JP6558777B2 - Organic compounds and their uses - Google Patents

Description

  The present invention relates to a novel organic compound useful as an organic semiconductor material and use thereof. More specifically, the present invention relates to a specific organic compound useful as an organic semiconductor material, and an organic semiconductor material, a transistor material, an ink for manufacturing a semiconductor device, an organic thin film, an organic semiconductor device, an organic transistor, and an organic material using the organic compound. The present invention relates to a method for manufacturing a semiconductor device.

  In recent years, interest in organic semiconductor devices has increased. The feature is that, unlike the conventional inorganic semiconductor device using amorphous silicon or polycrystalline silicon, the device itself has flexibility and the device can have a large area. Further, according to a film forming method known as a method for manufacturing an organic semiconductor device, such as a vacuum deposition method or a coating method, it is possible to suppress an increase in manufacturing cost, and further, a process required for film formation. Since the temperature can be made relatively low, there is an advantage that the range of selection of materials used for the substrate is widened, and research reports have been actively made for its practical use. In particular, since the use efficiency of the material can be improved and the cost can be significantly reduced by using the coating method as a film forming method, an organic semiconductor material suitable for the coating method is required.

  Typical organic semiconductor devices include organic EL (electroluminescence) elements, organic solar cell elements, organic photoelectric conversion elements, organic transistor elements, and the like. Organic EL elements are expected as main targets for next-generation display applications as flat panel displays, and are applied to mobile phone displays, TVs (TV receivers), etc., and development aimed at further enhancement of functionality continues. . Research and development have been made for the purpose of application to inexpensive displays such as organic solar cell elements, and organic transistor elements to flexible displays and inexpensive ICs (integrated circuits).

  In these organic semiconductor devices, the development of organic semiconductor materials constituting the devices is very important. For example, pentacene, which is an acene-based organic semiconductor compound, is used as a low molecular organic semiconductor material (organic transistor material). It has been actively studied. As heteroacene compounds having a heterocyclic ring, materials mainly containing atoms such as sulfur and selenium have been studied. Specific examples of such heteroacene compounds include benzodithiophene compounds (2,6-diphenylbenzo [1,2-b: 4,5-b ′] dithiophenes described in Patent Document 1 and Non-Patent Document 1). (DPh-BDT)), naphthodithiophene compounds (NDT) described in Patent Document 2 and Non-patent Document 4, benzothienobenzothiophene compounds (2,7-diphenyl described in Patent Document 3 and Non-Patent Document 2) [1] benzothieno [3,2-b] [1] benzothiophene (DPh-BTBT), 2,7-dialkyl [1] benzothieno [3,2-b] [ 1] benzothiophene (AlkylBTBT)), dinaphthothienothiophene compound (dinaphtho [2,3-b: 2 ′, 3′-f] thie described in Patent Document 5 and Non-Patent Document 5) [3,2-b] thiophene (DNTT) or 2,9-dialkyldinaphtho [2,3-b: 2 ′, 3′-f] thieno described in Patent Document 6 (AlkylDNTT)) and the like, and high-performance materials that are stable in the atmosphere. Heteroacene compounds with better semiconductor properties and atmospheric stability than pentacene have been developed, but none have yet satisfied the market demand and have not been commercialized at present.

  When a thin film of an organic semiconductor material is formed by a coating method, the organic semiconductor material is dissolved in a solvent to produce a coating solution. In general, an organic semiconductor material having high mobility is an organic compound in which a π-conjugated system spreads, and often exhibits poor solubility in a solvent.

  Basically, the solubility in a solvent is increased by heating, so that the coating liquid may be prepared by heating even if the organic semiconductor material is hardly soluble. However, when preparing a coating liquid by heating, temperature control and energy for heating are required in consideration of the volatilization amount of the solvent in the coating liquid preparation process and the film forming process.

  In order to solve this problem, an organic semiconductor compound that has both high carrier mobility and excellent storage stability and higher solubility in a solvent is desired.

  For example, it is known that the organic semiconductor compounds such as AlkylBTBT and AlkyLDNTT described above have a relatively high solubility in an organic solvent and can be formed by a coating method. However, since these organic semiconductor compounds have a phase transition temperature in the vicinity of 100 to 120 ° C., they have a problem of low heat resistance.

JP 2005-154371 A International Publication No. 2010/058692 International Publication No. 2006/077788 International Publication No. 2008/047896 International Publication No. 2008/050726 International Publication No. 2010/098372

“Journal of the American Chemical Society” (USA), 2004, No. 126, p. 5084-5085 “Journal of the American Chemical Society” (USA), 2006, No. 128, p. 12604-12605 “Journal of the American Chemical Society” (USA), 2007, No. 129, p. 15732-15733 “Journal of the American Chemical Society” (USA), 2011, No. 133, p. 5024-5035 “Journal of the American Chemical Society” (USA), 2007, No. 129, p. 2224-2225

  As described above, it is desired to develop a new organic semiconductor compound having high heat resistance and solubility that can be applied to a coating process. That is, an object of the present invention is to provide a novel organic compound having high heat resistance and solubility and useful as an organic semiconductor material, an organic semiconductor material using the same, a transistor material, an ink for manufacturing a semiconductor device, an organic thin film An organic semiconductor device, an organic transistor, and a method for manufacturing the organic semiconductor device.

  As a result of examining various organic compounds, the present inventors have found that an organic compound having a specific structure has high heat resistance and solubility, and is useful as an organic semiconductor material used for an organic transistor or the like. The present invention has been completed.

That is, the present invention
[1] The following formula (1)
(In the formula (1), A represents [1] benzothieno [3,2-b] [1] benzothiophene or dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b]. Represents a divalent linking group in which two hydrogen atoms have been removed from thiophene, and B represents the following formula (2)
(In the formula (2), n represents an integer of 1 to 10, and Z represents a cyclic aliphatic hydrocarbon residue having 3 to 10 carbon atoms having an alkyl group having 1 to 10 carbon atoms and / or a phenyl group as a substituent. Group or an unsubstituted cyclic aliphatic hydrocarbon residue having 3 to 10 carbon atoms)
And D represents a hydrogen atom, an alkyl group, an aromatic residue, or a heterocyclic residue)
An organic compound represented by
[2] The organic compound according to [1], wherein n is an integer of 1 to 4,
[3] The organic compound according to [1] or [2] above, wherein Z is a cyclic fat having 5 to 8 carbon atoms having an alkyl group having 1 to 10 carbon atoms and / or a phenyl group as a substituent. An organic compound which is an aromatic hydrocarbon residue or an unsubstituted cyclic aliphatic hydrocarbon residue having 5 to 8 carbon atoms,
[4] An organic semiconductor material containing the organic compound according to any one of [1] to [3],
[5] A transistor material containing the organic compound according to any one of [1] to [3],
[6] An ink for producing a semiconductor device containing the organic semiconductor material according to [4] or the transistor material according to [5],
[7] An organic thin film containing the organic compound according to any one of [1] to [3],
[8] The organic thin film according to [7], which is formed by a coating method,
[9] An organic semiconductor device containing the organic thin film according to [7] or [8].
[10] An organic transistor containing the organic thin film according to [7] or [8].
[11] A method for producing an organic semiconductor device, comprising: forming a semiconductor layer by applying the ink for producing a semiconductor device according to [6] above onto a substrate and drying it.

  According to the present invention, a novel organic compound having high heat resistance and solubility and useful as an organic semiconductor material, an organic semiconductor material using the same, a transistor material, an ink for manufacturing a semiconductor device, an organic thin film, an organic A semiconductor device, an organic transistor, and a method for manufacturing an organic semiconductor device can be provided.

It is a schematic sectional drawing which shows some examples of the organic transistor of this invention, (a) is a schematic sectional drawing which shows the example of an aspect of a bottom contact-bottom gate type organic transistor, (b) is a top contact-bottom. It is a schematic sectional drawing which shows the example of an aspect of a gate type organic transistor, (c) is a schematic sectional drawing which shows the example of an aspect of a top contact-top gate type organic transistor, (d) is a top & bottom contact-bottom gate type It is a schematic sectional drawing which shows the example of an aspect of an organic transistor, (e) is a schematic sectional drawing which shows the example of an aspect of an electrostatic induction transistor, (f) is a cross section which shows the example of an aspect of a bottom contact-top gate type organic transistor FIG. It is explanatory drawing for demonstrating the manufacturing method of the top contact-bottom gate type organic transistor as one example of the organic transistor of this invention, (a)-(f) is a schematic cross section which shows each process of the said manufacturing method FIG. It is a schematic sectional drawing which shows an example of the structure of the organic solar cell device as one aspect | mode of the organic-semiconductor device of this invention. It is a graph which shows the transfer characteristic of the organic thin-film transistor of Example 6 produced using the organic compound represented by Formula (20) of Example 2. FIG. It is a graph which shows the transfer characteristic of the organic thin-film transistor of Example 7 produced using the organic compound represented by Formula (92) of Example 3. FIG. It is a graph which shows the transfer characteristic of the organic thin-film transistor of Example 8 produced using the organic compound represented by Formula (68) of Example 4. FIG. It is a graph which shows the transfer characteristic of the organic thin-film transistor of Example 9 produced using the organic compound represented by Formula (32) of Example 5. FIG.

The present invention is described in detail below.
The organic compound of the present invention has a structure represented by the following formula (1).

  In the formula (1), A is represented by the following formula [1] benzothieno [3,2-b] [1] benzothiophene

Or dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene

Represents a divalent linking group in which two hydrogen atoms have been removed. The divalent linking group is a partial structure having a charge transporting property, and is obtained by removing two hydrogen atoms from a condensed ring compound containing a sulfur atom, so that an organic compound having high atmospheric stability and charge mobility can be obtained. realizable. In addition, since the divalent linking group has 4 or 6 aromatic rings and / or heterocyclic rings constituting the condensed ring, an organic compound having excellent solvent solubility can be realized. The divalent linking group is obtained by removing two hydrogen atoms from a condensed ring compound in which one or two benzene rings are condensed on both thiophene skeletons in thieno [3,2-b] thiophene. Therefore, an organic compound having a particularly high charge mobility can be realized.

  In formula (1), B represents a substituent represented by the following formula (2) (a substituent composed of an alkylene group having n carbon atoms and a substituent Z linked thereto).

  In formula (2), n represents an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 4. By setting the value of n within the above range, that is, by setting the length of the alkylene group within a specific range, the intermolecular interaction between the alkylene groups is reduced and the solubility in a solvent is improved. In addition, by setting the value of n within the above range, that is, by setting the length of the alkylene group within a specific range, an intermediate phase such as a liquid crystal phase does not appear in a temperature range of 140 ° C. or lower. Has the effect of excellent heat resistance.

  In formula (2), Z represents a cyclic aliphatic hydrocarbon residue having 3 to 10 carbon atoms. The term “cyclic aliphatic hydrocarbon residue” as used herein means a residue obtained by removing one hydrogen atom from a cyclic aliphatic hydrocarbon. The cyclic aliphatic hydrocarbon which can be the residue means a compound having one or more saturated or unsaturated carbocycles having no aromaticity, and the compound has 1 to 10 carbon atoms. May have an alkyl group and / or a phenyl group as a substituent. However, a residue obtained by removing one hydrogen atom from an aliphatic hydrocarbon having such a substituent is a residue obtained by removing one hydrogen atom from a cyclic aliphatic hydrocarbon part (part other than a substituent). Suppose that That is, the cyclic aliphatic hydrocarbon residue may have an alkyl group having 1 to 10 carbon atoms and / or a phenyl group as a substituent.

  Specific examples of the cyclic aliphatic hydrocarbon having 3 to 10 carbon atoms that can be a cyclic aliphatic hydrocarbon residue having 3 to 10 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Monocyclic cycloalkanes such as cyclopropene, cyclobutene, cyclohexane, cycloheptene, cyclooctene, cyclononene, and cyclodecene; decahydronaphthalene (decalin), bicyclooctane, adamantane, etc. A bicyclic alkene such as norbornene and norbornadiene; a polycyclic compound such as cubane, basketane, and hausan. The cyclic aliphatic hydrocarbon residue having 3 to 10 carbon atoms is preferably a cyclic aliphatic hydrocarbon residue having 5 to 8 carbon atoms from the viewpoint of the stability of the organic compound, and has 5 to 8 carbon atoms. A residue obtained by removing one hydrogen atom from a monocyclic cycloalkane is more preferable.

  In the present invention, the term “unsubstituted aliphatic hydrocarbon residue” means an aliphatic hydrocarbon residue having no substituent on the aliphatic hydrocarbon ring.

  In formula (1), D represents a hydrogen atom, an alkyl group, an aromatic residue, or a heterocyclic residue. The alkyl group represented by D in Formula (1) preferably has 1 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably a straight chain group having 4 to 10 carbon atoms. By setting the number of carbon atoms of the alkyl group represented by D within the above range, the organic compound of the present invention exhibits good solvent solubility.

  Examples of the aromatic residue represented by D in the formula (1) include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a benzopyrenyl group. Of these, a phenyl group and a naphthyl group are preferable, and a phenyl group is particularly preferable.

  The heterocyclic residue represented by D in the formula (1) includes pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indoleenyl group, imidazolyl group, carbazolyl group, thienyl group, furyl group, pyranyl group. And non-condensed heterocyclic residues such as pyridonyl group; condensed heterocyclic residues such as benzoquinolyl group, anthraquinolyl group, benzothienyl group and benzofuryl group. Among these, a pyridyl group and a thienyl group are preferable, and a thienyl group is particularly preferable.

  The position at which two hydrogen atoms are removed from the condensed ring compound that can be the divalent linking group represented by A in Formula (1) (that is, the bonding position of B and D to the condensed ring compound) is the molecular long axis of the condensed ring compound The position is preferably as parallel as possible to the direction. That is, when the organic compound of the present invention is used for an organic semiconductor device, for example, an organic transistor, a thin film is formed using an organic compound having a rod-like molecular structure, thereby forming a π of a condensed compound constituting a divalent linking group. High mobility is achieved by arranging the conjugate planes to form a highly efficient crystal structure for charge transport.

  For the above reasons, when A in Formula (1) is a divalent linking group obtained by removing two hydrogen atoms from [1] benzothieno [3,2-b] [1] benzothiophene, [1] benzothieno [ 3,2-b] [1] The position at which two hydrogen atoms are removed from benzothiophene is preferably in the 2,7-position or 3,8-position, and A in formula (1) is dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene is a divalent linking group in which two hydrogen atoms have been removed, [1] benzothieno [3,2-b] [1] benzothiophene The position excluding two hydrogen atoms from is preferably in the 2,9-position or the 3,10-position. That is, the organic compound represented by the formula (1) is preferably represented by any one of the following four formulas.

  Although the preferable specific example of the organic compound of this invention is shown to following formula (11) thru | or (118), this invention is not limited to these. In the organic compounds represented by the following formulas (11) to (118), A in formula (1) is obtained by removing two hydrogen atoms from [1] benzothieno [3,2-b] [1] benzothiophene. In the case of a divalent linking group, [1] benzothieno [3,2-b] [1] an organic compound having a substituent B and a substituent D (including a hydrogen atom) at positions 2 and 7 of benzothiophene, When A in Formula (1) is a divalent linking group obtained by removing two hydrogen atoms from dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene, 1] benzothieno [3,2-b] [1] An organic compound having a substituent B and a substituent D (including a hydrogen atom) at positions 2 and 9 of benzothiophene, but A in formula (1) is [1] ] Remove two hydrogen atoms from benzothieno [3,2-b] [1] benzothiophene In the following formula, an organic compound having a substituent at the 2nd and 7th positions at the 3rd and 8th positions, and A in the formula (1) is dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] a compound having two or nine-position substituents in the following formulas in the case where the divalent linking group is obtained by removing two hydrogen atoms from thiophene Is also a preferred specific example of the organic compound of the present invention.

<Organic semiconductor materials, transistor materials>
As described above, the organic compound represented by the formula (1) of the present invention can be used for an organic semiconductor material. That is, the organic semiconductor material according to the present invention contains an organic compound represented by the formula (1) of the present invention. Such an organic semiconductor material according to the present invention can be used as a material for an organic semiconductor device such as an organic transistor. That is, the transistor material according to the present invention contains an organic compound represented by the formula (1) of the present invention.

<Organic semiconductor devices, organic thin films>
An organic semiconductor device such as an organic transistor using the organic semiconductor material according to the present invention is manufactured by, for example, forming an organic thin film containing an organic compound represented by the formula (1) of the present invention on a substrate. Can do. That is, the organic thin film which concerns on this invention contains the organic compound represented by Formula (1) of this invention. The organic semiconductor device according to the present invention contains the organic thin film. The organic transistor according to the present invention contains the organic thin film.

  The thickness of the organic thin film of the present invention varies depending on the application and is not particularly limited, but is usually 0.1 nm to 10 μm, preferably 0.5 nm to 3 μm, more preferably 1 nm to 1 μm. It is.

<Formation method of organic thin film>
Various methods can be used as a method for forming the organic thin film of the present invention. Generally, the method for forming the organic thin film is roughly classified into a forming method by a vacuum process and a coating method by a solution process or the like, and any of them may be used. Examples of the method for forming an organic thin film by the vacuum process include resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination, CVD, molecular beam epitaxial growth, and vacuum vapor deposition. Application methods such as solution process include spin coating, casting (particularly drop casting), dip coating, spray, die coater, roll coater, bar coater, blade coating, etc .; flexo Letterpress printing methods such as printing and resin letterpress printing; flat plate printing methods such as offset printing methods, dry offset printing methods and pad printing methods; intaglio printing methods such as gravure printing methods; silk screen printing methods, photocopier printing methods and lithographic printing methods And stencil printing method; inkjet printing method; microcontact printing method and the like. The organic thin film can be formed by the above-described one forming method, or can be formed by combining a plurality of the above-described forming methods. Hereinafter, the method for forming the organic thin film will be described in detail.

  As a method for forming the organic thin film of the present invention, a coating method is preferable. That is, as the organic thin film of the present invention, an organic thin film formed by a coating method is suitable. In the coating method, a coating solution obtained by dissolving or dispersing the organic compound represented by the formula (1) of the present invention in an organic solvent is a surface on which an organic thin film is to be formed (hereinafter referred to as “attached surface”). An organic thin film is formed by applying (including printing) on the substrate and drying (evaporating the solvent).

  The organic solvent used in the coating solution is not particularly limited as long as it can form an organic thin film containing the organic compound on the adherend surface. Specific examples of the organic solvent include halogenated hydrocarbon solvents such as dichloromethane, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, and chloronaphthalene; ether solvents such as diethyl ether, anisole, ethoxybenzene, and tetrahydrofuran; dimethylacetamide Amide solvents such as dimethylformamide and N-methylpyrrolidone; Nitrile solvents such as acetonitrile, propionitrile and benzonitrile; Alcohol solvents such as methanol, ethanol, isopropanol, butanol and cyclohexanol; Octafluoropentanol and penta Fluorinated alcohol solvents such as fluoropropanol; ester solvents such as ethyl acetate, butyl acetate, ethyl benzoate, diethyl carbonate; benzene, toluene, Ren, mesitylene, ethylbenzene, tetrahydronaphthalene, aromatic hydrocarbon solvents such as phenyl cyclohexane; hexane, cyclohexane, octane, decane, hydrocarbon solvents such as decahydronaphthalene and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The content of the organic compound represented by the general formula (1) in the coating solution differs depending on the type of the organic solvent and the thickness of the organic thin film to be prepared, and it is difficult to determine it in general. On the other hand, it is preferably within a range of 0.001% by mass to 20% by mass, and more preferably within a range of 0.01% by mass to 10% by mass. Moreover, in the said coating liquid, although the organic compound represented by General formula (1) should just melt | dissolve or disperse | distribute in the said organic solvent, it is more preferable to melt | dissolve as a uniform solution.

  The said coating liquid can contain other organic semiconductors and various additives other than the organic compound represented by General formula (1) as needed.

  Examples of the additive include a semiconducting polymer compound exhibiting semiconductivity and an insulating polymer compound exhibiting insulation. Specific examples of the semiconducting polymer compound include polyacetylene polymer, polydiacetylene polymer, polyparaphenylene polymer, polyaniline polymer, polythiophene polymer, polyarylamine polymer, polypyrrole polymer. , Polythienylene vinylene polymer, polyaniline polymer, polyazulene polymer, polypyrene polymer, polycarbazole polymer, polyselenophene polymer, polyfuran polymer, poly (p-phenylene) polymer high Examples thereof include molecules, polyindole polymers, polypyridazine polymers, polysulfides polymers, polyparaphenylene vinylene polymers, polyethylenedioxythiophene polymers, nucleic acids, and derivatives thereof.

  On the other hand, specific examples of the insulating polymer material include acrylic polymer, polyethylene polymer, polymethacrylate polymer, polystyrene polymer, polyethylene terephthalate polymer, nylon polymer, polyamide polymer. Polyester polymer, vinylon polymer, polyisoprene polymer, cellulose polymer, copolymer polymer, and derivatives thereof.

  If a polymer material such as a semiconducting polymer compound or an insulating polymer compound is used, the amount of the polymer material used is generally 0.5% to 95% when the total amount of the coating solution is 1. , Preferably 1% to 90%, more preferably 3% to 75%, and most preferably 5% to 50%. It is not necessary to use a polymer material.

  In addition, other additives such as a carrier generating agent (dopant), a conductive substance, a viscosity modifier, a surface tension modifier, a leveling agent, a penetrating agent, a wetting agent may be used in the coating solution as long as the obtained effect is not impaired. Preparation agents, rheology modifiers and the like may be added. When adding the above-mentioned other additives, the amount of the above-mentioned other additives is usually 0.01 to 10% by mass, preferably 0.05 to 5% by mass when the total amount of the coating solution is 1. %, More preferably in the range of 0.1 to 3% by mass.

  In the above coating method, the environment such as the temperature of the adherend (the object on which the organic thin film is to be formed) and the coating solution at the time of forming the organic thin film is also important. Depending on the temperature of the deposit and the coating solution, Since the characteristics of the organic thin film change (when the organic thin film is used in an organic semiconductor device described later, the characteristics of the organic semiconductor device change), the temperature of the deposit and the coating solution during the formation of the organic thin film is carefully selected. It is preferable to do. The temperature of the adherend and the coating solution is usually 0 to 200 ° C., preferably 10 to 120 ° C., more preferably 15 to 100 ° C. Care must be taken because the temperature of the coating solution largely depends on the type of the organic solvent contained in the coating solution.

  The thickness of the organic thin film formed by the coating method is usually 0.1 nm to 10 μm, preferably 0.5 nm to 3 μm, and more preferably 1 nm to 1 μm.

  Next, as a method for forming an organic thin film similar to the above-described coating method, a monomolecular film of an organic thin film containing an organic compound represented by the general formula (1) is prepared by dropping the coating liquid on the water surface, Langmuir project method of transferring and laminating the monomolecular film on the adherend surface; introducing a liquid crystal state or melt state organic thin film forming material containing an organic compound represented by the general formula (1) between the substrates by capillary action Methods can also be adopted.

  Furthermore, as another method for forming an organic thin film, a method for forming an organic thin film containing the organic compound represented by the general formula (1) by the vacuum process described above will be described.

In this method, the organic thin film forming material containing the organic compound is evaporated by heating under vacuum in a container such as a crucible or a metal boat, and the evaporated organic thin film forming material is applied to the adherend. A method of adhering (depositing) to the contact surface, that is, a vacuum deposition method is preferably employed. The degree of vacuum at the time of this vapor deposition is usually 1.0 × 10 ⁻¹ Pa or less, preferably 1.0 × 10 ⁻³ Pa or less. Moreover, the characteristics of the organic thin film change depending on the temperature of the adherend during vapor deposition. When an organic thin film is used as a semiconductor layer of an organic semiconductor device (for example, an organic thin film transistor) to be described later, this changes the characteristics of the organic semiconductor device, so it is preferable to carefully select the temperature of the deposit during vapor deposition. . The temperature of the adherend during vapor deposition is usually 0 to 250 ° C, preferably 5 to 200 ° C, more preferably 10 to 180 ° C, still more preferably 15 to 150 ° C, and particularly preferably. 20 to 130 ° C. The deposition rate is usually 0.001 nm / second to 10 nm / second, preferably 0.01 nm / second to 1 nm / second. Moreover, the thickness of the organic thin film formed with the said coating liquid is 1 nm thru | or 1 micrometer normally, Preferably it is 5 nm to 500 nm, More preferably, it is 10 nm to 300 nm.

<Manufacturing method of organic semiconductor device, ink for manufacturing semiconductor device>
The method for producing an organic semiconductor device of the present invention includes forming a semiconductor layer by applying an ink for producing a semiconductor device onto a substrate and drying it. The ink for producing a semiconductor device of the present invention is suitably used for production of an organic semiconductor device including a step of forming an organic thin film by the coating method described above.
The ink for producing a semiconductor device of the present invention contains an organic semiconductor material or transistor material containing an organic compound represented by the general formula (1), and usually further contains an organic solvent, which is described above. It corresponds to the coating solution used in the applied coating method. The ink for producing a semiconductor device of the present invention containing such an organic solvent can be prepared by dissolving or dispersing the organic compound represented by the general formula (1) in the organic solvent.

<Organic transistor and manufacturing method thereof>
Next, an organic transistor which is one of organic semiconductor devices using an organic semiconductor material containing an organic compound represented by the formula (1) and a method for manufacturing the same will be described.

  First, the organic transistor will be described in detail. The organic transistor includes at least one organic semiconductor layer made of a thin film (organic thin film) containing an organic compound represented by the formula (1), and a source electrode and a drain disposed so as to be in contact with and separated from the organic semiconductor layer. An electrode, and a gate electrode disposed so as to face a region (channel region) between a surface in contact with the source electrode and a surface in contact with the drain electrode in the organic semiconductor layer. The current flowing between the source electrode and the drain electrode is controlled by the voltage applied to the gate electrode.

  In general, an organic transistor having a structure (Metal-Insulator-Semiconductor: MIS structure) in which a gate electrode is insulated from an organic semiconductor layer by an insulator layer made of an insulating film is often used as the organic transistor. A MIS structure using a metal oxide film as an insulating film is called a MOS (Metal-Oxide-Semiconductor) structure. Another example of the organic transistor is a structure in which a gate electrode is formed on the organic semiconductor layer through a Schottky barrier (Metal-Semiconductor; MES structure). In some cases, the MIS structure is often used.

  FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of an organic transistor according to the present invention. Organic transistors 10A to 10F shown in FIG. 1 (a) to FIG. 1 (f) include a source electrode 1, an organic semiconductor layer 2, a drain electrode 3, an insulator layer 4, a gate electrode 5, and a substrate 6. ing. In any of the organic transistors 10A to 10F, the organic semiconductor layer 2 is formed of a thin film using an organic semiconductor material containing an organic compound represented by the formula (1). The arrangement of the layers 2 and 4 and the electrodes 1, 3, and 5 can be appropriately selected depending on the use of the organic transistor as exemplified in FIGS. 1A to 1F.

  The organic transistors 10A to 10D and 10F are called lateral transistors because current flows in a direction parallel to the substrate 6, the source electrode 1, and the drain electrode 3. In the organic transistor 10A, the source electrode 1 and the drain electrode 3 are disposed on the lower surface of the organic semiconductor layer 2 (the surface on the side close to the substrate 6), and the gate electrode 5 is disposed below the insulator electrode 4 via the insulator layer 4. Therefore, it is called a bottom contact-bottom gate structure. The organic transistor 10B is called a top contact-bottom gate structure because the source electrode 1 and the drain electrode 3 are disposed on the upper surface of the organic semiconductor layer 2, and the gate electrode 5 is disposed on the lower surface of the insulator layer 4. The organic transistor 10C is called a top contact-top gate structure because the source electrode 1, the drain electrode 3, and the insulator layer 4 are provided on the organic semiconductor layer 2, and the gate electrode 5 is further formed thereon. ing. The organic transistor 10D is called a top & bottom contact-bottom gate structure because the source electrode 1 is disposed on the lower surface of the organic semiconductor layer 2 and the drain electrode 3 is disposed on the upper surface. The organic transistor 10F is called a bottom contact-top gate structure because the gate electrode 5 is disposed on the upper surface of the organic semiconductor layer 2 with the insulator layer 4 interposed therebetween.

  The organic transistor 10E is a kind of organic transistor having a vertical structure in which current flows in a direction perpendicular to the source electrode 1 and the drain electrode 3, and is an electrostatic induction transistor (SIT). The organic transistor 10E includes a source electrode 1 and a drain electrode 3 disposed so as to be parallel and spaced apart from each other, and an organic semiconductor layer 2 disposed so as to be sandwiched between the source electrode 1 and the drain electrode 3. A plurality of gate electrodes 5 embedded in the organic semiconductor layer 2 in a mesh shape parallel to the source electrode 1 and the drain electrode 3. In the organic transistor 10E, since the current flow in the organic semiconductor layer 2 spreads in a planar shape, a large amount of carriers 8 are transferred from the source electrode 1 side to the drain electrode 3 side at a time as indicated by an arrow in FIG. Can move. Although FIG. 1E does not show the substrate 6, in the normal case, a substrate similar to the substrate 6 is provided outside the source electrode 1 and the drain electrode 3 in the organic transistor 10 </ b> E.

  Each component in each embodiment will be described. The substrate 6 needs to be able to hold each component formed thereon without peeling off. Examples of the substrate 6 include an insulating substrate such as a resin plate, a resin film, paper, a glass plate, a quartz plate, and a ceramic plate; a substrate in which an insulating layer is formed by coating or the like on a conductive substrate made of metal or an alloy; A substrate composed of various combinations such as a combination of a resin and an inorganic material; a conductive substrate such as a semiconductor substrate (for example, a silicon wafer) can be used. Examples of the resin constituting the resin plate and the resin film include, for example, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyamide, polyimide, polycarbonate, cellulose triacetate, and polyetherimide. When a resin film or paper is used as the substrate 6, the organic transistors 10A to 10D and 10F can be made flexible. The organic transistors 10A to 10D and 10F are flexible and light, and the organic transistors 10A to 10D and 10F Practicality is improved. The thickness of the substrate 6 is usually 1 μm to 10 mm, preferably 5 μm to 5 mm.

For the source electrode 1, the drain electrode 3, and the gate electrode 5, a conductive material is used. Examples of the conductive material include platinum, gold, silver, aluminum, chromium, tungsten, tantalum, nickel, cobalt, copper, iron, lead, tin, titanium, indium, palladium, molybdenum, magnesium, calcium, and barium. Metals such as lithium, potassium and sodium and alloys containing them; conductive oxides such as InO ₂ , ZnO ₂ , SnO ₂ and ITO (indium tin oxide); polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene vinylene, Conductive polymer compounds such as polydiacetylene; semiconductors such as silicon, germanium, and gallium arsenide; carbon materials such as carbon black, fullerene, carbon nanotubes, graphite, and graphene can be used. Further, the conductive polymer compound or the semiconductor may be doped. In that case, as a dopant used for doping, for example, inorganic acids such as hydrochloric acid and sulfuric acid; organic acids having an acidic functional group such as sulfonic acid; Lewis acids such as PF ₅ , AsF ₅ and FeCl ₃ ; halogen atoms such as iodine A metal atom such as lithium, sodium or potassium. Boron, phosphorus, arsenic and the like are also frequently used as dopants for inorganic semiconductors such as silicon. Further, a conductive composite material in which particles such as carbon black and metal particles are dispersed in the above dopant is also used. Note that, for the source electrode 1 and the drain electrode 3 that are in contact with the organic semiconductor layer 2, selection of an appropriate work function for reducing contact resistance, surface treatment, and the like are important.

  The distance (channel length) between the source electrode 1 and the drain electrode 3 is an important factor that determines the characteristics of the organic transistors 10A to 10F. The channel length is usually 0.01 to 300 μm, preferably 0.1 to 100 μm. If the channel length is short, the amount of current that can be extracted increases, but conversely, short channel effects such as the influence of contact resistance occur and control becomes difficult, so an appropriate channel length is required. The length (channel width) of the source electrode 1 and the drain electrode 3 is usually 10 to 10,000 μm, preferably 100 to 5000 μm. In addition, this channel width can be made longer by forming the electrode structure into a comb structure, etc., and can be set to an appropriate length according to the required amount of current, device structure, etc. There is a need to.

  The structures (shapes) of the source electrode 1 and the drain electrode 3 will be described. The structures of the source electrode 1 and the drain electrode 3 may be the same or different. In the case of the bottom contact structure, it is generally preferable to form the source electrode 1 and the drain electrode 3 using a lithography method, and to form the source electrode 1 and the drain electrode 3 in a rectangular parallelepiped. Recently, printing accuracy by various printing methods has been improved, and it has become possible to produce the source electrode 1 and the drain electrode 3 with high accuracy using techniques such as ink jet printing, gravure printing, and screen printing. In the case of a top contact structure in which the source electrode 1 and the drain electrode 3 are provided on the organic semiconductor layer 2, the source electrode 1 and the drain electrode 3 can be produced by vapor-depositing the conductive material using a shadow mask or the like. . It has also become possible to directly print and form the electrode patterns of the source electrode 1 and the drain electrode 3 using a technique such as inkjet printing. The lengths of the source electrode 1 and the drain electrode 3 are the same as the channel width. The widths of the source electrode 1 and the drain electrode 3 are not particularly limited, but are preferably shorter in order to reduce the area of the device within a range where the electrical characteristics can be stabilized. The width of the source electrode 1 and the drain electrode 3 is usually 0.1 to 1000 μm, preferably 0.5 to 100 μm. The thicknesses of the source electrode 1 and the drain electrode 3 are usually 0.1 to 1000 nm, preferably 1 to 500 nm, more preferably 5 to 200 nm. Although wiring is connected to the source electrode 1 and the drain electrode 3, the wiring is also made of the same material as the source electrode 1 and the drain electrode 3.

As the insulator layer 4, an insulating material is used. Examples of the insulating material include polyparaxylylene, polyacrylate, polymethyl methacrylate, polystyrene, polyvinylphenol, polyamide, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, fluororesin, Polymers such as epoxy resins and phenol resins, and copolymers in which two or more structural units of these polymers are combined; oxides (non-ferroelectric) such as silicon dioxide, aluminum oxide, titanium oxide, tantalum oxide; SrTiO ₃ , BaTiO Ferroelectric oxides such as ₃ ; nitrides such as silicon nitride and aluminum nitride; dielectrics such as sulfides and fluorides can be used. In addition, as the material having the insulating property, a material in which particles of the dielectric (however, a material different from the polymer) are dispersed in a polymer can be used. As the material having the insulating property, a material having high electrical insulation characteristics is preferable in order to reduce the leakage current. Thereby, the thickness of the insulator layer 4 can be reduced, the insulation capacity can be increased, and the current that can be taken out. Can be more. Further, in order to improve the mobility of the organic semiconductor material, the insulator layer 4 is preferably a smooth film that can reduce the surface energy of the surface of the insulator layer 4 and has no unevenness. For this purpose, a self-assembled monolayer insulator layer 4 or a two-layer insulator layer 4 may be formed. The thickness of the insulator layer 4 varies depending on the material, but is usually 0.1 nm to 100 μm, preferably 0.5 nm to 50 μm, more preferably 1 nm to 10 μm.

  The organic semiconductor layer 2 has a thin film using an organic semiconductor material containing the organic compound of the present invention represented by the formula (1). The structure of the organic semiconductor layer 2 is formed, for example, as a single layer structure having only a layer made of a thin film containing the organic compound according to the present invention. However, for the purpose of improving the characteristics of the organic transistor, imparting other characteristics, etc., other organic semiconductor materials and various additives can be mixed with the organic compound according to the present invention as necessary. The organic semiconductor layer 2 can also be formed as a multilayer structure having a layer made of a thin film containing the organic compound according to the present invention.

  The thickness of the organic semiconductor layer 2 is preferably as thin as possible without losing necessary functions. In the horizontal type organic transistors such as the organic transistors 10A to 10D and 10F, the characteristics of the organic semiconductor transistor do not depend on the thickness as long as the thickness of the organic semiconductor layer 2 has a predetermined thickness or more. Since the leakage current often increases as the thickness increases, the thickness of the organic semiconductor layer 2 is preferably within an appropriate range. The thickness of the organic semiconductor layer 2 is usually 0.1 nm to 10 μm, preferably 0.5 nm to 3 μm, and more preferably for the organic semiconductor layer 2 to perform the function required for the organic semiconductor layer 2. Is 1 nm to 1 μm.

  In the organic transistors 10A to 10F, other layers may be provided as necessary between the above-described components or on the exposed surfaces of the above-described components. For example, a protective layer may be formed on the organic semiconductor layer 2 in the organic transistors 10A to 10F directly or via another layer. Thereby, the influence of external air such as humidity on the electrical characteristics of the organic transistor can be reduced, and the electrical characteristics of the organic transistor can be stabilized. In addition, electrical characteristics such as the on / off ratio of the organic transistor can be improved.

  Although it does not specifically limit as a material which comprises the said protective layer, For example, various resins, such as acrylic resins, such as an epoxy resin and polymethylmethacrylate, a polyurethane, a polyimide, polyvinyl alcohol, a fluororesin, polyolefin; silicon oxide, aluminum oxide, Inorganic oxides such as silicon nitride; and dielectrics such as nitrides are preferred, and resins (polymers) having low oxygen permeability, moisture permeability, and water absorption are more preferred. As a material constituting the protective layer, a gas barrier protective material developed for an organic EL display can also be used. The protective layer may have any thickness depending on the purpose, but is usually 100 nm to 1 mm.

  In addition, the surface of the organic semiconductor layer 2 (the surface of the substrate 6, the surface of the insulator layer 4, etc.) is subjected to surface treatment before the formation of the organic semiconductor layer 2, whereby the characteristics of the organic transistors 10 </ b> A to 10 </ b> F. It is possible to improve. For example, by adjusting the degree of hydrophilicity / hydrophobicity of the surface on which the organic semiconductor layer 2 is formed, the quality of the organic semiconductor layer 2 formed on the surface (for example, the film quality of the thin film constituting the organic semiconductor layer 2) And film formability) can be improved. In particular, the characteristics of the organic semiconductor layer 2 made of an organic semiconductor material may vary greatly depending on the state of the layer such as molecular orientation. Therefore, the surface treatment on the surface on which the organic semiconductor layer 2 is formed controls the molecular orientation at the interface between the surface on which the organic semiconductor layer 2 is formed and the organic semiconductor layer 2 formed on the surface. It is considered that the trap site in the base material (substrate 6, insulator layer 4, etc.) on which the organic semiconductor layer 2 is formed is reduced, thereby improving characteristics such as carrier mobility of the organic transistor.

  The trap site refers to a functional group such as a hydroxyl group present in an untreated substrate. When such a functional group exists in the base material on which the organic semiconductor layer 2 is formed, electrons are attracted to the functional group, and as a result, the carrier mobility of the organic transistor is lowered. Therefore, reducing trap sites in the base material on which the organic semiconductor layer 2 is formed is often effective for improving characteristics such as carrier mobility of the organic transistor.

  Examples of the surface treatment of the substrate on which the organic semiconductor layer 2 is formed include, for example, self-assembled monolayer treatment with hexamethyldisilazane, octyltrichlorosilane, octadecyltrichlorosilane, etc .; surface treatment with polymers, etc .; hydrochloric acid, Acid treatment with acids such as sulfuric acid and acetic acid; Alkaline treatment with alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia; Ozone treatment; Fluorination treatment; Plasma treatment with plasma such as oxygen plasma and argon plasma; Langmuir・ Blodgett film forming treatment; Other insulator or semiconductor thin film forming treatments; Mechanical treatments; Electrical treatments such as corona discharge; Rubbing treatments using fibers, etc., and combinations of these treatments be able to.

  In the organic transistors 10A to 10F shown in FIG. 1, a method of providing various layers on the base material (a method of providing the insulator layer 4 on the substrate 6, a method of providing the organic semiconductor layer 2 on the substrate 6, the insulator layer 4 As a method for providing the organic semiconductor layer 2 on the surface, various methods such as a vacuum deposition method, a coating method, a printing method, and a sol-gel method can be appropriately employed.

  Next, the manufacturing method of the organic transistor according to the present invention will be described. Here, the top contact-bottom gate type organic transistor 10B of the embodiment shown in FIG. This manufacturing method can be similarly applied to organic transistors of other modes such as the organic transistors 10A, 10C to 10F described above. FIG. 2 is a schematic view showing a process for producing an embodiment of the organic transistor according to the present invention.

(1) Surface Treatment of Substrate 6 In the method of manufacturing the organic transistor 10B according to the present invention, first, the substrate 6 is prepared (see FIG. 2A), and various layers and electrodes necessary for the substrate 6 are provided. An organic transistor 10B is produced. As the substrate 6, the materials described above are used. It is also possible to perform the above-described surface treatment on the substrate 6. The thickness of the substrate 6 is preferably thin as long as necessary functions are not hindered. The thickness of the substrate 6 varies depending on the material constituting the substrate 6, but is usually 1 μm to 10 mm, preferably 5 μm to 5 mm. If necessary, the substrate 6 may have an electrode function.

(2) Formation of Gate Electrode 5 Next, the gate electrode 5 is formed on the substrate 6 (see FIG. 2B). As the material constituting the gate electrode 5, the materials described above are used. As a method for forming the gate electrode 5, various methods can be used. For example, a vacuum deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method, a sol-gel method, or the like can be employed. When forming a layer of a material (electrode material) constituting the gate electrode 5, or after forming the layer, it is preferable to pattern the layer so as to have a desired shape as necessary. Various methods can be used as the layer patterning method, and examples thereof include a photolithography method in which patterning and etching of a photoresist are combined. Also, evaporation method using shadow mask: sputtering method; printing method such as ink jet printing, screen printing, offset printing, letterpress printing, etc .; soft lithography method such as micro contact printing method; or a combination of these methods Thus, the layer can be patterned. Although the thickness of the gate electrode 5 varies depending on the material constituting the gate electrode 5, it is usually 0.1 nm to 10 μm, preferably 0.5 nm to 5 μm, more preferably 1 nm to 3 μm. When a single conductive substrate serves as both the gate electrode 5 and the substrate 6, the thickness of the single conductive substrate may be larger than the above-described thickness range of the gate electrode 5.

(3) Formation of insulator layer 4 Next, the insulator layer 4 is formed on the gate electrode 5 (see FIG. 2C). As the material constituting the insulator layer 4, the materials described above are used. Various methods can be used to form the insulator layer 4. Examples of methods that can be used for forming the insulator layer 4 include spin coating, spray coating, dip coating, casting, bar coating, blade coating, and other coating methods; screen printing, offset printing, inkjet printing, and the like; Various methods such as a vacuum deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, an ion plating method, a sputtering method, an atmospheric pressure plasma method, and a dry process method such as a CVD method can be used. In addition to the sol-gel method; a method of forming alumite on aluminum or a method of forming silicon oxide on silicon, the surface layer of metal or metalloid is oxidized by a thermal oxidation method or the like as a method of forming the insulator layer 4. A method of forming an oxide film can also be employed.

  It should be noted that in the portion where the insulator layer 4 and the organic semiconductor layer 2 are in contact with each other, the molecule constituting the organic semiconductor layer 2 at the interface between the insulator layer 4 and the organic semiconductor layer 2, for example, represented by the above formula (1). In order to satisfactorily orient the molecules of the organic compound, a predetermined surface treatment can be performed on the insulator layer 4. As a surface treatment method for the insulator layer 4, the same surface treatment as that for the substrate 6 can be used. The thickness of the insulator layer 4 is preferably as thin as possible because the amount of electricity taken out can be increased by increasing the electric capacity of the insulator layer 4. However, since the leakage current increases as the insulator layer 4 is thinner, the insulator layer 4 is preferably thinner as long as the function is not impaired. The thickness of the insulator layer 4 is usually 0.1 nm to 100 μm, preferably 0.5 nm to 50 μm, more preferably 5 nm to 10 μm.

(4) Formation of Organic Semiconductor Layer 2 The organic semiconductor material containing the organic compound according to the present invention represented by the general formula (1) is used for forming the organic semiconductor layer 2 (see FIG. 2D). ). As a method for forming the organic semiconductor layer 2, the various organic thin film forming methods described above can be used. When the coating method described above is used as a method for forming an organic thin film, an ink for manufacturing a semiconductor device containing an organic semiconductor material or a transistor material containing an organic compound represented by the formula (1) of the present invention is used as an insulating material. It apply | coats to the body layer 4, the source electrode 1, the drain electrode 3, etc., and is dried. The film thickness of the organic semiconductor layer 2 produced by this method is preferably thinner as long as the function is not impaired. There is a concern that the leakage current increases as the film thickness increases. The thickness of the organic semiconductor layer 2 is usually 1 nm to 1 μm, preferably 5 nm to 500 nm, more preferably 10 nm to 300 nm.

(5) Post-treatment of organic semiconductor layer 2 The organic semiconductor layer 2 (see FIG. 2D) formed in this way can be further improved in characteristics by post-treatment. For example, by performing heat treatment, distortion in the film generated during film formation is alleviated, pinholes are reduced, and alignment / orientation in the film can be controlled. Improvement and stabilization can be achieved. In the production of the organic transistor according to the present invention, it is effective to improve the characteristics by performing such heat treatment. The heat treatment is performed by heating the substrate 6 after forming the organic semiconductor layer 2. The temperature of the heat treatment is not particularly limited, but is usually from room temperature to about 200 ° C., preferably 40 to 150 ° C., more preferably 45 to 120 ° C. The heat treatment time at this time is not particularly limited, but is usually about 10 seconds to 24 hours, preferably about 30 seconds to 3 hours. The atmosphere at that time may be air, but may be an inert atmosphere such as nitrogen or argon. In addition, the film shape can be controlled by solvent vapor.

  Further, as another post-treatment method of the organic semiconductor layer 2, a characteristic change due to oxidation or reduction can be achieved by treatment with an oxidizing or reducing gas such as oxygen or hydrogen, or an oxidizing or reducing liquid. Can also be induced. Such a post-treatment method is carried out for the purpose of increasing or decreasing the carrier density in the film, for example.

In addition, in a technique called doping, the characteristics of the organic semiconductor layer 2 can be changed by adding a trace amount of dopant (element, atomic group, molecule, or polymer) to the organic semiconductor layer 2. For example, oxidizing gases such as oxygen; reducing gases such as hydrogen; acids such as hydrochloric acid, sulfuric acid and sulfonic acid; Lewis acids such as PF ₅ , AsF ₅ and FeCl ₃ ; halogen atoms such as iodine; sodium and potassium The organic semiconductor layer 2 can be doped with a dopant such as a metal atom; a donor compound such as tetrathiafulvalene (TTF) or phthalocyanine. This is because the organic semiconductor layer 2 is brought into contact with a gaseous dopant (when the dopant is a gas), the organic semiconductor layer 2 is immersed in a solution state dopant (when the dopant is in a solution state), electrochemical This can be achieved by a method of performing a proper doping process. These dopants do not necessarily need to be added after the formation of the organic semiconductor layer 2, and are added during the synthesis of the material (organic semiconductor material) of the organic semiconductor layer 2, or the organic semiconductor layer 2 using a thin film forming composition. May be added to the composition for forming a thin film, or may be added in the process step of forming the organic semiconductor layer 2. Further, a dopant is added to the material forming the organic semiconductor layer 2 (organic semiconductor material) and co-evaporation is performed, or the dopant is mixed in an ambient atmosphere when forming the organic semiconductor layer 2 (the dopant is present). The organic semiconductor layer 2 is formed under an environment), and further, dopant ions can be accelerated in a vacuum and collide with the organic semiconductor layer 2 for doping.

  These doping effects include changes in electrical conductivity due to increase or decrease in carrier density, changes in carrier polarity (p-type and n-type), changes in Fermi level, and the like.

(6) Formation of Source Electrode 1 and Drain Electrode 3 Next, the source electrode 1 and the drain electrode 3 are formed on the organic semiconductor layer 2 (see FIG. 2E). The method for forming the source electrode 1 and the drain electrode 3 can be based on the method for forming the gate electrode 5. In forming the source electrode 1 and the drain electrode 3, various additives or the like can be used to reduce the contact resistance with the organic semiconductor layer 2.

(7) Formation of Protective Layer 7 In the step of forming the source electrode 1 and drain electrode 3 described above, the organic transistor 10B (see FIG. 1B and FIG. 2E) is completed. After the formation of the source electrode 1 and the drain electrode 3, a protective layer 7 may be formed on a portion exposed on the upper surface of the organic semiconductor layer 2, the upper surface of the source electrode 1, and the upper surface of the drain electrode 3 (FIG. 2). (Refer to (f)). By forming the protective layer 7 on the exposed portion of the upper surface of the organic semiconductor layer 2, the upper surface of the source electrode 1, and the upper surface of the drain electrode 3, the influence of outside air can be minimized, and the organic transistor There is an advantage that the electrical characteristics of 10B can be stabilized.

  As the material for the protective layer 7, the above-mentioned materials are used. Moreover, the thickness of the protective layer 7 can employ | adopt arbitrary thickness according to the objective, However, Usually, they are 100 nm thru | or 1 mm. As a method of forming the protective layer 7, various methods can be adopted. When the protective layer 7 is made of a resin, for example, a method of applying a solution containing a resin and drying it to obtain a resin layer; Examples thereof include a method of polymerizing after applying or vapor-depositing a resin monomer. You may perform a crosslinking process after formation of a resin layer. When the protective layer 7 is made of an inorganic material, as a method for forming the protective layer 7, for example, a forming method by a vacuum process such as a sputtering method or a vapor deposition method; a forming method by a solution process such as a sol-gel method can be used. .

  In the organic transistor, in addition to the organic semiconductor layer 2, a protective layer 7 can be provided between components as necessary. Such a protective layer 7 may help to stabilize the electrical characteristics of the organic transistor.

  Since the organic transistor which concerns on this invention uses the organic-semiconductor material containing the organic compound represented by said Formula (1) as a material which comprises the organic-semiconductor layer 2, an organic transistor can be manufactured by a comparatively low-temperature process. Is possible. Therefore, a flexible material such as a plastic plate or a plastic film that could not be used under conditions exposed to a high temperature can be used as the substrate 6 in the organic transistor according to the present invention. As a result, the organic transistor according to the present invention can realize an organic semiconductor device that is lightweight and flexible and is not easily broken by using a flexible material as the substrate 6. Therefore, the organic semiconductor device according to the present invention can be suitably used as a switching device for an active matrix display.

  The organic transistor according to the present invention can also be used as a digital device or an analog device such as a memory circuit device, a signal driver circuit device, and a signal processing circuit device. Further, by combining these, a display, an IC (integrated circuit) card, an IC tag, or the like can be manufactured. Furthermore, since the organic transistor according to the present invention can change its characteristics by an external stimulus such as a chemical substance, it can be used as a sensor.

(Organic solar cell device)
A flexible and low-cost organic solar cell device can be easily produced using the organic compound represented by the general formula (1) of the present invention. Since the organic solar cell device is a solid-state device, it is advantageous in terms of flexibility and improved life. Conventionally, development of solar cells using organic thin film semiconductors combined with conductive polymers, fullerenes, and the like has been the mainstream, but power generation conversion efficiency is a problem.

  In general, the structure of an organic solar cell device is similar to that of a silicon-based solar cell, in which a layer for generating power (a power generation layer) is sandwiched between an anode and a cathode, and holes and electrons generated by absorbing light are absorbed by each electrode. By receiving it functions as a solar cell. The power generation layer is composed of a p-type donor material, an n-type acceptor material, and other materials such as a buffer layer, and an organic solar cell is used in which an organic material is used.

  Structures include Schottky junctions, heterojunctions, bulk heterojunctions, nanostructure junctions, hybrids, etc. Each material efficiently absorbs incident light and generates charges, and the generated charges (holes and electrons) It functions as a solar cell by separating, transporting and collecting.

  In FIG. 3, the schematic sectional drawing of the example (organic solar cell device 20) of a heterojunction type organic solar cell device is shown.

  The organic solar cell device 20 includes a substrate 21, an anode 22 formed on the upper surface of the substrate 21, a power generation layer 23 formed on the upper surface of the anode 22, and a cathode 24 formed on the upper surface of the power generation layer 23. And the power generation layer 23 is formed on the upper surface of the anode 22, the n-type layer 232 formed on the upper surface of the p-type layer 231, and the upper surface of the n-type layer 232. And the buffer layer 233.

  Next, each component in the organic solar cell device will be described by taking the organic solar cell device 20 shown in FIG. 3 as an example.

  As the material of the substrate 21, the same materials as those of the substrate 6 of the organic transistors 10A to 10D and 10F described above can be used.

  As materials constituting the anode 22 and the cathode 24 in the organic solar cell device 20, the same materials as those constituting the source electrode 1, the drain electrode 3 and the gate electrode 5 of the organic transistors 10A to 10F described above are used. it can. Since the anode 22 and the cathode 24 need to capture light efficiently, it is desirable that the anode 22 and the cathode 24 have transparency in the absorption wavelength region of the power generation layer 23. In order for the organic solar cell device 20 to have good solar cell characteristics, the anode 22 and the cathode 24 have a sheet resistance of 20Ω / □ or less and a light transmittance of 85% or more. preferable.

  The power generation layer 23 is represented by the general formula (1) of the present invention even if the power generation layer 23 has a single layer structure composed only of a layer made of an organic thin film containing the organic compound represented by the general formula (1) of the present invention. In general, the power generation layer 23 includes a p-type layer 231 made of a p-type donor material, and a multi-layer structure including a plurality of layers including an organic thin film containing an organic compound. It is composed of an n-type layer 232 made of an n-type acceptor material and a buffer layer 233.

  As a p-type donor material constituting the p-type layer 231, a compound capable of transporting holes can be basically used. Specifically, a polyparaphenylene vinylene derivative, a polythiophene derivative, a polyfluorene derivative, a polyaniline derivative, etc. π-conjugated polymers; carbazole and other polymers having heterocyclic side chains. Examples of the p-type donor material include low molecular compounds such as pentacene derivatives, rubrene derivatives, porphyrin derivatives, phthalocyanine derivatives, indigo derivatives, quinacridone derivatives, merocyanine derivatives, cyanine derivatives, squalium derivatives, and benzoquinone derivatives.

  As the n-type acceptor material constituting the n-type layer 232, an n-type acceptor material containing an organic compound represented by the general formula (1) of the present invention can be used. That is, the n-type layer 232 is composed of an organic thin film containing an organic compound represented by the general formula (1) of the present invention. As the n-type acceptor material constituting the n-type layer 232, the organic compound represented by the general formula (1) of the present invention may be used alone, or represented by the general formula (1) of the present invention. The organic compound may be used in combination with other acceptor materials. Other acceptor materials to be mixed are basically compounds capable of transporting electrons, oligomers and polymers having pyridine or a derivative thereof as a skeleton, oligomers or polymers having a quinoline or a derivative thereof as a skeleton, benzophenanthrolines or Polymers having the derivatives, polymer materials such as cyanopolyphenylene vinylene derivatives (CN-PPV, etc.); low molecular materials such as fluorinated phthalocyanine derivatives, perylene derivatives, naphthalene derivatives, bathocuproine derivatives, fullerene derivatives such as C60, C70, PCBM Etc.

  As the p-type donor material and the n-type donor material, those capable of efficiently absorbing light and generating electric charges are preferable, and those having a high extinction coefficient are preferable.

  Examples of the material of the buffer layer 233 include copper phthalocyanine, molybdenum trioxide, calcium, nickel oxide, lithium fluoride, and polyethylenedioxythiophene doped with polystyrene sulfonic acid (PEDOT: PSS).

  As a method for forming a thin film for the power generation layer 23 in the organic solar cell device 20, a method similar to the method for forming the organic semiconductor layer in the organic transistor described above can be employed. The thickness of the power generation layer 23 varies depending on the configuration of the organic solar cell device. However, the thicker the layer is, the thicker the light is absorbed and the short circuit can be prevented. it can. For this reason, the thickness of the power generation layer 23 is preferably about 10 to 500 nm.

(Photoelectric conversion device)
The organic semiconductor device of the present invention can be used as a photoelectric conversion device by utilizing the semiconductor characteristics of the organic compound represented by the general formula (1) of the present invention.

  Examples of the photoelectric conversion device include a charge coupled device (CCD) having a function of converting a video signal such as a moving image or a still image into a digital signal as an image sensor that is a solid-state imaging device. The organic semiconductor material containing the organic compound represented by the general formula (1) of the present invention is inexpensive and can be used as a material for a photoelectric conversion device by taking advantage of large area processability, flexible functionality unique to organic matter, and the like. There is expected. As a photoelectric conversion device, the same structure as the organic solar cell device 20 shown in FIG. 3 can be used.

(Organic EL device)
The organic semiconductor device of the present invention can be used as an organic EL device.

  Organic EL devices have attracted attention because they can be used in applications such as solid, self-luminous large-area color display and illumination, and many developments have been made. The organic EL device has a structure in which two layers of a light emitting layer and a charge transport layer are provided between a counter electrode composed of a cathode and an anode; an electron transport layer, a light emitting layer and a positive electrode laminated between the counter electrodes. Known are those having a structure having three layers of hole transport layers; and those having a structure having three or more layers, and those having a single light emitting layer.

  When the organic semiconductor device of the present invention is used as an organic EL device, the organic thin film containing the organic compound represented by the general formula (1) can function as the charge transport layer or the electron transport layer.

(About organic semiconductor laser devices)
Since the organic compound represented by the general formula (1) of the present invention is a compound having semiconductor characteristics, it is expected to be used as an organic semiconductor laser device.

  That is, if a resonator structure is incorporated in the organic semiconductor device of the present invention and carriers are efficiently injected to sufficiently increase the density of the excited state, it is expected that light is amplified and laser oscillation occurs. Conventionally, only laser oscillation by optical excitation has been observed, and it is extremely difficult to inject high-density carriers required for laser oscillation by electrical excitation into an organic semiconductor device to generate a high-density excitation state. Although proposed, the use of an organic semiconductor device including an organic thin film containing the compound represented by the general formula (1) of the present invention is expected to cause highly efficient light emission (electroluminescence).

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples, “parts” means parts by mass unless otherwise specified. “M” indicates molar concentration (mol / l). Moreover, the reaction temperature described the internal temperature in a reaction system unless there is particular notice.

  The various compounds obtained in the following synthesis examples were confirmed for their structural formulas by analyzing spectra such as ES-MS spectrum (electrospray mass spectrometry spectrum) and proton nuclear magnetic resonance spectroscopy spectrum as necessary. . The measuring instruments used for measuring these spectra are as follows.

ES-MS spectrum: gas chromatograph mass spectrometer (manufactured by Shimadzu Corporation, model name “GCMS-QP2010SE”)
Proton nuclear magnetic resonance spectroscopy (hereinafter referred to as “ ¹ H-NMR” as appropriate) spectrum: Nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model name “JNM-Lambda 400”)

[Example 1] (Synthesis of an organic compound of an example of the present invention represented by the formula (14) in the above specific example)
(Step 1) Synthesis of Intermediate Compound Represented by the following Formula (a) In this step, an intermediate compound represented by the following formula (a) was synthesized according to the following reaction formula.

  Specifically, it was obtained by dissolving 2.0 parts (8.3 mmol) of [1] benzothieno [3,2-b] [1] benzothiophene in 150 ml of methylene chloride at −20 ° C. in a nitrogen atmosphere. To the solution, 4.0 parts (30.0 mmol) of aluminum chloride was added to obtain a reaction solution. The reaction solution was cooled to −70 ° C., 4.9 parts (33.4 mmol) of cyclohexanecarbonyl chloride was added dropwise to the reaction solution, stirred for 1.5 hours at −70 ° C., and then quenched by adding 75 ml of water. The reaction solution to which water was added was returned to room temperature to precipitate a solid, and the precipitated solid was collected by filtration. The solid collected by filtration was washed with water and methanol to obtain a crude product. The crude product was recrystallized with a mixed solvent of toluene and ethanol to obtain 2.4 parts (yield 81%) of the intermediate compound represented by the above formula (a) as a white solid.

The measurement results of the ES-MS spectrum of the intermediate compound represented by the above formula (a) were as follows.
ES-MS (70 eV): m / z = 350 (M ⁺ )

(Step 2) Synthesis of organic compound represented by formula (14) In this step, the intermediate compound represented by formula (a) obtained in step 1 is represented by formula (14) according to the following reaction formula. An organic compound was synthesized.

  Specifically, 1.40 parts (4.0 mmol) of the intermediate compound represented by the above formula (a) obtained in Step 1 in a nitrogen atmosphere, 0.61 part (11.0 mmol) of potassium hydroxide, 92 ml of diethylene glycol and 6.1 ml (51.0 mmol) of hydrazine monohydrate were mixed to obtain a mixture. The resulting mixture was heated to 100 ° C. and stirred for 1 hour, then heated to 210 ° C. and stirred for 5 hours. The mixture was then cooled to room temperature and the solid was collected by filtration. The obtained solid was washed with water and methanol, and then purified by sublimation twice to obtain 0.98 part (yield 73%) of the organic compound represented by the above formula (14) as a white solid.

The measurement results of the proton nuclear magnetic resonance spectrum and ES-MS spectrum of the organic compound represented by the above formula (14) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.9-1.05 (m, 2H), 1.15-1.28 (m, 3H), 1.55-1.86 (m, 6H) ), 2.64 (d, 2H), 7.25 (dd, 1H), 7.36-7.47 (m, 2H), 7.68 (d, 1H), 7.78 (d, 1H) , 7.86 (dd, 1H), 7.91 (dd, 1H);
ES-MS (70 eV): m / z = 350 (M ⁺ )

[Example 2] (Synthesis of an organic compound of an example of the present invention represented by the formula (20) in the above specific example)
(Step 3) Synthesis of Intermediate Compound Represented by the following Formula (b) In this step, an intermediate compound represented by the following formula (b) was synthesized according to the following reaction formula.

  Specifically, it was obtained by dissolving 2.0 parts (8.3 mmol) of [1] benzothieno [3,2-b] [1] benzothiophene in 150 ml of methylene chloride at −20 ° C. in a nitrogen atmosphere. To the solution, 4.0 parts (30.0 mmol) of aluminum chloride was added to obtain a reaction solution. The reaction solution was cooled to −70 ° C., and 5.3 parts (33.1 mmol) of cyclohexylacetyl chloride was added dropwise to the reaction solution, followed by stirring at −70 ° C. for 1.5 hours, and then quenched by adding 75 ml of water. The reaction solution to which water was added was returned to room temperature to precipitate a solid, and the precipitated solid was collected by filtration. The solid collected by filtration was washed with water and methanol to obtain a crude product. The crude product was recrystallized with a mixed solvent of toluene and ethanol to obtain 2.2 parts (yield 73%) of an intermediate compound represented by the above formula (b) as a white solid.

The measurement results of the ES-MS spectrum of the intermediate compound represented by the above formula (b) were as follows.
ES-MS (70 eV): m / z = 364 (M ⁺ )

(Step 4) Synthesis of organic compound represented by formula (20) In this step, the intermediate compound represented by formula (b) obtained in step 3 is represented by formula (20) according to the following reaction formula. An organic compound was synthesized.

  Specifically, in a nitrogen atmosphere, 1.46 parts (4.0 mmol) of the intermediate compound represented by the above formula (b) obtained in Step 3, 0.61 part (11.0 mmol) of potassium hydroxide, 92 ml of diethylene glycol and 6.1 ml (51.0 mmol) of hydrazine monohydrate were mixed to obtain a mixture. The resulting mixture was heated to 100 ° C. and stirred for 1 hour, then heated to 210 ° C. and stirred for 5 hours. The mixture was then cooled to room temperature and the solid was collected by filtration. The obtained solid was washed with water and methanol, and then purified by sublimation twice to obtain 1.12 parts (yield 80%) of the organic compound represented by the above formula (20) as a white solid.

The measurement results of the proton nuclear magnetic resonance spectrum and ES-MS spectrum of the organic compound represented by the above formula (20) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.9-1.05 (m, 2H), 1.15-1.39 (m, 4H), 1.55-1.85 (m, 7H) ), 2.79 (quart, 2H), 7.30 (dd, 1H), 7.38-7.48 (m, 2H), 7.74 (s, 1H), 7.80 (d, 1H) , 7.88 (d, 1H), 7.92 (d, 1H);
ES-MS (70 eV): m / z = 350 (M ⁺ )

Example 3 (Synthesis of Compound of Example of the Present Invention Represented by Formula (92) of the above Specific Example)
(Step 5) Synthesis of intermediate compound represented by following formula (e) In this step, an intermediate compound represented by the following formula (e) was synthesized according to the following reaction formula.

  Specifically, under a nitrogen atmosphere, 2.2 parts (90 mmol) of magnesium, 5.4 parts (62 mmol) of lithium bromide, and 20 ml of tetrahydrofuran were mixed, and 14 parts (75 mmol) of cyclohexylethyl bromide was added dropwise thereto, A Grignard reagent (cyclohexylethylmagnesium bromide) was prepared by heating at 60 ° C. for 2 hours. This Grignard reagent was charged with 7.3 parts (31 mmol) of 2-bromo-6-methoxynaphthalene and 0.85 parts (1.6 mmol) of a [1,3-bis (diphenylphosphino) propane] nickel (II) chloride complex. After dropwise addition to a solution obtained by dissolving in 150 ml of tetrahydrofuran, the mixture was heated to reflux for 2 hours. The reaction solution was cooled to room temperature and then quenched by adding water to the reaction solution. The organic layer was extracted with chloroform from the reaction solution to which water was added, the solvent (tetrahydrofuran and chloroform) was distilled off, and then the impurities were removed under reduced pressure while heating to 170 ° C. to obtain an intermediate represented by the above formula (e). Body compound 5.5 parts (yield 69%) was obtained as a white solid.

The measurement results of the proton nuclear magnetic resonance spectrum of the intermediate compound represented by the above formula (e) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.89-1.02 (m, 2H), 1.10-1.35 (m, 4H), 1.54-1.83 (m, 7H) ), 2.74 (t, 2H), 3.91 (s, 3H), 7.08-7.13 (m, 2H), 7.29 (dd, 1H), 7.53 (s, 1H) , 7.64-7.68 (m, 2H)

(Step 6) Synthesis of Intermediate Compound Represented by Formula (f) below In this step, the intermediate compound represented by the following formula (f) is converted from the intermediate compound represented by the following formula (e) according to the following reaction formula. Body compounds were synthesized.

  Specifically, in a nitrogen atmosphere, a solution obtained by dissolving 3.9 parts (15 mmol) of the intermediate compound represented by the formula (e) obtained in Step 5 in 200 ml of tetrahydrofuran was cooled to −40 ° C. Then, 14 ml (23 mmol) of a 1.6 M hexane solution of n-butyllithium was dropped. The reaction solution was stirred at room temperature for 1 hour, then cooled to 0 ° C., 2.2 parts (23 mmol) of dimethyl disulfide was added dropwise, and the mixture was stirred at room temperature for 17.5 hours. Thereafter, the reaction solution was quenched by adding water. The organic layer was extracted from the reaction solution to which water was added with methylene chloride, the organic layer was concentrated under reduced pressure to remove the organic solvent (tetrahydrofuran, hexane, and methylene chloride), and the resulting residue was subjected to column chromatography (silica gel). , Solvent chloroform) to obtain 2.9 parts (yield 62%) of an intermediate compound represented by the following formula (f) as a white solid.

The measurement results of the proton nuclear magnetic resonance spectrum of the intermediate compound represented by the formula (f) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.90-1.02 (m, 2H), 1.12-1.35 (m, 4H), 1.55-1.82 (m, 7H) ), 2.55 (s, 3H), 2.74 (t, 2H), 3.99 (s, 3H), 7.05 (s, 1H), 7.35 (dd, 1H), 7.41 (S, 1H), 7.48 (s, 1H), 7.62 (d, 1H)

(Step 7) Synthesis of Intermediate Compound Represented by the following Formula (g) In this step, the intermediate compound represented by the following formula (g) is converted from the intermediate compound represented by the following formula (f) according to the following reaction formula. Body compounds were synthesized.

  Specifically, a solution obtained by dissolving 2.6 parts (8.3 mmol) of the intermediate compound represented by the formula (f) obtained in Step 6 in 25 ml of methylene chloride under a nitrogen atmosphere is −78. The mixture was cooled to 0 ° C., and 4.3 ml (17 mmol) of 4 M boron chloride bromide solution was added dropwise thereto. Thereafter, the reaction solution was stirred at room temperature for 19 hours, and then quenched by adding water to the reaction solution. After extracting the organic layer from the reaction solution to which water has been added with methylene chloride, the organic layer is concentrated under reduced pressure to remove the organic solvent (methylene chloride), and the resulting residue is subjected to column chromatography (filler: silica gel, development). Purification with a solvent (chloroform) gave 2.4 parts (yield 96%) of an intermediate compound represented by the following formula (g) as a white solid.

The measurement result of the proton nuclear magnetic resonance spectrum of the intermediate compound represented by the formula (g) was as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.89-1.02 (m, 2H), 1.10-1.35 (m, 4H), 1.55-1.83 (m, 7H) ), 2.42 (s, 3H), 2.73 (t, 2H), 6.56 (s, 1H), 7.27-7.29 (m, 2H), 7.48 (s, 1H) , 7.60 (d, 1H), 7.94 (s, 1H)

  (Step 8) Synthesis of an intermediate compound represented by the following formula (h)

In this step, an intermediate compound represented by the following formula (h) was synthesized from an intermediate compound represented by the following formula (g) according to the following reaction formula.

  Specifically, 2.2 parts (7.3 mmol) of the intermediate compound represented by the formula (g) obtained in Step 7 and 2.2 parts (22 mmol) of triethylamine were dissolved in 25 ml of methylene chloride under a nitrogen atmosphere. The resulting solution was cooled to 0 ° C., and 4.2 parts (15 mmol) of trifluoromethanesulfonic anhydride was added dropwise to the solution, followed by stirring at room temperature for 17 hours. The reaction solution was quenched with water. Then, after extracting the organic layer from the reaction solution with methylene chloride, the organic layer was concentrated under reduced pressure to remove the organic solvent (methylene chloride) and triethylamine, and the resulting residue was subjected to column chromatography (filler: silica gel, development). Purification with a solvent (chloroform) gave 3.2 parts (yield 94%) of an intermediate compound represented by the following formula (h) as a white solid.

The measurement result of the proton nuclear magnetic resonance spectrum of the intermediate compound represented by the formula (h) was as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.9-1.03 (m, 2H), 1.13-1.35 (m, 4H), 1.56-1.83 (m, 7H) ), 2.60 (s, 3H), 2.78 (t, 2H), 7.33-7.37 (m, 1H), 7.57 (s, 1H), 7.63 (s, 1H) , 7.67 (s, 1H), 7.68 (s, 1H), 7.72 (d, 1H)

(Step 9) Synthesis of Intermediate Compound Represented by Formula (i) below In this step, an intermediate represented by the following formula (i) is converted from an intermediate compound represented by the following formula (h) according to the following reaction formula. Body compounds were synthesized.

Specifically, in a nitrogen atmosphere, 0.61 part (1.4 mmol) of the intermediate compound represented by the formula (h) obtained in Step 8 and a tetrakis (triphenylphosphine) palladium (0) complex 0.081. Parts (0.07 mmol), 0.24 parts (5.6 mmol) of lithium chloride, 1.35 parts (4.2 mmol) of 3-methylthio-2-naphthyl trifluoromethanesulfonate, and trans-1,2-bis (tributyl ester). Nyl) ethylene (1.7 parts, 2.8 mmol) was added to N, N-dimethylformamide (30 ml) and reacted at 100 ° C. for 24 hours. The reaction solution was cooled to room temperature and quenched by adding water. Then, the organic layer was extracted with toluene from the reaction solution to which water was added. The organic solvent (N, N-dimethylformamide and toluene) was removed by concentrating the organic layer under reduced pressure, and the resulting residue was purified by column chromatography (filler: silica gel, developing solvent: chloroform), and the following formula ( 0.15 parts (yield 22%) of the intermediate compound represented by i) was obtained as a yellow solid.

The measurement results of the proton nuclear magnetic resonance spectrum and ES-MS spectrum of the intermediate compound represented by the formula (i) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.92 to 1.03 (m, 2H), 1.15 to 1.37 (m, 4H), 1.57 to 1.85 (m, 7H) ), 2.59 (s, 6H), 2.78 (t, 2H), 7.27-7.30 (m, 1H), 7.41-7.48 (m, 2H), 7.52 ( s, 1H), 7.59-7.68 (m, 2H), 7.72-7.80 (m, 2H), 7.82-7.92 (m, 1H), 8.05-8. 07 (m, 1H), 8.10 (s, 1H);
ES-MS (70 eV): m / z = 482 (M ⁺ )

(Step 10) Synthesis of organic compound represented by formula (92) In this step, an organic compound represented by formula (92) is synthesized from an intermediate compound represented by formula (i) below according to the following reaction formula. did.

  Specifically, in a nitrogen atmosphere, 0.14 part (0.29 mmol) of the intermediate compound represented by the formula (i) obtained in Step 9, 2.2 part (9.3 mmol) of iodine, and 9 ml of chloroform The mixture was heated to reflux at 100 ° C. for 7 hours. After the mixture was cooled to room temperature, iodine was quenched with aqueous sodium bisulfite. Thereafter, the organic layer was separated from the mixture, and the organic solvent (chloroform) was removed from the organic layer under reduced pressure to obtain a solid. The obtained solid was purified by sublimation twice to obtain 95 mg (yield 73%) of an organic compound represented by the formula (92) as a yellow solid.

The measurement results of the ES-MS spectrum of the compound represented by the formula (92) were as follows.
ES-MS (70 eV): m / z = 450 (M ⁺ )

[Example 4] (Synthesis of an organic compound of an example of the present invention represented by the formula (68) of the above specific example)
(Step 11) Synthesis of Intermediate Compound Represented by Formula (j) below In this step, an intermediate compound represented by formula (j) below was synthesized according to the following reaction formula.

  Specifically, 1.1 parts (3.2 mmol) of the organic compound represented by the above formula (20) obtained in the same manner as in Example 2 was dissolved in 100 ml of methylene chloride to obtain a solution, and then an ice bath A solution prepared by dissolving 0.6 part (3.5 mmol) of bromine in 10 ml of methylene chloride was added dropwise to the solution cooled in step 1 to obtain a reaction solution. The reaction solution was returned to room temperature and stirred at room temperature for 15 hours, and then quenched by adding an aqueous sodium hydrogen sulfite solution. The reaction solution was concentrated to precipitate a solid, and the precipitated solid was collected by filtration. The solid collected by filtration was washed with water and methanol to obtain a crude product. The crude product was recrystallized with a mixed solvent of chloroform and ethanol to obtain 0.6 parts (yield 45%) of an intermediate compound represented by the above formula (j) as a white solid.

The measurement results of the proton nuclear magnetic resonance spectrum and ES-MS spectrum of the intermediate compound represented by the formula (j) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.9-1.02 (m, 2H), 1.13-1.36 (m, 4H), 1.52-1.83 (m, 7H) ), 2.78 (t, 3H), 7.29 (dd, 1H), 7.55 (dd, 1H), 7.72 (s, 1H), 7.72 (d, 1H), 7.78 (D, 1H), 8.04 (d, 1H)
ES-MS (70 eV): m / z = 428 (M ⁺ )

(Step 12) Synthesis of organic compound represented by formula (68) In this step, the intermediate compound represented by formula (j) obtained in step 11 is represented by formula (68) according to the following reaction formula. An organic compound was synthesized.

  Specifically, in a nitrogen atmosphere, 0.54 part (1.3 mmol) of the intermediate compound represented by the above formula (j) obtained in Step 11, 0.18 part (1.5 mmol) of phenylboronic acid, A mixture of 0.35 parts (2.5 mmol) of potassium carbonate, 0.073 parts (0.06 mmol) of tetrakis (triphenylphosphine) palladium (0) complex, 50 ml of N, N-dimethylformamide, and 2.5 ml of water was added. The mixture was heated to 0 ° C. and stirred for 16 hours. The reaction solution was cooled to room temperature, added to 100 ml of 1M aqueous hydrochloric acid solution to precipitate a solid, and the precipitated solid was collected by filtration. The solid collected by filtration was washed with water and methanol to obtain a crude product. The crude product was recrystallized with a mixed solvent of chloroform and ethanol to obtain 0.4 part (yield 75%) of an organic compound represented by the above formula (68) as a white solid.

The measurement results of the proton nuclear magnetic resonance spectrum and ES-MS spectrum of the organic compound represented by the formula (68) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.9-1.02 (m, 2H), 1.11-1.37 (m, 4H), 1.52-1.84 (m, 7H) ), 2.78 (t, 2H), 7.29 (dd, 1H), 7.35-7.41 (m, 1H), 7.46-7.51 (m, 2H), 7.67- 7.71 (m, 2H), 7.69 (d, 1H), 7.73 (d, 1H), 7.79 (d, 1H), 7.92 (d, 1H), 8.11 (d , 1H)
ES-MS (70 eV): m / z = 426 (M ⁺ )

[Example 5] (Synthesis of an organic compound of an example of the present invention represented by the formula (32) in the above specific example)
(Step 13) Synthesis of intermediate compound represented by following formula (k) In this step, an intermediate compound represented by the following formula (k) was synthesized according to the following reaction formula.

  Specifically, it was obtained by dissolving 6.0 parts (25.0 mmol) of [1] benzothieno [3,2-b] [1] benzothiophene in 20 ml of methylene chloride at −20 ° C. in a nitrogen atmosphere. To the solution, 12.3 parts (92.5 mmol) of aluminum chloride was added to obtain a reaction solution. The reaction solution was cooled to −70 ° C., 20.8 parts (110 mmol) of cyclohexanebutanoyl chloride was added dropwise to the reaction solution, stirred for 1.5 hours at −70 ° C., and then quenched by adding 210 ml of water. The reaction solution to which water was added was returned to room temperature to precipitate a solid, and the precipitated solid was collected by filtration. The solid collected by filtration was washed with water and methanol to obtain a crude product. The crude product was recrystallized with a mixed solvent of toluene and ethanol to obtain 4.5 parts (yield 46%) of an intermediate compound represented by the above formula (k) as a white solid.

The measurement results of the ES-MS spectrum of the intermediate compound represented by the above formula (k) were as follows.
ES-MS (70 eV): m / z = 392 (M ⁺ )

(Step 14) Synthesis of organic compound represented by formula (32) In this step, the intermediate compound represented by formula (k) obtained in step 13 is represented by formula (32) according to the following reaction formula. An organic compound was synthesized.

  Specifically, 3.6 parts (9.1 mmol) of the intermediate compound represented by the above formula (k) obtained in Step 13 in a nitrogen atmosphere, 1.39 parts (25.0 mmol) of potassium hydroxide, 210 ml of diethylene glycol and 13.9 ml (116 mmol) of hydrazine monohydrate were mixed to obtain a mixture. The resulting mixture was heated to 100 ° C. and stirred for 1 hour, then heated to 210 ° C. and stirred for 5 hours. The mixture was then cooled to room temperature and the solid was collected by filtration. The obtained solid was washed with water and methanol, and then purified by sublimation twice to obtain 2.55 parts (yield 74%) of the organic compound represented by the above formula (32) as a white solid.

The measurement results of the proton nuclear magnetic resonance spectrum and ES-MS spectrum of the organic compound represented by the above formula (32) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.78-0.91 (m, 2H), 1.08-1.44 (m, 6H), 1.60-1.73 (m, 6H) ), 2.76 (t, 3H), 7.28 (dd, 1H), 7.36-7.47 (m, 2H), 7.72 (d, 1H), 7.79 (d, 1H) , 7.86 (d, 1H), 7.91 (d, 1H)
ES-MS (70 eV): m / z = 378 (M ⁺ )

(Evaluation of Solubility and Heat Resistance of Organic Compound of the Present Invention and Comparative Organic Compound)
Organic compounds represented by Formula (14), Formula (20), Formula (92), Formula (68), and Formula (32) according to an example of the present invention obtained in Examples 1 to 5, and AlkylBTBT Comparative organic compound 1 (2,7-dioctyl [1] benzothieno [3, 2-b] [1] benzothiophene; Patent Document 4 and Non-Patent Document 3) having the structure described in Table 1 below, which is one type And a comparative organic compound 2 (2,9-didecyldinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene), which is a kind of Alkyl DNTT; And the heat resistance was evaluated. The solubility was measured using chloroform as a solvent at room temperature or heated to 50 ° C. The heat resistance is measured by measuring the phase transition temperature using a differential scanning calorimeter (model name “DSC7020” manufactured by SII NanoTechnology Co., Ltd. (currently Hitachi High-Tech Science Co., Ltd.)). The temperature at which the phase transition occurred in the region was evaluated as heat resistance. The evaluation results of solubility and heat resistance are shown in Table 1.

  From the results of Table 1, the organic compounds represented by Formula (14), Formula (20), Formula (92), Formula (68), and Formula (32) according to an example of the present invention have high solubility. At the same time, it is clear that it has higher heat resistance than known organic semiconductor compounds such as AlkylBTBT (Comparative Organic Compound 1) and AlkyLDNTT (Comparative Organic Compound 2).

  Next, the organic transistor created using the organic compound represented by Formula (20), Formula (92), Formula (68), and Formula (32) obtained in Examples 2-5 was evaluated.

[Example 6] (Production and evaluation of organic transistor 10B (see FIG. 1B)) using the organic compound represented by formula (20) obtained in Example 2)
An n-doped silicon wafer with a 200 nm SiO ₂ thermal oxide film (insulator layer 4 in FIG. 1B) treated with octadecyltrichlorosilane (surface resistance 0.02 Ω · cm or less, gate electrode 5 in FIG. 1B) And also the substrate 6) were placed in a vacuum vapor deposition apparatus and evacuated until the degree of vacuum in the apparatus became 1.0 × 10 ⁻³ Pa or less. On this n-doped silicon wafer with SiO ₂ thermal oxide film, it is represented by the formula (20) obtained in Example 2 under the condition of a substrate temperature (deposition temperature) of about 60 ° C. by resistance heating vapor deposition. The organic compound was deposited to a thickness of 50 nm at a deposition rate of 1 kg / sec to form an organic semiconductor layer (organic semiconductor layer 2 in FIG. 1B).

Next, a shadow mask for electrode preparation is attached on this organic semiconductor layer, placed in a vacuum deposition apparatus, evacuated until the degree of vacuum in the apparatus is 1.0 × 10 ⁻⁴ Pa or less, and by resistance heating deposition A gold electrode, that is, a source electrode (source electrode 1 in FIG. 1B) and a drain electrode (drain electrode 3 in FIG. 1B) are vapor-deposited to a thickness of 80 nm, and a top contact-bottom gate type is used. A field effect organic transistor (channel length 40 μm, channel width 1.5 mm) according to an example of the present invention was obtained.

  The obtained organic transistor was placed in a prober, and semiconductor characteristics were measured using a semiconductor parameter analyzer (model name “4200SCS”, manufactured by TFF Keithley Instruments).

FIG. 4 is a graph showing the semiconductor characteristics of the organic transistor obtained in this example. The drain voltage is fixed at −60 V which is a saturation region, the gate voltage is scanned from 20 V to −60 V, and the drain current−gate. The results of measuring voltage (transfer) characteristics are shown. Specifically, the horizontal axis represents the gate voltage (Vg / V), the vertical axis represents the drain current (−Id / A; left end scale), and the square root (| Id | ^1/2 / A) of the absolute value of the drain current. FIG. 18 is a graph showing the semiconductor characteristics of the organic transistor produced in Example 6 taking ^1/2 .

  From the measurement results shown in FIG. 4, the threshold voltage, the carrier mobility, and the on / off ratio were obtained as numerical values indicating the semiconductor characteristics of the organic transistor prepared in Example 6. The method for obtaining each numerical value indicating the semiconductor characteristics is as follows.

<Threshold voltage>
In the curve showing the relationship between the gate voltage (Vg / V) and the square root of the absolute value of the drain current (| Id | ^1/2 / A ^1/2 ) shown in FIG. 4, the slope changes greatly in the vicinity of 0V. doing. In the curve showing the relationship between the gate voltage (Vg / V) and the square root of the absolute value of the drain current (| Id | ^1/2 / A ^1/2 ) shown in FIG. 4, the slope of the curve is substantially constant. 4 (approx. -60 to -30 V in the measurement result illustrated in FIG. 4), and a straight line obtained by extrapolating the approximate line (indicated by a broken line in FIG. 4) intersects the X axis (Id = 0A). The voltage value at the point) was obtained as the threshold voltage.

<Carrier mobility>
Since the drain current-gate voltage characteristics in the saturation region are expressed by the following formula (a), the carrier mobility was calculated using the formula (a).

Id = (1/2) W · μ · Cp (Vg−Vth) ² / L (a)
Where Id: drain current
W: Channel width
μ: Carrier mobility
Cp: Capacitance of the insulator layer 4
Vg: gate voltage Vth: threshold voltage
L: Channel length

In this measurement, the channel width W is 1500 μm, the capacitance of the insulator layer 4 is 17.3 × 10 ⁻⁹ F, and the channel length L is 40 μm. The gate voltage Vg was set to −60 V that becomes a saturation region.

<On / off ratio>
The on / off ratio was calculated as a ratio between the maximum value of the drain current (current value when Vd = −60 V) and the minimum value of the drain current within the measurement range of the drain current-gate voltage characteristics.

From the above measurement and calculation, the organic transistor obtained in Example 6 has a carrier mobility of 3.7 × 10 ⁻² cm ² / Vs, a threshold voltage of −18 V, and an on / off ratio I _on / I. _off was 10 ^6. The carrier mobility, threshold voltage, and on / off ratio were calculated in the same manner for Examples 7 to 9.

[Example 7] (Production and evaluation of organic transistor 10B (see FIG. 1B) using the organic compound represented by formula (92) obtained in Example 3)
In place of the organic compound represented by the formula (20) obtained in Example 2, the organic compound represented by the formula (92) obtained in Example 3 was used, and the substrate temperature at the time of vapor deposition of the organic compound A field effect type field effect transistor according to an example of the present invention (channel length: 40 μm, channel width: 1.5 mm), except that (deposition temperature) was changed from about 60 ° C. to about 200 ° C. Got.

The drain current-gate voltage (transfer) characteristics of the obtained organic transistor were measured in the same manner as in Example 6. The measurement results are shown in FIG. From the drain current-gate voltage curve shown in FIG. 5, the threshold voltage, carrier mobility, and on / off ratio of the organic transistor of this example were determined in the same manner as in Example 6 (approximation for determining the threshold voltage). The line is indicated by a broken line in FIG. 5). As a result, the organic transistor of this example had a carrier mobility of 2.6 cm ² / Vs, a threshold voltage of −21 V, and an on / off ratio I _on / I _off of 10 ⁸ .

[Example 8] (Production and evaluation of organic transistor 10B (see FIG. 1B)) using the organic compound represented by formula (68) obtained in Example 4)
The same procedure as in Example 6 was used except that the organic compound represented by formula (68) obtained in Example 4 was used in place of the organic compound represented by formula (20) obtained in Example 2. Thus, a field effect type field effect transistor (channel length: 40 μm, channel width: 1.5 mm) according to an example of the present invention was obtained.

The drain current-gate voltage (transfer) characteristics of the obtained organic transistor were measured in the same manner as in Example 6. The measurement results are shown in FIG. From the drain current-gate voltage curve shown in FIG. 6, the threshold voltage, carrier mobility, and on / off ratio of the organic transistor of this example were obtained in the same manner as in Example 6 (approximation for obtaining the threshold voltage). The line is shown as a broken line in FIG. 6). As a result, the organic transistor of this example had a carrier mobility of 0.22 cm ² / Vs, a threshold voltage of −23 V, and an on / off ratio I _on / I _off of 10 ⁷ .

[Example 9] (Production and evaluation of organic transistor 10B (see FIG. 1B) using the organic compound represented by formula (32) obtained in Example 5)
The same procedure as in Example 6 was performed except that the organic compound represented by the formula (32) obtained in Example 5 was used instead of the organic compound represented by the formula (20) obtained in Example 2. Thus, a field effect type field effect transistor (channel length: 40 μm, channel width: 1.5 mm) according to an example of the present invention was obtained.

The drain current-gate voltage (transfer) characteristics of the obtained organic transistor were measured in the same manner as in Example 6. The measurement results are shown in FIG. From the drain current-gate voltage curve shown in FIG. 7, the threshold voltage, carrier mobility, and on / off ratio of the organic transistor of this example were obtained in the same manner as in Example 6 (approximation for obtaining the threshold voltage). The line is indicated by a broken line in FIG. 7). As a result, the organic transistor of this example has a carrier mobility of 1.1 × 10 ⁻³ cm ² / Vs, a threshold voltage of −25 V, and an on / off ratio I _on / I _off of 10 ⁵ . there were.

  As described above in detail, the organic compound (organic semiconductor material) according to the present invention has high heat resistance and solubility, and can be used as a thin film material for forming an organic semiconductor layer of an organic transistor. Since the organic compound of the present invention has a high carrier mobility as a material of the organic semiconductor layer, the organic transistor using the organic compound of the present invention has a high response speed (driving speed) and performance as a transistor. It can be used as an organic thin film light emitting transistor capable of emitting light.

  Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.

  The organic compound according to the present invention can be suitably used as an organic semiconductor material, as a material for an organic semiconductor device such as an organic transistor. In addition to organic transistors, the organic semiconductor device according to the present invention is also used in fields such as organic solar cell devices such as diodes, capacitors, photoelectric conversion devices, and dye-sensitized solar cell devices, organic EL devices, and organic semiconductor laser devices. It is possible to use.

DESCRIPTION OF SYMBOLS 1 Source electrode 2 Organic-semiconductor layer 3 Drain electrode 4 Insulator layer 5 Gate electrode 6 Substrate 7 Protective layer 10A-10F Organic transistor 20 Organic solar cell device 21 Substrate 22 Anode 23 Power generation layer 24 Cathode 231 P-type layer 232 N-type layer 233 Buffer layer

  The present invention can be implemented in various other forms without departing from the spirit or main features thereof. For this reason, the above-described embodiment is merely an example in all respects and should not be interpreted in a limited manner. The scope of the present invention is indicated by the claims, and is not restricted by the text of the specification. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.

This application claims a priority based on Japanese Patent Application No. 2014-246518 filed in Japan on December 5, 2014. This specification includes the content described in the specification and / or drawing of the Japan patent application 2014-246518 which is the foundation of the priority of this application. All publications, patents and patent applications cited herein are incorporated herein by reference in their entirety.

Claims (11)

Following formula (1)
(In the formula (1), A represents [1] benzothieno [3,2-b] [1] benzothiophene or dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b]. This represents a divalent linking group obtained by removing two hydrogen atoms from thiophene, and B represents the following formula (2)
(In the formula (2), n represents an integer of 1 to 10, and Z represents a cyclic aliphatic hydrocarbon residue having 3 to 10 carbon atoms having an alkyl group having 1 to 10 carbon atoms and / or a phenyl group as a substituent. Group or an unsubstituted cyclic aliphatic hydrocarbon residue having 3 to 10 carbon atoms)
And D represents a hydrogen atom, an alkyl group, an aromatic residue, or a heterocyclic residue)
An organic compound represented by The organic compound according to claim 1,
An organic compound in which n is an integer of 1 to 4. The organic compound according to claim 1, wherein
Z is a cyclic aliphatic hydrocarbon residue having 5 to 8 carbon atoms having an alkyl group having 1 to 10 carbon atoms and / or a phenyl group as a substituent, or an unsubstituted cyclic aliphatic hydrocarbon having 5 to 8 carbon atoms Organic compounds that are hydrocarbon residues.   The organic-semiconductor material containing the organic compound of any one of Claims 1 thru | or 3.   The transistor material containing the organic compound of any one of Claims 1 thru | or 3.   The ink for semiconductor device manufacture containing the organic-semiconductor material of Claim 4, or the transistor material of Claim 5.   The organic thin film containing the organic compound of any one of Claims 1 thru | or 3. The organic thin film according to claim 7,
An organic thin film formed by a coating method.   The organic-semiconductor device containing the organic thin film of Claim 7 or 8.   The organic transistor containing the organic thin film of Claim 7 or 8. The manufacturing method of the organic-semiconductor device including forming the semiconductor layer by apply | coating the ink for semiconductor device preparation of Claim 6 on a board | substrate, and making it dry.