TW201247676A - Method for producing dianthra [2,3-b:2',3'-f] thieno [3,2-b] thiophen and application thereof - Google Patents

Abstract

A dianthra[2,3-b:2',3'-f]thieno[3,2-b]thiophene is produced by subjecting a specific anthracene derivative to sulfur methylation, reacting the anthracene derivative with a specific tin compound, and then subjecting the reacted anthracene and tin compound to cyclization.

Description

201247676 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a novel process for producing bis-[2,3-b: 2',3'-f]thieno[3,2-b]thiophene. Furthermore, the present invention relates to an organic electronic device to which the compound is applied. [Prior Art] In recent years, attention to organic electronic devices has been increasing year by year. This feature can be exemplified by a flexible structure, a large area, and an inexpensive and fast printing method in the device manufacturing process. The organic photoelectric conversion element, the organic EL element, the organic transistor element, and the like are exemplified as the device. The organic photoelectric conversion element is developed as an organic thin film solar cell, a photo sensor, and an image sensor. In addition, the organic EL device is widely used in the display of mobile phones to τν, etc., and the organic transistor device is developed as an erasable device or a cheap 1C. The development of the materials that make up the device is extremely important. Therefore, a large number of materials have been explored in various fields, but sufficient performance has not yet been achieved, and development of materials useful for various devices has been actively carried out. By using an organic material, it can be fabricated in a low temperature process that does not require high temperature processing, and the range of materials that can be used is expanded. As a result, the production of a device that is flexible, lightweight, and susceptible to gamma can be gradually realized. Further, in the production steps of the respective devices, it is also possible to use a coating method in which a semiconductor material is dissolved, a printing method based on inkjet, etc., m-5-201247676, and the like, and it is possible to manufacture a large area at a low cost. The possibility of the device. Further, 'the compound for organic semiconductor materials has many types to choose from' and it is expected that the characteristics can be utilized and found to have a function that has not existed until now. The use of organic compounds as examples of semiconductor materials has been discussed so far. For example, it is known to use pentacene, thiophene or oligomers or polymers thereof as having a hole transport. Material of characteristics (refer to patent document) and patent document 2). Pentacene is an acene-based aromatic hydrocarbon in which five benzene rings are linearly condensed, and the field effect transistor which is used as a semiconductor material exhibits a charge comparable to that of a practical amorphous ruthenium. Mobility (carrier mobility). However, the use of a field-effect transistor of pentacene causes deterioration due to the environment, and stability still has problems. Further, when the thiophene-based compound is used, the same problem also exists, and it is still not considered to be a material having high practicality. In recent years, dinaphthyl [2,3-b: 2',3,-f]thieno[3,2-b]thiophene (DNTT), which is stable in the atmosphere and exhibits high carrier mobility, has been It has been developed and is attracting attention (see Patent Document 3 and Non-Patent Document 1). However, 'there is also a strong demand from these markets for these compounds', that is, when applied to display applications such as organic EL, it is necessary to have higher carrier mobility, and when applied to solar cells or light perception. When it is used for a detector or the like, it must have characteristic photoelectric conversion energy that can absorb a specific wavelength or the like. Further, in terms of durability, it is also required to develop high-quality and high-performance organic semiconductor materials. A compound of 201247676 which extends π of dinaphthyl [2,3-b: 2',3'-f]thieno[3,2-b]thiophene (DNTT), and is disclosed in Patent Document 3 [3, 2 -b] The thiophene (DATT) method, in order to use the compound, but the manufacturing method is still not industrially applicable, and it is necessary to establish a manufacturing method of the compound which can be applied industrially. [Prior Art Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. Hei-6-177780 (Patent Document 3) Japanese Patent Publication No. 2008-10541 [Patent Document 5] KR2008100982 publication [Patent Document 6] WO02010/098372 publication [Patent Document 7] JP-A-2009-196975 (Patent Document 8) WO02009/009790 publication [ [Patent Document 9] Japanese Laid-Open Patent Publication No. 2010-258214 [Non-Patent Document] [Non-Patent Document 1] J. Am. Chem. Soc., Vol. 129, 2224-2225 (2007) [Summary of the Invention] Solution to Problem) An object of the present invention is to provide a bismuth [2,3-b: 2',3'-f]thiophene 201247676 having a characteristic of a practical semiconductor which exhibits excellent carrier mobility and [3, 2-b] a novel method of producing thiophene, and an organic electronic device having a semiconductor layer formed by the compound. (Means for Solving the Problem) The present inventors have carefully studied to solve the above problems, and have succeeded in developing a simple and efficient synthesis of diterpene [2,3-b : 2', 3'- ^New method for the production of thieno[3,2-15]thiophene. Further, it has been found that the compound has characteristics as a practical semiconductor which exhibits excellent carrier mobility. Thereby, a semiconductor material composed of the compound and an organic electronic device having a semiconductor layer formed by the compound can be provided, and thus the present invention has been completed. That is, the present invention is a method for producing diterpene [2,3-b: 2,3,·f]thieno[3,2-b]thiophene, which is characterized by comprising: a step of reacting a compound represented by the formula (2) with a dimethyl sulfide to obtain a compound represented by the formula (2), and reacting the compound represented by the formula (2) with a tin compound represented by the formula (3) to obtain a compound represented by the formula (4) And a step of cyclizing the compound represented by the formula (4) to obtain diterpene [2,3_b : 2 ',3 ' - f ]thieno[3,2 - b ]thiophene;

[Chemical 2] (1) 201247676 [Chemical 3]

【化4】

(wherein R1 and R2 represent a substituent, and Me represents a methyl group). [2] An organic semiconductor material containing diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene obtained by the method of Π] [3] An ink for producing a semiconductor device, which comprises diterpene [2,3_b: 2',3'-f]thieno[3,2-b]thiophene obtained by the method of Π]. [4] An organic semiconductor thin film comprising diterpene [2,3-b ·· 2',3'-f]thieno[3,2-b]thiophene obtained by the method of [1]. [5] An organic electronic device which has the organic semiconductor thin film layer of [4]. [6] The organic electronic device of [5] is a photoelectric conversion element, an organic EL element, an organic semiconductor laser element, a liquid crystal display element or a thin film transistor element. [7] The organic electronic device as in [5] is a solar cell. [8] An organic electronic device such as [5], which is a light sensor. [9] A method for producing an organic electronic device according to [5], which comprises: a diterpene [2,3_b: 2,,3,_f] thiophene-9-201247676 which is obtained by the method of [1] A step of forming a semiconductor layer composed of [3,2-b]thiophene on a substrate. [10] The method of producing an organic electronic device according to [9], wherein the semiconductor layer is formed by an evaporation method. [11] The method of producing an organic electronic device according to [9], wherein the semiconductor layer is formed by coating the ink for semiconductor device production of [3]. Advantageous Effects of Invention: In the production method of the present invention, an intermediate of dioxonium [2,3-b: 2',3'-f]thieno[3,2-b]thiophene can be produced with high selectivity, and becomes Good industrial yield is a useful manufacturing process for diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene. Further, when diterpene [2,3-b:2',3'-f]pyrano[3,2-b]thiophene produced by the process is used in an organic electronic device, one can be provided with An organic electronic device exhibiting superior performance compared to an organic semiconductor material. [Embodiment] Hereinafter, the present invention will be described in detail. The present invention relates to a process for producing diterpene [2,3-b: 2,3 '-f]thieno[3,2 - b ]thiophene. Further, it relates to an organic electronic device obtained by forming a semiconductor layer using a fluorene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene as a semiconductor material. The following 3 sheep detail the production method of diterpene [2,3-6:2',3,-deutero[3,2-15]thiophene. According to the production method of the present invention, the compound can be produced very efficiently. The reaction formula of the present invention is as follows. The reaction formulas (1), (2), and (3) are explained in the following order. -10- 201247676 【化5】

First, the diterpene [2,3-b: 2',3'-f] thiophene is described. As the starting material of the reaction formula (1), the compound (1), the R1 group, will be used as the starting material. , pentafluorophenyl, trifluorofluorohexyl S02-based, 4-trifluoromethylphenyl S02-based, atom of aryl group substituted with a fluorine atom, trifluoromethyl, perfluorohexyl, 4-trifluoromethylbenzene The pentafluorophenyl S02 group of the substituted aryl group. More methyl, trifluoromethyl S02 groups. These compounds are obtained from commercial products. Next, the reaction formula (1) will be described in detail. The reaction is characterized in that SME is carried out using the position of the dimethyl disulfide (Me2S2) at the 2-position and the oxygen-bonded starting material. In order to develop this reaction, the present invention is a metallized, alkaline earth metal reagent formed by detachment of hydrogen at the 3-position, a reaction solvent, and a reaction temperature of 11 - reaction formula (1) reaction formula (2) reaction formula (3) [3,2-b] thiophene oxime (1). Preferably, a methyl group, a methyl group of all hydrogen atoms, a group of S02 groups, and all hydrogen atoms are fluorinated: preferably, R1 is exemplified by (1), and many of them may be a static reaction, which is highly selective. The three compounds of the compound (1) were investigated for the SME of the compound (1) at a high selectivity by using a base (alkali metal reagent degree, and operation step 201247676') with high selectivity to dimethyl disulfide. Manufacturing method.

In the reaction formula (1), it is preferable to use an alkali metal reagent lithium reagent, a sodium reagent, a potassium reagent, an alkaline earth metal reagent magnesium reagent, and a calcium reagent. Specifically, methyllithium, n-butyllithium, tertiary butyllithium, phenyllithium, vaporized methylmagnesium, butylmagnesium chloride or the like can be used. It is particularly preferred to use a stable and strong base butyl lithium. The amount of the base used is preferably 0.5 mol or more and 10 mol% or less based on 1 mol of the compound (1). The compound (1) is added to the reaction solution of the base, and a base may be added in the range of the above amount. By adding the base in such a two-stage manner, the detachment of the hydrogen atom at the 3-position of the compound (丨) can be carried out smoothly. Further, in the method for producing a compound of the present embodiment, it is also possible to add an inspectable compound (additive) together with an alkali metal reagent for the purpose of performing spike determination of a lithium reagent. The basic compound may, for example, be N, N, N'-trimethylethylenediamine, dimethylamine, diisopropylamine or morpholine. The reaction is preferably carried out under a nitrogen purge and under a stream of dry nitrogen. The reaction temperature at the time of reacting the above compound (1) with a base is preferably in the range of -100 ° C to 30 ° C, particularly preferably -30 ° C to 10 t · When the reaction is carried out, 'any solvent can be used' is preferably An ether solvent, an aliphatic solvent, or an aromatic solvent. Further, it is preferred to use a solvent such that -12-201247676 is used to dry the water. Examples of the ether solvent used in the reaction include tetrahydrofuran (THF), diethyl ether, dimethoxyethane, and dioxane. Examples of the aliphatic solvent include n-pentane, n-hexane, and n-heptane. Examples of the aromatic solvent include toluene and xylene. The amount of the dimethyl disulfide to be used in the reaction is preferably 〇5 mol or more and 10 mol or less based on 1 mol of the compound (1). When the compound (2) obtained above is purified, the purification method is not particularly limited, and a generally known purification method can be used depending on the physical properties of the compound. Specifically, it can be purified by recrystallization, column chromatography, or the like. Next, a compound which reacts with the compound (2) in the reaction formula (2) will be described.

In the formula (3) as a tin compound, R2 represents an alkyl group. The alkyl group may be a linear or branched alkyl group having a carbon number of from 1 to 8, preferably from 1 to 4, particularly preferably 4. Here, specific examples of the linear alkyl group include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, and a n-hexyl group. Specific examples of the branched alkyl group include a C3-C6 saturated branched alkyl group such as an isopropyl group, an isobutyl group, a tertiary butyl group, an isopentyl group or an isohexyl group. Preferably, the n-butyl group is easily obtained. -13-201247676 The following shows a specific example of the tin compound represented by the formula (3), but the present invention is not limited thereto. 【化8】

[Table 1] Compound No. R2 (3)-01 Me (3)-02 Et (3)-03 n-Pr (3)-04 r-Pr (3)-05 n-Bu (3)-06 hBu (3)-07 t-Bu The compound (compound (4)) produced by the reaction formula (2) is trans-1,2-bis(3-methylthioindol-2-yl)ethylene. In the prior reaction described in Patent Document 3 and Non-Patent Document 1, the synthesis of the aldehyde compound for synthesizing the raw material of the compound (4) is very difficult to carry out. However, the reaction of the reaction formula (2) of the present invention is a novel reaction. The compound (2) having two molecules having a MeS group at the 3-position is reacted with the compound (3) at the same time as the oxygen atom at the 2-position, and the compound (4) can be selectively produced. In general, the reaction of the reaction formula (2) employs a P d compound as a catalyst, but p d is easily attacked by sulfides, and sometimes it loses its activity immediately. Therefore, the inventors of the present invention have found that the oxygen of the compound (2) can be effectively removed as described above, and the catalyst, the reaction solvent, the reaction temperature, and the operation step of reacting with the compound (3) can be found to be capable of The compound (2) is highly selected and has a high yield of 14 to 201247676 to obtain a method for producing the compound (4). Here, R1 of the compound (2) can be used in the reaction of the reaction formula (2), if necessary, to be converted into an optimum substituent. The mixing ratio of the compound (2) to the compound (3) in the reaction of the reaction formula (2) is preferably 1.8 mol or more and 2.5 mol or less based on 1 mol of the compound (3). It is particularly preferably 1.95 mol or more and 2.10 mol or less, more preferably i_95 mol or more and 2.05 mol or less. The catalyst to be used in the reaction may be any Pd or Ni-based catalyst, and may contain at least one catalyst selected from the group consisting of tri-tertiary butylphosphine 'triamantane phosphine and 1,3-double (2, 4, 6). a trimethylphenyl)imidazolium chloride salt, a 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride salt, a 13-diadamantane chloride imidazolium salt, or a mixture thereof; Metal P d, P d / C (aqueous or non-aqueous), bis(triphenylphosphine)palladium dichloride (Pd(PPh3)2Cl2), palladium acetate (Pd(OAc)2), tetra (three) Phenylphosphine)palladium (pd(pph3)4), tetrakis(triphenylphosphine)nickel (Ni(PPh3)4), nickel(II) acetoacetate Ni(acac)2, dichlorination (2,2 '-bipyridine) nickel, bis(triphenylphosphine)nickel dibromide (Ni(PPh3)2Br2), bis(diphenylphosphino)propane nickel (Ni((dppp)Cl2), dichlorination A bis(diphenylphosphino) ethane nickel (Ni((dppe)Ch) or at least one compound of a nickel and palladium catalyst having a ligand composed of a mixture of such a mixture. Preferred catalyst For example, Pd/C (aqueous or non-aqueous), Pd(PPh3)2Cl2, Pd(PPh3)4 can be cited, and it is particularly preferable to cite Pd(PPh3)2Cl2, Pd(PPh3)4. The amount of the catalyst is preferably from 0.01 mol to 0.5 mol per mol of the compound (2). Further compound (2) -15- may be added. 201247676 In the reaction solution of the compound (3) and the catalyst, a catalyst is further added within the above-mentioned amount. Thus, by adding the catalyst to two or more stages, the reaction rate due to the loss of activity of the catalyst may be suppressed. The reaction temperature at the time of reacting the compound (2) with the compound (3) is usually carried out at -10 ° C to 200 ° C. More preferably 4 ° C to 180 ° C, more preferably 80 〇 C ~1 50 t: When the reaction is carried out, it is preferably carried out under an inert gas atmosphere such as nitrogen substitution or argon substitution, or under a dry nitrogen stream, etc. In the reaction, a solvent may be used or not used. It can be used by a user in general organic synthesis, and examples thereof include aromatic compounds such as chlorobenzene, o-dichlorobenzene, bromobenzene, nitrobenzene, toluene, and xylene, or n-hexane and n-heptane. Saturated aliphatic hydrocarbon such as n-pentane; cyclohexane, cycloheptane An alicyclic hydrocarbon such as cyclopentane; n-propyl bromide, n-butyl chloride, n-butyl bromide, dichloromethane, dibromomethane, dichloropropane, dibromopropane, dichloroethane Ethyl bromide, dichloropropane, dibromopropane, dichlorobutane, chloroform, tribromomethane, carbon tetrachloride, carbon tetrabromide, trichloroethane, tetrachloroethane, pentachloroethane, etc. a saturated aliphatic halogenated hydrocarbon; a halogenated cyclic hydrocarbon such as chlorocyclohexane, chlorocyclopentane or bromocyclopentane; ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, and C An ester of propyl acrylate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate or the like; a ketone of acetone, methyl ethyl ketone or methyl isobutyl ketone. These solvents may be used singly or in combination of two or more. Further, when at least one of -16 to 201247676, which uses a high boiling point solvent having a boiling point of 1 〇〇 ° C or more, is used as a reaction solvent, the reaction rate can be greatly increased or the selectivity of the reaction can be increased, which is preferable. A high boiling point solvent having a boiling point of 100 ° C or higher is preferably a guanamine (N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), hydrazine, hydrazine-dimethylformamide (hereinafter abbreviated) Known as DMF), hydrazine, hydrazine-dimethylacetamide (hereinafter abbreviated as DMAc); glycols (ethylene glycol, propylene glycol, polyethylene glycol): and fluorenes (dimethyl hydrazine ( Hereinafter, abbreviated as DMSO)), particularly preferably N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide oxime (4) In the case of the purification method, it is not particularly limited to use a general-known purification method depending on the physical properties of the compound (4). Specifically, it can be purified by recrystallization, column chromatography, or the like. In the reaction of the reaction formula (3), the following diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene is derived from the compound (4).

The film of the present invention means a film formed from the diterpene [2,3-b : 2', 3'-f] thieno[3,2-b]thiophene of the present invention or a composition containing the same. The film thickness of the film varies depending on the application, and is usually from 0.1 nm to 100/m, and the twist is preferably from 1 nm to 20/m. The method for forming the film of the present invention generally includes a vacuum program -17-201247676 resistance heating vapor deposition method, electron beam steaming method, sputtering method, molecular layering method, etc. or a spin coating method of a solution program, Lithographic printing method, gravure printing method, gravure printing method, dry lithography method, pad printing method, lithographic printing method, etc., lithography, gravure printing, etc., such as droplet coating method, immersion coating method, quick-drying printing, resin relief printing, etc. A method such as a gravure printing method, a screen printing method, a transfer printing method, a lithographic printing method, a stencil printing method, an inkjet printing method, a microcontact printing method, or the like, or a method of combining a plurality of such methods . Usually, it is preferably a resistance heating vapor deposition method of a vacuum program or a spin coating method of a solution program, a dip coating method, an ink jet method, a screen printing method, a letterpress printing method, or the like. In addition, the film forming methods required in the respective organic electronic devices are also different, and will be described in the items of the respective devices. The organic electronic device of the present invention is an electronic material containing the above-described diterpene [2,3-b:2',3'-phantomino[3,2-1)] peptidene as an electronic device. Examples of the organic electronic device include a thin film transistor and an organic EL element, a liquid crystal display element, a photoelectric conversion element, and an organic semiconductor laser element. These components will be described in detail below. First, the thin film transistor will be described in detail. The thin film transistor has two electrodes (a source electrode and a drain electrode) in contact with the semiconductor, and controls a current flowing between the electrodes by a voltage applied to the other electrode called a gate electrode. In general, a thin film transistor element is often constructed by insulating an electrode with an insulating film (Metal-Insulator-Semiconductor; MIS structure). A metal oxide film is used as an insulating film and is called a MOS structure. Others have a structure in which a gate electrode is formed by a Kentke barrier, and -18-201247676 is also a MES structure. However, in a thin film transistor using an organic semiconductor material, the MIS structure is mostly used. Hereinafter, the organic thin film transistor of the present invention will be described in more detail using the drawings, but the present invention is not limited to these configurations. Fig. 1 shows several types of examples of the thin film transistor (element) of the present invention. In each of the examples, 1 denotes a source electrode, 2 denotes a semiconductor layer, 3 denotes a drain electrode, 4 denotes an insulator layer, 5 denotes a gate electrode, and 6 denotes a substrate. The configuration of each layer and electrode can be appropriately selected depending on the use of the component. A to D, because the current flows in the direction parallel to the substrate, it is called a lateral transistor. A is called a bottom contact structure, and B is called a top contact structure. Further, the C system is provided with a source electrode and a drain electrode and an insulator layer on the semiconductor, and then a gate electrode is formed thereon, which is called a bottom gate structure. D is called the structure of the top and bottom contact type transistors. E is a transistor having a vertical structure, that is, a schematic diagram of an electrostatic induction transistor (SIT: electrostatic induction transistor). In this SIT, since the current flows in a planar manner, a large number of carriers can be transferred at a time. Further, since the source electrode and the drain electrode are arranged longitudinally, the distance between the electrodes can be reduced to achieve a high speed of the reaction. Therefore, it can be suitably applied to applications such as switching at a high speed accompanied by a large current. In the case of E in the first drawing, the substrate is not described. However, the substrate is usually provided on the outer side of the source electrode and the drain electrode indicated by 1 and 3 in the first drawing, and the substrate is described. Each component. The substrate 6 must be held without peeling off the layers formed thereon. For example, an insulating material such as a resin plate or a film, paper, glass, quartz, or ceramics; an insulating layer formed on a conductive substrate such as a metal or an alloy by coating -19-201247676 or the like; and a resin and an inorganic material may be used; Materials such as various combinations. The resin film which can be used, for example, polyethylene terephthalate, polyethylene naphthalate, polyether oxime, polyamine, polyimide, polycarbonate, cellulose triacetate , polyether phthalimide and the like. When a resin film or paper is used, the element can be made flexible, soft and lightweight, and the practicality can be improved. The thickness of the substrate is usually 1 #m to l〇mm, preferably 5/zm to 5 mme. The source electrode 1, the drain electrode 3, and the gate electrode 5 are made of a conductive material. For example, platinum, gold, silver, aluminum, chromium, tungsten, molybdenum, nickel, cobalt, copper, iron, lead, tin, titanium 'indium, palladium, molybdenum, magnesium, calcium, barium, lithium, potassium, sodium, etc. may be used. Metals and alloys containing the same; conductive oxides of In〇2, Zn〇2, Sn〇2, ITO, etc.; polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, ethylene, poly A conductive polymer compound such as acetylene; a semiconductor such as ruthenium, osmium or gallium arsenide; a carbon material such as carbon black, fullerene, carbon nanotube or graphite. In addition, conductive high molecular compounds or semiconductors can be cumbersome. Examples of the dopant in this case include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids having an acidic functional group such as sulfonic acid; Lewis acids such as PFS, AsFs, and FeCl3; and halogen atoms such as iodine: lithium and sodium. a metal atom such as potassium. Boron, phosphorus, arsenic, etc. are also widely used as dopants for inorganic semiconductors such as ruthenium. Further, a conductive composite material in which carbon black or metal particles or the like is dispersed in the above dopant may be used. Further, the distance (channel length) between the source and the drain electrode is an important factor for determining the characteristics of the device. The length of the channel is usually O.UOOym -20-201247676, preferably O.5~100ym. The shorter the channel length, the more the amount of current that can be drawn, but the leakage current, etc., so the proper channel length is necessary. The width (channel width) between the source and the drain electrode is usually 10 to 10000 " m, preferably 100 to 5000 νηη. Further, the width of the channel can be formed into a comb structure by forming the structure of the electrode, etc., and a longer channel width can be formed, and can be set to an appropriate length in accordance with the amount of current necessary or the structure of the element. Next, the respective configurations (forms) of the source and the drain electrodes will be described. The source and drain electrodes may be identical or different in configuration. The length of the electrode can be the same as the width of the aforementioned channel. The width of the electrode is not particularly limited, and it is preferably shorter in order to reduce the area of the element within a range in which the electrical characteristics are stabilized. The width of the electrode is usually from 0.1 to 1000 / / m, preferably from 0.5 to 100 / zm. The thickness of the electrode is usually from 0.1 to 100 nm, preferably from 1 to 500 nm, and more preferably from 5 to 200 nm. Wiring is connected to each of the electrodes 1, 3, and 5, and the wiring can be produced by using the same material as the electrode. The insulator layer 4 is made of an insulating material. For example, parylene, polyacrylate, polymethyl methacrylate, polystyrene, polyvinyl phenol, polyamide, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate can be used. a polymer of an ester, a polyurethane, a poly maple, an epoxy resin, a phenol resin, a fluorine resin, or the like, and a copolymer of the same; metal oxidation of cerium oxide, aluminum oxide, titanium oxide, cerium oxide, or the like a strong dielectric metal oxide such as SrTi03 or BaTi〇3; a nitride such as tantalum nitride or aluminum nitride; a sulfide; a derivative such as fluoride; or a polymerization which disperses particles of such a dielectric. Things and so on. The film thickness of the insulator layer 4 varies depending on the material -21 - 201247676 is usually 0.1 nm to 100 / / m, preferably 0.5 nm to 50 / im, and more preferably 1 nm to 1 0 / z m. As the material of the semiconductor layer 2, the diterpene [2,3-b: 2', 3'4] thieno[3,2-13] thiophene of the present invention or a composition containing the same is used. This material can be formed as a thin film as the semiconductor layer 2 by the aforementioned method. In this case, a single diterpene [2,3-b : 2',3'-f]thieno[3,2-b]thiophene is preferably used as the organic semiconductor material, but in order to improve the characteristics of the thin film transistor Or impart other characteristics 'may mix other organic semiconductor materials or various additives as necessary. These may include the case of co-evaporation with other organic semiconductor materials or dopants in the evaporation process, or the solvent, dispersant, surfactant, leveling agent, surface tension adjustment used in the solution procedure. A case where a composition or the like is mixed to form a composition is exemplified. Further, the semiconductor layer 2 may be composed of a plurality of layers. The above additive is usually added in an amount of 0.01 to 1% by weight, preferably 0 to 5 to 5% by weight, particularly preferably 0.1 to 3% by weight, based on the total amount of the organic semiconductor material. When the aforementioned semiconductor composition is used as the organic semiconductor material, it is not limited thereto. Further, although the semiconductor layer may be composed of a plurality of layers, it is particularly preferably a single layer structure. The film thickness of the semiconductor layer 2 is thinner in the range where the necessary function is not lost. β is a thin film transistor shown in A, B, and D shown in Fig. 1 when the film thickness is thick. The current increases, so the characteristics of the element do not depend on the film thickness when the film thickness is greater than or equal to the predetermined thickness. The film thickness of the semiconductor layer for exhibiting the necessary function is usually from 1 nm to 10/zm, preferably from 5 nm to 5 " m, and more preferably from 10 nm to 3/zm. -22- 201247676 In the thin film transistor of the present invention, for example, between the substrate layer and the insulating film layer or between the insulating film layer and the semiconductor layer, or on the outside of the element, other layers may be provided as necessary. For example, when a protective layer is formed by directly or interposing another layer on the organic semiconductor layer, the influence of external gas such as moisture can be reduced, and the electrical characteristics can be stabilized by improving the on/off ratio of the element and the like. The advantages. The material of the protective layer is not particularly limited, and for example, an acrylic resin such as an epoxy resin or polymethyl methacrylate, a polyurethane, a polyimide, a polyvinyl alcohol, a fluororesin, or a poly A film composed of various resins such as olefin: a film composed of an inorganic oxide film such as cerium oxide, aluminum oxide or tantalum nitride, or a dielectric such as a nitride film, etc., preferably having a transmittance of oxygen or moisture or A resin (polymer) having a small water absorption rate. It can also be used in recent years as a protective material for organic EL displays. The film thickness of the protective layer can be selected according to the purpose, and is usually from 10 nm to 1 mm. Further, by performing surface treatment in advance on a substrate or an insulator layer on which an organic semiconductor layer is laminated, the characteristics as a thin film transistor element can be improved. For example, by adjusting the degree of hydrophilicity/hydrophobicity of the surface of the substrate, the film quality of the film formed thereon can be improved. In particular, the acceptability of an organic semiconductor material greatly changes depending on the state of the film such as the alignment of the molecules. Therefore, by surface-treating the substrate or the like, it is possible to control the molecular alignment of the interface portion of the substrate or the like with the organic semiconductor layer to be subsequently formed, and to reduce the trapping portion on the substrate or the insulator layer, thereby improving carrier migration. Rate and other characteristics. The trapping site refers to a functional group such as a hydroxyl group -23-201247676 present on an untreated substrate. When such a functional group is present, electrons are pulled close by the functional group, resulting in a decrease in carrier mobility. . Therefore, those who have reduced the collection site are often effective in improving the characteristics of the carrier mobility and the like. The substrate treatment for improving the above characteristics may, for example, be a hydrophobization treatment according to hexamethyldiazepine, cyclohexene, octyltrichlorodecane or octadecyltrichloromethane; Acid treatment by sulfuric acid, acetic acid, etc.; alkali treatment according to sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, etc.: ozone treatment: fluorination treatment; plasma treatment of argon oxide, etc.; Langmuir-Blodgett membrane Formation treatment of other insulators or thin films of semiconductors; mechanical treatment; electrical treatment of corona discharge, etc.: in addition, brushing treatment using fibers or the like. In such a form, for example, a method of providing a substrate layer, an insulating film layer, or an insulating film layer and an organic semiconductor layer, for example, a vacuum deposition method, a sputtering method, a coating method, a printing method, or a sol-gel method can be suitably employed. Glue method, etc. Next, a bottom contact type thin film transistor shown in the type A of Fig. 1 will be described as an example. A method of manufacturing the thin film transistor element of the present invention will be described based on Fig. 2 . This production method can be similarly applied to the above-described other types of thin film transistors and the like. (Substrate and Substrate Treatment of Thin Film Transistor) The thin film transistor of the present invention is produced by providing various layers and electrodes necessary for the substrate 6 (see Fig. 2 (1)). The substrate can be used as described above. The surface treatment or the like may be performed on the substrate. The thickness of the substrate 6 is preferably as thin as possible within a range that does not hinder the necessary functions. Although it varies depending on the material -24- 201247676, it is usually lem~10mm, preferably 5/zm. Further, the substrate can be provided with an electrode function as necessary. (Formation of Gate Electrode) The gate electrode 5 is formed on the substrate 6 (see Fig. 2 (2)). The electrode material can be used as described above. The method of forming the electrode film into a film may be, for example, a vacuum deposition method, a sputtering method, a coating thermal transfer method, a printing method, a sol-gel method or the like by various methods. When forming a film or after film formation, it is necessary to form a pattern to form a desired shape. Various methods can be used for the pattern method, and examples thereof include a lithography technique for forming and etching a combined photoresist. Further, it is also possible to apply a printing method such as inkjet printing, lithography, and letterpress printing, a technique of flexible lithography such as microcontact printing, and a combination of a plurality of such techniques to form a pattern. The film thickness of the gate electrode 5 is usually from 0.1 nm to 10/zm, preferably from 0.5 nm to 1, and particularly preferably from 1 nm to 3 /zm, although it varies depending on the material. In addition, when both the gate electrode and the substrate are combined, the film thickness can be made larger. (Formation of Insulator Layer) The insulator layer 4 is formed on the gate electrode 5 (see Fig. 2 (: The insulator material can be used as described above. The insulator layer can be formed, and various methods can be used, and for example, spin coating can be used. Cloth method, spray method, dip coating method, die casting method, bar coating method, knife coating method, etc., screen printing, lithography, inkjet, etc., vacuum evaporation ~ 5mm. Compared with the formation of pattern and net brush method and S β m, )) coating method of coating at 25° - 201247676, molecular beam epitaxy growth method, ion clustering method, ion evaporation method, splashing Dry procedural methods such as plating, atmospheric piezoelectric slurry, and CVD. Other methods such as a sol-gel method or an oxide film formed on a metal such as an aluminum oxide film on aluminum or cerium oxide on a crucible may be employed. In the portion where the insulator layer and the semiconductor layer are in contact, at the interface between the two layers, in order to make a molecule constituting the semiconductor, for example, the diterpene [2,3-b: 2', 3'-f] thieno[ The molecules of 3,2-b]thiophenes are well aligned, and the insulator layer can be subjected to a predetermined surface treatment. The surface treatment method can be the same as the surface treatment of the substrate. The film thickness of the insulator layer 4 is preferably as thin as possible within a range that does not impair the function. It is usually 0.1 nm to 100/m, preferably 0.5 nm to 50/zm, and more preferably 5 nm to 10/m. (Formation of Source Electrode and Diode Electrode) The method of forming the source electrode 1 and the drain electrode 3 can be formed in accordance with the case of the gate electrode 5 (see Fig. 2 (4)). Further, in order to lower the contact resistance with the organic semiconductor layer, various additives and the like can be used. (Formation of Organic Semiconductor Layer) The organic semiconductor material, as described above, uses the diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene of the present invention. Or its constituents. When the organic semiconductor layer is formed into a film, various methods can be used. The method can be roughly classified into a vacuum program such as a sputtering method, a CVD method, a molecular beam epitaxial growth method, or a vacuum evaporation method; and a immersion coating method, a die casting coating method, a roll coating method, and a bar coating method. A coating method such as a method, a spin coating method, or the like; a method of forming a solution program such as a brush method, a lithography method, or a microcontact printing method by an inkjet method or a screen printing method -26-201247676. When the diterpene [2,3-b : 2',3,-f]thieno[3,2-b]thiophene of the present invention is used as a semiconductor material to form an organic thin film which becomes a semiconductor layer, it is preferred to borrow The method of forming an organic thin film formed by a vacuum process as a semiconductor layer is more preferably a vacuum distillation method. It is also possible to form a film according to a solution procedure, or a low-cost printing method. Next, a method of forming an organic semiconductor material by a vacuum process to form an organic semiconductor layer will be described. Preferably, the organic semiconductor material is heated under vacuum in a crucible or a metal dish, and the evaporated organic semiconductor material is attached (vapor-deposited) to the substrate (the exposed portion of the insulator layer, the source electrode, and the drain electrode). The method is vacuum evaporation. In this case, the degree of vacuum is usually 1.0 or less, preferably less than or equal to 〇xi〇-3pa. Further, sometimes the characteristics of the organic semiconductor film and the thin film transistor are changed by the difference in substrate temperature during vapor deposition, and it is preferable to carefully select the substrate temperature. The substrate temperature at the time of steaming is usually 0 to 20 (TC, preferably 10 to 15 (TC, particularly preferably 15 to 120 ° C, more preferably 25 to 100 ° C. In addition, the speed of the steamer is usually 0.001 〜10 nm / sec, preferably 〇·〇1 to lnm / sec. The film thickness of the organic semiconductor layer formed of the organic semiconductor material is usually from 1 nm to 10/zm, preferably from 5 nm to 5/m. Preferably, lOnm~3/m 〇 can also be used to form an organic semiconductor layer by causing the accelerated argon ions to collide with the material target, and the material atoms are struck and adhered to the substrate. The organic semiconductor material is heated and evaporated to adhere to the vapor deposition method of the substrate -27-201247676. Next, a method of forming an organic semiconductor layer by a solution process will be described. The second embodiment of the present invention can be used. -b : 2',3,-f]thieno[3,2-b]thiophene is dissolved or dispersed in a solvent, etc., and other low molecular compounds or polymer compounds, dopants, dispersants, and interfacial activities are added as necessary. Additives such as a agent, a flat agent, and a surface tension adjuster constitute a composition, and the composition is prepared as a composition The ink for the conductor device is applied to the substrate (the exposed portion of the insulator layer, the source electrode, and the drain electrode). The coating method may be a die casting method, a spin coating method, a dip coating method, or a knife coating method. Coating methods such as a method, a bar coating method, a spray coating method, a printing method such as inkjet printing, screen printing, lithography, and letterpress printing, and a method of flexible lithography such as a microcontact printing method. And a method of combining a plurality of such methods. Further, similarly to the coating method, the monomolecular film of the organic semiconductor layer prepared by dropping the ink on the water surface may be moved to the substrate to be laminated. The Langmuir-Blodgett method is a method in which a liquid crystal or a molten material is sandwiched between two substrates, and is introduced into the substrate by capillary phenomenon, etc. The temperature of the substrate or the composition at the time of film formation is also Importantly, since the characteristics of the transistor sometimes vary depending on the temperature of the substrate or the composition, it is necessary to carefully select the temperature of the substrate or the composition. The substrate temperature during vapor deposition is usually 〇~200°c'. It is preferably from 10 to 120 ° C, more preferably from 15 to 100 t. In particular, it is largely dependent on the solvent and the like in the composition to be used. Therefore, special care is required. The film thickness of the organic semiconductor layer produced by this method is Do not damage -28- 201247676 The thinner the better the range of this function. If the film thickness is thick, there will be doubts about leakage. The film thickness of the organic semiconductor layer is usually lnm~10; / 5nm~5vm, especially good It is 10 nm to 3/zm. The organic semiconductor layer thus formed (refer to Fig. 2 (5) to further improve the characteristics by subsequent treatment. For example, the heat treatment can alleviate the strain in the film which is formed when the film is formed, and reduces From the standpoint of controlling the arrangement and alignment of the film, etc., the semiconductor characteristics can be improved and stabilized. In the case of the film electroforming of the present invention, the heat treatment is effective for improving the characteristics. The treatment temperature by heating the substrate after forming the organic semiconductor layer is not particularly limited, and is usually room temperature to 150 ° C 40 to 120 ° C, more preferably 45 to 100 ° C. The heat treatment at this time is usually limited to 1 minute to 24 hours, preferably 2 minutes - at this time, the gas atmosphere may be in the atmosphere or in a nitrogen or argon active gas atmosphere. In addition, the subsequent treatment of other organic semiconductor layers is treated with an oxidizing or reducing gas such as oxygen or hydrogen, or an oxidizing or a bulk, etc., and the initiation of oxidation or reduction is particularly the case, for example, by a film. The increase or decrease in the density of the carrier is applied. Further, in a method called doping, the characteristics of the bulk layer can be changed by adding a trace amount of a group, a molecule, or a polymer to the organic semiconductor layer. For example, it can be doped with oxygen, hydrogen, hydrochloric acid, sulfuric acid, acid; Lewis acid such as PF5, AsF5, FeCl3, etc.; halogen current of iodine or the like is increased: m, preferably)), and can reach the organism by pinhole or the like The heat treatment was made. The heat treatment is preferably not particularly -3 hours. The gas can also be changed by reducing liquidity. A small atomic element, a primary atom such as an organic semi-conductive sulfonic acid; -29- 201247676 A metal atom such as sodium or potassium; various organic semiconductor materials. This can be achieved by contacting the gases with the organic semiconductor layer, by dipping into the solution, or by electrochemical doping. Such doping may be added to the ink after the preparation of the organic semiconductor layer, or during the synthesis of the organic semiconductor compound, or in the process of producing an organic semiconductor layer using an ink for producing an organic semiconductor device. It is added at the step of forming a film or the like. In addition, a doping material may be added to a material for forming an organic semiconductor layer during vapor deposition for co-evaporation, or may be mixed in a surrounding gas environment when an organic semiconductor layer is formed (in a doping material) The organic semiconductor layer is formed in the presence of the substrate, and further, the ions may be accelerated in a vacuum and doped with the film. The effect of such doping may be a change in electrical conductivity due to an increase or decrease in carrier density, a change in polarity of a carrier (P-type, N-type), a change in Fermi level, and the like. Such doping is often applied, particularly in semiconductor devices using an inorganic material such as germanium. (Regarding the protective layer) When the protective layer 7 is formed on the organic semiconductor layer, it has the advantage of suppressing the influence of the external gas to a minimum and stabilizing the electrical characteristics of the organic thin film transistor (refer to Fig. 2 (6) ). The material of the protective layer can be as described above. The film thickness of the protective layer 7 can be any film thickness depending on the purpose, and is usually from 10 nm to 1 mm. When the protective layer is formed into a film, various methods may be employed. When the protective layer is composed of a resin, for example, a method of applying a resin solution and drying it to form a -30-201247676 resin film; coating or vapor-depositing a resin may be mentioned. A method in which a monomer is subjected to polymerization, and the like. The film formation thickness can be cross-linked. When the protective layer is composed of an inorganic material, for example, a formation method in a vacuum program such as a sputtering method or a steaming method, or a formation method in a solution program such as a sol gel can be used. In the thin film transistor of the present invention, in addition to the organic semiconductor layer, a protective layer may be provided between the layers as necessary. These layers are sometimes beneficial for the stabilization of the electrical properties of the thin film transistor. According to the present invention, since diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene is used as an organic semiconductor material, it can be produced under a relatively low temperature process. Therefore, a flexible material such as a plastic sheet or a plastic film which cannot be used under conditions of exposure to high temperatures can be used as the substrate. As a result, it is possible to manufacture a lightweight and flexible component which is not easily damaged, and can be applied as a switching element of an active matrix of a display or the like. The thin film transistor of the present invention can also be applied as a digital component or analog component such as a memory circuit component, a signal driver circuit component, a signal processing circuit component, or the like. In addition, by combining these, a 1C card or a 1C tag can be created. Further, the thin film transistor of the present invention can be applied as a FET sensor by causing a change in the characteristics by external stimulation of a chemical substance or the like. Next, the organic EL device of the present invention will be described in detail. The organic EL element is a solid, and it can be used for applications such as self-luminous type large-area color display or illumination, and has been developed in many ways. This configuration is known to have a structure of a layer of a light-emitting layer and a charge transport layer between opposite electrodes of the cathode and the anode, and a structure between the counter electrodes. The structure of the electron transport layer, the light-emitting layer, and the hole transport layer: and a layer having three or more layers, and the like, and a single layer or the like. Here, the hole transport layer has a function of injecting a hole from the anode and transporting it to the light-emitting layer to facilitate the injection of the hole into the light-emitting layer and the function of blocking electrons. Further, the electron transport layer has a function of transferring electrons from the electrons and transporting the electrons to the light-emitting layer to facilitate electron injection, and a function of blocking the holes. In addition, the luminescence is detected by the recombination of the separately injected electrons and the holes, and the radiation emitted by the excitation photons during the process of radiation and loss of activity is detected as luminescence. The type of the organic EL device of the present invention will be described below. The organic EL device of the present invention has one or a plurality of organic thin films electrically formed on the anode and the cathode, and emits light by electric energy: the anode used in the organic EL device of the present invention is injected into the hole with holes. The function of the hole injection layer, the hole transport layer, and the light-emitting layer. In general, a metal oxide or alloy having a work function of 4.5 eV or more, a conductive material, or the like is suitable. Specifically, it is not particularly preferable, but a conductive metal oxide such as tin oxide (NESA), indium oxide, indium tin oxide (indium zinc oxide) or the like; gold, chromium, aluminum, iron, cobalt, or the like; a metal such as nickel or tungsten; an inorganic conductive material of copper iodide or sulfur; a polymer or carbon of polythiophene, polypyrrole, polyaniline, etc. Among these, ITO or NESA is preferably used. < Having a layer of the layer 3 The layer of light can be used to make the hole, in the layer of the cathode layer, the photon, the amount of the preferred interpole element. Electrode metal, limited, ITO) silver, platinum-plated copper, etc. Conductivity -32- 201247676 Anode, which can be used as many materials as necessary. The electric resistance of the anode is not particularly limited as long as it can supply a current to the element, and is preferably low in resistance. For example, since the ITO substrate below the sheet electrode has a substrate Ω/□ as the element electrode, it is preferably arbitrarily selected using a low-resistance resistor 値, and is usually used between 5 10 and 300 nm. Film formation by ITO or the like, plating method, electron beam method, sputtering method, and chemical reaction method. The electrode used in the organic EL device of the present invention is implanted in an electron injecting layer, an electron transporting layer, and a film. In general, the work function is small (approximately 4eV gold is more suitable. Specifically, uranium, gold, zinc 'aluminum, indium, chromium, lithium, sodium, potassium, calcium, and calcium are listed. In order to improve the efficiency of electron injection. In order to improve the element, sodium, potassium, calcium, and magnesium, an alloy containing such a low work function gold, or an electrode having a structure in which such a structure is laminated may be used. In the case of taking light from the cathode side, the film formation method may be low. The film formation method may be, for example, a vapor deposition method, an electron reaction method, or a coating method, but is not limited thereto. It is said that the current is limited, and from the viewpoint of the power consumption of the element, the power consumption of the charging of the two or more layers can be 300 Ω / □, but it can also be supplied. The thickness of the ITO may be -500 nm, preferably in the method, and may be, for example, steaming, coating, etc. The cathode is a metal or a combination of silver, copper, iron, and tin having an electro-optical layer function. Magnesium, etc., but without special limitation, preferably lithium, aluminum Silver and other metals. The electrode of the laminated structure is not on the anode side, the transparent electrode beam method of the warm film, the sputtering method, and the resistance of the cathode, as long as it is not particularly preferable as a low resistance, which is better than -33-201247676. The number is 1 〇〇 to several Ω / □. The film thickness is usually from 5 to 500 nm, preferably within the range. In addition, 'for the sealing and protection, it is also possible to use oxides such as cerium oxide, cerium oxide, cerium oxide, cerium oxide, nitrogen, etc., polyvinyl alcohol, vinyl chloride, hydrocarbon polymer molecules, etc. The cathode is protected and sealed together with cerium oxide, phosphorus pentoxide, and an oxygen dehydrating agent. Further, in order to take light, in general, it is preferable to form an electrode on a substrate having sufficient transparency in a long region of the element. A glass substrate or a polymer substrate is exemplified. The glass substrate can be used, an alkali-free glass, quartz or the like, and it is preferably a thickness of 0.5 mm or more as long as it has a thickness capable of maintaining mechanical and thermal separation. Regarding the quality, it is preferable that the amount of ions to be melted from the glass is small, and it is preferable that the glass is not used. The commercially available product may be used as a barrier coating film of SiO 2 or the like. Further, examples of the polymer other than glass include polycarbonate, polypropylene, polyether oxime, polyparaphenylene ester, and acrylic substrate. The organic thin film of the organic EL device of the present invention has one or a plurality of layers formed between the electrodes of the cathode. By having the fluorene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene contained therein, an element which emits light by electric energy can be obtained. In the present invention, one or more layers of an organic thin film, such as a hole transport layer, an electron transport layer, a hole transport light-emitting layer, a light-emitting layer, a hole barrier layer, an electron barrier layer, and a hole injection 1 0~3 OOnm Luminescent substrate with titanium, nitride, or fluorine-based calcium, etc. Glass-based alkali glass with a soda-lime glass strength. The substrate made of soda-lime glass is made of the second film of the invention of the anode, the "layer", the 'electronic input layer, the electric-34-201247676 sub-injection layer, the luminescent layer or the following composition example 9) A single layer that combines the functions of these layers. In the constitution of the layer forming the organic thin film in the present invention, the following constitution examples 1) to 9) can be used. Configuration Example 1) Hole transport layer/electron transport light-emitting layer. 2) Hole transport layer / luminescent layer / electron transport layer. 3) Hole transporting luminescent layer/electron transport layer. 4) Hole transport layer / luminescent layer / hole blocking layer. 5) Hole transport layer/light-emitting layer/hole stop layer/electron transport layer 〇 6) Hole transporting light-emitting layer/hole stop layer/electron transport layer. 7) In each of the combinations of the above 1) to 6), a hole injection layer is further provided before the hole transport layer or the hole transporting light-emitting layer. 8) In each of the combinations of the above 1) to 7), a layer of an electron injecting layer is further provided before the electron transporting layer or the electron transporting light emitting layer. 9) The materials used in the combination of the above 1) to 8) are separately mixed, and only one layer contains the composition of the mixed material. The above 9) may generally be a single layer formed by a material called a bi-carrier luminescent material; or a layer containing only a luminescent material and a hole transporting material or an electron transporting material. In general, by constructing a multilayer structure, it is possible to efficiently transport charges, i.e., holes and/or electrons, to recombine these charges. Further, since the quenching of the electric charge or the like -35 - 201247676 ' can be suppressed, the decrease in the stability of the element can be prevented and the luminous efficiency can be improved. The hole injection layer and the transport layer may be formed by laminating the hole transporting material alone or by laminating a mixture of two or more of the materials. As the hole transporting material, yttrium, ytterbium-diphenyl fluorene, bis-(3-methylphenyl)-4,4,-diphenyl-1,1'-diamine, Ν,Ν,-dinaphthyl-anthracene, anthracene,-diphenyl-4,4,-diphenyl-1, triphenylamines such as diamines; bis(indolyl carbazole) Or a bis(indenyl oxazole) type; a heterocyclic compound represented by a pyrazoline derivative, an anthraquinone compound, an anthraquinone compound, a triazole derivative, an oxadiazole derivative or a porphyrin derivative; In the system, a polycarbonate or a styrene derivative of the above monomer, a polyvinyl oxazole, a polydecane or the like is provided in the side chain. It is not particularly limited as long as it is a material which can form a film required for the production of a device and can inject a hole from the electrode and transport the hole. The hole injection layer which is provided between the hole transport layer and the anode for improving the hole injectability, and examples thereof include a phthalocyanine derivative, a starburst type amine such as m-MTDATA, and a polymer system. Produced by PEDOT and other polythiophene 'polyethylene carbazole derivatives. The electron transporting material must efficiently transport electrons from the negative electrode between the electrodes that impart electric fields. The electron transporting material, preferably having a high electron injection efficiency, can efficiently transport the injected electrons. Therefore, it is required to have a large electron affinity, a large electron mobility, a good stability, and it is difficult to produce a substance which is a trapping impurity at the time of manufacture and use. The substance satisfying such a condition can be exemplified by a quinoline derivative metal complex represented by a tris(8-quinoline)aluminum complex, a phenol ketone metal complex, an anthracene derivative, an anthrone derivative. , naphthoquinone imine derivatives, naphthalene dicarboxylic acid derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives -36-201247676, bisstyrene derivatives The compound, the pyrazine derivative, the phenolin derivative, the benzoxazole derivative 'quinoxaline derivative, and the like are not particularly limited thereto. These electron transport materials can be used alone or in combination or in combination with different electron transport materials. The electron injecting layer provided between the electron transporting layer and the cathode for enhancing the electron injecting property may be a metal such as lithium or tantalum or lithium fluoride. The hole blocking layer is formed by using a hole blocking substance alone or by laminating or mixing two or more kinds of the substance. a hole-blocking substance, preferably phenanthroline, 2,9-dimethyl-4,7-diphenyl-l, l-phenanthroline, etc. a diene derivative, a quinoline derivative metal complex, an oxadiazole derivative, an oxazole derivative, or the like. The hole blocking substance ' is not particularly limited as long as it can prevent the hole from flowing from the cathode side to the outside of the element and lowering the luminous efficiency. The light-emitting layer means an organic film which can emit light, for example, a hole transporting layer having a strong light-emitting property, an electron transporting layer or a double-carrier transporting layer. The light-emitting layer may be formed of a light-emitting material (host material, dopant material, etc.), which may be a mixture of the host material and the dopant material, or may be any of the host materials alone. The host material and the dopant material may each be a 'or a combination of a plurality of materials. The dopant material may be included in whole or in part of the host material. The dopant material may be laminated or dispersed' may be any of them. The light-emitting layer may, for example, be the above-mentioned hole transport layer or electron transport layer. The material used for the light-emitting layer may, for example, be a oxazole derivative, an anthracene derivative, a naphthalene derivative, a phenanthrene derivative, a phenylbutadiene derivative, a styryl derivative, a court derivative, a phenanthrene derivative, or a saliva.廖衍-37- 201247676 Biological, tetracene derivative, anthracene derivative, quinacridone derivative, coumarin derivative, porphyrin derivative or phosphorescent metal complex (Ir complex, Pt error Compound, Eu complex, etc.). The method for forming such a film generally includes a resistance heating vapor deposition method, an electron beam evaporation method, a sputtering method, a molecular layer method, or the like, or a die casting method, a spin coating method, or a soaking of a solution program. Coating method such as coating method, doctor blade coating method, wire bar coating method, spray coating method, or printing method such as inkjet printing, screen printing, lithography, letterpress printing, microcontact printing method, etc. The method of flammable lithography, or a combination of a plurality of such methods. The thickness of each layer cannot be limited depending on the resistance 値 and charge mobility of each substance, but may be selected from 0.5 to 50,000 nm. It is preferably from 1 to 1 000 nm, particularly preferably from 5 to 500 nm. In the organic thin film of the organic EL device of the present invention, the diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene of the present invention is contained in In one or a plurality of layers of a thin film such as a light-emitting layer, a hole transport layer, and an electron transport layer which are present between the electrodes of the anode and the cathode, an element which can efficiently emit light even with low electric energy can be obtained. In the organic EL device of the present invention, the diterpene [2,3-b: 2',3'-f]thiophene [3, of the present invention can be formed by forming one layer or a plurality of layers between the electrodes of the anode and the cathode. 2-b] thiophene. In particular, the site of the diterpene [2,3-b:2',3'-f]thieno[3,2-b]thiophene of the present invention is not limited, but can be preferably used as a hole transport. a layer or luminescent layer, or a host material in combination with a dopant material. In the organic EL device of the present invention, the diterpene [2,3-b: 2',3'--38-201247676 f]thieno[3,2-b]thiophene of the present invention can be preferably used as a hole Transport layer or luminescent layer. For example, it may be used in combination or in combination with the aforementioned electron transporting material or hole transporting material, luminescent material or the like. Preferably, a quinoline derivative metal complex represented by tris(8-quinoline)aluminum complex, a phenol ketone metal complex, an anthracene derivative, an anthrone derivative, naphthoquinone is exemplified. Imine derivative, naphthalene dicarboxylic acid derivative, bisstyrene derivative, pyrazine derivative, pheniramine derivative 'benzoxazole derivative, quinoxaline derivative, triphenylamine, double (N - allyl carbazole) or bis (N-alkyl azole), a heterocyclic compound represented by a pyrazoline derivative, a bottom compound, an anthraquinone compound, or an oxadiazole derivative, but no particular limited. These may be used alone or in combination or in combination with different materials. The specificity of the dopant material when the diterpene [2,3-b : 2,3,-f]thieno[3,2-b]thiophene of the present invention is used as a host material in combination with a dopant material For example, an anthracene derivative such as bis(diisopropylphenyl)phosphonium tetracarboxylate, an anthrone derivative, 4-(dicyanomethylene)-2-methyl·6-(pair can be used. Dimethylaminostyryl)-4Η-pyran (DCM) or a metal phthalocyanine derivative of the analog, magnesium phthalocyanine, aluminum chlorophthalocyanine, etc., rosin compound, deazaflavin derivative, fragrant Bean derivatives, oxazine compounds, squaraine compounds, lycopene compounds, Nile red, 5-cyanopyrrole-BF4 complexes, etc. Porphyrin or ortho-metal, such as Eu complex or phenanthroline or phenanthroline as a ligand, such as Eu complex or complex, RU complex, Pi complex, 〇s complex, etc. A metal complex or the like is used as the phosphorescent material, but is not limited thereto. In addition, when mixing two kinds of dopant materials, it is also possible to use a red fluorene-like auxiliary dopant to efficiently move the energy from the host pigment of -39-201247676 to obtain an improved color purity. In any case, in order to obtain high luminance characteristics, it is preferred that the doped fluorescence quantum yield is high. When the amount of the dopant material to be used is too large, concentration dimming is caused, and therefore it is usually used in an amount of 30% by mass or less based on the host material. It is preferably 20% by mass or less, more preferably 10% by mass or less. The method of doping the dopant material into the host material in the light-emitting layer may be formed by co-evaporation with the host material, or may be previously mixed with the host material and simultaneously vapor-deposited. In addition, it can also be sandwiched and used in the body material. At this time, it is also possible to cooperate with the host material layer as one or two or more dopant layers. These dopant layers may be formed separately or mixed. In addition, the dopant material may be dissolved or dispersed in polyvinyl chloride, polycarbonate, polystyrene, polystyrenesulfonic acid, poly(N-vinylcarbazole), poly(methyl) as a polymer binder. Methyl acrylate, polybutyl (meth) acrylate, polyester, polyfluorene, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyfluorene, polyamine, ethyl cellulose a solvent-soluble resin such as vinyl acetate, ABS resin, or urethane resin, or a phenol resin, a xylene resin, a petroleum resin, a urea resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, or a ring. A curable resin such as an oxygen resin or a polyfluorene oxide resin is used. The method for forming a film used in the organic EL device of the present invention may be a diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene or a composition of the present invention. And adopting the general vacuum program of resistance heating evaporation method, electron beam evaporation method 'sputtering method, molecular layering method, or solution programming die casting method-40-201247676, spin coating method, immersion coating method, Coating method such as blade coating method, wire bar coating method, spray coating method, or printing method such as inkjet printing, screen printing, lithography, letterpress printing, etc., micro-contact printing method, etc. The technique of the shadow technique, or a combination of a plurality of such methods to carry out the 〇 resistance heating evaporation method, the electron beam evaporation method, the sputtering method, the molecular layering method, or the dissolution or dispersion in a solvent or a resin to coat The method of the cloth (the spin coating method, the die casting method, the immersion coating method), the LB method, the inkjet method, and the like are not particularly limited. Generally, resistance heating vapor deposition is preferred in terms of characteristics. The thickness of each layer is set in accordance with the electric resistance 値 of the luminescent material, and therefore it is not limited, but may be selected from 0.5 to 500 nm. It is preferably 1 to 100 nm, and more preferably 5 to 5 OO nm. The organic EL device of the present invention can be preferably used as a flat display. In addition, it can also be used as a flat backlight, in which case any one that emits colored light or emits white light can be used. The backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light, and can be used in a liquid crystal display device, a watch, an audio device, a car dashboard, a display panel, a logo, and the like. In particular, a liquid crystal display device, in which a conventional backlight for personal computer use is composed of a fluorescent lamp and a light guide plate, is difficult to be thinned, and the backlight of the light-emitting element of the present invention is characterized by being thin and lightweight. Therefore, the above problems can be eliminated. The same is very useful for lighting. When the diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene of the present invention is used, an organic EL display device having high luminous efficiency and long life can be obtained. Further, by combining the thin film transistor of the present invention, it is possible to inexpensively supply an organic EL display device in which the on-off phenomenon of the applied voltage can be controlled with high precision in the electric characteristics of the -41 - 201247676. (Regarding Photoelectric Conversion Element) By applying the organic semiconductor characteristics of the diterpene [2,3-b : 2',3'-f]thieno[3,2-b]thiophene of the present invention, it is expected to be applicable. It is a photoelectric conversion element that is flexible, low-cost, and easy to manufacture. In the organic solar cell element, since the electrolyte is not used as the dye-sensitized solar cell, it is advantageous in terms of improvement in flexibility and life, and conventionally, a combination of a conductive polymer and fullerene is used. The development of solar cells for organic thin film semiconductors is mainstream, but there is still a problem of power conversion efficiency. In general, the structure of an organic solar cell element is the same as that of a lanthanide solar cell, and is a layer in which a cathode and an anode are sandwiched to generate electricity, and a hole and an electron generated by absorbing light are received on each electrode. The function of solar cells. 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 material is referred to as an organic solar battery. The structure includes a Kent base joint, a heterojunction joint, a bulk heterojunction, a nanostructure joint, a hybrid molding, etc., and each of the materials efficiently absorbs the incident light to generate a charge, and the resulting The charge (holes and electrons) is separated, transported, and collected to function as a solar cell. Next, the constituent elements in the solar battery element of the present invention will be described. The anode and cathode ' in the solar cell element of the present invention are the same as the organic EL element described in the aforementioned -42-201247676. Since it is necessary to efficiently take light, it is preferably constituted as an electrode having transparency in the absorption wavelength region of the power generation layer. Further, in order to have good solar cell characteristics, the sheet resistance is preferably 20 Ω / □ or less. The power generation layer in the solar cell element of the present invention is formed by forming an organic film containing at least the diterpene [2,3-b: 2,3,-f]thieno[3,2-b]thiophene of the present invention. One layer or a plurality of layers are formed. Although the configuration shown previously can be employed, it is basically composed of a P-type donor material and an N-type acceptor material and a buffer layer. The P-type donor material 'is basically a compound which can transport a hole like the hole injection and hole transport layer described in the item of the organic EL element, or a poly-p-stene derivative, polythiophene. A 7-conjugated polymer of a derivative such as a polyfluorene derivative or a polyaniline derivative, or a carbazole or other polymer having a side chain of a heterocyclic ring. Examples of the low molecular compound include a pentacene derivative, a erythrene derivative, a porphyrin derivative, a phthalocyanine derivative, a saturated blue derivative, a quinacridone derivative, a merocyanin derivative, and a cyanine. a derivative, a squaraine derivative, a benzoquinone derivative, and the like. The N-type acceptor material is basically a compound capable of transporting electrons in the same manner as the electron transport layer described in the item of the organic EL element, or an oligomer or a polymer having pyridine and the derivative in the skeleton, a polymer having quinoline and an oligomer or polymer of the derivative, a polymer having benzophenanthroline and the derivative, a cyano-polyphenylene derivative (CN_PVV, etc.) Material 'either a fluorinated phthalocyanine derivative, a phenanthrene derivative, a naphthalene derivative, 2,9-dimethyl-4,7-diphenyl-I, 10-phenrolene derivative-43-201247676, C60 Or a low molecular material such as a fullerene derivative such as C70 or PCBM. It is preferable to efficiently absorb various kinds of light and generate electric charges, and the higher the absorption coefficient of the materials used, the better. The diterpene [2,3-b: 2',3'-f]pyrano[3,2-b]thiophene of the present invention is particularly preferably used as a P-type donor material. The method for forming a film for a power generation layer of the organic solar cell of the present invention can be the same as that described in the prior art of an organic EL device. The film thickness of the film or the like varies depending on the configuration of the solar cell. However, in order to sufficiently absorb light and prevent short-circuiting, the thicker is better, but the shorter the distance of the charge generated by the transport, the better. Thinner. In general, the power generation layer is preferably 10 to 5000 (for photosensors, image sensors) by applying the diterpene [2,3-b: 2',3'-f]thiophene of the present invention. [3,2-b] The physical properties and semiconductor properties of thiophene are expected to be applicable as photosensors or image sensors. The device may be an image sensor as a solid-state image sensor or a charge-coupled device (CCD) having a function of converting an image signal such as an animation or a still image into a digital signal, and may also be expected to be used as a cheaper device. Further, various sensors such as a large-area processing property and a flexible function inherent to an organic substance can be utilized. (About Organic Semiconductor Laser Element) Since the diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene-44-201247676 of the present invention is a compound having organic semiconductor characteristics Therefore, it can be expected to be applied as an organic semiconductor laser element. That is, as long as the resonator structure can be assembled to the organic semiconductor element containing the diterpene [2,3-b : 2',3'-f]thieno[3,2-b]thiophene of the present invention, efficiently By injecting a carrier and sufficiently increasing the density of the excited state, it is expected that the laser can be amplified to generate laser oscillation. In the past, it has been proposed to observe only laser oscillations based on photoexcitation, and it is difficult to perform high-density carriers injected into an organic semiconductor element to be necessary for laser oscillation by electrical excitation. High-density excitation state, but by using an organic semiconductor element containing the diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene of the present invention The possibility of causing high-efficiency luminescence (field luminescence) is expected. [Examples] The present invention will be described in more detail in the following examples, but the present invention is not limited to the examples. In the embodiment, "%" indicates "% by mass" unless otherwise specified. Further, when the reaction temperature is not specifically specified, it is described as the internal temperature in the reaction system. The various compounds obtained in the examples can be determined by various measurements such as mp (melting point), NMR (1H, 13C), IR (infrared absorption spectrum) MS (mass spectrometry), elemental analysis, etc., as necessary. formula. The measuring machine is as follows. Mp : Liuben micro melting point measuring device MP-S3 NMR : JEOL Lambda 400 spectrometer IR : Shimadzu Fourier transform infrared spectrophotometer IR Prestige- -45 - 201247676 2400 CHN elemental analyzer MS Spectrum: Shimadzu QP-5 0 5 0A Elemental analysis :Synthesis of Parkin Elmer 2400 Diterpene [2,3-b : 2',3'-f]thieno[3,2-b]thiophene (Synthesis of 〇3-Methylsulfate-2_methoxyoxindole 1 0]

A 1.67 M solution of n-BuLi (86 ml, 144 mmol) in THF was added to a solution of 2-methoxyoxane (15.0 g, 72 mmol) in THF (520 ml) as Compound (1). After stirring at room temperature for 1 hour, dimethyl disulfide (13 ml, 150 mmol) was added at EtOAc and stirred at room temperature for 7 hr. The mixture was poured into water (100 ml), and the THF was concentrated by an evaporator, and the crystals precipitated were filtered. After filtration, it was washed with water (100 ml), and then washed with methanol (100 ml) to give 3-methylthio-2-methoxyindole (18.3 g, quantitative) as white crystal compound (2) 〇mp 176.5 -177.5 °C : 'H NMR ( 400MHz » CDC13 ) δ 2.58(s,3H) , 4.03(s,3H) ,7_16(s'lH) ,7.39( ddd,J= 8.2,4.9 * 1.9Hz ' 1H) ' 7.42 ( ddd, J = 8.2 ' 4.9, 1.9 Hz, 1H > 1H ) 7.93 ( d 7.55 ( s - 1H ) , 7.92 ( d, J = 9.5 Hz 9.5 Hz, 1 H ) , 8 · 22 ( s, 1H) , 8.24 -46 - 201247676 (s > 1Η ) ; 13C NMR ( 125MHz > CDC13) δ 14.7 > 56.2 »

128.4 > 128.9 > 131.0 ' 131.0 ' 131.7 > 131.8 >154.6; EIMS ( 70eV ) m / z = 2 5 4 ( M+ ) . Anal Calcd for C16H14OS: C, 75·55; H, 5.55%. Found: C, 75.26; H, 5.33%. (Π) Synthesis of 2-hydroxy-3-methylthioindole [Chemical 1 1]

At -78. (3) BBr3 (ca. 2M, 50 ml '100 mmol) in dichloromethane was added dropwise to 3-methylthio-2-methoxyindole (14.5 g, 57 mmol) in dichloromethane (2 0 0 m 1 ) In the solution, after stirring for 5 hours at room temperature, add ice (about 50 g) at 〇 ° C. Extract the mixture with dichloromethane (200 m 1 X 3 ) to saturate saline (l〇 〇mix3) was washed and concentrated with MgS04 to give a white crystal of 2-bromo-3-methylthioindole (13.7 g, quantitative). mp 1 75.6~1 76.5 ° C; NMR (400 MHz, CDC13) 5 2.49 ( s > 3H ) , 6.54 (s, lH) > 7.3 1 ( s > 1H ) , 7.39 ( ddd , J = 1 0.7, 6.6, 1.4 Hz, 1 H ) , 7.41 ( s, 1H) > 7.43 (ddd, J = 1 0.7, 6.6, 1.4 Hz, 1 H ) , 7 _ 9 1 ( d, J = 8 · 8 H z , 1H) - 7.93 ( d > J = 8.8 Hz &gt ; 1H ) , 8.14 (s, lH), 3.22 ( s * 1H ) , 8.30 ( s, 1H) ; 13C NMR ( 100MHz - -47 - 201247676 CDC13 ) <5 19.8 > 107.8 > 124.2 > 125.0 &gt ; 1 26.2 - 1 26.2 - 126.8, 128.0, 128.5, 128.6, 130.8, 132.8, 133.0, 1 33.8, 15 1 .7 ; IR ( KBr ) v 35 1 0cm· 1 ( OH ) ; EIMS ( 7 0 e V ) m/z = 240 ( M+ ) 0 A na 1 C a 1 cd fo r C i 5 Η 12 0 S : C, 74.66 ; H > 4.72%. Found: C >74.70; H, 4.84%. (III) Synthesis of 3-(methylthio)indol-2-yltrifluoromethanesulfonate [Chemical 1 2]

A solution of trifluoromethanesulfonic anhydride (10 ml, 54.6 mmol) in dichloromethane was added at 0 ° C to 2-hydroxy-3-methylthioindole (10 g, 42 mmol) and triethylamine ( 16_0ffll, 115 mmol) in dichloromethane (400 mL). After stirring for 4 hours at room temperature and diluting with water (50 m 1 ), dilute hydrochloric acid (4M, 100 ml) was added. This was extracted with dichloromethane (i 〇〇 ml x 3 ), and then washed with saturated brine (100 ml×3 ) together with the organic layer obtained by the three extractions, and concentrated by drying with MgS04 to give a yellow solid. -(Methylthio)indole-2-yltrifluoromethanesulfonate (15.5 g, quantitative). Mp 105.5-106.0 °C : 'H NMR (400MHz - CDC13) δ 2.63 (s,3H) ' 7.50 ( ddd, J=9.6, 6.3, 1. 8Hz > 1H )

, 7.51 (ddd, J=9.6, 6.3, l.8 Hz, 1H) > 7.78 ( s > 1H ), 7.88 (s, lH) > 7.97 ( dd - J = 5.5 > 2.0 Hz - 1 H ) , 7.98 ( dd > J = 5.5 > 2.0 Hz - 1 H ) , 8.34 (s, 1H ) , 8.38 -48 - 201247676 (s ' 1H) : 13c NMR ( 125MHz, CDC13 ) δ 15.8 · 119.0 , (q , J=319Hz), 119.5, 125.4, 126.2, 126.4, 126.8, 127.1, 1 2 8.4 ( x 2 ) - 1 29.0 - 1 3 0.6 > 131.0 > 132.0 ' 132.9, 145.3 ; IR ( KBr ) u 1 429 1 207cm_1 ( -O-SO2-); EIMS ( 70eV ) m / z = 3 72 ( M+ ). Anal Calcd for (:16^30: C, 51.61; H, 2.98%. Found: C, 51.57; H, 2.67%. (IV) Synthesis of tributylstannyl acetylene [Chemical 1 3]

NaC^-H -► Bu3Sn-^H Tributyltin chloride (8.6ml, 32mmol) was added to 18w% Na acetylene in toluene and mineral oil dispersion oil (10ml, 8_5g, under 氮气°C). 32 mmol) in THF (60 ml). After stirring at room temperature for 17 hours, the mixture was extracted with hexane and washed with brine. The organic layers were combined and dried over MgS04 and concentrated. Distillation under reduced pressure (85 to 120 ° C, about 0.7 mmHg) to give tributylstannyl acetylene (3.6 g, 34%) as a colorless oily material. <1H NMR (400 MHz - CDC13) <5 0.91 ( t , 9H, J = 8.0Hz ) , 1.02 ( t * 8H ' J — 8.0Hz ) > 1.35 ( sextet , 6H' T = 8.0Hz ) , 1.58 ( quintet ' 6H ' J = 8.0Hz ) , 2.20 ( s * 1H) (V) 1,2-bis(tributylstannyl)ethylene (compound (3) -〇5) -49- 201247676 Synthesis [Chemical 1 4]

Bu3Sn^H -^ BU3Sf1s^SnBu3 (3)-05 Add azobisisobutyronitrile (l〇〇mg, ) to tributylstannyl acetylene (1.6g, 5mmol) butyltin (1.3) under nitrogen atmosphere The mixture was stirred under a solution of ml (5 ml) in toluene (20 ml) for 1 hour, heated and stirred at 90 ° C, and then concentrated. The mixture was extracted with hexane and purified to give 1,2-bis(stannyl)ethene (compound (3)-05) (3.0 g, 90%) as a colorless oily material. 400MHz ' CDC13 ) <5 0.8 6-0.9 1 ( .1 5 H ) , 1.31 (sextet, 6H, J = 8.0Hz), 1.50 , 6H, J = 8.0Hz ), 6.88 ( s, 2H ) (VI) Trans-1,2-bis(3-methylsodium sulphate 2-yl) yoke compound [Chemical 15] 0 · 6 0 mm ο 1 with hydrogenation III. Add water at room temperature (salt washing with tributylmethyl hydrazine multiplet (quintet into

In a nitrogen atmosphere, 'Pd(PPh3)4 (i.2g 'K was added to 3-(methylsulfate) onion-2_based trifluoromethane H.2g, 30. "and!,2·double (tributyltinyl) compound (3) -05) ( ' 15.〇_〇丨) of DMF (in 1 liquid, and at 1 〇〇. (; under the dark for 17 hours. Cool and

Ommol » sulfonate (ethylene (1 ml) dissolved in water -50 - 201247676 'The crystals precipitated are filtered and washed with water (l〇〇ml ) 'ethanol (5 〇ml) to give a yellow solid The trans-1,2-bis(3-methylthioindol-2-yl)ethane of the compound (4) (3.9 g, 55%).

Mp > 3 00 ° C ; 'H NMR ( 400 MHz , CDC 13 ) δ 2.66 ( s , 6H ) ' 7.44 ( dd . J = 5.0, 4.4 Hz, 4H ) , 7.75 ( s, 2H ) ' 7.78 ( s ' 2H ), 7.97 ( d, J = 9.6 Hz, 2H ) , 7.98 ( d , J = 9.6 Hz, 2H) , 8.27 (s, 2H) > 8.30 ( s - 2H ), 8.44 ( s ' 2H) ; 13C NMR (100MHz > CDC13) <5 16.8 > 124.2, 124.9, 125.7, 125.7, 126.0, 126.8, 126.9, 128.5, 128.6, 129.2, 130.6, 132.0, 132.8, 136.5, 147.3; IR (KBr) 1485, 1426, 1024,957,862,741cnT 1 ; EIMS ( 70eV) m / z = 472 ( M+) o Anal Calcd for C32H24S2: C,81.31 ; H, 5.12%. Found: C,81.21 ; H, 4.90% » (VII) Synthesis of diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene [Chem. 1 6]

The iodine (59 g, 232 mmol) pulverized into powder form and trans-1,2-bis(3-methylthioindol-2-yl)ethane (3.8 g, 8.0 mmol) were added to acetic acid (250 ml). , heating and refluxing for 1 hour. Excess acetic acid was removed by distillation, and saturated NaHS03 7JC solution (200 ml) was added and stirred for 1 hour. Filtration and washing with water (l〇〇ml), acetone (l〇〇ml), dichloro-51 - 201247676 methane (100 ml) to obtain a dark red solid [2,3-b: 2 ',3'-f]thieno[3,2,b]thiophene (DATT) (3.8 g, fixed). Sublimation purification (about 400 ° C, l (less than T2Pa, nitrogen reflux)' is recrystallized from chlorobenzene to obtain bis[2,3-b: 2',3'- in terms of yield of 50%. f] thieno[3,2-b]thiophene m p. > 3 Ο 0 °C ; EIMS (70eV) m/z = 440 (Μ+) . Anal Calcd

C30H16S2: C, 81.78: H, 3.66%. Found : c,81 38 ; H 3.52%. Amax = 550-570 nm (when film is used). Comparative Example 1 According to Patent Document 3, the synthesis of bis [2,3-b: 2',3'-f]thieno[3,2-b]thiophene was carried out in accordance with the following reaction formula (4). In the reaction formula (4-1), the 3-(methylthio) onion formic acid of the objective compound is obtained by a mixture of 80% in a yield and a foreign substance having a methylthio group introduced at the 1-position. From the identification of φ by the proton N MR, a mixture of the target (position 3) and the by-product (position 1) of 4:1 was obtained. By using the mixture to carry out the reaction shown in the reaction formula (4-2), trans-1,2-bis(3-) containing a target substance can be obtained with a purity of about 50% (identified by proton NMR). A crude product of methylthioindole-2-yl). Finally, a crude reaction containing diindole [2,3-b: 2',3'-f]thieno[3,2-b]thiophene is obtained by a cyclization reaction represented by the reaction formula (4-3). By repeating the sublimation refining and recrystallization, the desired combination can be obtained. However, compared with the manufacturing method of the present application, the intermediate impurities are extremely large, and the amount of 蒽 for 蒽2- constitutive rate is evenly calculated. The product only • 52- 201247676 The final total yield is greatly degraded 'The refining step to remove these impurities is also extremely cumbersome. [化1 7]

As described above, the diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene can be synthesized simply and efficiently by the present invention. Next, a field effect transistor having a semiconductor layer composed of diterpene [2,3-b : 2',3'-f]thieno[3,2-b]thiophene will be described in detail. Example 2 (top contact type field effect transistor) An n-doped germanium wafer (face resistance of 0.02 Ω·cm or less) with a 300 nm SiO 2 thermal oxide film treated with octadecyltrichloromethane was placed in The inside of the vacuum vapor deposition apparatus is 'exhausted until the degree of vacuum in the apparatus becomes 3.0 x 1 0_3 Pa or less. The diterpene [2,3-b: 2', 3'-f] obtained in Example 1 was obtained by a resistance heating evaporation method at a substrate temperature of about 100 t at a thickness of 25 nm. Thio[3,2-b]thiophene is evaporated on the electrode to form a semiconductor layer (2). Next, the electrode fabrication mask is mounted on the substrate, and is disposed in the vacuum vapor deposition apparatus to perform the evacuation until the degree of vacuum in the apparatus becomes 1.Ox l〇_4 Pa or less, and by the resistance heating evaporation method. 53- 201247676 The thickness of 4 Onm is used to vapor-deposit the gold electrode, that is, the source electrode (1) and the drain electrode (3), to obtain the field effect transistor of the present invention of TC (top contact type). In the field effect transistor of the present embodiment, the thermal oxide film in the n-doped germanium wafer with the thermal oxide film has the function of the insulating layer (4), and the n-doped germanium wafer also has the substrate (6) and The function of the gate electrode (5). The obtained field effect transistor was placed in a probe machine, and semiconductor characteristics were measured using a semiconductor parameter analyzer 41 55C (manufactured by Agilent Co., Ltd.). The semiconductor characteristic is that the gate voltage is scanned in a 20V phase from 10V to -100V, the drain voltage is scanned in 10V to -100V, and the drain current-thortion voltage is measured. As a result, current saturation was observed, and from the obtained voltage-current curve, it was found that the device was a p-type semiconductor, and the carrier mobility was 2.5 to 3.0 c m 2 /V s . Next, an organic solar cell element having a semiconductor layer composed of diterpene [2,3-b : 2',3'-f]thieno[3,2·b]thiophene will be described in detail. (Example 3) A glass substrate (manufactured by Tokyo Sanken Vacuum Co., Ltd., 20 Ω/□ or less) in which a 1T0 transparent conductive film was deposited by a 1T0 transparent conductive film was subjected to UV-ozone cleaning. The glass substrate was placed in a vacuum vapor deposition apparatus, and evacuated until the degree of vacuum in the apparatus was 3.0 x 1 (T3 Pa or less. The enthalpy obtained in Example 1 was obtained by a resistance heating vapor deposition method at a thickness of 40 nm [ 2,3-b: 2',3'-f]thieno[3,2-b]thiophene is evaporated on the electrode to form a semiconductor layer, and then C60 is deposited at a thickness of 40 nm to 1 〇nm -54 - 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline was evaporated to a thickness of 201247676. Then, a mask was deposited by vapor deposition of aluminum at a thickness of 100 nm to form a cathode. φ 2mm round organic solar cell component. Using the AM 1.5 solar simulation system, the photoelectric conversion efficiency was measured at l〇〇mW/cm, and the open voltage was 0.42V, and the short-circuit current was 5.04mA/cm2. An organic solar cell having a factor of 0.56 and a conversion efficiency of 1.19 %. Fig. 4 is a diagram showing the j_V characteristic of the organic solar cell element of the present embodiment. As described above, an airport effect transistor and an organic thin film solar energy can be produced. The battery element is confirmed for its practicability. The second and the second are produced by the present invention [2,3- b: 2',3'-f]thieno[3,2-b]thiophene, because of its excellent properties, can be said to be used as an organic field effect transistor, organic light-emitting diode, organic light-emitting transistor A compound which is extremely useful for materials for various organic electronic devices such as organic solar cells, organic lasers, organic photosensors, etc. [Simplified description of the drawings] Fig. 1 shows a form of the field effect transistor of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 2 is a schematic diagram showing the steps of a form (bottom contact type thin film transistor) for fabricating the field effect transistor of the present invention. Fig. 3 is a schematic diagram showing a form of organic EL. Fig. 4 is a TV characteristic diagram of the organic solar cell element of Example 3. -55-201247676 [Description of main component symbols] The same reference numerals are given to the same names in Fig. 1. 1 : source electrode 2: semiconductor layer 3 : Bipolar electrode 4: Insulator layer 5: Gate electrode 6: Substrate · 7 = Protective layer - 56-

Claims (1)

201247676 VII. Application for Patent Park: The method 'is a method for producing diterpene [2,3-b: 2',3,-f]thieno[3,2·b]thiophene, which is characterized by a step of reacting a compound represented by the formula (1) with dimethyl sulfide to obtain a compound represented by the formula (2), and reacting a compound represented by the formula (2) with a tin compound represented by the formula (3) to obtain a formula (4) a step of expressing a compound, and a step of cyclizing the compound represented by the formula (4) to obtain diterpene [2,3-b: 2',3'-f]thieno[3,2-b]thiophene; 1] [Chemical 2] [化3] 【化4】 (wherein R1 and R2 represent a substituent, and Me represents a methyl group). -57- 201247676 2 - an organic semiconductor material containing diterpene [2,3-b: 2',3'-f]thieno[3, obtained by the method of claim 1 2-b] thiophene. 3. An ink for fabricating a semiconductor device comprising diterpene [2,3-b: 2',3'-f]thieno[3,2- obtained by the method of claim 1 of the patent application. b] thiophene. 4. An organic semiconductor thin film comprising diterpene [2,3-b: 2',3'-f]pyrano[3,2-b] obtained by the method of claim 1 Thiophene. 5. An organic electronic device having an organic semiconductor film as in claim 4 of the patent application. 6. The organic electronic device of claim 5, which is a photoelectric conversion element, an organic EL element, an organic semiconductor laser element, a liquid crystal display element or a thin film transistor element. 7. An organic electronic device as claimed in claim 5, which is a solar battery. 8. An organic electronic device as claimed in claim 5, which is a light sensor. 9. A method of manufacturing an organic electronic device according to claim 5, which comprises: a second 蒽 [2, 3-b: 2', 3' obtained by the method of claim 1 -f] a step of forming a semiconductor layer composed of thieno[3,2-b]thiophene on a substrate. 10. The method of producing an organic electronic device according to claim 9, wherein the semiconductor layer is formed by an evaporation method. The method for producing an organic electronic device according to claim 9, wherein the semiconductor layer is formed by coating an ink of a semiconductor device as claimed in claim 3 of the patent application.