the present invention. FIG. 3 shows the structure of a top contact / bottom gate type device using the amphiphilic hexaperihexabenzocoronene derivative of the present invention as a semiconductor film of a semiconductor material. FIG. 4 shows the FET (Output) characteristics of the nanotube thin film of the compound (9) of the present invention. FIG. 5 shows the FET (transfer) characteristics of the nanotube thin film of the compound (9) of the present invention. FIG. 6 is a photograph replacing a drawing, showing an FE-SEM image of the self-assembly of the compound (9) of the present invention in a dichloromethane solution (1 mg / 1 ml). FIG. 7 is a photograph replacing a drawing, showing a TEM photograph of the self-assembled body of the compound (9) of the present invention in a dichloromethane solution (1 mg / 1 ml). FIG. 8 is a photograph replacing a drawing, showing a TEM photograph of the self-assembled body in a dichloromethane solution (1 mg / 1 ml) of the compound (11) of the present invention. FIG. 9 is a photograph replacing a drawing, showing a TEM photograph of the self-assembled body in a THF solution (1 mg / 1 ml) of the compound (11) of the present invention. FIG. 10 is a photograph replacing a drawing, showing a TEM photograph of the self-assembled body of the compound (14) of the present invention in a dichloromethane solution (1 mg / 1 ml). FIG. 11 is a photograph replacing a drawing, showing a TEM photograph of the self-assembled body in a THF solution (1 mg / 1 ml) of the compound (14) of the present invention. FIG. 12 is a photograph replacing a drawing, showing an FE-SEM image of the amorphous film of the compound (9) of the present invention. FIG. 13 shows the output characteristics (left side) and transfer characteristics (right side) of the FET characteristics of the nanotube thin film of the compound (11) of the present invention. FIG. 14 shows the output characteristics (left side) and transfer characteristics (right side) of the FET characteristics of the nanotube thin film of the compound (14) of the present invention. FIG. 15 shows the output characteristics (left side) and transfer characteristics (right side) of the FET characteristics of the nanotube thin film of the compound (13) of the present invention. FIG. 16 shows the output characteristics (left side) and transfer characteristics (right side) of the FET characteristics of the nanotube thin film of the amorphous film of the compound (9) of the present invention.

Claims (6)

The following general formula [1]
[Wherein, each R ¹ independently represents an alkyl group,
R ² is independently —C ₆ H ₄ O (—R ⁴ —O—) nR ³ (where R ³ represents an alkyl group, R ⁴ represents an alkylene group, and n represents 0 or a positive integer) Represent)
X represents each independently a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an ethynyl group, a cyano group, a pyridyl group, a terpyridyl group, and a porphyrinyl group. ]
A hexaperihexabenzocoronene derivative represented by the following formula is dissolved in a solvent, and after heating this, the suspension obtained by returning to room temperature is applied on a substrate to form a thin film:
The manufacturing method of the organic-semiconductor layer containing the organic-semiconductor material containing the hexaperihexabenzocoronene derivative represented by the said General formula [1]. The manufacturing method according to claim 1 , wherein the surface of the substrate is pretreated with a silyl compound. The production method according to claim 2 , wherein the silyl compound is 1,1,1,3,3,3-hexamethyldisilazane (HMDS). The following general formula [1]
[Wherein, each R ¹ independently represents an alkyl group,
R ² is independently —C ₆ H ₄ O (—R ⁴ —O—) nR ³ (where R ³ represents an alkyl group, R ⁴ represents an alkylene group, and n represents 0 or a positive integer) Represent)
X represents each independently a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an ethynyl group, a cyano group, a pyridyl group, a terpyridyl group, and a porphyrinyl group. ]
It has an organic semiconductor layer containing an organic semiconductor material made of a nano-sized tubular self-assembled body formed in a solution comprising a hexaperihexabenzocoronene derivative represented by the formula (1) and one or more solvents. Semiconductor device. The following general formula [1]
[Wherein, each R ¹ independently represents an alkyl group,
R ² is independently —C ₆ H ₄ O (—R ⁴ —O—) nR ³ (where R ³ represents an alkyl group, R ⁴ represents an alkylene group, and n represents 0 or a positive integer) Represent)
X represents each independently a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an ethynyl group, a cyano group, a pyridyl group, a terpyridyl group, and a porphyrinyl group. ]
It has an organic semiconductor layer containing an organic semiconductor material made of a nano-sized tubular self-assembled body formed in a solution comprising a hexaperihexabenzocoronene derivative represented by the formula (1) and one or more solvents. Field effect transistor. The field effect transistor according to claim 5 , wherein the field effect transistor is a p-type field effect transistor.