JP2012126876A - Conjugated compound, and organic thin film and organic thin film device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conjugated compound that can be used as an n-type semiconductor excellent in electron transportability, and is excellent in solubility to a solvent.SOLUTION: The conjugated compound is represented by formula (I), wherein Rand Rare a monovalent group containing an alkane skeleton; R, R, Rand Rare a hydrogen atom, a halogen atom or a monovalent group; X, X, Xand Xdenote =O, =S or =CA(A denotes a hydrogen atom, a halogen atom or a monovalent group, but at least one thereof is an electron-withdrawing group); Zand Zdenote one group of -O-, -S-, -Se-, -Te-, -SO- and the like; Ar, Arand Ardenote an aromatic hydrocarbon group or a heterocyclic group; r denotes an integer of 1 to 6; and s and t denote an integer of 0 to 6.

Description

  The present invention relates to a conjugated compound, an organic thin film containing the same, an organic thin film element including the organic thin film, an organic thin film transistor, and an organic thin film solar cell.

  Thin films containing an organic material having an electron transport property or a hole transport property are expected to be applied to organic thin film elements such as organic thin film transistors, organic thin film solar cells, and optical sensors. However, since organic n-type semiconductors (showing electron transport properties) have been difficult to obtain compared to organic p-type semiconductors (showing hole transport properties), various organic n-type semiconductors have been studied.

  In recent years, as an electron transporting material applicable to organic n-type semiconductors, in order to increase the electron accepting property of a π-conjugated compound, a study in which a fluoroalkyl group is introduced into a thiophene ring has been actively conducted (for example, patents). Reference 1).

  Also, various polythiophenes having a crosslinked structure have been studied in order to improve the planarity of the molecular structure and improve the electron transport property (Patent Document 2).

US Patent Application Publication No. 2004/186266 JP 2004-339516 A

  However, even with the conventional materials as described above, it has still been difficult to obtain sufficient performance as an organic n-type semiconductor.

  Moreover, when forming an organic thin film element on a flexible substrate, it is advantageous if the organic thin film can be formed by a printing method. For this purpose, a material excellent in solubility in an organic solvent is required. However, it has been extremely difficult to obtain a material having sufficient characteristics as an organic n-type semiconductor and sufficiently excellent in solubility.

  Therefore, the present invention has been made in view of such circumstances, and is intended to provide a conjugated compound that can be used as an n-type semiconductor having excellent electron transport properties and also has excellent solubility in a solvent. Objective.

  Another object of the present invention is to provide an organic thin film containing such a conjugated compound, an organic thin film element including the organic thin film, an organic thin film transistor, and an organic thin film solar cell.

In order to achieve the above object, the conjugated compound of the present invention is represented by the formula (I).

In formula (I), R ⁰¹ and R ⁰² each independently represent a monovalent group containing an alkane skeleton, and R ¹¹ , R ¹² , R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom, A monovalent group which may be substituted with an atom or a substituent is shown. X ¹¹ , X ¹² , X ²¹ and X ²² each independently represent an oxygen atom, a sulfur atom or a group represented by the formula (a). However, at least one of X ¹¹ , X ¹² , X ²¹ and X ²² is a sulfur atom or a group represented by the formula (a). Z ¹ and Z ² are each independently a group represented by Formula (i), a group represented by Formula (ii), a group represented by Formula (iii), or a group represented by Formula (iv) , A group represented by formula (v), a group represented by formula (vi), a group represented by formula (vii), a group represented by formula (viii), and a group represented by formula (ix) (Hereinafter, the same notation represents any one group selected from the group consisting of “groups represented by formulas (i) to (ix)”). Ar ⁰ , Ar ¹ and Ar ² each independently represent a divalent aromatic hydrocarbon group having 6 or more carbon atoms or a divalent heterocyclic group having 4 or more carbon atoms, and these have a substituent. It may be. r shows the integer of 1-6, s and t show the integer of 0-6 each independently.

  In formula (a), A represents a hydrogen atom, a halogen atom or a monovalent group, and a plurality of A may be the same or different, but at least one A is an electron-withdrawing group. .

Furthermore, in formula (vii), formula (viii) and formula (ix), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or a monovalent group, and R ³ And R ⁴ may be bonded to each other to form a ring. Note that the group represented by the formula (viii) may be horizontally reversed.

The conjugated compound of the present invention having the above-described structure has a sufficiently low LUMO (lowest orbital orbital) because the π-conjugated planarity between the rings is good and terminal groups having a specific structure are introduced at both ends. ). Therefore, it can be used as an organic n-type semiconductor having excellent electron transport properties. In addition to having high π-conjugated planarity, the conjugated compound has a group containing an alkane skeleton represented by R ⁰¹ and R ⁰² in addition to being highly stable, Moreover, the solubility in organic solvents is excellent. Therefore, according to the conjugated compound of the present invention, an organic thin film can be formed by a coating method, and an organic thin film element having excellent performance can be obtained.

In the conjugated compound of the present invention, at least one of X ¹¹ and X ¹² in the formula (I) is a group represented by the formula (a), and at least one of X ²¹ and X ²² is represented by the formula (a). It is preferable that it is a group. Since the group represented by the formula (a) has an electron-withdrawing property, the conjugated compound can exhibit a lower LUMO by having such a group. As a result, the electron transport property is further improved.

Ar ⁰ is more preferably a group having no substituent containing an alkane skeleton. By setting it as such a structure, the outstanding electron transport property is obtained. Even if Ar ⁰ does not have an alkane skeleton, the conjugated compound can have more excellent solubility because it has the specific end group as described above.

As the conjugated compound, Ar ⁰ in formula (I) is more preferably a group represented by formula (II) or a group represented by formula (III). By having such a configuration, the electron transport property tends to be further improved.

In Formula (II), Z ³ represents any one group selected from the group consisting of groups represented by Formula (xi) to Formula (xix). Note that the group represented by the formula (xviii) may be horizontally reversed.

In Formula (III), Ar ³ and Ar ⁴ are each independently a trivalent aromatic hydrocarbon group having 6 or more carbon atoms or a trivalent heterocyclic group having 4 or more carbon atoms, and includes an alkane skeleton. represents a group which has no substituent, X ³ represents an oxygen atom, a group represented by a sulfur atom or the formula (a).

［式（ＩＶ）中、Ｘ^３は前記と同義であり、Ｙ^１及びＹ^２は、それぞれ独立に、炭素原子又は窒素原子を示し、Ｚ^４及びＺ^５は、それぞれ独立に、式（ｘｘｉ）〜式（ｘｘｉｘ）で表される基からなる群より選ばれるいずれか１種の基を示す。なお、式（ｘｘｖｉｉｉ）で表される基は左右反転していてもよい。］ Since it becomes easy to acquire the said effect, it is preferable in it that the group represented by Formula (III) is a group represented by Formula (IV).

[In Formula (IV), X ³ is as defined above, Y ¹ and Y ² each independently represent a carbon atom or a nitrogen atom, and Z ⁴ and Z ⁵ are each independently Formula (xxi). To any one group selected from the group consisting of groups represented by formula (xxix). Note that the group represented by the formula (xxviii) may be horizontally reversed. ]

Particularly, in the conjugated compound of the present invention, one of X ¹¹ and X ¹² is an oxygen atom, the other one of X ¹¹ and X ¹² is a group represented by the formula (a1), and , X ²¹ and X ²² are each preferably an oxygen atom, and the other of X ²¹ and X ²² is preferably a group represented by the formula (a1). Z ⁴ and Z ⁵ are preferably a group represented by the formula (xxii) or a group represented by the formula (xxvii). By having these structures, the conjugated compound of the present invention can more easily obtain excellent electron transport properties and solubility.

  The present invention also provides an organic thin film containing the conjugated compound of the present invention, an organic thin film element comprising the same, an organic thin film transistor, and an organic thin film solar cell. Since such an organic thin film, an organic thin film transistor, and an organic thin film solar cell are equipped with the organic thin film containing the conjugated compound of this invention which shows the outstanding electron transport property as mentioned above, manufacture of an element by using a printing method Is easy and can exhibit excellent performance.

  According to the present invention, it is possible to provide a conjugated compound that can be used as an n-type semiconductor having excellent electron transport properties and also has excellent solubility in a solvent. Moreover, according to this invention, it becomes possible to provide the organic thin film containing this conjugated compound, an organic thin film element provided with the said organic thin film, an organic thin-film transistor, and an organic thin-film solar cell.

It is a schematic cross section of the organic thin-film transistor which concerns on 1st Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 2nd Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 3rd Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 4th Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 5th Embodiment. It is a schematic cross section of the organic thin-film transistor concerning 6th Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 7th Embodiment. It is a schematic cross section of the organic thin-film solar cell which concerns on embodiment. It is a schematic cross section of the photosensor concerning a 1st embodiment. It is a schematic cross section of the optical sensor which concerns on 2nd Embodiment. It is a schematic cross section of the photosensor concerning a 3rd embodiment.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Conjugated compounds]
The conjugated compound of the present invention has a structure represented by the above formula (I). Here, in this specification, the conjugated compound includes a structure in which a single bond and an unsaturated bond, a lone electron pair, a radical, or a non-bonding orbital are alternately connected in the main skeleton of the compound, An electron delocalization due to the interaction of nonbonding orbitals occurs in a part or the whole of the main skeleton. The main skeleton is the longest of the chain of structural units constituting the conjugated compound, and the structure in which the aromatic rings are linked is the main skeleton of the portion where the aromatic rings are continuously bonded. . Among the conjugated compounds, π conjugated compounds based on π orbital interaction are preferable.

In the formula (I), R ⁰¹ and R ⁰² each independently represent a monovalent group containing an alkane skeleton. Here, the alkane skeleton is a residue obtained by removing one or two hydrogen atoms from a chain saturated hydrocarbon represented by the general formula C _n H _{2n + 2} (where n represents an integer of 1 or more). Represents a skeleton consisting of The monovalent group containing an alkane skeleton represents a group comprising such a chain saturated hydrocarbon or a group having at least a part of the chain saturated hydrocarbon. Examples of the monovalent group containing an alkane skeleton include an alkyl group, an alkoxy group, a thioalkyl group, an alkylphenyl group, an alkoxyphenyl group, an alkylthiophenyl group, an alkoxycarbonyl group, an alkylsilyl group, and an alkylamino group.

  In the monovalent group including the alkane skeleton, the number of carbon atoms of the alkane skeleton is preferably 1 to 30, and more preferably 3 to 24. In particular, since the solubility to an organic solvent becomes high, it is more preferable that the alkane skeleton has 6 to 20 carbon atoms. The alkane skeleton may be linear or branched. However, a linear alkane skeleton is preferable for improving the intermolecular arrangement, but a branched alkane skeleton is preferable because of its high solubility in organic solvents, and is selected according to the desired properties. be able to.

  The monovalent group containing an alkane skeleton is preferably an alkyl group. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, more preferably a linear or branched alkyl group having 3 to 24 carbon atoms, and linear or branched. The alkyl group having 6 to 20 carbon atoms is more preferable. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, 3-methylbutyl group, pentyl group, hexyl group, 2-ethylhexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, lauryl group, 3,7-dimethyloctyl group, and 3,7,11-trimethyldodecyl group. In addition, the same thing can be illustrated also about the alkane skeleton which the monovalent group including the alkane skeleton other than the alkyl group has.

In the formula (I), X ¹¹ , X ¹² , X ²¹ and X ²² each independently represent an oxygen atom, a sulfur atom or a group represented by the formula (a). However, at least one of X ¹¹ , X ¹² , X ²¹ and X ²² is a sulfur atom or a group represented by formula (a), and at least one of X ¹¹ and X ¹² is a sulfur atom or formula ( It is a group represented by a), and at least one of X ²¹ and X ²² is more preferably a sulfur atom or a group represented by the formula (a). Since the planarity of the terminal group containing X ¹¹ , X ¹² , X ²¹ and X ²² in formula (I) is increased, X ¹² or X ²² is more preferably an oxygen atom or a sulfur atom.

In Formula (I), it is preferable that at least one of X ¹¹ and X ¹² is a group represented by Formula (a), and at least one of X ²¹ and X ²² is a group represented by Formula (a). . In the formula (a), A represents a hydrogen atom, a halogen atom or a monovalent group. A plurality of A may be the same or different, but at least one A is an electron-withdrawing group, and it is preferable that both are electron-withdrawing groups. Thus, by having an electron withdrawing group as A, the LUMO of the conjugated compound can be lowered. Examples of the electron-withdrawing group include a cyano group, a nitro group, a formyl group, an acyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, and a halogen atom. A cyano group, a nitro group, and a halogen atom are preferable, and a cyano group is particularly preferable. preferable.

In formula (I), R ¹¹ , R ¹² , R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom or a monovalent group which may be substituted with a substituent. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, as a halogen atom demonstrated in this specification, all can apply the same atom. The monovalent group includes a linear or branched low molecular chain, a monovalent cyclic group (this cyclic group is monocyclic, condensed, hydrocarbon, heterocyclic, saturated, or saturated. And may be saturated and may or may not have a substituent), and a part or all of the hydrogen atoms of these groups may be substituted with a halogen atom.

Since the LUMO of the conjugated compound can be further reduced, at least one of R ¹¹ , R ¹² , R ²¹ and R ²² is preferably an electron-withdrawing group, and at least one of R ¹¹ and R ¹² or R ²¹ and More preferably, at least one of R ²² is an electron-withdrawing group, and it is further preferred that all of R ¹¹ , R ¹² , R ²¹ and R ²² are electron-withdrawing groups. These electron-withdrawing groups are preferably halogen atoms and monovalent groups in which some or all of the hydrogen atoms are substituted with halogen atoms, and fluorine atoms and some or all of the hydrogen atoms are fluorine. An alkyl group substituted with an atom is more preferred, and a fluorine atom is particularly preferred.

In the formula (I), Z ¹ and Z ² each independently represent any one group selected from the group consisting of groups represented by the above formulas (i) to (ix). R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or a monovalent group, and R ³ and R ⁴ may be bonded to each other to form a ring. Note that the group represented by the formula (viii) may be horizontally reversed.

Z ¹ and Z ² in formula (I) are preferably groups represented by any of formulas (i), (ii), (iii), (vii), (viii) and (ix), The group represented by either (ii) or (vii) is more preferred, and the group represented by formula (ii) is particularly preferred. When the ring containing Z ¹ and Z ² in formula (I) is a thiophene ring, a furan ring, a pyrrole ring or a pyridine ring, particularly a thiophene ring, characteristic electrical properties (for example, LUMO suitable for electron transport) Level and a property that easily takes a stable quinoid structure) and various electrical characteristics (for example, high electron transport properties) are exhibited.

In formula (I), Ar ⁰ represents a divalent aromatic hydrocarbon group having 6 or more carbon atoms or a divalent heterocyclic group having 4 or more carbon atoms. Ar ⁰ is a divalent aromatic hydrocarbon group having 6 or more carbon atoms not having a substituent containing an alkane skeleton as described above, or 4 or more carbon atoms having no substituent having an alkane skeleton. These divalent heterocyclic groups are preferred. As described above, Ar ^{0 in} the central portion of the conjugated compound represented by formula (I) does not have a substituent containing an alkane skeleton, so that π stacking between molecules is easily performed, and thus a charged molecule Since the interfacial migration is likely to occur, the performance as an organic n-type semiconductor tends to be improved.

R in the formula (I) represents the number of repeating groups represented by Ar ⁰ , is an integer of 1 to 6, and is preferably an integer of 1 to 3. When r is 2 or more, the plurality of Ar ⁰ may be the same or different.

Ar ⁰ is preferably a group represented by the formula (II). In formula (II), Z ³ represents any of the groups represented by formulas (xi) to (xix), and the group represented by formula (xviii) may be horizontally reversed.

Z ³ in the formula (II) is preferably a group represented by any one of the formulas (xi), (xii), (xiii), (xvii), (xviii), and the formulas (xii), (x a group represented by either xiii) or (xvii) is more preferred, a group represented by any of formulas (xii) or (xvii) is more preferred, and a group represented by formula (xii) is particularly preferred. . When the ring containing Z ³ in formula (II) is a thiophene ring, a furan ring, a pyrrole ring or a pyridine ring, particularly a thiophene ring, characteristic electrical properties (for example, LUMO level suitable for electron transport and stable Properties that facilitate the formation of a quinoid structure) are obtained, and various electrical characteristics (for example, high electron transport properties) are exhibited.

Ar ⁰ in the formula (I) is preferably a group represented by the formula (III) because the planarity of the molecule is increased.

In formula (III), Ar ³ and Ar ⁴ each independently represent a trivalent aromatic hydrocarbon group having 6 or more carbon atoms or a trivalent heterocyclic group having 4 or more carbon atoms, and these are as described above. It is a group having no substituent that contains an alkane skeleton. X ³ represents an oxygen atom, a sulfur atom or a group represented by the formula (a).

  Here, the trivalent aromatic hydrocarbon group refers to a group consisting of the remaining atomic group obtained by removing three hydrogen atoms from a benzene ring or condensed ring. The carbon number of the trivalent aromatic hydrocarbon group is preferably 6 to 60, and more preferably 6 to 20. Examples of the condensed ring include naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, perylene ring, and fluorene ring. Of these, the trivalent aromatic hydrocarbon group is particularly preferably a group composed of the remaining atomic group obtained by removing three hydrogen atoms from the benzene ring. The trivalent aromatic hydrocarbon group may have a substituent other than the substituent containing the alkane skeleton. In that case, the carbon number of the substituent is not included in the carbon number of the trivalent aromatic hydrocarbon group. Examples of the substituent include a halogen atom, an aryl group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group.

The trivalent heterocyclic group refers to a group composed of the remaining atomic group obtained by removing three hydrogen atoms from a heterocyclic compound. Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring are not only carbon atoms, but also oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, silicon atoms, etc. In the ring. The carbon number of the trivalent heterocyclic group is preferably 4 to 60, and more preferably 4 to 20. Examples of the trivalent heterocyclic group include groups consisting of the remaining atomic groups obtained by removing three hydrogen atoms from a thiophene ring, thienothiophene ring, furan ring, pyrrole ring, pyridine ring, thiazole ring, oxazole ring or imidazole ring. Is done. In particular, when Ar ³ or Ar ⁴ is a group consisting of the remaining atomic group obtained by removing three hydrogen atoms from a thiophene ring, thienothiophene ring, or thiazole ring, it has characteristic electrical properties (for example, suitable for electron transport). It is also expected that the LUMO level and the property of easily taking a stable quinoid structure) will be obtained, and new electrical characteristics that have not existed before will be developed.

  As such a trivalent heterocyclic group, a trivalent aromatic heterocyclic group is preferable. The trivalent heterocyclic group may have a substituent other than the substituent including the alkane skeleton. In that case, the carbon number of the substituent is not included in the carbon number of the trivalent heterocyclic group. Examples of the substituent include a halogen atom, an aryl group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group.

As the group represented by the formula (III), a group represented by the formula (IV) is preferable. In formula (IV), X ³ has the same meaning as described above. Y ¹ and Y ² each independently represent a carbon atom or a nitrogen atom. Z ⁴ and Z ⁵ each independently represent any of the groups represented by the formulas (xxi) to (xxix), and the group represented by the formula (xxviii) may be horizontally reversed.

Z ⁴ and Z ⁵ in the formula (IV) are preferably groups represented by any one of the formulas (xxi), (xxii), (xxiii), (xxvii), (xxviii), xxii), (xxiii), a group represented by any one of (xxvii) is more preferred, a group represented by any one of the formulas (xxii), (xxvii) is more preferred, represented by a formula (xxii) The group is particularly preferred. In addition, since at least one of Y ¹ and Y ^{2 in} the formula (IV) can lower the LUMO, a nitrogen atom is preferable, and both Y ¹ and Y ² are more preferably nitrogen atoms.

X ³ in the formula (III) or (IV) is preferably an oxygen atom or a group represented by the formula (a) because the LUMO of the conjugated compound can be lowered, and at least in the oxygen atom or the formula (a) A group in which one A is a cyano group is more preferable, and an oxygen atom or a group in which both A are cyano groups in the formula (a) is more preferable.

Examples of the group represented by the formula (III) or (IV) include groups represented by the following chemical formulas.

Ar ¹ and Ar ² in formula (I) each independently represent a divalent aromatic hydrocarbon group having 6 or more carbon atoms or a divalent heterocyclic group having 4 or more carbon atoms, and these have a substituent. May be. In the formula (I), s represents the number of repeating groups represented by Ar ¹ , and t represents the number of repeating groups represented by Ar ² . s and t are each independently an integer of 0 to 6, and preferably an integer of 0 to 2. When s or t is 2 or more, a plurality of Ar ¹ or a plurality of Ar ² may be the same or different.

  Here, the divalent aromatic hydrocarbon group refers to a group composed of the remaining atomic group obtained by removing two hydrogen atoms from a benzene ring or condensed ring. The divalent aromatic hydrocarbon group preferably has 6 to 60 carbon atoms, and more preferably 6 to 20 carbon atoms. Examples of the condensed ring include naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, perylene ring, and fluorene ring.

  The divalent aromatic hydrocarbon group is preferably a group consisting of the remaining atomic group obtained by removing two hydrogen atoms from a benzene ring, pentacene ring, pyrene ring or fluorene ring. The divalent aromatic hydrocarbon group may further have a substituent. In that case, the carbon number of the substituent is not included in the carbon number of the divalent aromatic hydrocarbon group. Examples of the substituent include a halogen atom, a saturated or unsaturated hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group.

  On the other hand, a divalent heterocyclic group refers to a group consisting of the remaining atomic groups obtained by removing two hydrogen atoms from a heterocyclic compound. The divalent heterocyclic group preferably has 3 to 60 carbon atoms, and more preferably 3 to 20 carbon atoms. Examples of the divalent heterocyclic group include compounds in which 2 to 6 thiophene rings such as a thiophene ring, a thienothiophene ring, and a dithienothiophene ring are condensed, a thiazole ring, a pyrrole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring. And a group consisting of the remaining atomic group obtained by removing two hydrogen atoms from the triazine ring. Preferably, it is a group consisting of the remaining atomic group obtained by removing two hydrogen atoms from a compound in which 2 to 6 thiophene rings such as a thiophene ring, a thienothiophene ring, and a dithienothiophene ring are condensed. In particular, a group composed of the remaining atomic group obtained by removing two hydrogen atoms from a thiophene ring or thienothiophene ring is preferable.

  The divalent heterocyclic group may further have a substituent. In that case, the carbon number of the substituent is not included in the carbon number of the divalent heterocyclic group. Examples of the substituent include a halogen atom, a saturated or unsaturated hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group.

Examples of the conjugated compound of the present embodiment as described above include compounds represented by the following chemical formula.

R ⁰⁰ in these chemical formulas has the same meaning as R ⁰¹ or R ⁰² described above. R ^* represents a hydrogen atom, an alkyl group having 3 to 24 carbon atoms, a fluoroalkyl group having 3 to 24 carbon atoms, an alkoxy group having 3 to 24 carbon atoms, or a fluoroalkoxy group having 1 to 20 carbon atoms, and a hydrogen atom Alternatively, an alkyl group having 3 to 24 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 6 to 20 carbon atoms is more preferable. In addition, when several ^R00 and R ^* exist in a molecule | numerator, these may be same or different, respectively.

[Method for producing conjugated compound]
The conjugated compound of the preferred embodiment as described above may be produced by any method as long as the above structure is obtained. Examples of suitable manufacturing methods include the following examples. In addition, reaction conditions, reaction reagents, and the like in the following production methods can be selected in addition to the following examples.

In the following example, in Formula (I), Ar ⁰ is a group represented by Formula (IV) having an oxygen atom as X ³ , s and t are 0, that is, Ar ¹ and Ar ² are not included, A preferred embodiment of a method for producing a conjugated compound having a group represented by the formula (aa) in which both A are cyano groups as X ¹¹ , X ¹² , X ²¹ and X ²² will be described. To do.

  In the production of the conjugated compound, first, as shown in the following scheme (S1), the starting materials represented by the formulas (a) and (a ′) are used and reacted to produce the precursor (b). Then, the obtained precursor (b) is further reacted with a carbonyl crosslinking agent (c) to obtain an intermediate (d).

  Next, as shown in the following scheme (S2), a reaction via the synthesis of the compound (f) or (n) is performed to obtain the compound (o). In this reaction, first, intermediate (d) is reacted with alcohol (e) to form compound (f) in which the carbonyl group in intermediate (d) is protected. The carbonyl group may be protected, for example, by reacting 2,2-dibutyl-1,3-propenediol or the like to form an acetal group instead of the alcohol (e).

Then, a compound (h) is obtained by adding a predetermined reactive group (V ″) to the compound (f) in which the carbonyl group is protected to obtain a compound (h), and then a raw material compound (n) for forming a terminal group therewith To form compound (o).

In the schemes (S1) and (S2), Z ^* represents Z ⁴ or Z ⁵ in the formula (IV), and Y ^* represents Y ¹ or Y ² in the formula (IV). Z ^** represents Z ¹ or Z ² in formula (I), R ^* represents R ¹¹ , R ¹² , R ²¹ or R ²² in formula (I), and R ^{0 *} represents formula (I) R ⁰¹ or R ⁰² in I) is represented.

V, V ′, and V ″ each represent a reactive group, and may be the same or different. Examples of the reactive group include a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, an alkyl star group. Nyl group, arylstannyl group, arylalkylstannyl group, boric acid ester residue, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, monohalogenated methyl group, boric acid residue (-B (OH) ₂ ) Examples of the boric acid ester residue include groups represented by the following formula.

  V, V ′ and V ″ each independently represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, an alkylstannyl group, a boric acid ester residue, or a boron atom because the reactivity in synthesis is improved. It is preferably an acid residue.

  X, X ′, and X ″ each independently represent a halogen atom, and W, W ′, and W ″ each independently represent a leaving group. Examples of the leaving group include an amino group and an alkoxy group.

  And the conjugated compound which concerns on suitable embodiment can be obtained by removing the protecting group of a carbonyl group from the compound (o) obtained by the said reaction, and setting it as a carbonyl compound. In the case of forming an organic thin film using a conjugated compound, the organic thin film is not necessarily formed after removing the protective group for the carbonyl group. For example, a compound having a protective group (compound) After forming the organic thin film using (o) etc., the protective group may be removed by heating or the like in the state of becoming an organic thin film, thereby forming the inside of the organic thin film containing the conjugated compound. In this case, in the organic thin film, the compound in the state before the protecting group is removed or its by-product may remain as long as the characteristics are not greatly affected.

Although a conjugated compound of a preferred embodiment can be obtained by the method as described above, for example, in the formula (I), s and t are 1 or more, that is, a conjugated compound containing Ar ¹ and Ar ² is formed. When doing so, the following manufacturing method can be applied.

In this case, first, using the compound represented by the formula (p) (preferably the formula (q)) and the compound represented by the formula (r), an intermediate of the formula (s) (preferably The compound (s) or the compound (t) represented by the formula (t)) is produced. And the compound of formula (r) had by reacting the obtained compound (s) or compound (t) with the raw material compound (n) for forming the terminal group as described above. A conjugated compound represented by the formula (I) having a group represented by Ar ¹ and Ar ² derived from Ar ^** in the molecule, that is, s and t are 1 or more can be obtained.

In the above formula, Ar ^* represents Ar ⁰ in formula (I), and Ar ^** represents Ar ¹ or Ar ² in formula (I). V, V ′, and Z ³ are as defined above. When the compound represented by the formula (q) is used as the compound represented by the formula (p), this compound is represented by, for example, a heterocyclic compound corresponding to a heterocyclic ring containing Z ³ and represented by V and V ′. Can be obtained by adding a reactive group. As the compound represented by the formula (p), the above compound (h) can also be used. In that case, the compound (h) can be synthesized by the same method as described above.

  In the method for producing a conjugated compound as described above, the carbonyl group is protected by, for example, synthesizing the compound (f) in the middle. Similarly, an unnecessary reaction is performed for a highly reactive functional group. In order to avoid the occurrence of the above, a step of converting to an inactive functional group (protecting group) in the subsequent reaction and removing the protecting group after completion of the target reaction may be performed. The protecting group can be selected depending on the functional group to be protected and the reaction used. For example, trimethylsilyl (TMS), triethylsilyl (TES), tert-butyldimethylsilyl (TBS or TBDMS), triisopropylsilyl (TIPS), or tert-butyldiphenylsilyl (TBDPS) is preferably used for protecting active hydrogen. .

  In each reaction for synthesizing the conjugated compound as described above, a solvent may be used. As a solvent to be used, a solvent that does not inhibit the target reaction as much as possible is preferable. For example, aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as benzene and toluene, nitriles such as acetonitrile, ethers such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane, dichloromethane, 1,2-dichloroethane, tetrachloride Examples thereof include halogenated solvents such as carbon. These may be used alone or in combination of two or more. A suitable solvent includes, for example, dichloromethane.

  And when using the obtained conjugated compound as a material for an organic thin film element, since the purity may affect the element characteristics, after synthesis of the conjugated compound, the obtained product is distilled, It is preferable to purify by a method such as sublimation purification or recrystallization.

[Organic thin film]
Next, an organic thin film according to a preferred embodiment will be described. The organic thin film of this embodiment contains the conjugated compound of the present invention described above.

  The thickness of the organic thin film is preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and still more preferably 20 nm to 200 nm.

  The organic thin film may contain one kind of the conjugated compound according to a preferred embodiment alone, or may contain two or more kinds of conjugated compounds. In addition, in order to increase the electron transport property or the hole transport property, the organic thin film has a low molecular compound or a polymer compound having an electron transport property or a hole transport property in addition to the conjugated compound (these low molecular compounds and polymers). The compounds can be collectively referred to as “electron transporting material” and “hole transporting material”).

  A well-known material can be used as the hole transporting material. For example, pyrazoline derivative, arylamine derivative, stilbene derivative, triaryldiamine derivative, oligothiophene and its derivative, polyvinylcarbazole and its derivative, polysilane and its derivative, polysiloxane derivative having aromatic amine in side chain or main chain, polyaniline And derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyarylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

As the electron transporting material, known materials can be used. For example, oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, or 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, fullerenes and derivatives thereof such as C _60.

Further, the organic thin film may contain a charge generating material in order to generate a charge by light absorbed in the organic thin film. As the charge generation material, known materials can be used. For example, azo compounds and derivatives thereof, diazo compounds and derivatives thereof, metal-free phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, perylene compounds and derivatives thereof, polycyclic quinone compounds and derivatives thereof, squarylium compounds and derivatives thereof, azulenium compounds and their derivatives, thiapyrylium compounds and their derivatives, fullerenes and derivatives thereof such as C _60.

  Furthermore, the organic thin film may contain materials necessary for developing various functions. Such materials include, for example, sensitizers for sensitizing the function of generating charge by absorbed light, stabilizers for increasing stability, UV for absorbing ultraviolet (UV) light. An absorbent is mentioned.

  Further, the organic thin film may contain a polymer compound material other than the conjugated compound of the above-described embodiment as a polymer binder in order to improve mechanical properties. As the polymer binder, those not extremely disturbing the electron transport property or hole transport property are preferable, and those having no strong absorption against visible light are preferably used.

  Examples of such a polymer binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof. And polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  As a manufacturing method of an organic thin film, the method by the film-forming using the solution containing a conjugated compound, the electron transport material or hole transport material mixed as needed, and a polymer binder is mentioned, for example. When the conjugated compound has sublimability, a thin film can also be formed by a vacuum deposition method.

  As a solvent used for film formation using a solution, any conjugated compound, other electron-transporting material or hole-transporting material to be mixed, or a polymer binder may be used. Solvents include toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, unsaturated hydrocarbon solvents such as n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, Halogenated saturated hydrocarbon solvents such as chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, tetrahydrofuran And ether solvents such as tetrahydropyran. Depending on the structure and molecular weight of the conjugated compound, for example, 0.1% by mass or more can be dissolved in these solvents.

  Examples of film forming methods using a solution include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing. Application methods such as a flexographic printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, and a capillary coating method can be used. Of these, spin coating, flexographic printing, ink jet printing, dispenser printing, nozzle coating, and capillary coating are preferred.

  The step of manufacturing the organic thin film may include a step of orienting the conjugated compound. By performing such a process, in the organic thin film, the main chain or the side chain of the conjugated compound is arranged in one direction, so that the charge mobility tends to be further improved.

  As a method of aligning the conjugated compound, a method known as a liquid crystal alignment method can be used. Among them, the rubbing method, the photo-alignment method, the sharing method (shear stress application method) and the pulling coating method are simple, useful and easy to use as the alignment method, and the rubbing method and the sharing method are preferable.

  Further, the step of manufacturing the organic thin film may include a step of performing an annealing process after the film formation. By this step, the film quality of the organic thin film is improved, for example, the interaction between the conjugated compounds is promoted, and the charge mobility is improved. The annealing temperature is preferably a temperature between 50 ° C. and the vicinity of the glass transition temperature (Tg) of the conjugated compound, more preferably a temperature between (Tg−30 ° C.) and Tg. The annealing time is preferably 1 minute to 10 hours, and more preferably 10 minutes to 1 hour. The atmosphere for annealing treatment is preferably in a vacuum or in an inert gas atmosphere.

  Since the organic thin film containing the conjugated compound of the present invention has excellent electron transport properties, it is possible to control the transport of electrons injected from the electrode and charges generated by light absorption. It can be used for various organic thin film elements such as organic thin film solar cells and optical sensors. When using an organic thin film for these organic thin film elements, it is preferable to use the organic thin film by aligning it by an alignment treatment because the electron transport property is improved.

[Organic thin film element]
Since the organic thin film mentioned above contains the conjugated compound of this invention, it has the outstanding electric charge (especially electron) transportability. Therefore, this organic thin film can be applied to various electric elements (organic thin film elements). In addition, since the conjugated compound of the present invention is excellent in environmental stability, it is possible to produce an organic thin film element whose performance is stable even in normal air by forming a thin film using these compounds. It becomes possible. Hereinafter, examples of organic thin film elements will be described.

(Organic thin film transistor)
First, the organic thin film transistor of the present invention comprises the conjugated compound of the present invention. Hereinafter, an organic thin film transistor according to a preferred embodiment will be described. An organic thin film transistor according to a preferred embodiment controls a source electrode and a drain electrode, an active layer (organic thin film layer) including the conjugated compound of the preferred embodiment as a current path between them, and a current amount passing through the current path. Any structure having a gate electrode may be used, and a field effect type and an electrostatic induction type are exemplified.

  The field-effect organic thin film transistor includes a source electrode and a drain electrode, an active layer including a conjugated compound according to a preferred embodiment serving as a current path between them, a gate electrode for controlling the amount of current passing through the current path, and an active layer, It is preferable to include an insulating layer disposed between the gate electrode. In particular, the source electrode and the drain electrode are preferably provided in contact with the active layer containing the conjugated compound according to the preferred embodiment, and further, the gate electrode is preferably provided with an insulating layer in contact with the active layer interposed therebetween. .

  The electrostatic induction type organic thin film transistor has a source electrode and a drain electrode, an active layer containing a conjugated compound of a preferred embodiment as a current path between them, and a gate electrode for controlling an amount of current passing through the current path. The gate electrode is preferably provided in the active layer. In particular, the source electrode, the drain electrode, and the gate electrode provided in the organic thin film layer are preferably provided in contact with the active layer containing the conjugated compound according to a preferred embodiment. The structure of the gate electrode may be any structure as long as a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. It is done.

  FIG. 1 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a first embodiment. An organic thin film transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the substrate 1 with a predetermined interval, and a source electrode 5 and a drain electrode 6 so as to cover the substrate 1. Formed on the insulating layer 3 so as to cover the region of the insulating layer 3 between the source electrode 5 and the drain electrode 6, the insulating layer 3 formed on the active layer 2, and the insulating layer 3 formed between the source electrode 5 and the drain electrode 6. And a gate electrode 4.

  FIG. 2 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a second embodiment. An organic thin film transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the substrate 1 so as to cover the source electrode 5, a source electrode 5 and a predetermined electrode. Of the drain electrode 6 formed on the active layer 2 with an interval of, the insulating layer 3 formed on the active layer 2 and the drain electrode 6, and the insulating layer 3 between the source electrode 5 and the drain electrode 6. And a gate electrode 4 formed on the insulating layer 3 so as to cover the region.

  FIG. 3 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a third embodiment. The organic thin film transistor 120 shown in FIG. 3 includes a substrate 1, an active layer 2 formed on the substrate 1, a source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval, and a source electrode. 5 and the drain electrode 6 so as to partially cover the insulating layer 3 formed on the active layer 2, the region of the insulating layer 3 where the source electrode 5 is formed below, and the drain electrode 6 are formed below. And a gate electrode 4 formed on the insulating layer 3 so as to partially cover the region of the insulating layer 3.

  FIG. 4 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a fourth embodiment. 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. A part of the source electrode 5 and the drain electrode 6 and a part of the source electrode 5 and the drain electrode 6 formed on the insulating layer 3 with a predetermined interval so as to partially cover the region of the insulating layer 3 formed on And an active layer 2 formed on the insulating layer 3 so as to cover it.

  FIG. 5 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a fifth embodiment. An organic thin film transistor 140 shown in FIG. 5 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. A source electrode 5 formed on the insulating layer 3 so as to partially cover the region of the insulating layer 3 formed on the active layer 2 and an active layer 2 formed on the insulating layer 3 so as to partially cover the source electrode 5. And a drain electrode 6 formed on the insulating layer 3 at a predetermined interval so as to partially cover the region of the active layer 2 formed below the gate electrode 4 It is.

  FIG. 6 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a sixth embodiment. An organic thin film transistor 150 shown in FIG. 6 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. The active layer 2 is formed on the insulating layer 3 so as to partially cover the region of the active layer 2 formed under the active layer 2 and the gate electrode 4 formed below. The source electrode 5 and the drain electrode 6 formed on the insulating layer 3 with a predetermined distance from the source electrode 5 so as to partially cover the region of the active layer 2 where the gate electrode 4 is formed below. , Are provided.

  FIG. 7 is a schematic cross-sectional view of an organic thin film transistor (static induction organic thin film transistor) according to a seventh embodiment. The organic thin film transistor 160 shown in FIG. 7 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the source electrode 5, and a plurality on the active layer 2 with a predetermined interval. The formed gate electrode 4 and the active layer 2a formed on the active layer 2 so as to cover the gate electrode 4 (the material constituting the active layer 2a may be the same as or different from that of the active layer 2). And a drain electrode 6 formed on the active layer 2a.

  In the organic thin film transistors according to the first to seventh embodiments, the active layer 2 and / or the active layer 2a contain the conjugated compound of the preferred embodiment, and the current between the source electrode 5 and the drain electrode 6 It becomes a passage (channel). The gate electrode 4 controls the amount of current passing through the current path (channel) in the active layer 2 and / or the active layer 2a by applying a voltage.

  Such a field effect type organic thin film transistor can be manufactured by a known method, for example, a method described in JP-A-5-110069. The electrostatic induction organic thin film transistor can be manufactured by a known method, for example, a method described in JP-A-2004-006476.

  The substrate 1 may be of any material that does not impair the characteristics of the organic thin film transistor, and a glass substrate, a flexible film substrate, or a plastic substrate can be used.

  When forming the active layer 2, it is very advantageous and preferable to use an organic solvent-soluble compound, so that the active layer 2 is formed by using the organic thin film manufacturing method of the present invention described above. An organic thin film can be formed.

As the insulating layer 3 in contact with the active layer 2, any material having high electrical insulation may be used, and a known material can be used. Examples thereof include SiOx, SiNx, Ta ₂ O ₅ , polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass, and photoresist. Since the voltage can be lowered, a material having a high dielectric constant is preferable.

When the active layer 2 is formed on the insulating layer 3, the surface of the insulating layer 3 is treated with a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the active layer 2. It is also possible to form the active layer 2 after the modification. Examples of the surface treatment agent include silylamine compounds such as long-chain alkylchlorosilanes, long-chain alkylalkoxysilanes, fluorinated alkylchlorosilanes, fluorinated alkylalkoxysilanes, and hexamethyldisilazane. Prior to the treatment with the surface treatment agent, the surface of the insulating layer can be treated with ozone UV or O ₂ plasma.

  Moreover, it is preferable to form a protective film on the organic thin film transistor after the organic thin film transistor is manufactured in order to protect the element. Thereby, an organic thin-film transistor is interrupted | blocked from air | atmosphere and the fall of the characteristic of an organic thin-film transistor can be suppressed. Moreover, the influence from the process of forming the display device driven on an organic thin-film transistor with a protective film can be reduced.

  Examples of the method for forming the protective film include a method of covering with a UV curable resin, a thermosetting resin, or an inorganic SiONx film. In order to effectively cut off from the atmosphere, it is preferable to perform the steps from the preparation of the organic thin film transistor to the formation of the protective film without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

(Organic thin film solar cell)
Next, application to an organic thin film solar cell will be described. FIG. 8 is a schematic cross-sectional view of the organic thin-film solar cell according to the embodiment. The organic thin film solar cell 200 shown in FIG. 8 contains the substrate 1, the first electrode 7a formed on the substrate 1, and the conjugated compound of a preferred embodiment formed on the first electrode 7a. An active layer 2 made of an organic thin film and a second electrode 7b formed on the active layer 2 are provided.

  In the organic thin film solar cell according to the present embodiment, a transparent or translucent electrode is used for one of the first electrode 7a and the second electrode 7b. As an electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used. In order to obtain a high open circuit voltage, each electrode is preferably selected so that the difference in work function is large. In the active layer 2, a charge generating agent, a sensitizer and the like can be added and used in order to increase photosensitivity. As the substrate 1, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.

(Optical sensor)
Next, application of an organic thin film to an optical sensor will be described. FIG. 9 is a schematic cross-sectional view of the photosensor according to the first embodiment. An optical sensor 300 shown in FIG. 9 includes an organic thin film containing a substrate 1, a first electrode 7a formed on the substrate 1, and a conjugated compound of a preferred embodiment formed on the first electrode 7a. An active layer 2 made of the above, a charge generation layer 8 formed on the active layer 2, and a second electrode 7 b formed on the charge generation layer 8.

  FIG. 10 is a schematic cross-sectional view of an optical sensor according to the second embodiment. An optical sensor 310 illustrated in FIG. 10 is formed on the substrate 1, the first electrode 7a formed on the substrate 1, the charge generation layer 8 formed on the first electrode 7a, and the charge generation layer 8. The active layer 2 made of an organic thin film containing a conjugated compound according to a preferred embodiment and a second electrode 7b formed on the active layer 2 are provided.

  FIG. 11 is a schematic cross-sectional view of an optical sensor according to the third embodiment. An optical sensor 320 shown in FIG. 11 includes an organic thin film containing a substrate 1, a first electrode 7a formed on the substrate 1, and a conjugated compound of a preferred embodiment formed on the first electrode 7a. And the second electrode 7 b formed on the active layer 2.

  In the optical sensor according to the first to third embodiments, a transparent or translucent electrode is used for one of the first electrode 7a and the second electrode 7b. The charge generation layer 8 is a layer that absorbs light and generates charges. As an electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used. In the active layer 2, a carrier generating agent, a sensitizer and the like can be added and used in order to increase the photosensitivity. Moreover, as the base material 1, a silicon substrate, a glass substrate, a plastic substrate, etc. can be used.

  The present invention has been described in detail based on the embodiments. However, the present invention is not limited to the above embodiment. The present invention can be variously modified without departing from the gist thereof.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to a following example at all.

(Measurement conditions, etc.)
First, measurement conditions performed in the following examples and comparative examples will be described. The nuclear magnetic resonance (NMR) spectrum is obtained using the product name JMN-270 (270 MHz at ¹ H measurement) manufactured by JEOL (JEOL Ltd.) or the product name JMNLA-600 (600 MHz at ¹⁹ F measurement) manufactured by the same company. It was measured. In the results, the chemical shift is expressed in parts per million (ppm). Tetramethylsilane (TMS) was used for the internal standard of 0 ppm. The coupling constant (J) is shown in hertz, and the abbreviations s, d, t, q, m, and br are singlet, doublet, triplet, quadruple, respectively. Represents a line, a multiplet, and a broad line.

  Moreover, mass spectrometry (MS) was performed by the electron ionization (EI) method and the direct sample introduction (DI) method using GCMS-QP5050A (trade name) manufactured by Shimadzu Corporation. As silica gel in the column chromatography separation, trade name Silicagel 60N (40-50 μm) manufactured by Kanto Chemical Co., Ltd. was used. All chemical substances are reagent grade and purchased from Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., Kanto Chemical Co., Ltd., Nacalai Tesque Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Daikin Chemicals Co., Ltd.

Furthermore, the reaction under microwave irradiation was performed by Initiator ^™ Ver. Manufactured by Biotage AB. 2.5 was used and the output was 400 W and 2.45 GHz. Cyclic voltammetry (CV) uses the product name “CV-50W” manufactured by BAS Co., Ltd. (BAS) as the measuring device, Pt electrode manufactured by BAS as the working electrode, Pt wire as the counter electrode, Measurement was performed using Ag wire as a reference electrode. The sweep rate during this measurement was 100 mV / s, and the scanning potential region was −2.8 V to 1.6 V. The reduction potential and oxidation potential were measured by dissolving 1 × 10 ⁻³ mol / L of the compound and polymer and 0.1 mol / L of tetrabutylammonium hexafluorophosphate (TBAPF6) as a supporting electrolyte in a monofluorobenzene solvent. And measured.

[Example 1: Synthesis of conjugated compound (E)]
A conjugated compound (E) was synthesized through synthesis of various intermediates shown below.

(Synthesis of Compound (B))
First, the following reaction was performed to synthesize a compound (B) which is a raw material compound for forming a terminal group.

That is, a compound (A-1) synthesized by the method described in J. Org. Chem. 2006, 71, 9475-9483 is used as a raw material, and a reaction according to the following scheme is carried out to obtain a compound that is an intermediate ( A-3) was synthesized.

Here, in the synthesis of compound (A-3), first, compound (A-1) (1 g, 3.43 mmol) and thionyl chloride (SOCl ₂ ) (1 mL, 13.74 mmol) were added to a 50 mL three-necked flask. Further, after refluxing for 1 hour, SOCl ₂ was distilled off. At room temperature, 40 mL of nitrobenzene (PhNO ₂ ) was added, and further, malonyl chloride (532 mg, 3.78 mmol) and aluminum chloride (1.37 g, 13.72 mmol) were added, and the temperature was raised to 80 ° C., and the mixture was heated for 4 hours. Stir. Then, 10 wt% oxalic acid solution was added to stop the reaction, and the reaction solution was washed with water and extracted with ethyl acetate. The obtained organic layer was dried with sodium sulfate, and the solvent was distilled off, followed by vacuum drying. The obtained product was purified with a silica gel column (hexane / ethyl acetate = 10/1 (volume ratio)) to obtain a white solid compound (A-2) (606 mg, yield 56%) as an intermediate. Obtained.

In a 100 ml eggplant flask, compound (A-2) (606 mg, 1.92 mmol) and a fluorinating agent “Selectfluor ^™ (registered trademark)” (1.63 g, 4.61 mmol) were placed, and tetrahydrofuran (THF) was added thereto. (30 mL) was added and dissolved. Tetrabutylammonium hydroxide (TBAH) (10 wt% methanol solution) (19.94 g, 4.61 mmol) was added thereto, and the mixture was stirred at 0 ° C. for 2 hours, and then warmed to room temperature. The stirred solution was washed with water and extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate, and the solvent was distilled off, followed by vacuum drying. The obtained product was purified by a silica gel column (hexane / ethyl acetate = 10/1 (volume ratio)) to obtain a white solid compound (A-3) (527 mg, yield 78%) as an intermediate. It was.

After synthesizing the compound (A-3) in this way, the obtained compound (A-3) (1.09 g, 3.10 mmol), malononitrile (409 mg, 6.20 mmol), ammonium acetate was added to a 100 mL eggplant flask. (358 mg, 4.64 mmol), toluene (40 mL), and acetic acid (4 mL) were added and refluxed for 4 hours. The refluxed solution was washed with water and extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate, and the solvent was distilled off, followed by vacuum drying. Then, the obtained product was purified by a silica gel column (hexane / ethyl acetate = 10/1 (volume ratio)) to obtain a green solid compound (B) (627 mg, yield 50%) as a target product. Obtained. The analysis results and chemical formula of compound (B) are as follows.
TLC R _f = 0.5 (hexane / ethyl acetate = 10/1 (volume ratio))
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.90 (m, 3H), 1.34 (m, 6H), 1.62 (m, 2H), 2.89 (m, 2H) )
GC-MS (DI): m / z = 398 (M ⁺ )

(Synthesis of Compound (D))
First, the compound (C) as a raw material for constituting the central part of the conjugated compound is converted into Philippe Lucas et al. Synthesis, 2000 No.9 p.1253 and Myung-HanYoon et al., Chemistry Materials vol.19 ( 2007) according to the method described in p.4864.

Then, in a 5 mL test tube, compound (B) (215 mg, 0.54 mmol) obtained above, compound (C) (200 mg, 0.25 mmol), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) (12 mg, 0.013 mmol), tri-o-tolylphosphine (8 mg, 0.026 mmol), and chlorobenzene (3 mL) were added and reacted under microwave irradiation (180 ° C. , 5 minutes). The product after the reaction was purified using a silica gel column (chloroform) and a gel permeation chromatograph (GPC) to obtain the target compound (D) (142 mg, 66% yield) as a dark blue black solid. Obtained. The analysis results and chemical formula of compound (D) are as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.97 (m, 6H), 1.35 (m), 1.47 (m), 1.67 (m), 3.11 ( m, 4H), 4.42 (s, 4H), 7.39 (s, 2H)
MALDI TOFMS: m / z = 872

(Synthesis of Conjugated Compound (E))
The compound (D) obtained above (142 mg, 0.16 mmol), hydrochloric acid (0.5 mL), and acetic acid (4 mL) were placed in a test tube with a lid, and the mixture was stirred at 100 ° C. overnight. The stirred solution was washed with water and extracted with dichloromethane. The obtained organic layer was dried over sodium sulfate, and the solvent was distilled off, followed by vacuum drying. The obtained product was purified by a silica gel column (chloroform) and GPC to obtain the target compound, a deep blue-black solid conjugated compound (E) (118 mg, yield 88%). The analysis results and chemical formula of the conjugated compound (E) are as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.91 (m, 6H), 0.97 (m), 1.35 (m), 1.47 (m), 1.67 ( m), 3.08 (m, 4H), 7.44 (s, 2H)
MALDI TOFMS: m / z = 828

  When CV measurement was performed on the obtained conjugated compound (E), a reversible reduction wave and oxidation wave were observed at −0.82 V and +1.04 V, respectively. It was confirmed that the LUMO level was lower than the reduction wave.

[Example 2: Synthesis of conjugated compound (G)]
Using the compound (B) obtained above, a conjugated compound (G) was synthesized.

(Synthesis of Conjugated Compound (G))
First, 5,5′-bis (tri-n-butylstannyl) -2,2′-dithiophene (compound (F)) as a raw material was added to Jia Huang et al., J. Am. Chem. Soc., Vol. (2007) was synthesized according to the method described in p.9366.

Next, the compound (B) obtained above (148 mg, 0.37 mmol), the compound (F) (124 mg, 0.17 mmol), Pd ₂ (dba) ₃ (7 mg, 0.008 mmol) was placed in a 5 mL test tube. ), Tri-o-tolylphosphine (5 mg, 0.016 mmol) and chlorobenzene (3 mL) were allowed to react under microwave irradiation (180 ° C. , 5 minutes). The obtained product was purified by a silica gel column (chloroform) and GPC to obtain a target compound, a deep blue-black solid conjugated compound (G) (93 mg, yield 70%). The analysis results and chemical formula of the conjugated compound (G) are as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.91 (m, 6H), 1.35 (m), 1.47 (m), 1.69 (m), 3.12 ( m, 4H), 7.39 (m, 2H), 7.49 (m, 2H)
MALDI TOFMS: m / z = 802

  When CV measurement was performed on the conjugated compound (G), a reversible reduction wave and oxidation wave were observed at −0.86 V and +1.06 V, respectively. The LUMO energy estimated from the reduction wave was −3.94 eV, and it was confirmed that the LUMO level was low.

[Example 3: Synthesis of conjugated compound (J)]
A conjugated compound (J) is synthesized through synthesis of various intermediates shown below.

(Synthesis of Compound I)
First, a compound (H) as a raw material for constituting the central portion of the conjugated compound is synthesized according to the method described in Yutaka Ie et al., Advanced Functional Materials, vol. 20 (2010) p. 907.

Next, the compound (B), compound (H), Pd ₂ (dba) ₃ , tri-o-tolylphosphine, and chlorobenzene obtained above were put into a 5 mL test tube, and these were reacted under microwave irradiation. Let And the obtained product is refine | purified with a silica gel column (chloroform) and GPC, and the target compound (I) is obtained.

(Synthesis of conjugated compound (J))
In a test tube with a lid, add hydrochloric acid and acetic acid and stir at 100 ° C. overnight. The solution after stirring is washed with water and then extracted with dichloromethane. The obtained organic layer is dried with sodium sulfate, and the solvent is distilled off, followed by vacuum drying. The obtained product is purified by a silica gel column (chloroform) and GPC to obtain the target conjugated compound (J).

[Example 4: Preparation of organic transistor element 1 and evaluation of transistor characteristics]
A silicon oxide film having a thickness of 300 nm formed by thermal oxidation was prepared on the surface of a heavily doped p-type silicon substrate serving as a gate electrode. On the substrate, comb source and drain electrodes having a channel width of 38 mm and a channel length of 5 μm were formed by a lift-off method. The obtained substrate with electrodes was ultrasonically cleaned with acetone for 10 minutes and then with isopropyl alcohol for 10 minutes, and then the surface was cleaned by irradiation with ozone UV for 30 minutes.

  Here, when the conjugated compound (E) synthesized in Example 1 was dissolved in chloroform and a solution was prepared so as to have a concentration of 1% by weight, it was completely dissolved, so that the conjugated compound (E) Was confirmed to be soluble in an organic solvent.

  Using the obtained chloroform solution of the conjugated compound (E) as a coating solution, an organic thin film of the conjugated compound (E) is deposited on the washed substrate by a spin coating method, whereby the organic transistor element 1 is obtained. Produced.

  About the obtained organic transistor element 1, using a semiconductor parameter analyzer (trade name “4200-SCS” manufactured by Keithley), the gate voltage Vg and the source-drain voltage Vsd are changed in the range of 0 to 80 V in vacuum. When the transistor characteristics were measured under the conditions, good drain current (Id) -gate voltage (Vg) characteristics of an n-type semiconductor were obtained.

Mobility at this time was ^{1.2 × 10 -3 cm 2 / Vs} , the threshold voltage is 32V, the on / off ratio was 10 ^5, both were good value. From this, it was confirmed that the organic transistor element 1 using the conjugated compound (E) functions effectively as an n-type organic transistor. And it was confirmed that a conjugated compound (E) can be utilized as an organic n-type semiconductor excellent in electron transport property.

[Example 5: Production of organic transistor element 2 and evaluation of transistor characteristics]
The conjugated compound (G) synthesized in Example 2 was dissolved in chloroform and a solution was prepared so as to have a concentration of 1% by weight. As a result, the conjugated compound (G) was organically dissolved. It was confirmed that it was soluble in a solvent.

  The conjugated compound (G) is contained instead of the conjugated compound (E) in the same manner as in Example 4 except that the chloroform solution of the conjugated compound (G) thus prepared is used as the coating solution. The organic transistor element 2 provided with the organic thin film was produced.

When the transistor characteristics of the obtained organic transistor element 2 were measured in the same manner as in Example 4, good Id-Vg characteristics of an n-type semiconductor were obtained. The mobility at this time was 0.016 cm ² / Vs, the threshold voltage was 11 V, and the on / off ratio was 10 ⁵ , which was favorable. From this, it was confirmed that the organic transistor element 2 using the conjugated compound (G) functions effectively as an n-type organic transistor. Further, it was confirmed that the conjugated compound (G) can be used as an organic n-type semiconductor having excellent electron transport properties.

[Comparative Example 1: Synthesis of Conjugated Compound (L)]
Through the synthesis of the intermediate shown below, a conjugated compound (L) was synthesized.

(Synthesis of Compound (K))
First, the following reaction was performed to synthesize a compound (K) which is a raw material compound for forming a terminal group. That is, using the compound (K-1) as a raw material, a reaction was performed according to the following scheme to obtain the compound (K) as a brown solid.

<Synthesis of Compound (K-1)>
Hereafter, the process of synthesize | combining the compound (K) mentioned above is demonstrated in detail. In the synthesis of compound (K), first, compound (K-1) is prepared according to the method described in the literature (J. Chem. Soc. Perkin Trans 1. Organic and Bio-Organic Chemistry 1992, 21, 2985-2988). Synthesized.

<Synthesis of Compound (K-2)>
Subsequently, compound (K-1) (1.00 g, 6.58 mol) and the fluorinating agent “Selectfluor ^™ (registered trademark)” (5.60 g, 15.8 mol) were placed in a 300 mL three-necked flask, and THF ( 65 mL) was added and dissolved. Tetrabutylammonium hydroxide (TBAH) (10 wt% methanol solution) (3.76 g, 14.5 mol) was added thereto, and the mixture was stirred at 0 ° C. for 12 hours. The solvent was distilled off from the stirred solution under reduced pressure, water was added, the aqueous phase was extracted with ethyl acetate, and the organic phase was dried over magnesium sulfate and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 3/1 (volume ratio)) to give compound (K-2) (0.934 g, yield 75%) as a pale yellow solid. Obtained. The analysis result of the compound (K-2) is as follows.
mp: 156-158 ° C
TLC R _f = 0.29 (2: 1 = hexane: ethyl acetate (volume ratio))
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 7.60 (d, 1H, J = 4.8 Hz), 8.28 (d, 1H, J = 4.8 Hz)
MS (EI) m / z = 188 (M +)

<Synthesis of Compound (K-3)>
Compound (K-2) (1.97 g, 10.48 mmol) is placed in a 200 mL three-necked flask, dissolved by adding N, N′-dimethylformamide (DMF) (50 mL), and further 2-chloromethanol (3. 37 g, 41.91 mmol) was added. To the solution, potassium tert-butoxide dissolved in DMF (50 mL) was added dropwise at -60 ° C. After completion of dropping, the mixture was stirred at room temperature for 4 hours, and water was added to stop the reaction. Next, the aqueous layer was extracted with ethyl acetate and washed with water, and then the organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 3/1 (volume ratio)) to obtain compound (K-3) (1.58 g, yield 55%) as a white solid. It was. The analysis result of the compound (K-3) is as follows.
mp: 117-122 ° C
TLC R _f = 0.34 (2: 1 = hexane: ethyl acetate (volume ratio))
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 4.26 (s, 8H), 7.02 (d, 1H, J = 4.8 Hz), 7.51 (d, 1H, J = 5.1Hz)
MS (EI) m / z = 276 (M ⁺ )

<Synthesis of Compound (K)>
In a 100 mL three-necked flask, the compound (K-3) (1.00 g, 3.62 mmol) was added, and THF (30 mL) was added and dissolved. Thereto was added n-butyllithium (1.58M, 2.75 mL, 4.34 mmol) at -78 ° C. After stirring for 0.5 hour, bromine (0.29 mL, 5.43 mmol) was added and the temperature was gradually raised to room temperature. After 1 hour, water was added to stop the reaction. The aqueous layer was extracted with ethyl acetate, washed with a saturated aqueous sodium thiosulfate solution, washed with water, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the crude product was passed through silica gel column chromatography (hexane / ethyl acetate = 3/1 (volume ratio)) to obtain a crude product of intermediate compound (K-4).

The obtained intermediate compound (K-4) was placed in a 100 mL eggplant flask and dissolved in THF (30 mL). Concentrated sulfuric acid (30 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was poured onto ice and extracted with water. The organic layer was washed with a saturated aqueous sodium bicarbonate solution and water in that order, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (ethyl acetate) to obtain compound (K) (877 mg, yield 91% in 2steps) as a brown solid. The analysis results of the compound (K) are as follows.
TLC: R _f = 0.21 (3: 1 = hexane: ethyl acetate (volume ratio))
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 7.60 (s, 1H); MS (EI) m / z = 266 (M ⁺ )

(Synthesis of Conjugated Compound (L))
Compound (K) obtained above (326 mg, 1.22 mmol), 5,5′-bis (tributylstannyl) -2,2′-bithiophene (413 mg, 0.555 mmol), and tetrakis (triphenylphosphine) ) Palladium (0) (64 mg, 0.056 mmol) was placed in a test tube and dissolved by adding toluene (6 mL). This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. The reaction solution was filtered through Celite and the solvent was distilled off under reduced pressure. The resulting solid was washed with hexane to obtain the conjugated compound (L) (35 mg, yield 74%) as a dark purple solid. The analysis results and chemical formula of the conjugated compound (L) are as follows.
mp:> 300 ° C
MS (EI): m / z = 538 (M ⁺ )

When the conjugated compound (L) thus obtained was dissolved in chloroform, it was found that it was not completely dissolved at a concentration higher than 1 × 10 ⁻⁴ mol / L and was hardly soluble in an organic solvent. .

[Comparative Example 2]
(Synthesis of Conjugated Compound (N))
Through the synthesis of the compound (M) shown below, a conjugated compound (N) was synthesized. First, 5,5′-dibromo-4,4′-dihexyl-2,2′-bithiophene (492 mg, 1.00 mmol) was placed in a 20 mL three-necked flask and dissolved by adding THF (10 mL). N-Butyllithium (1.58M, 1.39mL, 2.20mmol) was added thereto at -78 ° C. After stirring for 1 hour, tributyltin chloride (0.543 ml, 2.00 mmol) was added, and the temperature was gradually raised to room temperature. After 2 hours, the reaction was stopped by adding water and a small amount of hydrochloric acid. The aqueous layer was extracted with diethyl ether, washed with water, and the organic layer was dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained liquid was purified by GPC (chloroform (CHCl ₃ )) to obtain Compound (M) (630 mg, yield 69%) as a yellow liquid. The analysis results and chemical formula of the compound (M) are as follows.
TLC: R _f = 1.0 (hexane)
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.84-0.94 (m, 24H), 1.02-1.20 (m, 12H), 1.26-1.39 ( m, 24H), 1.46-1.61 (m, 16-H), 2.51 (t, 4H, 8.0 Hz), 7.13 (s, 2H)
MS (EI): m / z = 912 (M ^<+> ).

Next, the compound (M) obtained above (50 mg, 0.055 mmol), the compound (K) synthesized in Comparative Example 1 (32 mg, 0.12 mmol), and tetrakis (triphenylphosphine) palladium (0) ( 6 mg, 0.005 mmol) was placed in a test tube with a lid, and toluene (1 mL) was added to dissolve. This was stirred at 120 ° C. for 12 hours and then allowed to cool at room temperature. Next, the solvent was distilled off under reduced pressure, and the crude product was passed through silica gel column chromatography (chloroform) and then purified by GPC (chloroform) to give the conjugated compound (N) (19 mg, yield 49%) as an orange solid. Got as. The analysis results and chemical formula of the conjugated compound (N) are as follows.
TLC: R _f = 0.43 (5: 1 = hexane: ethyl acetate (volume ratio))
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.88-0.96 (m, 6H), 1.28-1.49 (m, 12H), 1.65-1.76 ( m, 4H), 2.85 (t, 4H, J = 7.9 Hz), 7.19 (s, 2H), 7.51 (s, 2H)
MS (EI) m / z = 706 (M ⁺ )

(Production of organic transistor element 3 and evaluation of transistor characteristics)
When the conjugated compound (N) was dissolved in chloroform and a solution was prepared so as to have a concentration of 1% by weight, it could be completely dissolved, so that it could be confirmed that it could be dissolved in an organic solvent.

  The conjugated compound (N) is contained instead of the conjugated compound (E) in the same manner as in Example 4 except that the chloroform solution of the conjugated compound (N) thus prepared is used as the coating solution. The organic transistor element 3 provided with the organic thin film was produced.

When the transistor characteristics of the obtained organic transistor element 3 were measured in the same manner as in Example 4, the Id-Vg characteristics of the n-type semiconductor were obtained. The mobility at this time was 1.8 × 10 ^{− It was 5} cm ² / Vs, which was lower than that of the example.

[Example 5: Synthesis of conjugated compound (P)]
Through the synthesis of various intermediates shown below, a conjugated compound (P) was synthesized.

(Synthesis of Compound (O))
In a 30 mL two-necked eggplant flask, compound (A-3) (100 mg, 0.28 mmol), malononitrile (75 mg, 1.12 mmol), pyridine (180 mg, 2.24 mmol), titanium tetrachloride (210 mg, 1.12 mmol), And after adding chloroform (10 mL) and making it recirculate | reflux for 8 hours, it washed with water and extracted with chloroform. The organic layer was dried over sodium sulfate, the solvent was distilled off, and vacuum dried. The obtained solid was purified by a silica gel column (hexane / ethyl acetate = 10/1 (volume ratio)) to obtain the target compound (O) as a yellow solid (88 mg, yield 69%). . The analysis results and chemical formula of the obtained compound (O) are as follows.
TLC R _f = 0.5 (hexane / ethyl acetate = 10/1 (volume ratio))
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.90 (m, 3H), 1.34 (m, 4H), 1.43 (m, 2H), 1.58 (m, 2H) ), 3.14 (m, 2H)
GC-MS (DI): m / z = 446 (M ⁺ )

(Synthesis of Conjugated Compound (P))
In a 2 mL test tube, compound (O) (100 mg, 0.22 mmol), compound (F) (75 mg, 0.16 mmol), Pd ₂ (dba) ₃ (2 mg, 0.002 mmol), tri-o-tolylphosphine (3 mg, 0.008 mmol) and chlorobenzene (1 mL) were added, and they were reacted under microwave irradiation (180 ° C., 5 minutes). Purification was performed with a silica gel column (chloroform) and GPC to obtain the target compound, a dark blue-black solid conjugated compound (P) (15 mg, 17% yield). The analysis results and chemical formula of the conjugated compound (P) are as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.89 (m, 6H), 1.32 (m), 1.46 (m), 1.64 (m), 3.34 ( m, 4H), 7.40 (m, 2H), 7.46 (m, 2H)
MALDI TOFMS: m / z = 898.1

  When CV measurement was performed on the conjugated compound (P), a reversible reduction wave at -0.62 V was observed. The LUMO energy estimated from the reduction wave was −4.18 eV, and it was confirmed that the LUMO was low.

[Example 6: Synthesis of conjugated compound (Q)]
(Synthesis of Conjugated Compound (Q))
Put the compound (O), 2,2′-bis (tributylstannyl) thienothiophene, Pd ₂ (dba) ₃ , and tri-o-tolylphosphine and chlorobenzene into a test tube and react them under microwave irradiation Let The reaction product is purified by silica gel column (chloroform) and GPC to obtain the target conjugated compound (Q).

[Example 7: Production of organic transistor element 4 and evaluation of transistor characteristics]
The conjugated compound (P) can be dissolved in an organic solvent because the conjugated compound (P) was dissolved in chloroform and a solution was prepared to a concentration of 1% by weight. I was able to confirm that.

  An organic thin film containing a conjugated compound (P) in the same manner as in Example 4 except that a chloroform solution of the conjugated compound (P) was used as the coating solution instead of the chloroform solution of the conjugated compound (E). An organic transistor element 4 comprising:

When the transistor characteristics of the obtained organic transistor element 4 were measured in vacuum in the same manner as in Example 4, good Id-Vg characteristics of an n-type semiconductor were obtained. The mobility at this time was 4.9 × 10 ⁻³ cm ² / Vs, the threshold voltage was 25 V, and the on / off ratio was 10 ⁶ , which was favorable. Further, when the transistor characteristics of the organic transistor element 4 were measured in the atmosphere, the mobility was 2.8 × 10 ⁻³ cm ² / Vs, the threshold voltage was 23 V, the on / off ratio was 10 ^6, and the vacuum It was almost the same as the inside characteristics. From this, it was confirmed that the organic transistor element 4 using the conjugated compound (P) functions effectively as an n-type organic transistor and operates stably in the atmosphere. Further, it was confirmed that the conjugated compound (P) can be used as an organic n-type semiconductor having excellent electron transport properties.

  DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Active layer, 2a ... Active layer, 3 ... Insulating layer, 4 ... Gate electrode, 5 ... Source electrode, 6 ... Drain electrode, 7a ... 1st electrode, 7b ... 2nd electrode, 8 ... Charge generation layer, 100 ... organic thin film transistor according to the first embodiment, 110 ... organic thin film transistor according to the second embodiment, 120 ... organic thin film transistor according to the third embodiment, 130 ... organic thin film transistor according to the fourth embodiment, 140 ... Organic thin film transistor according to fifth embodiment, 150... Organic thin film transistor according to sixth embodiment, 160. Organic thin film transistor according to seventh embodiment, 200... Organic thin film solar cell according to embodiment, 300. Optical sensor 310... Optical sensor according to the second embodiment, 320... Optical sensor according to the third embodiment.

Claims (11)

A conjugated compound represented by the formula (I).

[In Formula (I), R ⁰¹ and R ⁰² each independently represent a monovalent group containing an alkane skeleton, and R ¹¹ , R ¹² , R ²¹ and R ²² each independently represent a hydrogen atom, A monovalent group which may be substituted with a halogen atom or a substituent is shown. X ¹¹ , X ¹² , X ²¹ and X ²² each independently represent an oxygen atom, a sulfur atom or a group represented by the formula (a). However, at least one of X ¹¹ , X ¹² , X ²¹ and X ²² is a sulfur atom or a group represented by the formula (a). Z ¹ and Z ² are each independently a group represented by Formula (i), a group represented by Formula (ii), a group represented by Formula (iii), or a group represented by Formula (iv) , A group represented by formula (v), a group represented by formula (vi), a group represented by formula (vii), a group represented by formula (viii), and a group represented by formula (ix) Any one group selected from the group consisting of: Ar ⁰ , Ar ¹ and Ar ² each independently represent a divalent aromatic hydrocarbon group having 6 or more carbon atoms or a divalent heterocyclic group having 4 or more carbon atoms, and these have a substituent. It may be. r shows the integer of 1-6, s and t show the integer of 0-6 each independently.
In formula (a), A represents a hydrogen atom, a halogen atom or a monovalent group, and a plurality of A may be the same or different, but at least one A is an electron-withdrawing group.
In formula (vii), formula (viii) and formula (ix), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or a monovalent group, and R ³ and R ⁴ may be bonded to each other to form a ring. Note that the group represented by the formula (viii) may be horizontally reversed. ] The at least one of the X ¹¹ and the X ¹² is a group represented by the formula (a), and at least one of the X ²¹ and the X ²² is a group represented by the formula (a). Conjugated compound of The conjugated compound according to claim 1 or 2, wherein Ar ⁰ is a group having no substituent containing an alkane skeleton. The conjugated compound according to any one of claims 1 to 3, wherein Ar ⁰ is a group represented by formula (II) or a group represented by formula (III).

[In the formula (II), Z ³ represents a group represented by the formula (xi), a group represented by the formula (xii), a group represented by the formula (xiii), or a group represented by the formula (xiv). , A group represented by formula (xv), a group represented by formula (xvi), a group represented by formula (xvii), a group represented by formula (xviii), and a group represented by formula (xix) Any one group selected from the group consisting of: Note that the group represented by the formula (xviii) may be horizontally reversed.
In Formula (III), Ar ³ and Ar ⁴ are each independently a trivalent aromatic hydrocarbon group having 6 or more carbon atoms or a trivalent heterocyclic group having 4 or more carbon atoms, and includes an alkane skeleton. represents a group which has no substituent, X ³ represents an oxygen atom, a group represented by a sulfur atom or the formula (a). ] The conjugated compound according to claim 4, wherein the group represented by the formula (III) is a group represented by the formula (IV).

[In Formula (IV), X ³ is as defined above, Y ¹ and Y ² each independently represent a carbon atom or a nitrogen atom, and Z ⁴ and Z ⁵ are each independently Formula (xxi). A group represented by formula (xxii), a group represented by formula (xxiii), a group represented by formula (xxiv), a group represented by formula (xxv), a formula (xxvi) Any one group selected from the group consisting of a group represented by formula (xxvii), a group represented by formula (xxviii) and a group represented by formula (xxix). Note that the group represented by the formula (xxviii) may be horizontally reversed. ] One of X ¹¹ and X ¹² is an oxygen atom, the other one of X ¹¹ and X ¹² is a group represented by formula (a1), and X ²¹ and 6. One of X ²² is an oxygen atom, and the other of X ²¹ and X ²² is a group represented by formula (a1). Conjugated compound of

The conjugated compound according to claim 5 or 6, wherein Z ⁴ and Z ⁵ are a group represented by the formula (xxii) or a group represented by the formula (xxvii).   The organic thin film containing the conjugated compound as described in any one of Claims 1-7.   An organic thin film element comprising the organic thin film according to claim 8.   An organic thin-film transistor provided with the organic thin film of Claim 8.   An organic thin film solar cell comprising the organic thin film according to claim 8.

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