JP5600267B2 - Novel compounds and their use - Google Patents

Description

  The present invention relates to a novel compound and use thereof. More specifically, the present invention relates to a specific heterocyclic organic compound and an organic electronic device containing the same.

In recent years, interest in organic electronics devices has increased. Its features include a flexible structure and a large area, and further enabling an inexpensive and high-speed printing method in the electronic device manufacturing process. Typical devices include organic solar cell elements, organic photoelectric conversion elements, organic EL elements, organic transistor elements, and the like. Organic EL elements are applied from mobile phone displays to TVs, etc., and development aimed at further enhancement of functionality continues. Organic solar cell elements and the like have been actively researched and developed as inexpensive energy sources, and organic transistor elements and the like have been actively developed into flexible displays and inexpensive ICs.
In developing these organic electronic devices, it is very important to develop materials constituting the devices. For this reason, many materials have been studied in each field, but they cannot be said to have sufficient performance, and even now, materials that are useful for various devices are being actively developed.
Among them, a benzotrithiophene (hereinafter abbreviated as BTT) derivative is also expected, but only a few types have been synthesized, and there are almost no application developments. No compound having a body structure is known (Non-Patent Documents 1 and 2).

J. et al. Org. Chem. 1989, Vol. 54, 4203-4205. Org. Lett. , Vol. 6, no. 2, 273-276 (2004).

  The present invention is to provide a novel compound for use in an organic electronic device and its application. More specifically, it is to provide a novel multimeric compound having semiconductor characteristics applicable to organic electronic devices such as organic solar cell elements and organic transistor elements.

  In order to solve the above-mentioned problems, the present inventors have developed a novel multimeric compound, further studied its possibility as an organic electronic device, and completed the present invention.

That is, the present invention has the following configuration.
(1) A multimeric compound having two or more partial structures represented by the general formula (1).

(In formula (1), X ¹ , X ² and X ³ each independently represent a sulfur atom or a selenium atom.)
(2) The multimeric compound according to (1), wherein the multimeric compound having two or more partial structures represented by the general formula (1) is an oligomer or a dendrimer.
(3) The multimeric compound according to (1) or (2), which has two or more partial structures represented by the general formula (2),

(In formula (2), X ¹ , X ² and X ³ each independently represent a sulfur atom or a selenium atom. At least one portion of R ^{1 to} R ⁶ is combined with another partial structure to form a multimer. The remaining R ^{1 to} R ⁶ are each independently an aromatic hydrocarbon group, aliphatic hydrocarbon group, halogen atom, hydroxyl group, alkoxyl group, mercapto group, alkylthio group, boronic acid group, nitro group, amino group A group, an amide group, an acyl group, a carboxyl group, an acyloxy group, a cyano group, a sulfo group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group, an alkylcarbamoyl group, an alkyltin group, an aryltin group, or a hydrogen atom.
(4) The multimeric compound according to (3), wherein X ¹ , X ² and X ³ in the general formula (2) are all sulfur atoms.
(5) The multimeric compound according to any one of (1) to (3), which is represented by the general formula (3).

(In Formula (3), X ^{4 to} X ⁹ each independently represents a sulfur atom or a selenium atom. R ^{7 to} R ¹⁶ each independently represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a halogen atom, or a hydroxyl group. , Alkoxyl group, mercapto group, alkylthio group, boronic acid group, nitro group, amino group, amide group, acyl group, carboxyl group, acyloxy group, cyano group, sulfo group, sulfamoyl group, alkylsulfamoyl group, carbamoyl group, Represents an alkylcarbamoyl group, an alkyltin group, an aryltin group or a hydrogen atom.)
(6) The multimeric compound according to any one of (1) to (3), which is represented by the general formula (4).

(In formula (4), X ^{10 to} X ¹⁸ each independently represents a sulfur atom or a selenium atom. R ^{17 to} R ³⁰ each independently represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a halogen atom, or a hydroxyl group. , Alkoxyl group, mercapto group, alkylthio group, boronic acid group, nitro group, amino group, amide group, acyl group, carboxyl group, acyloxy group, cyano group, sulfo group, sulfamoyl group, alkylsulfamoyl group, carbamoyl group, Represents an alkylcarbamoyl group, an alkyltin group, an aryltin group or a hydrogen atom.)
(7) The multimeric compound according to any one of (1) to (3), which is represented by the general formula (5).

(Equation (5) ^{in, X 19} to ^{X 30 .R} independently represents a sulfur atom or a selenium atom 31 ^{to R 48} are each independently an aromatic hydrocarbon group, aliphatic hydrocarbon group, a halogen atom, a hydroxyl group , Alkoxyl group, mercapto group, alkylthio group, boronic acid group, nitro group, amino group, amide group, acyl group, carboxyl group, acyloxy group, cyano group, sulfo group, sulfamoyl group, alkylsulfamoyl group, carbamoyl group, Represents an alkylcarbamoyl group, an alkyltin group, an aryltin group or a hydrogen atom.)
(8) The multimeric compound according to any one of (1) to (3), which is represented by the general formula (6).

(In formula (6), X ^{31 to} X ⁴⁸ each independently represents a sulfur atom or a selenium atom. R ^{49 to} R ⁷⁴ each independently represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a halogen atom, or a hydroxyl group. , Alkoxyl group, mercapto group, alkylthio group, boronic acid group, nitro group, amino group, amide group, acyl group, carboxyl group, acyloxy group, cyano group, sulfo group, sulfamoyl group, alkylsulfamoyl group, carbamoyl group, Represents an alkylcarbamoyl group, an alkyltin group, an aryltin group or a hydrogen atom.)
(9) The multimeric compound according to any one of (1) to (3), which is represented by General Formula (7).

(In formula (7), X ^{49 to} X ⁷⁸ each independently represents a sulfur atom or a selenium atom. R ^{75 to} R ¹¹⁶ each independently represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a halogen atom, or a hydroxyl group. , Alkoxyl group, mercapto group, alkylthio group, boronic acid group, nitro group, amino group, amide group, acyl group, carboxyl group, acyloxy group, cyano group, sulfo group, sulfamoyl group, alkylsulfamoyl group, carbamoyl group, Represents an alkylcarbamoyl group, an alkyltin group, an aryltin group or a hydrogen atom.)
(10) An organic semiconductor material comprising the multimeric compound according to any one of (1) to (9).
(11) An organic electronic device containing the organic semiconductor material according to (10).
(12) The organic electronic device according to (11), wherein the device is a photoelectric conversion element, an organic solar cell element, an organic EL element, an organic semiconductor laser element, a liquid crystal display element, or a thin film transistor element.
(13) A composition comprising the multimeric compound according to any one of (1) to (9).
(14) A thin film containing the multimeric compound or composition according to any one of (1) to (9) or (13).
(15) The method for producing a multimeric compound according to any one of (1) to (9), comprising a coupling reaction between compounds having a partial structure represented by the general formula (1).
About.

  The present invention relates to a BTT derivative. An organic electronic device can be provided using the compound of the present invention, and a flexible electronic product can also be provided.

It is the schematic which shows the structural example of the structure of the thin-film transistor of this invention. It is the schematic of the process for manufacturing the example of 1 aspect of the thin-film transistor of this invention. 6 is a schematic view of a thin film transistor of the present invention obtained in Example 4. FIG. The structure of the organic EL element in Example 5 is shown. The drain current-drain voltage curve of the organic thin-film transistor in Example 4 is shown. The drain current-gate voltage curve of the organic thin-film transistor in Example 4 is shown. The IVL characteristic view of the organic EL element in Example 6 is shown. The JV characteristic view of the organic solar cell element in Example 7 is shown.

The present invention is described in detail below.
The present invention relates to a compound having two or more specific partial structures and use thereof.
First, the multimeric compound in the present invention will be described. The multimeric compound of the present invention has two or more partial structures represented by the following general formula (1).

In formula (1), X ¹ , X ² and X ³ each independently represent a sulfur atom or a selenium atom.
By having two or more partial structures of the general formula (1), the compound of the present invention can form an oligomer or a dendrimer.
When formula (1) is described in detail, it can be written as the following general formula (2).

Here, X ¹ , X ² and X ³ are each independently a sulfur atom or a selenium atom, but a sulfur atom is preferred. X ¹ , X ² and X ³ are preferably the same. Here, at least one of R ^{1 to} R ⁶ is combined with other partial structures to form a multimer. The remaining R ^{1 to} R ⁶ not used for the formation of the multimer are each independently an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a halogen atom, a hydroxyl group, an alkoxyl group, a mercapto group, an alkylthio group, or a boronic acid group. , Nitro group, amino group, amide group, acyl group, carboxyl group, acyloxy group, cyano group, sulfo group, sulfamoyl group, alkylsulfamoyl group, carbamoyl group, alkylcarbamoyl group, alkyltin group, aryltin group or hydrogen atom Represent.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a benzopyrenyl group. Among these, a phenyl group, a naphthyl group, and a pyrenyl group are preferable.
The substituent that the aromatic hydrocarbon group can have is not particularly limited, but for example, an aliphatic hydrocarbon group (which may have a substituent, such as a halogen atom, a hydroxyl group, , Mercapto group, carboxylic acid group, sulfonic acid group, nitro group, alkoxyl group, alkyl-substituted amino group, aryl-substituted amino group, unsubstituted amino group, aryl group, acyl group, alkoxycarbonyl group, etc.); aromatic Hydrocarbon group (this may have a substituent, such as an alkyl group, halogen atom, hydroxyl group, mercapto group, carboxylic acid group, sulfonic acid group, nitro group, alkoxyl group, alkyl-substituted amino group) , Aryl-substituted amino group, unsubstituted amino group, aryl group, acyl group, alkoxycarbonyl group, etc.); cyano Isocyano group; thiocyanato group; isothiocyanato group; nitro group; nitroso group; acyl group; acyloxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; mercapto group; substituted or unsubstituted amino group An alkoxyl group, an alkoxyalkyl group, a thioalkyl group, an aromatic oxy group, a sulfonic acid group, a sulfinyl group, a sulfonyl group, a sulfonic acid ester group, a sulfamoyl group, a carboxyl group, a carbamoyl group, a formyl group, and an alkoxycarbonyl group. . Among these, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a cyano group, a nitro group, an acyl group, a halogen atom, a hydroxyl group, a mercapto group, a substituted or unsubstituted amino group, an alkoxyl group, an areneoxy group, and the like are preferable. Examples of the aromatic hydrocarbon group shown in the above are condensed polycyclic hydrocarbon groups such as pyrenyl group and benzopyrenyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indolenyl group. Heterocyclic hydrocarbon groups such as imidazolyl group, carbazolyl group, thienyl group, furyl group, pyranyl group, pyridonyl group and the like, condensed heterocyclic hydrocarbon groups such as benzoquinolyl group, anthraquinolyl group, benzothienyl group, benzofuryl group, Etc.

  Moreover, as an aliphatic hydrocarbon group, a saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon group is mentioned, As for the carbon number, 1-20 are preferable. Here, examples of the saturated or unsaturated linear or branched aliphatic hydrocarbon group include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group, allyl group, t -Butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-stearyl group, n-butenyl group and the like can be mentioned. Examples of the cyclic aliphatic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms such as a cyclohexyl group, a cyclopentyl group, an adamantyl group, and a norbornyl group. Examples of the substituent that the aliphatic hydrocarbon group may have are not particularly limited, and examples thereof include a halogen atom, a cyano group, a hydroxyl group, a mercapto group, a nitro group, an alkoxyl group, a carboxylic acid group, and a sulfonic acid. A group, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group, an acyl group, an aromatic hydrocarbon group (these may have a substituent, such as an alkyl group, a halogen atom, a hydroxyl group) Group, mercapto group, carboxylic acid group, sulfonic acid group, nitro group, alkoxyl group, alkyl-substituted amino group, aryl-substituted amino group, unsubstituted amino group, aryl group, acyl group, alkoxycarbonyl group and the like. Among these, an aromatic hydrocarbon group, a cyano group, a nitro group, an acyl group, a halogen atom, a hydroxyl group, a mercapto group, a substituted or unsubstituted amino group, an alkoxyl group, an optionally substituted areneoxy group, and the like are preferable. . The aromatic hydrocarbon groups shown therein are the same as described above.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom, and a bromine atom are preferable.
Examples of the alkoxyl group include an alkoxyl group having 1 to 24 carbon atoms, and an alkoxyl group having 1 to 18 carbon atoms is preferable.
Examples of the alkylthio group include an alkylthio group having 1 to 24 carbon atoms, and an alkylthio group having 1 to 18 carbon atoms is preferable.
Examples of the amino group include an unsubstituted amino group, a monosubstituted amino group, and a disubstituted amino group.
As the substituent, an aromatic hydrocarbon group (which may have a substituent, such as an alkyl group, a halogen atom, a hydroxyl group, a mercapto group, a carboxylic acid group, a sulfonic acid group, a nitro group). An alkoxyl group, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group, an aryl group, an acyl group, an alkoxycarbonyl group, etc.), an aliphatic hydrocarbon group (which may have a substituent) As the substituent, a halogen atom, hydroxyl group, mercapto group, carboxylic acid group, sulfonic acid group, nitro group, alkoxyl group, alkyl-substituted amino group, aryl-substituted amino group, unsubstituted amino group, aryl group, acyl group, alkoxy A carbonyl group and the like). The aromatic hydrocarbon group and the aliphatic hydrocarbon group are the same as those described above.

  Examples of the amide group include an amide group having an aliphatic hydrocarbon group such as acetamido and an amide group having an aromatic hydrocarbon group such as benzamide. Examples of the acyl group include an acyl group having an aliphatic hydrocarbon group such as formyl group and acetyl group, and an acyl group having an aromatic hydrocarbon group such as benzoyl group. The acyl group in the acyloxy group is the same as that described above for the acyl group. Examples of the sulfamoyl group include an unsubstituted sulfamoyl group and a substituted sulfamoyl group. Examples of the carbamoyl group include an unsubstituted carbamoyl group and a substituted carbamoyl group. As those substituents, aromatic hydrocarbon groups (which may have a substituent, such as an alkyl group, a halogen atom, a hydroxyl group, a mercapto group, a carboxylic acid group, a sulfonic acid group, A nitro group, an alkoxyl group, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group, an aryl group, an acyl group, an alkoxycarbonyl group, etc.), an aliphatic hydrocarbon group (this may have a substituent, As the substituent, a halogen atom, hydroxyl group, mercapto group, carboxylic acid group, sulfonic acid group, nitro group, alkoxyl group, alkyl-substituted amino group, aryl-substituted amino group, unsubstituted amino group, aryl group, acyl group, alkoxycarbonyl Group) and the like. Examples of the alkyl tin group include octyl tin and tributyl tin, and examples of the aryl tin include triphenyl tin. The aromatic hydrocarbon group and the aliphatic hydrocarbon group are the same as those described above. In the aromatic hydrocarbon group, aliphatic hydrocarbon group and the like mentioned here, the hydrogen atom may be substituted with an appropriate substituent.

The following compound (3) is mentioned as a multimeric compound having two partial structures represented by the general formula (1).

X ^{4 to} X ⁹ shown here are the same as X ^{1 to} X ³ shown above.
In the compound of the general formula (3), any part of R ¹ , R ³ and R ⁵ of the partial structure represented by the general formula (2) is different from R ¹ , R ³ and R of the other general formula (2). ⁵ is bonded to any part of ⁵ to form a dimer. R ^{7 to} R ¹⁶ are the same as R ^{1 to} R ⁶ described above.

The following compound (4) may be mentioned as a compound having three partial structures represented by the general formula (1).

X ^{11 to} X ¹⁸ shown here are the same as X ^{1 to} X ³ shown above. R ^{17 to} R ³⁰ are the same as R ^{1 to} R ⁶ described above.

The following compound (5) may be mentioned as a compound having four partial structures represented by the general formula (1).

X ^{19 to} X ³⁰ shown here are the same as X ^{1 to} X ³ shown above. R ^{31 to} R ⁴⁸ are the same as R ^{1 to} R ⁶ described above.

The following compound (6) is mentioned as a compound which has six partial structures represented by General formula (1).

X ^{31 to} X ⁴⁸ shown here are the same as X ^{1 to} X ³ shown above. R ^{49 to} R ⁷⁴ are the same as R ^{1 to} R ⁶ described above.

The following compound (7) is mentioned as a compound having ten partial structures represented by the general formula (1).

X ^{49 to} X ⁷⁸ shown here are the same as X ^{1 to} X ³ shown above. R ^{75 to} R ¹¹⁶ are the same as R ^{1 to} R ⁶ described above.

  The compound represented by the general formula (1) is obtained by first using tetrabutylthiophene-3 by using butyllithium as a raw material dibromothiophene at a low temperature of −70 ° C. as in the known method disclosed in Non-Patent Document 2. The -one can then be synthesized by sequentially reacting 2-thienylmagnesium bromide and finally cyclizing and condensing by a photooxidation reaction. Alternatively, as shown in Scheme 1, the Sonogashira reaction is carried out from trichlorotriiodobenzene (100) using the corresponding acetylene derivative to synthesize compound (101), and then (102) can be efficiently converted by cyclization reaction. I can get it. At this time, the same reaction is possible not only with sulfur but also with selenium atoms (when R is a hydrogen atom, desilylation occurs during the cyclization reaction when trimethylsilylacetylene is used as the acetylene derivative).

The derivative thus obtained (compound 103 in which R is a hydrogen atom) can give a tribrominated compound (104) as described in Scheme 2 below, and a Sonogashira reaction using an acetylene derivative for this. To obtain a compound (105) having an unsaturated aliphatic hydrocarbon group, and further to carry out a reduction reaction, a compound (106) having a saturated aliphatic hydrocarbon group can be obtained. Moreover, the compound (107) which has an aromatic hydrocarbon group is obtained by performing cross coupling with the boronic acid derivative of an aromatic hydrocarbon compound. By controlling bromination at this time, the number of substituents (mono-, di-, tri-, tetra-, etc.) can be changed.

  The compound of the partial structure (1) obtained as described above may be coupled several times in some cases to obtain the multimeric compound of the present application which is the target product. As a coupling method, for example, if a derivative having an alkyltin group such as tributyltin as a substituent and a derivative having a halogen atom as a substituent are used as intermediates, a palladium catalyst such as Ueda-Kosugi-Still coupling was used. A cross-coupling reaction can be performed efficiently. In addition, a method of performing oxidative homocoupling by lithiation using a base such as butyl lithium between the portions in which the substituent of the partial structure (1) is a hydrogen atom is efficient. Other examples include Ullman coupling and a method using Suzuki-Miyaura coupling of a compound of partial structure (1) having a boronic acid group.

  As the first production method of the present invention, a base such as n-butyllithium is used in an anhydrous solvent such as tetrahydrofuran (hereinafter abbreviated as THF) for the parts in which the substituents of the partial structure (1) are hydrogen atoms. In this method, the product is obtained by lithiation and using an oxidative coupling reaction using a metal catalyst such as iron or copper to obtain a dimer of the target product. At this time, ether solvents such as dialkyl ether, THF, and dimethoxyethane can be preferably used as the solvent. Although there is no restriction | limiting in particular as the amount of solvents with respect to a raw material, Usually, it is 1-100 times amount. Preferably 2-20 times amount is mentioned. As the base for lithiation, n-butyllithium, t-butyllithium, metallic lithium or the like can be preferably used. The amount of base used is usually about 1 to 3 moles per mole of substrate. Examples of the metal catalyst include iron compounds such as iron triacetate and iron chloride, copper compounds such as metal copper, copper iodide and copper oxide, and palladium compounds. Preferably, iron compounds such as iron triacetate are used. As a usage-amount of a catalyst, it is 0-10 mol normally with respect to 1 mol of substrates, and about 0.1-5 mol is preferable. The reaction temperature is usually −70 to 200 ° C., preferably −20 to 100 ° C., and more preferably near room temperature to 80 ° C.

  The second production method of the present invention includes a cross-coupling reaction using a derivative having an alkyltin group such as tributyltin as a substituent and a derivative having a halogen atom as a substituent as an intermediate. According to this method, in addition to the dimer body, a multimer having the partial structure (1) as a core can be efficiently produced, which is suitable for reactions such as dendrimers. Derivatives and bromo compounds having tributyltin are synthesized in advance and used as raw materials. Although there is no restriction | limiting in particular as a solvent, Amides, such as aromatic solvents, such as toluene, xylene, and chlorobenzene, N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide, etc. are mentioned. Although there is no restriction | limiting in particular as a solvent amount with respect to a raw material, Usually, it is 1-100 times amount, Preferably it is 2-20 times amount. Examples of the catalyst include a palladium catalyst and a nickel catalyst. Of these, a palladium-based catalyst is preferable. The addition amount of the catalyst is usually 0 to 1 mol with respect to 1 mol of the substrate, preferably about 0.001 to 0.1 mol. The reaction temperature is usually room temperature to 250 ° C, preferably 50 to 200 ° C. The compound can be efficiently obtained by appropriately adjusting with the substituent introduced into the compound. In the reaction formula, an example in which X is a sulfur atom is given, but a compound having a selenium atom can be obtained in the same manner.

  The purification method of the multimeric compound of the present invention is not particularly limited, and known methods such as recrystallization, column chromatography, and vacuum sublimation purification can be employed. Moreover, you may use these methods in combination as needed.

  Specific examples of the above multimeric compound are listed below, but not limited thereto. At this time, CH represents a cyclohexyl group, Ph represents a phenyl group, DP represents a 4-dodecylphenyl group, Np represents a 1-naphthyl group, and Th represents a 2-thienyl group.

  The multimeric compound of the present invention can be used as a composition containing this multimeric compound, a solvent, and / or a binder. As the solvent, any solvent can be used as long as it dissolves or disperses the multimeric compound and the binder and becomes a liquid in an appropriate temperature range. Specific examples of the solvent include benzene, toluene, xylene, mesitylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, tetrahydrofuran, methylene chloride, chloroform, ether, hexane, cyclohexane, heptane, acetonitrile, acetone, cyclopentanone, Examples include, but are not limited to, cyclohexanone, 2-butanone, 2,4-dimethyl-3-pentanone, ethyl acetate, 1-butanol, fluorobenzene, 1,2-dimethoxyethane, methylnaphthalene, decalin, and tetrahydronaphthalene. . These solvents may be used alone or in combination of two or more.

  As the binder, a polymer compound and, if necessary, a mixture of various other low molecular compounds and additives can be used. A polymer compound is a macromolecule formed by chemical bonding of a very large number of atoms, and a polymer having a repeating structural unit of a monomer is also included in the polymer compound. Generally, a polymer having a molecular weight of about 10,000 or more is regarded as a polymer compound, but in a broad sense, a polymer having a low molecular weight called an oligomer is also called a polymer compound. The polymer compound in the present invention includes not only a compound having a high molecular weight but also a polymer having a relatively small molecular weight.

  The binder used in the present invention is preferably a polymer compound that is solid at room temperature and is soluble in a solvent. Specific examples of these polymer compounds are roughly classified into organic synthetic polymer compounds, organic natural polymer compounds, and inorganic polymer compounds. Specific examples thereof include the following compounds and derivatives, copolymers, and mixtures thereof. All of these high molecular compounds described below can be used alone or in combination of two or more.

  Organic synthetic polymer compounds include synthetic resins, plastics, polyvinyl chloride polymers, polyethylene polymers, phenol resin polymers, polystyrene polymers, acrylic resin polymers, amide resin polymers, esters. Resin polymer, nylon polymer, vinylon polymer, polyethylene terephthalate polymer, synthetic rubber polymer, polyisoprene polymer, acrylic rubber polymer, acrylonitrile rubber polymer, urethane rubber polymer Preferred are synthetic resins, plastics, polyvinyl chloride polymers, polyethylene polymers, phenol resin polymers, polystyrene polymers, acrylic resin polymers, amide resin polymers, ester resins. Polymer, nylon polymer, vinylon polymer, polyethylene terephthalate And the like bets based polymers, more preferably synthetic resins, plastics, polyvinyl chloride polymers, polystyrene polymers, polyethylene polymer, a phenolic resin polymer, acrylic resin-based polymer.

  Examples of the organic natural polymer include cellulose, starch, and natural rubber, and cellulose and starch are more preferable. Examples of the inorganic polymer compound include silicone resin and silicone rubber.

  When these polymer compounds are classified from the viewpoint of electrical characteristics, they are roughly classified into conductive polymer compounds, semiconducting polymer compounds, and insulating polymer compounds.

  The conductive polymer compound is a polymer compound characterized by having a π electron skeleton developed in the molecule and exhibiting electrical conductivity. Specific examples of the conductive polymer compound include polyacetylene polymer, polydiacetylene polymer, polyparaphenylene polymer, polyaniline polymer, polythiophene polymer, polypyrrole polymer, polyparaphenylene vinylene polymer. , Polyethylenedioxythiophene polymer, polyethylenedioxythiophene / polystyrenesulfonic acid mixture (generic name, PEDOT-PSS), nucleic acids and derivatives thereof, many of which have improved conductivity by doping. Among these conductive polymer compounds, polyacetylene polymers, polyparaphenylene polymers, polyaniline polymers, polythiophene polymers, polypyrrole polymers, polyparaphenylene vinylene polymers, and the like are more preferable.

  A semiconducting polymer compound is a polymer compound exhibiting semiconductor properties. Specific examples of semiconducting polymer compounds include polyacetylene polymers, polydiacetylene polymers, polyparaphenylene polymers, polyaniline polymers, polythiophene polymers, polypyrrole polymers, polyparaphenylene vinylene polymers. , Polyethylenedioxythiophene polymers, nucleic acids and derivatives thereof. Specific examples thereof include polyacetylene polymers, polyaniline polymers, polythiophene polymers, polypyrrole polymers, polyparaphenylene vinylene polymers, and the like. The semiconducting polymer compound exhibits conductivity by doping, and may have conductivity depending on the doping amount.

  The insulating polymer compound is a polymer compound characterized by exhibiting insulating properties, and most of the polymer compound other than the conductive or semiconducting polymer compound is an insulating polymer compound. Specific examples include acrylic polymers, polyethylene polymers, polymethacrylate polymers, polystyrene polymers, polyethylene terephthalate polymers, nylon polymers, polyamide polymers, polyester polymers, vinylon polymers. Examples thereof include molecules, polyisoprene polymers, cellulose polymers, copolymer polymers, and derivatives thereof.

  As long as the effects obtained with the composition of the present invention are not impaired, other additives such as a carrier generating agent, a conductive substance, a viscosity adjusting agent, a surface tension adjusting agent, a leveling agent, a penetrating agent, and a wetting preparation agent are necessary. , Rheology modifiers and the like may be added.

  The content of the multimeric compound in the composition of the present invention is usually 0.01 to 95%, preferably 0.05 to 50%, more preferably 0.1 to 20%. The “%” is based on weight, and the same applies hereinafter unless otherwise specified.

  The content of the solvent in the composition of the present invention is usually in the range of 5 to 99.99%, preferably 50 to 99.95%, more preferably 80 to 99.9%.

  The binder in the composition of the present invention may be used, but may not be used. As content when using, it is good to use normally in 1-500% with respect to the multimeric compound of this invention, Preferably it is 5-300% of range.

  Other additives in the composition of the present invention may be used but may not be used. The content when used is usually in the range of 0.1 to 100%, preferably 0.2 to 50%, more preferably 0.5 to 30% with respect to the multimeric compound.

  The composition of the present invention can be prepared, for example, by dissolving or dispersing a multimeric compound and a binder in a solvent so as to have the above content, and heat-treating and stirring according to the respective solubility. This is not the case. Further, as described above, a binder and other additives may or may not be used. When the other additives are added, they may be added appropriately so as not to leave undissolved components, or undissolved components may be removed by a treatment such as filtration.

  The thin film of the present invention refers to a thin film formed from the multimeric compound of the present invention or a composition containing the same. Although the film thickness of a thin film changes with the uses, it is 0.1 nm-100 micrometers normally, Preferably it is 0.5 nm-30 micrometers, More preferably, it is 1 nm-20 micrometers.

  The thin film forming method of the present invention generally includes resistance heating evaporation, which is a vacuum process, electron beam evaporation, sputtering, molecular lamination, etc., and spin coating, drop casting, dip coating, and spraying, which are solution processes. Letterpress printing methods such as printing, flexographic printing, resin letterpress printing, offset printing methods, dry offset printing methods, pad printing methods, lithographic printing methods such as lithographic printing methods, intaglio printing methods such as gravure printing methods, silk screen printing methods, Examples thereof include a stencil printing method such as a stencil printing method and a lithographic printing method, an ink jet printing method, a microcontact printing method, and a method in which a plurality of these methods are combined. Usually, a resistance heating vapor deposition method that is a vacuum process, a spin coating method that is a solution process, a dip coating method, an ink jet method, screen printing, letterpress printing, and the like are preferable. Moreover, since the film forming method required in each organic electronic device is different, it will be described later in the section of each device.

  The organic electronic device of the present invention contains the multimeric compound as an electronic material for electronics. Examples of the organic electronic device include a thin film transistor, an organic EL element, a liquid crystal display element, a photoelectric conversion element, an organic solar cell element, and an organic semiconductor laser element. These will be described in detail.

First, the thin film transistor will be described in detail.
A thin film transistor has two electrodes (a source electrode and a drain electrode) in contact with a semiconductor, and a current flowing between the electrodes is controlled by a voltage applied to another electrode called a gate electrode.

  In general, a thin film transistor element often has a structure in which a gate electrode is insulated by an insulating film (Metal-Insulator-Semiconductor: MIS structure). An insulating film using a metal oxide film is called a MOS structure. In addition, there is a structure in which a gate electrode is formed through a Schottky barrier, that is, an MES structure, but in the case of a thin film transistor using an organic semiconductor material, an MIS structure is often used.

Hereinafter, the organic thin film transistor according to the present invention will be described in more detail with reference to the drawings. However, the present invention is not limited to these structures.
FIG. 1 shows some embodiments of the thin film transistor (element) of the present invention. In each example, 1 is a source electrode, 2 is a semiconductor layer, 3 is a drain electrode, 4 is an insulator layer, 5 is a gate electrode, and 6 is a substrate. In addition, arrangement | positioning of each layer and an electrode can be suitably selected according to the use of an element. A to D are called lateral transistors because current flows in a direction parallel to the substrate. A is called a bottom contact structure, and B is called a top contact structure. C has a source and drain electrode and an insulator layer on a semiconductor and further has a gate electrode formed thereon, which is called a bottom gate structure. D has a structure called a top & bottom contact type transistor. E is a schematic diagram of a transistor having a vertical structure, that is, a static induction transistor (SIT). In this SIT, a large amount of carriers can move at a time because the current flow spreads in a plane. Further, since the source electrode and the drain electrode are arranged vertically, the distance between the electrodes can be reduced, so that the response is fast. Therefore, it can be preferably applied to uses such as high-speed switching with a large current. Note that although a substrate is not described in E in FIG. 1, a substrate is usually provided outside the source and drain electrodes represented by 1 and 3 in E in FIG. 1.

Each component in each embodiment will be described.
The substrate 6 needs to be able to hold each layer formed thereon without peeling off. For example, insulating materials such as resin plates, films, paper, glass, quartz, ceramics, etc .; those in which an insulating layer is formed on a conductive substrate such as metal or alloy by coating; materials consisting of various combinations such as resin and inorganic materials Can be used. Examples of the resin film that can be used include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyamide, polyimide, polycarbonate, cellulose triacetate, and polyetherimide. When a resin film or paper is used, the element can have flexibility, is flexible and lightweight, and improves practicality. The thickness of the substrate is usually 1 μm to 10 mm, preferably 5 μm to 5 mm.

A conductive material is used for the source electrode 1, the drain electrode 3, and the gate electrode 5. For example, platinum, gold, silver, aluminum, chromium, tungsten, tantalum, nickel, cobalt, copper, iron, lead, tin, titanium, indium, palladium, molybdenum, magnesium, calcium, barium, lithium, potassium, sodium, and other metals And alloys containing them; conductive oxides such as InO ₂ , ZnO ₂ , SnO ₂ , ITO; conductive polymer compounds such as polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, vinylene, polydiacetylene; silicon, germanium And semiconductors such as gallium arsenide; carbon materials such as carbon black, fullerene, carbon nanotubes, and graphite; In addition, the conductive polymer compound or the semiconductor may be doped. Examples of the dopant 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 PF ₅ , AsF ₅ and FeCl ₃ ; halogen atoms such as iodine; lithium, Metal atoms such as sodium and potassium; and the like. Boron, phosphorus, arsenic and the like are also frequently used as dopants for inorganic semiconductors such as silicon. In addition, a conductive composite material in which carbon black, metal particles, or the like is dispersed in the above dopant is also used.

Further, the distance (channel length) between the source and drain electrodes is an important factor that determines the characteristics of the device. The channel length is usually 0.1 to 300 μm, preferably 0.5 to 100 μm. If the channel length is short, the amount of current that can be extracted increases. However, since a leak current or the like occurs, an appropriate channel length is required. The width (channel width) between the source and drain electrodes is usually 10 to 10,000 μm, preferably 100 to 5000 μm. Further, this channel width can be made longer by forming the electrode structure into a comb structure, etc., and may be set to an appropriate length depending on the required amount of current or the structure of the element. .
Each structure (shape) of the source and drain electrodes will be described. The structure of the source and drain electrodes may be the same or different. The length of the electrode may be the same as the channel width. There is no particular limitation on the width of the electrode, but a shorter one is preferable in order to reduce the area of the element as long as the electrical characteristics can be stabilized. The width of the electrode is usually 0.1 to 1000 μm, preferably 0.5 to 100 μm. The thickness of an electrode is 0.1-1000 nm normally, Preferably it is 1-500 nm, More preferably, it is 5-200 nm. A wiring is connected to each of the electrodes 1, 3, and 5, but the wiring is also made of substantially the same material as the electrode.

An insulating material is used for the insulator layer 4. For example, polymers such as polyparaxylylene, polyacrylate, polymethyl methacrylate, polystyrene, polyvinyl phenol, polyamide, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, epoxy resin, phenol resin, and combinations thereof Copolymers; metal oxides such as silicon dioxide, aluminum oxide, titanium oxide and tantalum oxide; ferroelectric metal oxides such as SrTiO ₃ and BaTiO ₃ ; nitrides such as silicon nitride and aluminum nitride; sulfides; Dielectric materials such as chemical compounds; or polymers in which particles of these dielectric materials are dispersed can be used. The film thickness of the insulator layer 4 varies depending on the material, but is usually 0.1 nm to 100 μm, preferably 0.5 nm to 50 μm, more preferably 1 nm to 10 μm.

As the material of the semiconductor layer 2, the multimeric compound of the present invention or a composition thereof is used. The semiconductor layer 2 is formed as a thin film using the above method. In order to improve the characteristics of the thin film transistor and to impart other characteristics, other organic semiconductor materials and various additives may be mixed as necessary. The semiconductor layer 2 may be composed of a plurality of layers.
In the thin film transistor of the present invention, at least one compound of the multimeric compound of the present invention is used as the organic semiconductor material. When a thin film is formed using the multimeric compound of the present invention and the composition thereof, and a solvent is used as the composition, it can be used after substantially evaporating it. As will be described later, when an organic semiconductor layer is formed by an evaporation method, it may be preferable to use a single multimeric compound as the organic semiconductor material rather than using a mixture of multimeric compounds. However, additives such as dopants can be used for the purpose of improving the characteristics of the transistor as described above. This is particularly effective when a semiconductor layer is formed by a solution process.

The above additives are usually added in the range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, when the total amount of the organic semiconductor material is 1. It is good to do. This is not the case when the semiconductor composition is used as the organic semiconductor material.
A plurality of layers may also be formed for the semiconductor layer, but a single layer structure is more preferable. The thickness of the semiconductor layer 2 is preferably as thin as possible without losing necessary functions. In a horizontal thin film transistor as shown in A, B, and D, since the leakage current increases as the film thickness increases, the element characteristics do not depend on the film thickness if the film thickness exceeds a predetermined value. The film thickness of the semiconductor layer for exhibiting necessary functions is usually 1 nm to 10 μm, preferably 5 nm to 5 μm, more preferably 10 nm to 3 μm.

  In the thin film transistor of the present invention, for example, other layers can be provided as necessary between the substrate layer and the insulating film layer, between the insulating film layer and the semiconductor layer, or on the outer surface of the element. For example, when a protective layer is formed directly on the organic semiconductor layer or via another layer, the influence of outside air such as humidity can be reduced, and the ON / OFF ratio of the element can be increased. There is also an advantage that the electrical characteristics can be stabilized.

  The material of the protective layer is not particularly limited. For example, films made of various resins such as acrylic resin such as epoxy resin and polymethyl methacrylate, polyurethane, polyimide, polyvinyl alcohol, fluororesin, polyolefin, etc .; silicon oxide, aluminum oxide, nitriding A film made of an inorganic oxide film such as silicon and a dielectric film such as a nitride film is preferably used, and a resin (polymer) having a low oxygen or moisture permeability and a low water absorption rate is particularly preferable. In recent years, protective materials developed for organic EL displays can also be used. Although the film thickness of a protective layer can select arbitrary film thickness according to the objective, Usually, it is 100 nm-1 mm.

In addition, it is possible to improve characteristics as a thin film transistor element by performing surface treatment in advance on a substrate or an insulator layer on which an organic semiconductor layer is stacked. For example, by adjusting the degree of hydrophilicity / hydrophobicity of the substrate surface, the film quality of the film formed thereon can be improved. In particular, the characteristics of organic semiconductor materials can vary greatly depending on the state of the film, such as molecular orientation. For this reason, the surface treatment on the substrate or the like can control the molecular orientation at the interface between the substrate and the organic semiconductor layer to be formed thereafter, and can reduce the trap sites on the substrate and the insulator layer. Therefore, it is considered that characteristics such as carrier mobility are improved.
The trap site refers to a functional group such as a hydroxyl group present in an untreated substrate. When such a functional group is present, electrons are attracted to the functional group, and as a result, carrier mobility is lowered. Therefore, reducing trap sites is often effective for improving characteristics such as carrier mobility.

  Examples of the substrate treatment for improving the characteristics as described above include hydrophobization treatment with hexamethyldisilazane, cyclohexene, octyltrichlorosilane, octadecyltrichlorosilane, etc .; acid treatment with hydrochloric acid, sulfuric acid, acetic acid, etc .; sodium hydroxide, Alkaline treatment with potassium hydroxide, calcium hydroxide, ammonia, etc .; ozone treatment; fluorination treatment; plasma treatment with oxygen or argon; Langmuir / Blodgett film formation treatment; other insulator or semiconductor thin film formation treatment; Examples include mechanical treatment; electrical treatment such as corona discharge; and rubbing treatment using fibers and the like.

  In these embodiments, for example, a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method, or the like can be appropriately employed as a method of providing each layer such as a substrate layer and an insulating film layer or an insulating film layer and an organic semiconductor layer. .

  Next, a method for manufacturing a thin film transistor element according to the present invention will be described below with reference to FIG. 2 by taking the bottom contact type thin film transistor shown in the embodiment example A of FIG. 1 as an example. This manufacturing method can be similarly applied to the thin film transistors of other embodiments described above.

(Thin film transistor substrate and substrate processing)
The thin film transistor of the present invention is manufactured by providing various layers and electrodes necessary on the substrate 6 (see FIG. 2A). As the substrate, those described above can be used. It is also possible to perform the above-described surface treatment or the like on this substrate. The thickness of the substrate 6 is preferably thin as long as necessary functions are not hindered. Although it varies depending on the material, it is usually 1 μm to 10 mm, preferably 5 μm to 5 mm. Moreover, you may make it give the function of an electrode to a board | substrate as needed.

(About formation of gate electrode)
A gate electrode 5 is formed on the substrate 6 (see FIG. 2B). The electrode material described above is used as the electrode material. As a method for forming the electrode film, various methods can be used. For example, a vacuum deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method, a sol-gel method, and the like are employed. It is preferable to perform patterning as necessary so as to obtain a desired shape during or after film formation. Various methods can be used as the patterning method, and examples thereof include a photolithography method in which patterning and etching of a photoresist are combined. Moreover, it is also possible to perform patterning using a printing method such as ink jet printing, screen printing, offset printing, letterpress printing or the like, a soft lithography method such as a micro contact printing method, and a method combining a plurality of these methods. The thickness of the gate electrode 5 varies depending on the material, but is usually 0.1 nm to 10 μm, preferably 0.5 nm to 5 μm, more preferably 1 nm to 3 μm. Moreover, when it serves as a gate electrode and a board | substrate, it may be larger than said film thickness.

(About formation of insulator layer)
An insulator layer 4 is formed over the gate electrode 5 (see FIG. 2 (3)). As the insulator material, those described above are used. Various methods can be used to form the insulator layer 4. For example, spin coating, spray coating, dip coating, casting, bar coating, blade coating and other coating methods, screen printing, offset printing, inkjet printing methods, vacuum deposition, molecular beam epitaxial growth, ion cluster beam method, ion plating Examples thereof include dry process methods such as a coating method, a sputtering method, an atmospheric pressure plasma method, and a CVD method. In addition, a sol-gel method, alumite on aluminum, a method of forming an oxide film on a metal such as silicon dioxide on silicon, and the like are employed. In the portion where the insulator layer and the semiconductor layer are in contact with each other, a predetermined surface treatment is applied to the insulator layer in order to satisfactorily orient the molecules constituting the semiconductor at the interface between the two layers, for example, the molecules of the multimeric compound of the present invention. Can also be done. As the surface treatment method, the same surface treatment as that of the substrate can be used. The thickness of the insulator layer 4 is preferably as thin as possible without impairing its function. Usually, it is 0.1 nm-100 micrometers, Preferably it is 0.5 nm-50 micrometers, More preferably, it is 5 nm-10 micrometers.

(Formation of source electrode and drain electrode)
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)). Various additives can be used to reduce the contact resistance with the organic semiconductor layer.

(Formation of organic semiconductor layer)
As the organic semiconductor material, as described above, one type of the multimeric compound of the present invention or a composition thereof is used. In forming the organic semiconductor layer, various methods can be used. Formation method in a vacuum process such as sputtering method, CVD method, molecular beam epitaxial growth method, vacuum deposition method; coating method such as dip coating method, die coater method, roll coater method, bar coater method, spin coating method, ink jet method, It is roughly classified into solution forming methods such as screen printing, offset printing, and microcontact printing.

  In addition, when using the multimeric compound of this invention as an organic-semiconductor material and forming an organic-semiconductor layer, the method of forming into a film by solution processes, such as printing, and a vacuum process, and forming an organic-semiconductor layer is mentioned.

First, a method for obtaining an organic semiconductor layer by forming an organic semiconductor material by a vacuum process will be described. A method in which the organic semiconductor material is heated in a crucible or a metal boat under vacuum, and the evaporated organic semiconductor material is attached (evaporated) to a substrate (exposed portions of the insulator layer, the source electrode and the drain electrode), that is, vacuum. A vapor deposition method is preferably employed. Under the present circumstances, a vacuum degree is 1.0 * 10 < ^-1 > Pa or less normally, Preferably it is 1.0 * 10 < ^-3 > Pa or less. In addition, since the characteristics of the organic semiconductor film and thus the thin film transistor may change depending on the substrate temperature during vapor deposition, it is preferable to select the substrate temperature carefully. The substrate temperature at the time of vapor deposition is usually 0 to 200 ° C, preferably 10 to 150 ° C, more preferably 15 to 120 ° C, still more preferably 25 to 100 ° C, and particularly preferably 40 to 80 ° C. ° C.
Moreover, a vapor deposition rate is 0.001-10 nm / sec normally, Preferably it is 0.01-1 nm / sec. The film thickness of the organic semiconductor layer formed from the organic semiconductor material is usually 1 nm to 10 μm, preferably 5 nm to 5 μm, more preferably 10 nm to 3 μm.
Instead of the vapor deposition method in which the organic semiconductor material for forming the organic semiconductor layer is heated and evaporated to adhere to the substrate, accelerated ions such as argon collide with the material target to knock out the material atoms and adhere to the substrate. A sputtering method may be used.

Next, a method for obtaining an organic semiconductor layer by forming a film by a solution process will be described. The polymer compound of the present invention is dissolved in a solvent or the like, and further applied to a substrate (exposed portions of the insulator layer, source electrode and drain electrode) using a composition obtained by adding a binder if necessary. . Coating methods include casting, spin coating, dip coating, blade coating, wire bar coating, spray coating, and other coating methods, inkjet printing, screen printing, offset printing, letterpress printing, and other micro contact printing methods. The method of soft lithography, etc., or a method combining a plurality of these methods may be employed.
Furthermore, as a method similar to the coating method, a Langmuir project method in which a monomolecular film of an organic semiconductor layer produced by dropping the above ink on a water surface is transferred to a substrate and laminated, and two materials of liquid crystal or a melt state are used. It is also possible to adopt a method of sandwiching between substrates or introducing between substrates by capillary action. The environment such as the temperature of the substrate and the composition at the time of film formation is also important, and the characteristics of the transistor may change depending on the temperature of the substrate and the composition. Therefore, it is preferable to carefully select the temperatures of the substrate and the composition. The substrate temperature at the time of vapor deposition is usually 0 to 200 ° C, preferably 10 to 120 ° C, more preferably 15 to 100 ° C. Special care must be taken because it depends greatly on the solvent in the composition to be used.

  The film thickness of the organic semiconductor layer produced by this method is preferably thinner as long as the function is not impaired. There is a concern that the leakage current increases as the film thickness increases. The film thickness of the organic semiconductor layer is usually 1 nm to 10 μm, preferably 5 nm to 5 μm, more preferably 10 nm to 3 μm.

The characteristics of the organic semiconductor layer thus formed (see FIG. 2 (5)) can be further improved by post-processing. For example, it is considered that the heat treatment reduces strain in the film generated at the time of film formation, reduces pinholes, etc., and can control the arrangement and orientation in the film. The semiconductor characteristics can be improved and stabilized. When the thin film transistor of the present invention is produced, this heat treatment is effective for improving the characteristics. This heat treatment is performed by heating the substrate after forming the organic semiconductor layer. The temperature of the heat treatment is not particularly limited, but is usually room temperature to 150 ° C, preferably 40 to 120 ° C, more preferably 45 to 100 ° C. Although there is no restriction | limiting in particular about the heat processing time at this time, Usually, it is about 1 minute-24 hours, Preferably it is about 2 minutes-3 hours. The atmosphere at that time may be air, but may be an inert atmosphere such as nitrogen or argon.
In addition, as a post-treatment method for other organic semiconductor layers, a property change due to oxidation or reduction is induced by treatment with an oxidizing or reducing gas such as oxygen or hydrogen or an oxidizing or reducing liquid. You can also. This is often used for the purpose of increasing or decreasing the carrier density in the film, for example.

In addition, in a technique called doping, characteristics of the organic semiconductor layer can be changed by adding a trace amount of elements, atomic groups, molecules, and polymers to the organic semiconductor layer. For example, oxygen, hydrogen, hydrochloric acid, sulfuric acid, sulfonic acid and other acids; PF ₅ , AsF ₅ , FeCl _{3 and} other Lewis acids; iodine and other halogen atoms; sodium and potassium and other metal atoms; various organic semiconductor materials and the like can do. This can be achieved by bringing these gases into contact with the organic semiconductor layer, immersing them in a solution, or performing an electrochemical doping treatment. These dopings may be added during the synthesis of the organic semiconductor compound, even after the organic semiconductor layer is not prepared, or may be added to the ink in the process of preparing the organic semiconductor layer using the ink for preparing the organic semiconductor element. It can be added in the process step of forming a thin film. In addition, a doping material is added to the material that forms the organic semiconductor layer during vapor deposition and co-evaporation is performed, or the organic semiconductor layer is mixed with the surrounding atmosphere when the organic semiconductor layer is formed (in the environment where the doping material is present, the organic semiconductor It is also possible to perform doping by accelerating ions in a vacuum and colliding with the film.

  These doping effects include changes in electrical conductivity due to increase or decrease in carrier density, changes in carrier polarity (P-type and N-type), changes in Fermi level, and the like. Such doping is often used particularly in semiconductor elements using inorganic materials such as silicon.

(Protective layer)
When the protective layer 7 is formed on the organic semiconductor layer, there is an advantage that the influence of outside air can be minimized and the electrical characteristics of the organic thin film transistor can be stabilized (see FIG. 2 (6)). The materials described above are used as the material for the protective layer. Although the film thickness of the protective layer 7 can employ | adopt arbitrary film thickness according to the objective, it is 100 nm-1 mm normally.
Various methods can be employed to form the protective layer. When the protective layer is made of a resin, for example, a method of applying a resin solution and then drying to form a resin film; applying or vapor-depositing a resin monomer And then a method of polymerizing. Cross-linking treatment may be performed after film formation. When the protective layer is made of an inorganic material, for example, a formation method in a vacuum process such as a sputtering method or a vapor deposition method, or a formation method in a solution process such as a sol-gel method can be used.
In the thin film transistor of the present invention, a protective layer can be provided between the layers in addition to the organic semiconductor layer as necessary. These layers may help stabilize the electrical characteristics of the thin film transistor.

  According to the present invention, since a multimeric compound is used as an organic semiconductor material, it can be manufactured in a relatively low temperature process. Therefore, flexible materials such as plastic plates and plastic films that could not be used under conditions exposed to high temperatures can also be used as the substrate. As a result, it is possible to manufacture a light, flexible, and hard-to-break element, which can be used as a switching element for an active matrix of a display.

  The thin film transistor of the present invention can also be used as a digital element or an analog element such as a memory circuit element, a signal driver circuit element, and a signal processing circuit element. Further, by combining these, it is possible to produce an IC card or an IC tag. Furthermore, since the thin film transistor of the present invention can change its characteristics by an external stimulus such as a chemical substance, it can be used as an FET sensor.

Next, the organic EL device of the present invention will be described in detail.
Organic EL elements are attracting attention and can be used for applications such as solid, self-luminous large-area color display and illumination, and many developments have been made. The structure has a structure having two layers of a light emitting layer and a charge transport layer between a counter electrode composed of a cathode and an anode; an electron transport layer, a light emitting layer and a hole transport layer stacked between the counter electrodes. Known are those having a structure having three layers; and those having three or more layers; and those having a single light-emitting layer.
Here, the hole transport layer has a function of injecting holes from the anode, transporting holes to the light emitting layer, facilitating injection of holes into the light emitting layer, and a function of blocking electrons. The electron transport layer has a function of injecting electrons from the cathode, transporting electrons to the light emitting layer, facilitating injection of electrons into the light emitting layer, and blocking holes. Further, in the light emitting layer, excitons are generated by recombination of the injected electrons and holes, and the energy emitted in the process of radiative deactivation of the excitons is detected as light emission. Preferred embodiments of the organic EL device of the present invention are described below.

The organic EL device of the present invention is a device that emits light by electric energy, in which one or a plurality of organic thin films are formed between the anode and the cathode.
The anode that can be used in the organic EL device of the present invention is an electrode having a function of injecting holes into a hole injection layer, a hole transport layer, and a light emitting layer. In general, metal oxides, metals, alloys, conductive materials, and the like having a work function of 4.5 eV or more are suitable. Specifically, although not particularly limited, conductive metal oxides such as tin oxide (NESA), indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), gold, silver, platinum, chromium And metals such as aluminum, iron, cobalt, nickel and tungsten, inorganic conductive materials such as copper iodide and copper sulfide, conductive polymers such as polythiophene, polypyrrole and polyaniline, and carbon. Among these, it is preferable to use ITO or NESA.
If necessary, the anode may be made of a plurality of materials or may be composed of two or more layers. The resistance of the anode is not limited as long as it can supply a current sufficient for light emission of the element, but it is preferably low resistance from the viewpoint of power consumption of the element. For example, an ITO substrate having a sheet resistance value of 300Ω / □ or less functions as an element electrode, but since it is possible to supply a substrate of several Ω / □, it is desirable to use a low-resistance product. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually 5 to 500 nm, preferably 10 to 300 nm. Examples of film forming methods such as ITO include a vapor deposition method, an electron beam method, a sputtering method, a chemical reaction method, and a coating method.

  The cathode that can be used in the organic EL device of the present invention is an electrode having a function of injecting electrons into an electron injection layer, an electron transport layer, and a light emitting layer. In general, a metal or an alloy having a small work function (approximately 4 eV or less) is suitable. Specific examples include platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, calcium, and magnesium, but are not particularly limited. Lithium, sodium, potassium, calcium, and magnesium are preferable for increasing the electron injection efficiency and improving the device characteristics. As the alloy, an alloy with a metal such as aluminum or silver containing these low work function metals or an electrode having a structure in which these are laminated can be used. An inorganic salt such as lithium fluoride can be used for the electrode having a laminated structure. Moreover, when light emission is taken out not to the anode side but to the cathode side, a transparent electrode that can be formed at a low temperature may be used. Examples of the film forming method include a vapor deposition method, an electron beam method, a sputtering method, a chemical reaction method, and a coating method, but are not particularly limited. The resistance of the cathode is not limited as long as it can supply a current sufficient for light emission of the element, but it is preferably low resistance from the viewpoint of power consumption of the element, and preferably about several hundred to several Ω / □. The film thickness is usually 5 to 500 nm, preferably 10 to 300 nm. Furthermore, for sealing and protection, oxides such as titanium oxide, silicon nitride, silicon oxide, silicon nitride oxide, germanium oxide, nitrides, or mixtures thereof, polyvinyl alcohol, vinyl chloride, hydrocarbon polymers, fluorine The cathode can be protected with a polymer, etc., and sealed with a dehydrating agent such as barium oxide, phosphorus pentoxide, or calcium oxide.

In order to extract light emission, it is generally preferable to form an electrode on a substrate that is sufficiently transparent in the light emission wavelength region of the element. Examples of the transparent substrate include a glass substrate and a polymer substrate. As the glass substrate, soda lime glass, non-alkali glass, quartz, or the like is used. The glass substrate may have a thickness sufficient to maintain mechanical and thermal strength, and a thickness of 0.5 mm or more is preferable. As for the material of the glass, it is better that there are few ions eluted from the glass, and alkali-free glass is preferred. As such, since soda lime glass provided with a barrier coat such as SiO ₂ is commercially available, it can also be used. Examples of the substrate made of a polymer other than glass include polycarbonate, polypropylene, polyethersulfone, polyethylene terephthalate, and an acrylic substrate.

  The organic thin film of the organic EL device of the present invention is formed of one layer or a plurality of layers between the anode and cathode electrodes. By incorporating the multimeric compound of the present invention into the organic thin film, an element that emits light by electric energy can be obtained.

  The “layer” of one or more layers forming the organic thin film in the present invention is a hole transport layer, an electron transport layer, a hole transport light-emitting layer, an electron transport light-emitting layer, a hole block layer, an electron block As shown in the layer, the hole injection layer, the electron injection layer, the light emitting layer, or the following structural example 9), it means a single layer having the functions of these layers. Examples of the configuration of the layer forming the organic thin film in the present invention include the following configuration examples 1) to 9), and any configuration may be used.

Configuration Example 1) Hole transport layer / electron transport light emitting layer.
2) Hole transport layer / light emitting layer / electron transport layer.
3) Hole transporting light emitting layer / electron transporting layer.
4) Hole transport layer / light emitting layer / hole blocking layer.
5) Hole transport layer / light emitting layer / hole blocking layer / electron transport layer.
6) Hole transporting light emitting layer / hole blocking layer / electron transporting layer.
7) In each of the combinations 1) to 6), a hole injection layer is further provided in front of the hole transport layer or the hole transport light emitting layer.
8) A structure in which an electron injecting layer is further provided in front of the electron transporting layer or the electron transporting light emitting layer in each of the combinations 1) to 7).
9) A configuration in which materials used in the combinations 1) to 8) are mixed, and only one layer containing the mixed materials is included.

  In the above 9), a single layer formed of a material generally called a bipolar luminescent material; or only one layer including a luminescent material and a hole transport material or an electron transport material may be provided. In general, with a multilayer structure, charges, that is, holes and / or electrons can be efficiently transported and these charges can be recombined. In addition, by suppressing the quenching of charges, the stability of the element can be prevented from being lowered and the light emission efficiency can be improved.

  The hole injection layer and the transport layer are formed by laminating a hole transport material alone or a mixture of two or more kinds of the materials. As the hole transport material, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, Triphenylamines such as N′-diphenyl-4,4′-diphenyl-1,1′-diamine, bis (N-allylcarbazole) or bis (N-alkylcarbazole) s, pyrazoline derivatives, stilbene compounds, hydrazones In the case of a polymer compound, a triazole derivative, a heterocyclic compound typified by an oxadiazole derivative or a porphyrin derivative, or a polymer system, a polycarbonate, a styrene derivative, polyvinyl carbazole, polysilane, or the like having the monomer in the side chain can be preferably used. There is no particular limitation as long as a thin film necessary for device fabrication is formed, holes can be injected from the electrodes, and holes can be transported. The hole injection layer provided between the hole transport layer and the anode for improving the hole injection property includes phthalocyanine derivatives, starburst amines such as m-MTDATA, polythiophene such as PEDOT in the polymer system, polyvinyl Those prepared with carbazole derivatives and the like can be mentioned.

  As an electron transport material, it is necessary to efficiently transport electrons from the negative electrode between electrodes to which an electric field is applied. The electron transport material has high electron injection efficiency, and it is preferable to transport the injected electrons efficiently. For that purpose, it is required that the substance has a high electron affinity, a high electron mobility, excellent stability, and a substance that does not easily generate trapping impurities during manufacturing and use. As substances satisfying such conditions, quinolinol derivative metal complexes represented by tris (8-quinolinolato) aluminum complexes, tropolone metal complexes, perylene derivatives, perinone derivatives, naphthalimide derivatives, naphthalic acid derivatives, oxazole derivatives, oxadiazoles Derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, bisstyryl derivatives, pyrazine derivatives, phenanthroline derivatives, benzoxazole derivatives, quinoxaline derivatives, and the like are exemplified, but are not particularly limited. These electron transport materials are used alone, but may be laminated or mixed with different electron transport materials. Examples of the electron injection layer provided between the electron transport layer and the cathode for improving the electron injection property include metals such as cesium, lithium, and strontium, lithium fluoride, and the like.

  The hole blocking layer is formed by laminating and mixing hole blocking substances alone or two or more kinds. As the hole blocking substance, phenanthroline derivatives such as bathophenanthroline and bathocuproin, silole derivatives, quinolinol derivative metal complexes, oxadiazole derivatives and oxazole derivatives are preferable. The hole blocking substance is not particularly limited as long as it is a compound that can prevent holes from flowing out from the cathode side to the outside of the device and thereby reducing luminous efficiency.

  The light emitting layer means an organic thin film that emits light, and can be said to be, for example, a hole transporting layer, an electron transporting layer, or a bipolar transporting layer having strong light emitting properties. The light emitting layer only needs to be formed of a light emitting material (host material, dopant material, etc.), which may be a mixture of a host material and a dopant material or a host material alone. Each of the host material and the dopant material may be one kind or a combination of a plurality of materials. The dopant material may be included in the host material as a whole, or may be included partially. The dopant material may be either laminated or dispersed. Examples of the light emitting layer include the above-described hole transport layer and electron transport layer. Materials used for the light-emitting layer include carbazole derivatives, anthracene derivatives, naphthalene derivatives, phenanthrene derivatives, phenylbutadiene derivatives, styryl derivatives, pyrene derivatives, perylene derivatives, quinoline derivatives, tetracene derivatives, perylene derivatives, quinacridone derivatives, coumarin derivative porphyrins. Derivatives and phosphorescent metal complexes (Ir complex, Pt complex, Eu complex, etc.) can be mentioned.

  These thin film formation methods are generally vacuum heating processes such as resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, solution processes such as casting, spin coating, dip coating, blade coating, wire bar coating, spraying. A coating method such as coating, a printing method such as ink jet printing, screen printing, offset printing, and relief printing, a soft lithography method such as a microcontact printing method, and a combination of these methods may be employed. The thickness of each layer depends on the resistance value and charge mobility of each substance and cannot be limited, but is selected from 0.5 to 5000 nm. Preferably it is 1-1000 nm, More preferably, it is 5-500 nm.

  Among the organic thin films of the organic EL device of the present invention, the multimeric compound of the present invention is formed in one or more thin films such as a light emitting layer, a hole transport layer, and an electron transport layer, which are present between the anode and cathode electrodes. By containing the element, an element that emits light efficiently even with low electric energy can be obtained.

  The organic EL device of the present invention can be obtained by forming one or more layers of the multimeric compound of the present invention between the anode and cathode electrodes. Although there is no restriction | limiting in particular in the site | part which uses the multimer compound of this invention, It can use suitably as a host material combined with the utilization in a positive hole transport layer or a light emitting layer, and a dopant material.

  In the organic EL device of the present invention, the multimeric compound of the present invention can be suitably used as a hole transport layer or a light emitting layer. For example, it can be used in combination with the above-described electron transport material, hole transport material, light emitting material, or the like. Preferably, quinolinol derivative metal complex represented by tris (8-quinolinolato) aluminum complex, tropolone metal complex, perylene derivative, perinone derivative, naphthalimide derivative, naphthalic acid derivative, bisstyryl derivative, pyrazine derivative, phenanthroline derivative, benzoxazole derivative Quinoxaline derivatives, triphenylamines, bis (N-allylcarbazole) or bis (N-alkylcarbazole) s, pyrazoline derivatives, stilbene compounds, hydrazone compounds, heterocyclic compounds represented by oxadiazole derivatives, etc. Although it is mentioned, it is not particularly limited. These can be used alone, but can also be used by laminating or mixing different materials.

Specific examples of the dopant material when the multimeric compound of the present invention is used as a host material in combination with a dopant material include perylene derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, perinone derivatives, 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM) and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, oxazine compounds, squarylium compounds, violanthrone compound, Nile red, 5- Shianopirometen -BF ₄ pyrromethene derivatives complexes, further acetylacetone and benzoyl acetone and phenanthro as phosphorescent material Eu complexes having phosphorus as a ligand, porphyrins such as Ir complexes, Ru complexes, Pt complexes, Os complexes, ortho metal metal complexes, and the like can be used, but are not particularly limited thereto. In addition, when two kinds of dopant materials are mixed, it is also possible to obtain light emission with improved color purity by efficiently transferring energy from the host dye using an assist dopant such as rubrene. In any case, in order to obtain high luminance characteristics, it is preferable to dope those having a high fluorescence quantum yield.

  If the amount of dopant material used is too large, a concentration quenching phenomenon will occur, so it is usually used at 30 mass% or less with respect to the host material. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. As a method for doping the host material with the dopant material in the light emitting layer, it can be formed by a co-evaporation method with the host material. It is also possible to use it sandwiched between host materials. In this case, you may laminate | stack with host material as a dopant layer of one layer or two layers or more.

  These dopant layers can form each layer alone, or may be used by mixing them. In addition, as a polymer binder, the dopant material may be polyvinyl chloride, polycarbonate, polystyrene, polystyrene sulfonic acid, poly (N-vinylcarbazole), poly (methyl) (meth) acrylate, polybutyl methacrylate, polyester, polysulfone, Solvent-soluble resins such as polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polysulfone, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane resin, phenol resin, xylene resin, petroleum resin, urea resin, melamine resin In addition, it can be used by being dissolved or dispersed in a curable resin such as an unsaturated polyester resin, an alkyd resin, an epoxy resin, or a silicone resin.

  The method for forming a thin film used in the organic EL device according to the present invention is generally a vacuum process using the multimeric compound or composition of the present invention, such as resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, Software such as solution processes such as casting, spin coating, dip coating, blade coating, wire bar coating, spray coating, ink jet printing, screen printing, offset printing, letterpress printing, and micro contact printing A lithography method or the like, or a method combining a plurality of these methods may be employed.

  Resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, coating method by dissolving and dispersing in solvent or resin (spin coating, casting, dip coating, etc.), LB method, ink jet method, etc. are not particularly limited. . Usually, resistance heating vapor deposition is preferable in terms of characteristics. The thickness of each layer is set according to the resistance value of the luminescent material, and thus cannot be limited, but is selected from 0.5 to 5000 nm. Preferably it is 1-1000 nm, More preferably, it is 5-500 nm.

  The organic EL device of the present invention can be suitably used as a flat panel display. It can also be used as a flat backlight. In this case, either a light emitting colored light or a light emitting 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 is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display board, a sign, and the like. In particular, it has been difficult to reduce the thickness of a conventional backlight for a liquid crystal display device, particularly a personal computer application, because it is made of a fluorescent lamp or a light guide plate. However, the backlight using the light emitting element of the present invention is thin, The above problem is solved because of its light weight. Similarly, it can be usefully used for illumination.

  When the multimeric compound of the present invention is used, an organic EL display device with high luminous efficiency and long life can be obtained. Further, by combining the thin film transistor element of the present invention, it becomes possible to supply an organic EL display device in which the applied voltage on / off phenomenon is electrically controlled with high accuracy at low cost.

(About organic solar cell elements)
By utilizing the organic semiconductor characteristics of the multimeric compound of the present invention, it is expected to be used as an organic solar cell element that is flexible, low-cost and easy to manufacture. In other words, the organic solar cell element is advantageous in terms of flexibility and longevity because it does not use an electrolyte solution unlike the dye-sensitized solar cell, and conventionally an organic thin film combining a conductive polymer, fullerene, etc. Development of solar cells using semiconductors is the mainstream, but power generation conversion efficiency is a problem.
In general, the structure of an organic solar cell element is the same as that of a silicon-based solar cell, in which a layer for generating power is sandwiched between an anode and a cathode, and holes and electrons generated by absorbing light are received by each electrode as a solar cell. Function. The power generation layer is composed of a P-type donor material, an N-type acceptor material, and other materials such as a buffer layer, and an organic solar cell is used in which an organic material is used.
The structures include Schottky junctions, heterojunctions, bulk heterojunctions, nanostructure junctions, hybrids, etc., but each material efficiently absorbs incident light and generates charges. It functions as a solar cell by separating, transporting and collecting electrons).
Next, components in the solar cell 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 those of the organic EL element described above. Since it is necessary to take in light efficiently, it is desirable to use an electrode having transparency in the absorption wavelength region of the power generation layer. Moreover, in order to have a favorable solar cell characteristic, it is preferable that sheet resistance is 20 ohms / square or less.
The power generation layer in the solar cell element of the present invention is formed of one or more layers that form an organic thin film containing at least the multimeric compound of the present invention. Although the structure shown above can be adopted, it is basically composed of a P-type donor material, an N-type acceptor material, and a buffer layer.

P-type donor materials include compounds that can transport holes in the same manner as the hole injection and hole transport layers described in the section of organic EL elements, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives. Π-conjugated polymers such as polyaniline derivatives, and polymers having carbazole and other heterocyclic side chains. Examples of the low molecular compound include pentacene derivatives, rubrene derivatives, porphyrin derivatives, phthalocyanine derivatives, indigo derivatives, quinacridone derivatives, merocyanine derivatives, cyanine derivatives, squalium derivatives, benzoquinone derivatives, and the like.
The N-type acceptor layer basically has a compound capable of transporting electrons, such as the electron transport layer described in the section of the organic EL element, an oligomer or polymer having a skeleton of pyridine and its derivative, and a quinoline and its derivative as a skeleton. Polymers such as oligomers and polymers, polymers having benzophenanthrolines and derivatives thereof, cyanopolyphenylene vinylene derivatives (CN-PPV, etc.), fluorinated phthalocyanine derivatives, perylene derivatives, naphthalene derivatives, bathocuproine derivatives, C60 and C70 And low molecular weight materials such as fullerene derivatives such as PCBM.
Each of them preferably absorbs light efficiently and generates a charge, and the material used has a high extinction coefficient.

  The multimeric compound of the present invention can be suitably used particularly as a P-type donor material. The method for forming the thin film for the power generation layer of the organic solar cell of the present invention may be the same as the method described in the above-mentioned section of the organic EL element. Although the thickness of the thin film varies depending on the configuration of the solar cell, it is better to thicken it in order to absorb light sufficiently and prevent short circuiting. The thinner is suitable. Generally, about 10 to 5000 nm is suitable for the power generation layer.

(About photoelectric conversion elements)
By utilizing the semiconductor characteristics of the multimeric compound of the present invention, utilization as an organic photoelectric conversion element is expected. As the photoelectric conversion element, an image sensor that is a solid-state imaging element includes a charge coupled device (CCD) having a function of converting a video signal such as a moving image or a still image into a digital signal. Utilization as an organic photoelectric conversion element is expected by making use of processability, flexible functionality unique to organic matter, and the like.

(About organic semiconductor laser elements)
Since the multimeric compound of the present invention is a compound having organic semiconductor properties, it is expected to be used as an organic semiconductor laser element. That is, if a resonator structure is incorporated in the organic semiconductor element containing the multimeric compound of the present invention, and carriers can be efficiently injected to sufficiently increase the density of excited states, light is amplified and laser oscillation occurs. Things are expected. Conventionally, only laser oscillation by optical excitation has been observed, and it is very difficult to inject high-density carriers necessary for laser oscillation by electrical excitation into an organic semiconductor element to generate a high-density excitation state. Although proposed, the use of the organic semiconductor element containing the multimeric compound of the present invention is expected to cause highly efficient light emission (electroluminescence).

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to these examples. In Examples, unless otherwise specified, parts are parts by mass,% is mass%, compound No. Corresponds to the compounds described in the specific examples. Moreover, the reaction temperature described the internal temperature in a reaction system unless there is particular notice.
Various compounds obtained in the synthesis examples are MS (mass spectrometry spectrum), maximum absorption (λmax), and mp (melting point), ¹ H ( ¹³ C) -NMR (nuclear magnetic resonance spectrum) as necessary. The structural formula was determined by performing various measurements. The measuring equipment is as follows.
EI-MS: Shimadzu QP-5050A
MS: Shimadzu MALDI-TOF
Absorption spectrum: Shimadzu UV-3150
¹ H ( ¹³ C) -NMR: JEOL Lambda 400 and JEOL EX-270

Example 1
2,2′-bibenzo [1,2-b: 3,4-b ′: 5.6-b ″] trithiophene (Compound 10)

Under a nitrogen atmosphere, a 30 ml round bottom flask was charged with benzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (compound 103) (369 mg, 1.5 mmol) and anhydrous THF (6 ml). ), N-butyllithium in hexane (1.66 M, 1.1 ml, 1.8 mmol) was added dropwise in an ice bath, and the mixture was stirred at room temperature for 1.5 hours. Subsequently, Fe (acac) ₃ (349 mg, 2.25 mmol) was added and stirred at room temperature for 18 hours. After completion of the reaction, 2N hydrochloric acid solution (6 ml) was added and the precipitated solid was collected by filtration. After washing with water (20 ml), ethanol (20 ml) and benzene (20 ml), it was dried and purified by sublimation (350 ° C.) to obtain a yellow solid of compound 10 (224 mg, 61%).
Physical properties of compound 10: MS (70 eV, EI) m / z = 490 (M ⁺ ), mp.> 300 ° C., EI-MS m / z 490 (M ⁺ ),
Anal.Calcd for C ₂₄ H ₁₀ S ₆ : C, 58.74; H, 2.05%; Found: C, 58.60; H, 1.98%,
UV-vis spectra in dichloromethane solution: λmax 377nm

Synthesis example 1
2,5-Dioctylbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 200)

Under a nitrogen atmosphere, 800 mg (3.25 mmol) of benzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (compound 103) and anhydrous THF (80 ml) were added to the flask. Then, a hexane solution of n-butyllithium (1.65 M, 4.64 ml, 7.24 mmol) was added dropwise in an ice bath, heated to 60 ° C., and stirred for 2 hours. 1-Bromooctane (2.3 ml, 13 mmol) was added and stirred at 60 ° C. for 12 hours. Saturated ammonium chloride solution (80 ml) was added, followed by extraction with dichloromethane (10 ml × 2 times) and washing with saturated brine (80 ml × 3 times). The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by column chromatography (silica gel, hexane, Rf = 0.47) gave colorless solid (597 mg, 39%) of compound 200 (2,5,8-trioctyl [1,2-b at the time of synthesis) : 3,4-b ′: 5,6-b ″] trithiophene is also by-produced together).
Physical properties of compound 200: mp. 36-38 ° C., EI-MS m / z = 470 (M ⁺ ),
¹ H-NMR (270 MHz, CDCl ₃ ) δ 7.53 (d, J = 5.3 Hz, 1 H), 7.47 (d, J = 5.3 Hz, 1 H), 7.27 (s, 1 H), 7.22 (s, 1 H), 2.98 (t, J = 7.6Hz, 4H), 1.80 (quint, J = 7.6Hz, 4H), 1.28-1.55 (m, 20H), 0.86-0.88 (m, 6H),
¹³ C-NMR (99.5 MHz, CDCl ₃ ) δ 145.9, 145.8, 131.6, 131.5, 131.4, 130.5, 130.2, 129.9, 124.6, 122.3, 119.1, 119.0, 32.0 (× 2), 31.6 (× 2), 30.9 (× 2), 29.5 (× 2), 29.4 (× 2), 29.3 (× 2), 22.8 (× 2), 12.3 (× 2), Anal.Calcd for C ₂₈ H ₃₈ S ₃ : C, 71.43; H, 8.14%; Found: C, 71.42; H, 8.34%

Example 2
2,2′-bi (5,8-dioctylbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 13)

Under a nitrogen atmosphere, in a flask, 2,5-dioctylbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (compound 200) (100 mg, 0.21 mmol) and anhydrous THF (2.5 ml) was added, and a hexane solution (1.59 M, 0.20 ml, 0.32 mmol) of n-butyllithium was added dropwise in an ice bath, and the mixture was heated to 60 ° C. and stirred for 1.5 hours. Subsequently, Fe (acac) ₃ (111 mg, 0.32 mmol) was added and stirred at 60 ° C. for 20 hours. After completion of the reaction, a saturated ammonium chloride solution (5 ml) was added, followed by extraction with chloroform (20 ml × 2 times) and washing with saturated brine (50 ml × 3 times). The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by column chromatography (silica gel, hexane: dichloromethane (3: 1), Rf = 0.5) and recrystallization from hexane gave Compound 13 as a pale yellow solid (90 mg, 90%).
Physical properties of compound 13: mp. 158-160 ° C,
¹ H-NMR (400MHz, CDCl ₃ ) δ7.63 (s, 2H), 7.19 (s, 2H), 7.17 (s, 1H), 2.97 (t, J = 7.0Hz.8H), 1.81 (quint, J = 7.0Hz, 8H), 1.32 (m, 16H), 0.89 (t, J = 7.0Hz, 12H),
¹³ C-NMR (99.5 MHz, CDCl ₃ ) δ 146.2, 146.1, 136.0, 132.0, 131.9, 131.2, 130.7, 129.9, 129.6, 119.1, 119.0, 118.9, 32.0 (× 2), 31.6 (× 2), 30.9 (× 2), 30.0 (× 2), 29.4 (× 2), 29.3 (× 2), 22.8 (× 2), 14.3 (× 2),
MALDI-TOF MS (1,8,9-trihydroxyanthracene matrix) m / z = 939.70 (M ⁺ ), 842.03 (M ⁺ -C ₇ H ₁₅ ),
Anal.Calcd for C ₅₄ H ₇₆ S ₆ : C, 71.58; H, 7.94%; Found: C, 71.40; H, 7.93%.
UV-vis spectra in dichloromethane solution: λmax.380nm (logε: 4.59),
Emission spectra in dichloromethane solution ： PLmax.442nm

Synthesis example 2
2,5-Dioctyl-8- (tributyltin) benzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 201)

2,5-Dioctylbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (compound 200) (285 mg, 0.61 mmol) and anhydrous THF in a nitrogen atmosphere (20 ml) was added, and a hexane solution of n-butyllithium (1.65 M, 0.84 ml, 1.38 mmol) was added dropwise in an ice bath, followed by stirring at room temperature for 1.5 hours. Tributyltin chloride (0.37 ml, 1.38 mmol) was added and stirring was continued for 1.5 hours. Saturated ammonium chloride solution (20 ml) was added, followed by extraction with dichloromethane (10 ml × 2 times) and washing with saturated brine (20 ml × 3 times). The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by column chromatography (alumina, hexane) and GPC (JAIGEL 1H-2H, CHCl ₃ , R _v = 148 mL) gave Compound 201 as a yellow solid (388 mg, 74%).
Physical properties of compound 201:
¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.59 (s, 1H), 7.29 (s, 1H), 7.20 (s, 1H), 2.95-2.99 (m, 4H), 1.76-1.83 (m, 4H) , 1.58-1.66 (m, 8H), 1.15-1.42 (m, 30H), 0.86-0.96 (m, 15H),
¹³ C-NMR (99.5 MHz, CDCl ₃ ) δ 145.5, 143.4, 137.5, 135.6, 133.1, 131.4, 131.3, 130.1, 129.5, 129.4, 119.6, 119.0, 32.0 (× 2), 31.6 (× 2), 30.9 (× 2), 29.5 (× 2), 29.4 (× 2), 29.3 (× 2), 29.1, 27.4, 22.8 (× 2), 14.3 (× 2), 13.9, 11.1, EI-MS m / z = 760 ( M ⁺ ),
Anal.Calcd for C ₄₀ H ₆₄ S ₃ Sn: C, 63.23; H, 8.49%; Found: C, 63.36; H, 8.34%.

Synthesis example 3
2,5,8-Tribromobenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 104)

Under a nitrogen atmosphere, benzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (compound 103) (50 mg, 0.20 mmol), methylene chloride (2.9 mL) was placed in a three-necked flask. ), Acetic acid (0.7 mL) was added. NBS (120 mg, 0.67 mmol) was added little by little under light-shielding conditions, and the mixture was stirred at room temperature for 18 hours. After completion of the reaction, water (4 mL) was added and the precipitated solid was collected by filtration, washed with water (4 ml × 2 times), ethanol (4 ml × 2 times), and recrystallized from chlorobenzene to give a pale purple solid of Compound 104 (52.6 mg, 54%) was obtained.
Properties of compound 104:
mp. 230.0 ° C., EI-MS m / z = 480 (M ⁺ ), ¹ H-NMR (270 MHz, CDCl ₃ ) · 7.51 (s, 3H),
Anal.Calcd for C ₁₂ H ₃ S ₃ Br ₃ : C, 29.84; H, 0.63%; Found: C, 30.05; H, 0.67%.

Example 3
2,5,8-tris (5,8-dioctylbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophen-2-yl) benzo [1,2-b : 3,4-b ′: 5,6-b ″] trithiophene (Compound 33)

Under a nitrogen atmosphere, 2,5,8-tribromobenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (compound 104) (182 mg, 0.37 mmol) and 2 , 5-Dioctyl-8-tributyltin-benzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (compound 201) (1.04 g, 1.36 mmol) in toluene ( 9.4 ml) and degassed with a nitrogen stream. Pd (PPh ₃ ) ₄ (108 mg, 94 mol) was added and reacted at reflux temperature for 24 hours. After completion of the reaction, a saturated ammonium chloride solution (5 ml) was added, followed by extraction with dichloromethane (20 ml × 2 times) and washing with saturated brine (50 ml × 3 times). The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Column chromatography (silica, hexane-CS ₂ (1: 1), R _f = 0.50) and recrystallization from chloroform further gave a yellow solid (169 mg, 27%) of Compound 33.
Physical property value of compound 33: mp: 223-225 ° C.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.17 (s, 3H), 7.01 (s, 3H), 6.75 (s, 3H), 6.68 (s, 3H), 2.75 (m, 12H), 1.71 (m , 12H), 1.34 (m, 60H), 0.94 (t, J = 6.3Hz, 18H),
MALDI-TOF MS (1,8,9-trihydroxyanthracene matrix) m / z = 1651.81 (M ⁺ ),
Anal.Calcd for C ₉₆ H ₁₁₄ S ₁₂ : C, 69.77; H, 6.95%; Found: C, 69.50; H, 6.72%
UV-vis spectra in dichloromethane solution: λmax 387nm (logε: 4.99),
Emission spectra in dichloromethane solution: PLmax 448nm

Example 4
Preparation and Evaluation of Thin Film Transistor Element A 0.4% chloroform solution (the composition of the present application) of Compound 13 was dropped on an n-doped silicon wafer with a 200 nm SiO ₂ thermal oxide film treated with octyltrichlorosilane and spin-coated ( Film formation was performed at 3000 rpm for 30 seconds to obtain a thin film of the present invention. Next, a shadow mask for electrode preparation is attached to this substrate, and it is placed in a vacuum vapor deposition apparatus. The vacuum in the apparatus is evacuated to 1.0 × 10 ⁻⁴ Pa or less, and a gold electrode is formed by resistance heating vapor deposition. That is, the source electrode (1) and the drain electrode (3) were deposited to a thickness of 80 nm to obtain a TC (top contact) type organic transistor element of the present invention.

In the field effect transistor of this example, the thermal oxide film in the n-doped silicon wafer with the thermal oxide film has the function of the insulating layer (4), and the n-doped silicon wafer is the substrate (6) and the gate electrode (5). ) (See FIG. 3). The obtained field effect transistor was installed in a prober, and semiconductor characteristics were measured using a semiconductor parameter analyzer (Keutley 4200). For semiconductor characteristics, the gate voltage was scanned from 10 V to -100 V in 20 V steps, the drain voltage was scanned from 0 V to -60 V, and the drain current-drain voltage was measured. As a result, current saturation was observed. The drain current was set to −60V, the gate voltage was scanned from 20V to −50V, and the gate voltage−drain current was measured. From the obtained voltage-current curve, this device showed a p-type semiconductor, the carrier mobility was 0.14 cm ² / Vs, and the on / off ratio was 10 ⁵ . FIG. 5 shows a drain current-drain voltage curve of the organic thin film transistor of this example, and FIG. 6 shows a drain current-gate voltage curve.

Example 5
Preparation and Evaluation of Organic EL Element A glass substrate (manufactured by Tokyo Sanyo Vacuum Co., Ltd., 14Ω / □ or less) on which an ITO transparent conductive film was deposited to 150 nm was subjected to UV-ozone cleaning before element preparation. A 0.27% chloroform solution of the compound (33) (corresponding to the composition of the present invention) is dropped onto this substrate, spin-coated (1500 rpm for 30 seconds) to form a film, dried in a vacuum, and the thin film of the present invention (about 20 nm). This substrate was placed in a vacuum deposition apparatus and evacuated until the degree of vacuum in the apparatus was 2 × 10 ⁻³ Pa or less. Tris (8-quinolinolato) aluminum (AlQ3) was vapor-deposited to a thickness of 50 nm as a light emitting layer / electron transport layer by resistance heating vapor deposition. Further, lithium fluoride was vapor-deposited to a thickness of 0.8 nm and aluminum was vapor-deposited to a thickness of 100 nm through a shadow mask to form a cathode, thereby producing a φ2 mm round organic EL device. The configuration of this organic EL element is shown in FIG. The current efficiency of the organic EL element of this example was 3.03 cd / A (1000 cd / m ² ). FIG. 7 shows an IVL characteristic diagram of the organic EL element of this example.

Example 6
Preparation of organic solar cell element and evaluation thereof In the same manner as in Example 5, a thin film of compound 33 was prepared on ITO. Next, this substrate was placed in a vacuum deposition apparatus and evacuated until the degree of vacuum in the apparatus was 2 × 10 ⁻³ Pa or less. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline was deposited to a thickness of 30 nm by a resistance heating vapor deposition method to a thickness of 30 nm. Further, aluminum was deposited to a thickness of 100 nm through a shadow mask to form a cathode, and a φ2 mm round organic solar cell element was produced. The photoelectric conversion efficiency was measured at 100 mW / cm using an AM1.5 solar simulator. An organic solar cell having an open-circuit voltage of 0.85 V, a short-circuit current of 2.11 mA / cm ² , a fill factor of 0.51, and a conversion efficiency of about 1% was obtained. FIG. 8 shows a JV characteristic diagram of the organic solar cell element of this example.

Example 7
2,5-Dioctyl-8-iodobenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 202)

2,5-Dioctylbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 200) (940 mg, 2.0 mmol) in a 50 ml round bottom flask under nitrogen atmosphere ) Was dissolved in THF (28 ml), cooled to 0 ° C., a hexane solution of n-butyllithium (1.57 M, 1.60 ml, 2.50 mmol) was added dropwise, and the mixture was stirred at room temperature for 1.5 hours. Subsequently, a solution of iodine (660 mg, 2.6 mmol) in THF (28 ml) was added dropwise and stirred for 1.5 hours. After adding NaHSO ₃ aqueous solution (10 ml), the crude product was extracted with dichloromethane (20 ml × 2 times). The extract was washed with an aqueous NaHSO ₃ solution (20 ml × 3 times), dehydrated with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 2,5-Dioctyl-8-iodobenzo [1,2-b: 3,4-b ′: 5,6-b ″] by purification by column chromatography (silica gel, hexane, Rf = 0.6) A white solid of trithiophene (920 mg, 78%) was obtained.
Physical properties of compound 202:
¹ H NMR (400 MHz, CDCl ₃ ) ・ δ7.70 (s, 1H), 7.19 (s, 1H), 7.16 (s, 1H), 2.96 (t, J = 8.0 Hz, 4H), 1.77 (m, 4H), 1.28-1.42 (m, 40H), 0.88 (t, J = 6.3 Hz, 6H); EI-MS m / z 550 (M ⁺ ).
Anal. Calcd for C ₂₈ H ₃₇ IS ₃ : C, 56.36; H, 6.25%. Found: C, 56.36; H, 6.25%

Example 8
5,5 ″, 8,8 ″ -tetraoctyl-8 ′-(trimethyltin) -2,2 ′; 5 ′, 2 ″ -terbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 204)

2,5-Dioctyl-8-iodobenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 202) (282 mg, 282 mg) in a 20 ml round bottom flask under nitrogen atmosphere. 473 μmol) and 2,5,8-tris (trimethyltin) benzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (compound 203) (194 mg, 264 μmol) in DMF Dissolved in (9.4 ml), added Pd (PPh ₃ ) ₄ (30 mg, 12 mμmol), heated at 80 ° C. for 12 hours, cooled, and added water (5 ml) to precipitate the product. The precipitate was separated by filtration, washed with water (5 ml × 2 times), washed with ethanol (5 ml × 2 times), and dried under reduced pressure to obtain a crude product as a yellow solid. The crude product was eluted with dichloromethane by flash column chromatography (alumina gel) and purified by GPC (JAIGEL-1H, 2H, CHCl ₃ ) to give a yellow solid of 5,5 ″, 8,8 ″. Tetraoctyl-8 ′-(trimethyltin) -2,2 ′; 5 ′, 2 ″ -terbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene ( Compound 204) (265 mg, 83%) was obtained.
Properties of compound 204:
¹ H NMR (400MHz, CDCl ₃ ) ・ δ7.75 (s, 1H), 7.74 (s, 1H), 7.71 (s, 1H), 7.70 (s, 1H), 7.64 (s, 1H), 7.24 (s , 2H), 7.20 (s, 1H), 7.18 (s, 1H), 3.01-2.96 (m, 8H), 1.84-1.82 (m, 8H), 1.51-1.31 (m, 40H), 0.90 (t, J = 6.4 Hz, 12H), 0.53 (s, ³ J _Sn-H = 28.6 Hz, 9H)
: MALDI-TOF MS (1,8,9-trihydroxyanthracene matrix) m / z 1263 (M ⁺ )

Example 9
2,5-Dioctyl-8- (tributyltin) benzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 205)

2,5-Dioctylbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 200) (600 mg, 1.27 mmol) in a 100 ml round bottom flask under nitrogen atmosphere. ) Was dissolved in THF (40 ml), cooled to 0 ° C., n-butyllithium (1.57M, 2.0 ml, 3.14 mmol) was added dropwise, and the mixture was warmed to room temperature and stirred for 1.5 hours. . Thereafter, trimethyltin chloride (586 mg, 3.14 mmol) was added, and the mixture was further stirred for 1.5 hours. Saturated ammonium chloride aqueous solution (20 ml) was added, and the crude product was extracted with dichloromethane (10 ml × 2 times), washed with saturated brine (20 ml × 3 times), dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. Was distilled off. The resulting concentrate was eluted with dichloromethane by flash column chromatography (alumina gel) and purified by GPC (JAIGEL-1H, 2H, CHCl ₃ , R _v = 148 mL) to give 2,5-dioctyl as a white solid. -8- (Trimethyltin) benzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (707 mg, 88%) was obtained.
Physical properties of compound 205:
¹ H NMR (270 MHz, CDCl ₃ ) ・ δ7.58, 7.27 (s, 1H), 7.21 (s, 1H), 2.95-3.00 (m, 4H), 1.77-1.83 (m, 4H), 1.55-1.28 (m, 20H), 0.86-0.96 (m, 6H), 0.46 (s, ³ J _Sn-H = 28.6 Hz, 9H). EI-MS m / z 634 (M ⁺ )
Anal. Calcd for C ₃₁ H ₄₆ S ₃ Sn: C, 58.76; H, 7.32%. Found: C, 59.03; H, 7.35%

Example 10
8′-bromo-5,5 ″, 8,8 ″ -tetraoctyl-2,2 ′; 5 ′, 2 ″ -terbenzo [1,2-b: 3,4-b ′: 5,6 -B "] trithiophene (compound 206)

2,5-Dioctyl-8- (tributyltin) benzo [1,2-b: 3,4-b ′: 5,6-b ″ in DMF (5 ml) in a test tube with a reflux condenser under a nitrogen atmosphere ] Trithiophene (Compound 201) (222 g, 350 μmol) and 2,5,8-tribromobenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 104) (94 mg, 195 μmol) was dissolved, Pd (PPh ₃ ) ₄ (16 mg, 14 μmol) was added, heated at 80 ° C. for 12 hours, cooled, and then water (5 ml) was added to precipitate the product. The precipitate was separated by filtration, washed with water (5 ml × 2 times), washed with ethanol (5 ml × 2 times), and dried under reduced pressure to obtain a crude product as a yellow solid. The crude product was eluted with dichloromethane by flash column chromatography (alumina gel) and purified by GPC (JAIGEL-1H, 2H, CHCl ₃ ) to give a yellow solid 8′-bromo-5,5 ″, 8 , 8 ″ -tetraoctyl-2,2 ′; 5 ′, 2 ″ -terbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (94 mg, 42% )
Physical properties of compound 206:
¹ H NMR (400MHz, CDCl ₃ ) ・ δ7.00 (s, 1H), 6.92 (s, 1H), 6.88 (s, 1H), 6.83 (s, 1H), 6.77 (s, 1H), 6.71 (s , 1H), 6.68 (s, 1H), 6.67 (s, 1H), 6.63 (s, 1H), 2.75-2.67 (m, 8H), 1.66-1.62 (m, 8H), 1.38-1.26 (m, 40H ), 0.92 (t, J = 6.4, Hz 12H);
MALDI-TOF MS (1,8,9-trihydroxyanthracene matrix) m / z 1263 (M ⁺ ).
Anal. Calcd for C ₆₈ H ₇₇ BrS ₉ : C, 64.67; H, 6.15%. Found: C, 64.72; H, 6.04%

Example 11
2,2′-bis {5,8-bis (5 ′, 8′-dioctylbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophen-2′-yl )} Benzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 207)

In a test tube with a reflux condenser in a nitrogen atmosphere, 5,5 ″, 8,8 ″ -tetraoctyl-8 ′-(trimethyltin) -2,2 ′; 5 ′, 2 ′ in toluene (1 ml) '-Terbenzo [1,2-b: 3,4-b': 5,6-b ''] trithiophene (compound 204) (53 mg, 40 μmol) and 5,5 '', 8,8 ''-tetra Octyl-8′-bromo-2,2 ′; 5 ′, 2 ″ -terbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 206) (50 mg , 40 μmol) was dissolved, Pd (PPh ₃ ) ₄ (3 mg, 2.4 μmol) was added, and the mixture was refluxed for 16 hours. After cooling, water (1 ml) was added, extracted with dichloromethane (10 ml × 2 times), washed with saturated brine (20 ml × 3 times), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product was obtained. The crude product was eluted with dichloromethane by flash column chromatography (alumina gel) and purified by GPC (JAIGEL-1H, 2H, CHCl ₃ ) to give 2,2′-bis {5,8-bis as a brown solid. (5 ′, 8′-Dioctylbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene-2′-yl)} benzo [1,2-b: 3, 4-b ′: 5,6-b ″] trithiophene (55 mg, 58%) was obtained.
Properties of compound 207:
MALDI-TOF MS (1,8,9-trihydroxyanthracene matrix) m / z 2365 (M ⁺ ),
Anal. Calcd for C ₁₃₆ H ₁₅₄ S ₁₈ : C, 69.04; H, 6.56%. Found: C, 68.96; H, 6.54%,
UV-vis spectra in dichloromethane solution: λmax.393nm (logε: 5.19)

Example 12
2,5,8-tri {5 ′, 5 ′ ″, 8 ′, 8 ′ ″-tetraoctyl-2 ′, 2 ″; 5 ″, 2 ′ ″-terbenzo [1,2-b : 3,4-b ′: 5,6-b ″] trithiophene-8 ″ -yl} benzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 208)

In a test tube with a reflux condenser in a nitrogen atmosphere, 2,5,8-tribromobenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene (Compound 104) ( 20 mg, 41 μmol) and 5,5 ″, 8,8 ″ -tetraoctyl-8 ′-(trimethyltin) -2,2 ′; 5 ′, 2 ″ -terbenzo [1,2-b: 3, 4-b ′: 5,6-b ″] trithiophene (compound 204) (200 mg, 148 μmol) was dissolved in toluene (2 ml), Pd (PPh ₃ ) ₄ (5 mg, 4 μmol) was added, and the mixture was refluxed for 16 hours. did. After cooling, water (1 ml) was added, extracted with dichloromethane (10 ml x 2), washed with saturated brine (20 ml x 2), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to produce crude I got a thing. The crude product was eluted with dichloromethane by flash column chromatography (alumina gel), purified by GPC (JAIGEL-1H, 2H, CHCl ₃ ) and mixed with a brown solid BTT, 2,5,8-tri { 5 ′, 5 ′ ″, 8 ′, 8 ′ ″-tetraoctyl-2 ′, 2 ″; 5 ″, 2 ′ ″-terbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene-8 ″ -yl} benzo [1,2-b: 4,5-b ′: 5,6-b ″] trithiophene and 2,2′-bis { 5,8-bis (5 ′, 8′-dioctylbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophene-2′-yl)} benzo [1,2 -B: 3,4-b ′: 5,6-b ″] trithiophene was obtained. Further purification by GPC (JAIGEL-2H, 3H, CHCl ₃ ) twice revealed that 2,5,8-tri {5 ′, 5 ′ ″, 8 ′, 8 ′ ″-tetraoctyl-2 was a brown solid. ', 2 ″; 5 ″, 2 ′ ″-terbenzo [1,2-b: 3,4-b ′: 5,6-b ″] trithiophen-8 ″ -yl} benzo [1 , 2-b: 3,4-b ′: 5,6-b ″] trithiophene (51 mg, 32%).
Physical properties of compound (208):
MALDI-TOF MS (1,8,9-trihydroxyanthracene matrix) m / z 3762 (M ⁺ ),
Anal. Calcd for C ₂₁₆ H ₂₃₄ S ₃₀ : C, 68.41; H, 6.22%. Found: C, 68.13; H, 6.03%,
UV-vis spectra in dichloromethane solution: λmax.395nm (logε: 5.36)

  As is clear from the above examples, the multimeric compound obtained by the present invention exhibits excellent characteristic values as an organic thin film transistor, an organic EL element, and an organic solar battery, and has high versatility as an organic electronic device. It can be said that this is a very useful compound.

The same number is attached | subjected to the same name in FIGS. 1-3.
1 source electrode 2 semiconductor layer 3 drain electrode 4 insulator layer 5 gate electrode 6 substrate 7 protective layer

Claims (14)

Formula a partial structure represented by (2) having two or more multi-dimer compound.

(In the formula ^(2), at least one of the ^.R 1 to R ⁶ representing the X 1, ^{X 2} and ^{X 3} are each independently a sulfur atom or a selenium atom is a single bond, bonded to the other of the partial structure Te to form multimers. the remaining R ¹ to R ⁶ are each independently an aromatic hydrocarbon group, aliphatic hydrocarbon group, a halogen atom, a hydroxyl group, an alkoxyl group, a mercapto group, an alkylthio group, amino group, or it represents a hydrogen atom.) The multimeric compound according to claim 1, wherein the multimeric compound having two or more partial structures represented by the general formula (2) is an oligomer or a dendrimer. The multimeric compound according to claim ³ , wherein in the general formula (2), X ¹ , X ² and X ³ are all sulfur atoms. The multimeric compound of Claim 1 or 2 represented by General formula (3).

(In Formula (3), X ^{4 to} X ⁹ each independently represents a sulfur atom or a selenium atom. R ^{7 to} R ¹⁶ each independently represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a halogen atom, or a hydroxyl group. , an alkoxyl group, a mercapto group, an alkylthio group, amino group, or a hydrogen atom.) The multimeric compound of Claim 1 or 2 represented by General formula (4).

(In formula (4), X ^{10 to} X ¹⁸ each independently represents a sulfur atom or a selenium atom. R ^{17 to} R ³⁰ each independently represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a halogen atom, or a hydroxyl group. , an alkoxyl group, a mercapto group, an alkylthio group, amino group, or a hydrogen atom.) The multimeric compound of Claim 1 or 2 represented by General formula (5).

(In formula (5), X ^{19 to} X ³⁰ each independently represents a sulfur atom or a selenium atom. R ^{31 to} R ⁴⁸ each independently represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a halogen atom, or a hydroxyl group. , an alkoxyl group, a mercapto group, an alkylthio group, amino group, or a hydrogen atom.) The multimeric compound of Claim 1 or 2 represented by General formula (6).

(In formula (6), X ^{31 to} X ⁴⁸ each independently represents a sulfur atom or a selenium atom. R ^{49 to} R ⁷⁴ each independently represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a halogen atom, or a hydroxyl group. , an alkoxyl group, a mercapto group, an alkylthio group, amino group, or a hydrogen atom.) The multimeric compound of Claim 1 or 2 represented by General formula (7).

(In formula (7), X ^{49 to} X ⁷⁸ each independently represents a sulfur atom or a selenium atom. R ^{75 to} R ¹¹⁶ each independently represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group, a halogen atom, or a hydroxyl group. , an alkoxyl group, a mercapto group, an alkylthio group, amino group, or a hydrogen atom.) The organic-semiconductor material which consists of a multimer compound as described in any one of Claims 1 thru | or 8 . An organic electronic device comprising the organic semiconductor material according to claim 9 . The organic electronic device according to claim 10 , wherein the device is a photoelectric conversion element, an organic solar cell element, an organic EL element, an organic semiconductor laser element, a liquid crystal display element, or a thin film transistor element. The composition containing the multimeric compound as described in any one of Claims 1 thru | or 8 . A thin film containing the multimeric compound or composition according to any one of claims 1 to 8 or 12 . The manufacturing method of the multimeric compound as described in any one of Claims 1 thru | or 8 including carrying out coupling reaction of the compounds which have the partial structure represented by General formula (2) .