JP2014047196A - Compound and polymer compound, organic semiconductor material containing compound or polymer compound and organic semiconductor element using organic semiconductor material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having a sufficiently large absolute value of LUMO and a polymer compound.SOLUTION: A compound has at least two structures represented by the formula (1). In Formula (1), Zand Zrepresent an oxygen atom, a sulfur atom, a selenium atom, a group represented by =C(R)(R) or a group represented by =N(R); At least one of Zand Zis a sulfur atom or a selenium atom; R, Rand Rrepresent a cyano group or a group represented by -C(=O)R; Rrepresents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group or a heterocyclic group; Erepresents an oxygen atom, a sulfur atom, a selenium atom, a group represented by -N(R)- or a group represented by -C(R)=C(R)-; R, Rand Rrepresent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a heterocyclic group, a halogen atom or a cyano group; and a ring Arepresents an aromatic carbocyclic ring or a heterocyclic ring.

Description

  The present invention relates to a compound and a polymer compound, an organic semiconductor material containing the compound or the polymer compound, and an organic semiconductor element using the organic semiconductor material.

  An organic semiconductor material having charge (electron or hole) transportability is expected to be applied to organic semiconductor elements such as organic solar cells, organic transistors, and organic electroluminescence elements.

  A semiconductor element containing an inorganic semiconductor material has been manufactured using a vacuum deposition method. On the other hand, an organic semiconductor element can be produced by a printing method using a solution in which an organic semiconductor material is dissolved in a solvent, and a reduction in manufacturing cost is expected. Therefore, research and development of organic semiconductor materials are actively performed. ing.

  In general, the HOMO (maximum occupied orbit) value of an organic semiconductor material is close to the work function value of a metal such as gold, which is usually used as an electrode of an organic semiconductor element, and it is easy to inject holes from the electrode into the organic semiconductor material. The organic semiconductor material has p-type semiconductor characteristics. On the other hand, the conventional organic semiconductor material has a small LUMO (minimum unoccupied orbital) absolute value, makes it difficult to inject electrons from the electrode into the organic semiconductor material, and has a large LUMO absolute value. Development of materials is required.

  Further, when an organic semiconductor material having n-type semiconductor characteristics is used for the active layer of the organic transistor, the larger the absolute value of the LUMO of the organic semiconductor material, the more effective the stability of the organic transistor to the atmosphere is.

  As organic semiconductor materials having n-type semiconductor characteristics, for example, the following compounds have been proposed (Non-Patent Document 1).

Chemical Communications, 2011, 47, p. 11840-11842

  However, the absolute value of LUMO of the above compound was 3.4 eV, and the absolute value of LUMO was not sufficiently large.

  The present invention has been made in view of such circumstances, and an object thereof is to provide a compound and a polymer compound having a sufficiently large LUMO absolute value. Another object of the present invention is to provide an organic semiconductor material containing the compound or the polymer compound and an organic semiconductor element using the organic semiconductor material.

  The present invention provides the following compound and polymer compound, an organic semiconductor material containing the compound or the polymer compound, and an organic semiconductor element using the organic semiconductor material.

（式（１）中、Ｚ^１及びＺ^２は、それぞれ独立に、酸素原子、硫黄原子、セレン原子、＝Ｃ（Ｒ^１）（Ｒ^２）で表される基又は＝Ｎ（Ｒ^３）で表される基を表す。Ｚ^１及びＺ^２のうちの少なくとも１つは硫黄原子又はセレン原子である。Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、シアノ基又は−Ｃ（＝Ｏ）Ｒ^４で表される基を表す。Ｒ^４は、水素原子、ヒドロキシル基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基又は置換基を有していてもよい複素環基を表す。Ｒ^４が２個ある場合、それらは同一であっても異なっていてもよい。Ｅ^１は、酸素原子、硫黄原子、セレン原子、−Ｎ（Ｒ^５）−で表される基又は−Ｃ（Ｒ^６）＝Ｃ（Ｒ^７）−で表される基を表す。Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子、ヒドロキシル基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリール基、置換基を有していてもよい複素環基、ハロゲン原子又はシアノ基を表す。Ｒ^６及びＲ^７は互いに結合してそれぞれが結合している炭素原子と共に五員環又は六員環を形成していてもよい。環Ａ^１は、置換基を有していてもよい芳香族炭素環又は置換基を有していてもよい複素環を表す。）
［２］ 下記式（２）で表される、［１］に記載の化合物。

（式（２）中、Ｚ^１、Ｚ^２、Ｅ^１及び環Ａ^１は、前記と同じ意味を表す。２個あるＺ^１は同一であっても異なっていてもよい。２個あるＺ^２は同一であっても異なっていてもよい。２個あるＥ^１は同一であっても異なっていてもよい。２個ある環Ａ^１は同一であっても異なっていてもよい。Ｂは、置換基を有していてもよいアリーレン基、置換基を有していてもよい２価の複素環基、−Ｃ≡Ｃ−で表される基又は−Ｃ（Ｒ^８）＝Ｃ（Ｒ^９）−で表される基を表す。Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、ヒドロキシル基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリール基、置換基を有していてもよい複素環基、ハロゲン原子又はシアノ基を表す。ｎは、０以上の整数を表す。Ｂが複数個ある場合、それらは同一であっても異なっていてもよく、Ｒ^８及びＲ^９が複数個ある場合、それらは同一であっても異なっていてもよい。）
［３］ 下記式（３）で表される構造単位を含む高分子化合物。

（式（３）中、Ｚ^１及びＺ^２は、それぞれ独立に、酸素原子、硫黄原子、セレン原子、＝Ｃ（Ｒ^１）（Ｒ^２）で表される基又は＝Ｎ（Ｒ^３）で表される基を表す。Ｚ^１及びＺ^２のうちの少なくとも１つは硫黄原子又はセレン原子である。Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、シアノ基又は−Ｃ（＝Ｏ）Ｒ^４で表される基を表す。Ｒ^４は、水素原子、ヒドロキシル基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基又は置換基を有していてもよい芳香族複素環基を表す。Ｒ^４が２個ある場合、それらは同一であっても異なっていてもよい。Ｅ^１は、酸素原子、硫黄原子、セレン原子、−Ｎ（Ｒ^５）−で表される基又は−Ｃ（Ｒ^６）＝Ｃ（Ｒ^７）−で表される基を表す。Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子、ヒドロキシル基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリール基、置換基を有していてもよい複素環基、ハロゲン原子又はシアノ基を表す。Ｒ^６及びＲ^７は互いに結合してそれぞれが結合している炭素原子と共に五員環又は六員環を形成してもよい。環Ａ^１は、置換基を有していてもよい芳香族炭素環又は置換基を有していてもよい複素環を表す。）
［４］ Ｚ^１及びＺ^２が、硫黄原子である、［１］〜［３］のいずれか１つに記載の化合物又は高分子化合物。
［５］ Ｅ^１が、−Ｎ（Ｒ^５）−で表される基である、［１］〜［４］のいずれか１つに記載の化合物又は高分子化合物。
［６］ 環Ａ^１が、チオフェン環、ベンゼン環、ピリジン環又はナフタレン環である、［１］〜［５］のいずれか１つに記載の化合物又は高分子化合物。
［７］ ［１］〜［６］のいずれか１つに記載の化合物又は高分子化合物を含有する、有機半導体材料。
［８］ ［７］に記載の有機半導体材料を含有する有機層を有する、有機半導体素子。
［９］ 一対の電極と、該一対の電極の間に設けられた［７］に記載の有機半導体材料を含む層と、を備える有機太陽電池。
［１０］ ソース電極、ドレイン電極、ゲート電極及び活性層を有し、該活性層に［７］に記載の有機半導体材料を含有する、有機トランジスタ。 [1] A compound containing at least two structures represented by the following formula (1).

(In Formula (1), Z ¹ and Z ² are each independently an oxygen atom, a sulfur atom, a selenium atom, a group represented by ═C (R ¹ ) (R ² ), or ═N (R ³ ). Represents at least one of Z ¹ and Z ² is a sulfur atom or a selenium atom, R ¹ , R ² and R ³ each independently represents a cyano group or —C (═O); R ⁴ represents a group represented by R ^4. R ⁴ has a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An aryl group which may be substituted or a heterocyclic group which may have a substituent, when two R ^{4 s} are present, they may be the same or different, and E ¹ represents an oxygen atom, sulfur atom, a selenium atom, -N ^{(R 5)} - group or a ^-C represented by ^{(R 6) = C (R} 7) - is represented by .R ^5, R ⁶ and R ⁷ represents a group each independently represent a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an alkoxy group which may have a substituent, R ⁶ and R ⁷ are each an alkylthio group optionally having a substituent, an aryl group optionally having a substituent, a heterocyclic group optionally having a substituent, a halogen atom, or a cyano group. They may be bonded to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which each is bonded.Ring A ¹ has an aromatic carbocyclic ring or a substituent which may have a substituent. Represents a heterocyclic ring which may be
[2] The compound according to [1], represented by the following formula (2).

(In formula (2), Z ¹ , Z ² , E ¹ and ring A ¹ represent the same meaning as described above. Two Z ^{1 s} may be the same or different. Two Z ^{2 s.} May be the same or different, and two E ¹ may be the same or different, and two rings A ¹ may be the same or different. An arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, a group represented by —C≡C—, or —C (R ⁸ ) ═C (R ⁹ R ⁸ and R ⁹ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent. , An alkylthio group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent Represents a halogen atom or a cyano group, n represents an integer of 0 or more, and when there are a plurality of B, they may be the same or different, and when there are a plurality of R ⁸ and R ⁹ , They may be the same or different.)
[3] A polymer compound containing a structural unit represented by the following formula (3).

(In Formula (3), Z ¹ and Z ² are each independently an oxygen atom, a sulfur atom, a selenium atom, a group represented by ═C (R ¹ ) (R ² ), or ═N (R ³ ). Represents at least one of Z ¹ and Z ² is a sulfur atom or a selenium atom, R ¹ , R ² and R ³ each independently represents a cyano group or —C (═O); R ⁴ represents a group represented by R ^4. R ⁴ has a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. If even also have an aryl group or a substituted group represents an aromatic heterocyclic group .R ⁴ there are two, they may .E ¹ be different even if the same is oxygen atom , a sulfur atom, a selenium atom, -N ^{(R 5)} - group or a ^-C represented by ^{(R 6) = C (R} 7) - in Is .R ^5, R ⁶ and R ⁷ represents a group that is independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an alkoxy group which may have a substituent, R ⁶ and R ⁷ each represents an alkylthio group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom or a cyano group. May be bonded to each other to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which each is bonded.Ring A ¹ represents an aromatic carbocyclic ring or a substituent which may have a substituent. It represents a heterocyclic ring that may have.)
[4] The compound or polymer compound according to any one of [1] to [3], wherein Z ¹ and Z ² are sulfur atoms.
[5] The compound or polymer compound according to any one of [1] to [4], wherein E ¹ is a group represented by —N (R ⁵ ) —.
[6] The compound or polymer compound according to any one of [1] to [5], wherein Ring A ¹ is a thiophene ring, a benzene ring, a pyridine ring, or a naphthalene ring.
[7] An organic semiconductor material containing the compound or polymer compound according to any one of [1] to [6].
[8] An organic semiconductor element having an organic layer containing the organic semiconductor material according to [7].
[9] An organic solar cell comprising a pair of electrodes and a layer containing the organic semiconductor material according to [7] provided between the pair of electrodes.
[10] An organic transistor having a source electrode, a drain electrode, a gate electrode, and an active layer, wherein the active layer contains the organic semiconductor material according to [7].

  The present invention relates to a compound and a polymer compound having a sufficiently large LUMO absolute value, an organic semiconductor material containing the compound and the polymer compound, and an organic semiconductor element having an organic layer containing the organic semiconductor material, particularly an organic solar device. Since a battery and an organic transistor can be provided, the present invention is extremely useful.

FIG. 1 is a schematic cross-sectional view showing a first structural example of an organic transistor of the present invention. FIG. 2 is a schematic cross-sectional view showing a second configuration example of the organic transistor of the present invention. FIG. 3 is a schematic cross-sectional view showing a third configuration example of the organic transistor of the present invention. FIG. 4 is a schematic cross-sectional view showing a fourth configuration example of the organic transistor of the present invention. FIG. 5 is a schematic cross-sectional view showing a fifth configuration example of the organic transistor of the present invention. FIG. 6 is a schematic cross-sectional view showing a sixth configuration example of the organic transistor of the present invention. FIG. 7 is a schematic cross-sectional view showing a seventh configuration example of the organic transistor of the present invention. FIG. 8 is a schematic cross-sectional view showing an eighth configuration example of the organic transistor of the present invention. FIG. 9 is a schematic cross-sectional view showing a ninth configuration example of the organic transistor of the present invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings used for the following description, the same components may be denoted by the same reference numerals, and redundant descriptions may be omitted.

  In the present specification, “optionally substituted” means that all hydrogen atoms constituting the compound or group are unsubstituted, and that one or more hydrogen atoms are partially or completely substituted. Includes both embodiments when substituted by a group.

  Examples of the “substituent” not particularly specified in the present specification include a halogen atom, a cyano group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfo group, a phosphoric acid group, a phosphorous acid group, a nitro group, and a carbon atom. Examples thereof include hydrocarbyl groups having 1 to 30 carbon atoms, hydrocarbyloxy groups having 1 to 30 carbon atoms, hydrocarbylthio groups having 1 to 30 carbon atoms, and substituted silyl groups having 1 to 30 carbon atoms. Among these substituents, a halogen atom, a hydrocarbyl group having 1 to 18 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylthio group having 1 to 18 carbon atoms, and 1 carbon atom. A substituted silyl group having 18 to 18 carbon atoms is preferred, a hydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbylthio group having 1 to 12 carbon atoms, and 1 to 1 carbon atoms. 12 substituted silyl groups are more preferable, a hydrocarbyl group having 1 to 12 carbon atoms, and a hydrocarbyloxy group having 1 to 12 carbon atoms are more preferable. Each of the hydrocarbyl group, hydrocarbyloxy group and hydrocarbylthio group may be linear, branched or cyclic.

<Compound>
The compound of the present invention is a compound containing at least two structures represented by the following formula (1).

In Formula (1), Z ¹ and Z ² are each independently an oxygen atom, a sulfur atom, a selenium atom, a group represented by ═C (R ¹ ) (R ² ), or ═N (R ³ ). Represents a group. At least one of Z ¹ and Z ² is a sulfur atom or a selenium atom. R ¹ , R ² and R ³ each independently represent a cyano group or a group represented by —C (═O) R ⁴ . R ⁴ has a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent or a substituent. Represents an optionally substituted heterocyclic group. When there are two R ⁴ , they may be the same or different.
In the compound, when there are a plurality of R ¹ , R ² and R ³ , they may be the same or different.

  In the present specification, the alkyl group may be linear, branched or cyclic. The number of carbon atoms of the alkyl group is usually 1-30, preferably 1-20. The number of carbon atoms does not include the number of carbon atoms of the substituent.

  Specific examples of the alkyl group include a straight chain alkyl group such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group, hexadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert. Examples thereof include branched alkyl groups such as -butyl group, 2-ethylhexyl group and 3,7-dimethyloctyl group, and cycloalkyl groups such as cyclopentyl group and cyclohexyl group.

  Examples of the substituent that the alkyl group may have include an alkoxy group, an aryl group, and a halogen atom. Specific examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.

  In the present specification, the alkoxy group may be linear, branched, or cyclic. The number of carbon atoms of the alkoxy group is usually 1-30, preferably 1-20. The number of carbon atoms does not include the number of carbon atoms of the substituent.

  Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butyloxy group, a hexyloxy group, an octyloxy group, a dodecyloxy group, a straight-chain alkoxy group such as a hexadecyloxy group, an isopropyloxy group, and an isobutyloxy group. , Sec-butyloxy group, tert-butyloxy group, 2-ethylhexyloxy group, branched alkoxy groups such as 3,7-dimethyloctyloxy group, and cycloalkoxy groups such as cyclopentyloxy group and cyclohexyloxy group.

  Examples of the substituent that the alkoxy group may have include an alkoxy group, an aryl group, and a halogen atom.

  In the present specification, the aryl group means a remaining atomic group obtained by removing one hydrogen atom bonded to a carbon atom constituting a ring from an aromatic hydrocarbon, a group having a condensed ring, a benzene ring and a condensed ring. And a group in which two or more rings selected from the group consisting of are directly bonded. The number of carbon atoms of the aryl group is preferably 6-30, more preferably 6-20, and even more preferably 6-10. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the substituent that the aryl group may have include an alkoxy group, an alkylthio group, a heterocyclic group, and a halogen atom.

  Specific examples of the aryl group which may have a substituent include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 4-phenylphenyl group, 4-hexadecylphenyl group, 3,5-dimethoxyphenyl group, and pentafluorophenyl Groups. As the aryl group, a phenyl group substituted with an alkyl group is preferable.

  In the present specification, a heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom bonded to a carbon atom constituting a ring from a heterocyclic compound, and a group having a heterocyclic ring that is a condensed ring. And a group in which two or more rings selected from the group consisting of an independent monocyclic heterocyclic ring and a condensed heterocyclic ring are directly bonded. A 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, selenium atoms, nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, etc. A compound containing a heteroatom in the ring. The number of carbon atoms of the heterocyclic group is preferably 2-30, more preferably 2-20, and even more preferably 2-10. The number of carbon atoms does not include the number of carbon atoms of the substituent. Specific examples of the heterocyclic group include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-oxazolyl group, 2-thiazolyl group, 2 -Imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group, and 4- (2,1,3-benzothiadiazolyl) Groups.

  Examples of the substituent that the heterocyclic group may have include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, and a halogen atom. Examples of the heterocyclic group having a substituent include a 5-octyl-2-thienyl group and a 5-phenyl-2-furyl group. The substituent that the heterocyclic group may have is preferably an alkyl group. As the heterocyclic group, an aromatic heterocyclic group is preferable.

  In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Z ¹ is preferably a sulfur atom or a selenium atom, and more preferably a sulfur atom.

Z ² is preferably a sulfur atom or a selenium atom, and more preferably a sulfur atom.

In Formula (1), E ¹ is an oxygen atom, a sulfur atom, a selenium atom, a group represented by —N (R ⁵ ) — or a group represented by —C (R ⁶ ) ═C (R ⁷ ) —. Represents. R ⁵ , R ⁶ and R ⁷ each independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An alkylthio group which may be substituted, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom or a cyano group; R ⁶ and R ⁷ may be bonded to each other to form a 5-membered ring or a 6-membered ring together with adjacent carbon atoms.
In the compound, when there are a plurality of E ^{1 s} , they may be the same or different, and when there are a plurality of R ⁵ , R ⁶ and R ⁷ , they may be the same. May be different.

  In the present specification, the alkylthio group may be linear, branched, or cyclic. The number of carbon atoms of the alkylthio group is usually 1 to 30 (usually 3 to 30 for branched alkylthio groups and cycloalkylthio groups), and 1 to 20 (3 to 20 for branched alkylthio groups and cycloalkylthio groups). Preferably there is. The number of carbon atoms does not include the number of carbon atoms of the substituent.

  Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a hexylthio group, an octylthio group, a dodecylthio group, a straight-chain alkylthio group such as a hexadecylthio group, an isopropylthio group, an isobutylthio group, and a sec-butylthio group. , Tert-butylthio group, 2-ethylhexylthio group, branched alkylthio group such as 3,7-dimethyloctylthio group, and cycloalkylthio group such as cyclopentylthio group and cyclohexylthio group.

  Examples of the substituent that the alkylthio group may have include an alkoxy group, an aryl group, and a halogen atom.

When R ⁶ and R ⁷ are bonded to each other to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which they are bonded, specific examples of the 5-membered ring include a furan ring, a thiophene ring, a pyrrole ring, And a thiazole ring, and specific examples of the six-membered ring include a benzene ring and a pyridine ring.

  The 5-membered ring and 6-membered ring may have a substituent. Examples of the substituent include an alkyl group which may have a substituent and an alkoxy group which may have a substituent. , An aryl group which may have a substituent, and a halogen atom.

From the viewpoint of improving the solubility of the compound of the present invention in an organic solvent, E ¹ is represented by a group represented by —N (R ⁵ ) — and —C (R ⁶ ) ═C (R ⁷ ) —. And a group represented by —N (R ⁵ ) — is more preferable. R ⁵ is preferably an alkyl group.

In formula (1), ring A ¹ represents an aromatic carbocyclic ring which may have a substituent or a heterocyclic ring which may have a substituent.

Aromatic carbon ring represented by ring A ¹ may be a condensed ring be a benzene ring.
The number of carbon atoms in the aromatic carbocycle is preferably 6-30, more preferably 6-20, and even more preferably 6-10. The number of carbon atoms does not include the number of carbon atoms of the substituent.

  Specific examples of the aromatic carbocycle include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a pentacene ring, and a fluorene ring.

  Examples of the substituent that the aromatic carbocycle may have include, for example, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, and a substituent. Examples thereof include a good alkylthio group, a heterocyclic group which may have a substituent, and a halogen atom. When the aromatic carbocycle has a substituent, the substituent is preferably an alkyl group which may have a substituent and a halogen atom.

The heterocyclic ring represented by the ring A ¹ may be a single ring or a condensed ring.
The number of carbon atoms in the heterocyclic ring is preferably 2-30, more preferably 3-20, and even more preferably 3-10. The number of carbon atoms does not include the number of carbon atoms of the substituent.

  Specific examples of the heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a benzothiophene ring, and a 2,1,3-benzothiadiazole ring.

  Examples of the substituent that the heterocyclic ring may have include, for example, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, and an alkylthio that may have a substituent. Group, a heterocyclic group which may have a substituent, and a halogen atom. When the heterocyclic ring has a substituent, the substituent is preferably an alkyl group which may have a substituent and a halogen atom.

From the viewpoint of ease of synthesis of the compound of the present invention, ring A ¹ is preferably a thiophene ring, a benzene ring, a pyridine ring, and a naphthalene ring, and more preferably a thiophene ring and a benzene ring.

  As the compound containing at least two structures represented by the formula (1), a compound represented by the following formula (2) is preferable.

In formula (2), Z ¹ , Z ² , E ¹ and ring A ¹ represent the same meaning as described above. Two Z ¹ may be the same or different. Two Z ² may be the same or different. Two E ¹ may be the same or different. Two rings A ¹ may be the same or different. B is an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, a group represented by —C≡C—, or —C (R ⁸ ) ═C. The group represented by (R < ⁹ >)-is represented. R ⁸ and R ⁹ each independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. It represents an alkylthio group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom or a cyano group. n represents an integer of 0 or more. When there are a plurality of B, they may be the same or different, and when there are a plurality of R ⁸ and R ⁹ , they may be the same or different.

  In the present specification, an arylene group means an atomic group remaining after removing two hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The number of carbon atoms of the arylene group is preferably 6 to 60, more preferably 6 to 20. The number of carbon atoms does not include the number of carbon atoms of the substituent.

  The arylene group includes a group having a benzene ring, a group having a condensed ring, a group in which two or more rings selected from the group consisting of an independent benzene ring and a condensed ring are directly bonded, an independent benzene ring and a condensed ring. A group in which two or more rings selected from the group are bonded via a group such as vinylene is included.

  Examples of the substituent that the arylene group may have include, for example, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, and a complex that may have a substituent. Examples thereof include a ring group and a halogen atom.

  Examples of the arylene group which may have a substituent include groups represented by the following formulas 1 to 12.

  In formulas 1 to 12, R ″ represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or an alkylthio group that may have a substituent. Represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a halogen atom. A plurality of R ″ may be the same or different.

  In the present specification, the divalent heterocyclic group is a remaining atomic group obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from a heterocyclic compound. The number of carbon atoms of the divalent heterocyclic group is preferably 2-30, more preferably 3-20. The number of carbon atoms does not include the number of carbon atoms of the substituent. The divalent heterocyclic group is preferably a divalent aromatic heterocyclic group.

  The divalent heterocyclic group includes a group in which two or more rings selected from the group consisting of a heterocyclic ring that is a condensed ring, an independent monocyclic heterocyclic ring, and a heterocyclic ring that is a condensed ring are directly bonded. included.

  The divalent heterocyclic group may have a substituent. Examples of the substituent include an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Examples thereof include an alkylthio group which may have a group, an aryl group which may have a substituent, and a halogen atom.

  Examples of the divalent heterocyclic group which may have a substituent include divalent heterocyclic groups represented by the following formulas 13 to 63.

  In Formula 13 to Formula 63, R ″ represents the same meaning as described above. a and b represent the integer of 0-5 each independently.

  a and b are each independently preferably an integer of 0 to 3, more preferably an integer of 0 to 1.

From the viewpoint of enhancing the electron transport property of the compound of the present invention, B is a divalent heterocyclic group which may have a substituent, a group represented by —C≡C—, and —C (R ⁸ ). Is preferably a group represented by ═C (R ⁹ ) —, more preferably a divalent heterocyclic group which may have a substituent, and the above-mentioned formula 26, formula 30, formula 36, It is a divalent heterocyclic group optionally having a substituent represented by Formula 38 to Formula 40, Formula 42, Formula 49 to Formula 54, Formula 57 to Formula 60, and Formula 62 to Formula 63. Is more preferable.

  In formula (2), n represents an integer of 0 or more. From the viewpoint of ease of synthesis of the compound of the present invention, n is preferably an integer of 0 to 5, more preferably an integer of 1 to 5, and further preferably an integer of 1 to 3.

  As the compound containing at least two structures represented by the formula (1), compounds represented by the following formulas (1-1) to (1-26) are preferable, and the formulas (1-1) to (1) -24) is more preferred, compounds represented by formula (1-1) to formula (1-16) are more preferred, and formula (1-1) to formula (1-12) are preferred. Are particularly preferred.

<Method for Producing Compound Represented by Formula (S2)>
Next, the preferable manufacturing method of the compound of this invention is demonstrated using an example.

  A compound containing at least two structures represented by the following formula (S2), which is an embodiment of the compound of the present invention, reacts a compound containing at least two structures represented by the following formula (S1) with a sulfurizing reagent. Can be manufactured.

In formula (S1) and formula (S2), E ¹ and ring A ¹ represent the same meaning as described above.

  As said sulfurization reagent, the compound represented by a following formula (S3) is mentioned, for example.

In formula (S3), R ^A represents an alkyl group which may have a substituent, or an aryl group which may have a substituent.

^RA is preferably a methyl group, an ethyl group, an isopropyl group, a benzyl group, a phenyl group, a 4-methoxyphenyl group, and a phenoxyphenyl group.

  The reaction is preferably performed in the presence of a solvent in an inert gas atmosphere such as nitrogen gas or argon gas. The reaction temperature is preferably -80 ° C to the boiling point of the solvent.

  Examples of the solvent used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, dimethyl ether, diethyl ether, and methyl-tert-butyl ether. , Ethers such as tetrahydrofuran, tetrahydropyran, and dioxane. These may be used alone or in combination as a solvent.

  After the reaction, for example, after adding water to stop the reaction, the product is extracted with an organic solvent and subjected to usual post-treatment such as distilling off the solvent, whereby the structure represented by the formula (S2) Can be produced. If necessary, purification such as fractionation by chromatography or recrystallization may be further performed.

<Method for Producing Compound Represented by Formula (2)>
Next, the manufacturing method of the compound represented by Formula (2) is demonstrated using an example.

  The compound represented by the following formula (S5), which is one embodiment of the compound represented by the formula (2), can be produced by reacting a compound represented by the following formula (S4) with a sulfurizing reagent. .

In formula (S4) and formula (S5), E ¹ , ring A ¹ , B and n represent the same meaning as described above.

  Examples of the sulfurizing reagent include compounds represented by the formula (S3).

  The reaction is preferably performed in the presence of a solvent in an inert gas atmosphere such as nitrogen gas or argon gas. The reaction temperature is preferably -80 ° C to the boiling point of the solvent.

  Examples of the solvent used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, dimethyl ether, diethyl ether, and methyl-t-butyl ether. , Ethers such as tetrahydrofuran, tetrahydropyran, and dioxane. These may be used alone or in combination as a solvent.

  After the reaction, for example, after adding water to stop the reaction, the product is extracted with an organic solvent and subjected to usual post-treatment such as evaporation of the solvent, and the compound represented by the formula (S5) Can be manufactured. If necessary, purification such as fractionation by chromatography or recrystallization may be further performed.

<Polymer compound>
(First structural unit)
One embodiment of the polymer compound of the present invention is a polymer compound having a structural unit represented by the following formula (3) (hereinafter sometimes referred to as “first structural unit”).

In formula (3), Z ¹ and Z ² are each independently an oxygen atom, a sulfur atom, a selenium atom, a group represented by ═C (R ¹ ) (R ² ), or ═N (R ³ ). Represents a group. When there are a plurality of Z ¹ and Z ² , these may be the same or different. At least one of Z ¹ and Z ² is a sulfur atom or a selenium atom. R ¹ , R ² and R ³ each independently represent a cyano group or a group represented by —C (═O) R ⁴ . R ⁴ has a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent or a substituent. Represents an aromatic heterocyclic group which may be substituted. When there are two R ⁴ , they may be the same or different. E ¹ represents an oxygen atom, a sulfur atom, a selenium atom, a group represented by —N (R ⁵ ) — or a group represented by —C (R ⁶ ) ═C (R ⁷ ) —. R ⁵ , R ⁶ and R ⁷ each independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An alkylthio group which may be substituted, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom or a cyano group; R ⁶ and R ⁷ may be bonded to each other to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which they are bonded. Ring A ¹ represents an aromatic carbocyclic ring which may have a substituent or a heterocyclic ring which may have a substituent.

1 type of 1st structural units may be contained in the high molecular compound, or may be contained 2 or more types. That is, when there are a plurality of R ¹ , R ² and R ^{3 in the} polymer compound, they may be the same or different. When there are a plurality of E ^{1 s} , they may be the same or different. When there are a plurality of R ⁵ , R ⁶ and R ⁷ , they may be the same or different. Wherein ring A ¹ there are a plurality, they may be be the same or different.
The polymer compound of the present invention is preferably a conjugated polymer compound.

  The structural unit represented by the formula (3) is preferably a structural unit represented by the following formula (3-1) to formula (3-10), and the following formula (3-1) to formula (3-4), And structural units represented by the following formulas (3-6) to (3-9) are more preferable, and the following formulas (3-1) to (3-3) and the following formulas (3-6) to (3) The structural unit represented by 3-8) is more preferable, and the structural unit represented by the following formulas (3-1) and (3-6) is particularly preferable.

(Second structural unit)
In addition to the structural unit represented by the above formula (3), the polymer compound of the present invention is further represented by the following structural unit represented by the following formula (4) (hereinafter sometimes referred to as “second structural unit”). It is preferable that it contains.

  In formula (4), Ar represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. However, Ar is different from the structural unit represented by the formula (3).

When the polymer compound of the present invention includes the second structural unit, it is preferable that the structural unit represented by the formula (3) and the structural unit represented by the formula (4) form a conjugate.
Conjugation in this specification refers to a combination of “unsaturated bond / single bond / unsaturated bond” in the compound, two π bonds in the π orbit are adjacent, and each π electron is bonded. It is arranged in parallel to the direction, and π electrons are not localized on unsaturated bonds, but π electrons are spread on single bonds between unsaturated bonds and π electrons are delocalized. Say. Here, the unsaturated bond means a double bond or a triple bond.

The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as “GPC”) of the polymer compound of the present invention is usually 1 × 10 ³ to 1 × 10 ⁷ . Since a good thin film can be formed, the polymer compound of the present invention preferably has a polystyrene-equivalent number average molecular weight of 3 × 10 ³ or more. Since the solubility in a solvent can be increased and the production of a thin film can be facilitated, the number average molecular weight in terms of polystyrene of the polymer compound of the present invention is preferably 1 × 10 ⁶ or less.

  The polymer compound of the present invention has high solubility in a solvent (particularly an organic solvent). Specifically, the solvent preferably has a solubility capable of producing a solution containing 0.1% by weight (hereinafter sometimes referred to as “wt%”) or more of the polymer compound of the present invention. More preferably, it has a solubility capable of producing a solution containing 4 wt% or more.

  In the polymer compound of the present invention, the content of the structural unit represented by the formula (3) may be at least one in the polymer compound. The content of the structural unit represented by the formula (3) is preferably 3 or more in the polymer compound, and more preferably 5 or more in the polymer compound.

The polymer compound of the present invention may be a homopolymer or any type of copolymer, for example, any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer. There may be.
The polymer compound of the present invention is preferably an alternating copolymer of a structural unit represented by formula (3) and a structural unit represented by formula (4).

  When the polymer compound of the present invention has a group (polymerization reactive group) that is active in a polymerization reaction at the molecular chain end, the field effect mobility of an organic transistor produced using the polymer compound may be reduced. There is sex. For this reason, the molecular chain terminal of the polymer compound of the present invention is preferably a group that is inactive to a polymerization reaction such as an aryl group or an aromatic heterocyclic group.

<Method for producing polymer compound>
Next, a method for producing the polymer compound of the present invention will be described.
The polymer compound of the present invention may be produced by any method. For example, a compound represented by the following formula (5) and a compound represented by the following formula (6) It can be produced by a known polymerization method (Method 1) such as aryl coupling using an appropriate catalyst after dissolving in a solvent and adding a base as necessary.
^{X 11 -A 11 -X 12 (5} )

^{X 13 -A 12 -X 14 (6} )

In the formula (5) and ^{(6), A 11} represents a structural unit represented by the formula ^{(3), A 12} represents a structural unit represented by the formula (4). X ¹¹ , X ¹² , X ¹³ and X ¹⁴ each independently represent a polymerization reactive group.

Examples of the polymerization reactive group include a halogen atom, a boric acid ester residue, a dihydroxyboryl group (—B (OH) ₂ ), and a stannyl group substituted with three alkyl groups.

  Examples of the halogen atom that is a polymerization reactive group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The boric acid ester residue that is a polymerization reactive group means a group obtained by removing a hydroxyl group from a boric acid diester, and examples thereof include a group represented by the following formula.

  Examples of the stannyl group substituted with three alkyl groups that are polymerization reactive groups include a stannyl group substituted with three methyl groups and a stannyl group substituted with three butyl groups.

  As a polymerization method such as aryl coupling, a polymerization method by Suzuki coupling reaction (Chemical Review, 1995, 95, 2457-2483), a polymerization method by Stille coupling reaction (European Polymer Journal, 2005). Year 41, 2923-2933).

  Examples of the polymerization reactive group in the case of a reaction using a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction include a halogen atom, a boric acid ester residue, and a dihydroxyboryl group. From the viewpoint of simplicity of the polymerization reaction, a bromine atom, an iodine atom, and a boric acid ester residue are preferable.

  When the polymer compound of the present invention is polymerized by Suzuki coupling reaction, it has a total number of moles of a compound having a bromine atom or iodine atom as a polymerization reactive group used for polymerization, and a boric acid ester residue as a polymerization reactive group The ratio of the total number of moles of the compound is preferably 0.7 to 1.3, more preferably 0.8 to 1.2.

  Examples of the polymerization reactive group in the case of using a palladium catalyst such as Stille coupling reaction include a halogen atom and a stannyl group substituted with three alkyl groups. A stannyl group substituted with a bromine atom, an iodine atom, and three alkyl groups is preferable because the polymerization reaction can be easily performed.

  When the polymer compound of the present invention is polymerized by a Stille coupling reaction, the total number of moles of the compound having a bromine atom or iodine atom as a polymerization reactive group used for polymerization is substituted with three alkyl groups as a polymerization reactive group. The ratio with respect to the total number of moles of the compound having a stannyl group is preferably 0.7 to 1.3, and more preferably 0.8 to 1.2.

  Examples of the organic solvent used for polymerization include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, and dioxane. These organic solvents may be used alone or in combination of two or more.

  Examples of the base used for polymerization include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabromide. Organic bases such as butylammonium, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide are listed.

  Examples of the catalyst used for the polymerization include transition metal complexes such as tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, dichlorobistriphenylphosphine palladium and the like, and if necessary. , Triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, and other ligands. As these catalysts, those synthesized in advance may be used, or those prepared in the reaction system may be used as they are. Moreover, these catalysts may be used individually by 1 type, or may use 2 or more types together.

  The polymerization reaction temperature is preferably 0 to 200 ° C, more preferably 0 to 150 ° C, and still more preferably 0 to 120 ° C.

  The polymerization reaction time is usually 1 hour or longer, preferably 2 hours to 500 hours.

  The post-treatment of the polymerization can be carried out by a known method, for example, it can be carried out as a treatment for adding a reaction liquid obtained by the above polymerization to a lower alcohol such as methanol and filtering and drying the precipitate. .

  When the purity of the polymer compound of the present invention is low, it is preferable to increase the purity by purification by a method such as recrystallization, continuous extraction with a Soxhlet extractor, or column chromatography.

(Method 2)
The polymer compound of the present invention can also be produced by a method (Method 2) in which a polymer compound having a carbonyl group is converted to a thiocarbonyl group using a sulfurizing reagent. The manufacturing method according to this (Method 2) will be described using an example.

  The polymer compound represented by the following formula (S7), which is an embodiment of the polymer compound of the present invention, is produced, for example, by reacting the polymer compound represented by the following formula (S6) with a sulfurizing reagent. can do.

In formulas (S6) and (S7), E ¹ , ring A ¹ and Ar represent the same meaning as described above.

  As a sulfurization reagent, the compound represented by the said Formula (S3) is mentioned, for example.

  The reaction with the sulfurizing reagent is preferably carried out in the presence of a solvent in an inert gas atmosphere such as nitrogen gas or argon gas. The reaction temperature is preferably -80 ° C to the boiling point of the solvent.

  Examples of the solvent used for the reaction with the sulfurizing reagent include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, dimethyl ether, diethyl ether, methyl- Examples include ethers such as tert-butyl ether, tetrahydrofuran, tetrahydropyran, and dioxane. These solvents may be used alone or in combination.

  The post-treatment of the reaction with the sulfurizing reagent can be carried out by a known method, for example, as a treatment for filtering and drying the precipitate deposited by adding the reaction liquid obtained in the above reaction to a lower alcohol such as methanol. It can be carried out.

  When the purity of the polymer compound of the present invention is low, it is preferable to increase the purity by purification by a method such as recrystallization, continuous extraction with a Soxhlet extractor, or column chromatography.

<Organic semiconductor materials>
The organic semiconductor material of the present invention may contain one kind of the compound of the present invention or the polymer compound of the present invention alone, or may contain two or more kinds. In addition to the compound of the present invention, the organic semiconductor material of the present embodiment may further contain a compound having a carrier transport property (may be a low molecular compound or a high molecular compound). . When the organic semiconductor material of this embodiment contains components other than the compound of the present invention and the polymer compound of the present invention, it is preferable that the compound of the present invention and the polymer compound of the present invention contain 30% by weight or more, 50 More preferably, it is contained at 70% by weight or more.

  Compounds having carrier transport properties include arylamine derivatives, stilbene derivatives, oligothiophenes and derivatives thereof, oxadiazole derivatives, fullerenes and derivatives thereof, polyvinylcarbazole and derivatives thereof, polyaniline and derivatives thereof, polythiophene and Examples thereof include polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, and the like.

  In order to improve the characteristics, the organic semiconductor material may contain a polymer compound different from the compound of the present invention and the polymer compound of the present invention as a polymer binder. As the polymer binder, a polymer binder that does not excessively reduce carrier transportability is preferable.

  Examples of polymer binders 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 , Polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

<Organic semiconductor element>
Since the compound of the present invention and the polymer compound of the present invention have high charge mobility, when the organic thin film containing the compound of the present invention or the polymer compound of the present invention is used for an organic semiconductor element, it is injected from the electrode. Electrons and holes, or charges generated by light absorption can be transported. Taking advantage of these characteristics, the compound of the present invention and the polymer compound of the present invention can be suitably used for various organic semiconductor elements such as a photoelectric conversion element, an organic transistor, and an organic electroluminescence element. Hereinafter, these elements will be described individually.

(Photoelectric conversion element)
The photoelectric conversion element containing the compound of the present invention or the polymer compound of the present invention has one or more active layers containing the compound of the present invention or the polymer compound of the present invention between a pair of electrodes.
As a preferable form of the photoelectric conversion element containing the compound of the present invention or the polymer compound of the present invention, a pair of electrodes at least one of which is transparent or translucent, a p-type organic semiconductor compound, and an n-type organic semiconductor compound, An active layer formed from a composition comprising The compound of the present invention or the polymer compound of the present invention is preferably used as an n-type organic semiconductor compound.

  The photoelectric conversion element manufactured using the compound of the present invention or the polymer compound of the present invention is usually formed on a substrate. The substrate may be any substrate that does not chemically change when an electrode is formed and an organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (ie, the electrode far from the opaque substrate) is preferably transparent or translucent.

  In another aspect of the photoelectric conversion device having the compound of the present invention or the polymer compound of the present invention, a first active layer containing the compound of the present invention between a pair of electrodes, at least one of which is transparent or translucent, A photoelectric conversion element including a second active layer containing an electron donating compound such as poly (3-hexylthiophene) bonded to the first active layer.

  Examples of the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film. Specific examples of the transparent or translucent electrode material include indium oxide, zinc oxide, tin oxide, and indium tin oxide (hereinafter also referred to as “ITO”) that is a composite thereof, indium zinc oxide. (Hereinafter, sometimes referred to as “IZO”), a film made using a conductive material made of, etc., a film made using NESA, gold, platinum, silver, copper, or the like is used. ITO, IZO Films made using tin oxide are preferred. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

  One electrode may not be transparent, and as an electrode material of the electrode that is not transparent, a metal, a conductive polymer, or the like can be used. Specific examples of the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, etc. And one or more alloys selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin. Examples include alloys with metals, graphite, graphite intercalation compounds, polyaniline and derivatives thereof, and polythiophene and derivatives thereof. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

  An additional intermediate layer other than the active layer may be provided as a structure for improving the photoelectric conversion efficiency. Examples of the material for the intermediate layer include alkali metal halides such as lithium fluoride, alkaline earth metal halides, oxides such as titanium oxide, and PEDOT (poly-3,4-ethylenedioxythiophene). .

  The active layer may contain the compound of the present invention or the polymer compound of the present invention singly or in combination of two or more. In addition, a compound other than the compound of the present invention or the polymer compound of the present invention can be mixed and used as the electron donating compound and / or the electron accepting compound in the active layer. In the active layer, whether the compound is an electron donating compound or an electron accepting compound is relatively determined from the energy levels of the compounds.

  Examples of the electron donating compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and aromatic amines in side chains or main chains. Examples thereof include polysiloxane derivatives having a residue, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

  Examples of the electron-accepting compound include carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyano Anthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, 2 Phenanthrene derivatives such as 9,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocuproin), fullerenes, fullerene derivatives, preferably titanium oxide, carbon Bruno tube, fullerene, a fullerene derivative, particularly preferably a fullerene, a fullerene derivative.

  Examples of fullerene and fullerene derivatives include C60 fullerene, C70 fullerene, C76 fullerene, C78 fullerene, C84 fullerene and derivatives thereof. As a fullerene derivative, the fullerene derivative which has the following structure is mentioned, for example.

  Examples of fullerene derivatives include [6,6] phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6] -Phenyl C61 butyric acid methyl ester), [6,6] phenyl-C70 butyric acid methyl ester (C70PCBM). [6,6] -Phenyl C70 butyric acid methyl ester), [6,6] Phenyl-C84 butyric acid methyl ester (C84PCBM, [6,6] -Phenyl C84 butyric acid methyl ester), [6,6] Examples thereof include C60 butyric acid methyl ester ([6,6] -Thienyl C60 butyric acid methyl ester).

  When the active layer contains the compound of the present invention or the polymer compound of the present invention and an electron donating compound such as poly (3-hexylthiophene), the amount of the electron donating compound in the active layer is the compound of the present invention. Or it is preferable that it is 10 weight part-1000 weight part with respect to 100 weight part of high molecular compounds of this invention, and it is more preferable that it is 20 weight part-500 weight part.

  The thickness of the active layer is usually preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and more preferably 20 nm to 200 nm.

  The active layer may be formed by any method, and examples thereof include formation from a solution containing the compound of the present invention or the polymer compound of the present invention (film formation) and formation by a vacuum deposition method.

  A preferred method for producing a photoelectric conversion element is a method for producing a photoelectric conversion element having a first electrode and a second electrode, and having an active layer between the first electrode and the second electrode. And applying a solution (ink) containing the compound of the present invention or the polymer compound of the present invention and a solvent on the first electrode by a coating method to form an active layer, and forming a second on the active layer. Forming an electrode.

  The solvent used for film formation from a solution may be any solvent that dissolves the compound of the present invention or the polymer compound of the present invention. Examples of the solvent include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, Halogenated saturated hydrocarbon solvents such as dichloroethane, 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. The compound of the present invention or the polymer compound of the present invention can be usually dissolved in the solvent in an amount of 0.1% by weight or more.

  When forming a film using a solution, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, Coating methods such as spray coating, screen printing, gravure printing, flexographic printing, offset printing, ink jet printing, dispenser printing, nozzle coating, capillary coating, etc. can be used, slit coating, capillary A coating method, a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, a nozzle coating method, an ink jet printing method, and a spin coating method are preferable.

  From the viewpoint of film formability, the solvent used preferably has a surface tension at 25 ° C. of greater than 15 mN / m, more preferably greater than 15 mN / m and less than 100 mN / m, and greater than 25 mN / m and greater than 60 mN. More preferably, it is smaller than / m.

(Organic thin film solar cell)
In the photoelectric conversion element using the compound of the present invention or the polymer compound of the present invention, photovoltaic light is generated between the electrodes when light such as sunlight enters from the transparent or translucent electrode side, and the organic thin film It can be operated as a solar cell. It can also be used as a module by integrating a plurality of organic thin-film solar cells.

  In addition, when light is incident from the transparent or translucent electrode side in a state where a voltage is applied between the electrodes or in a state where no voltage is applied, a photocurrent flows and the organic light sensor can be operated. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

  The organic thin film solar cell can basically have the same module structure as a conventional module. The solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, or a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known. The organic thin film solar cell produced using the compound of the present invention or the polymer compound of the present invention can also be appropriately selected from these module structures depending on the purpose of use, the place of use and the environment.

  In a typical super straight type or substrate type module, cells are arranged at regular intervals between support substrates that are transparent on one or both sides and subjected to antireflection treatment, and adjacent cells are metal leads or flexible wiring, etc. Are connected to each other, and a collecting electrode is arranged on the outer edge, so that the generated power is taken out to the outside. Various types of plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filled resin in order to protect the cell and improve the current collection efficiency. In addition, when the module is used in places where it is not necessary to cover the surface with a hard material, such as where there is little impact from the outside, the surface protective layer is made of a transparent plastic film or protected by curing the filling resin. It is possible to provide a function and eliminate the support substrate on one side. The periphery of the support substrate is sandwiched and fixed by a metal frame in order to ensure internal sealing and module rigidity, and a sealing material is hermetically sealed between the support substrate and the frame. In addition, if a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.

  In the case of a solar cell using a flexible support such as a polymer film, cells are sequentially formed on the support while feeding the roll-shaped support, and after cutting to a desired size, the periphery is flexible and moisture-proof. The battery body can be produced by sealing with a certain material. A module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 can also be used. Furthermore, a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.

(Organic electroluminescence device)
The compound of the present invention and the polymer compound of the present invention can also be used for an organic electroluminescence device (hereinafter sometimes referred to as “organic EL device”), and the polymer compound of the present invention is used for an organic EL device. Is preferred. An organic EL element has a light emitting layer between a pair of electrodes, at least one of which is transparent or translucent. The organic EL element may include a hole transport layer and an electron transport layer in addition to the light emitting layer. The compound of the present invention or the polymer compound of the present invention is contained in any one of the light emitting layer, the hole transport layer, and the electron transport layer. In addition to the compound of the present invention or the polymer compound of the present invention, the light emitting layer may contain an electron transport material or a hole transport material (these may be collectively referred to as a charge transport material). Good. As an organic EL element, an element having an anode, a light emitting layer, and a cathode, and further having an electron transport layer containing an electron transport material adjacent to the light emitting layer between the cathode and the light emitting layer, A device having an electron transport layer and a cathode, and further having a hole transport layer containing a hole transport material adjacent to the light emitting layer between the anode and the light emitting layer, the anode, the hole transport layer, the light emitting layer, and the cathode And an element having an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.

(Organic transistor)
As the structure of the organic transistor, for example, a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the compound of the present invention or the polymer compound of the present invention, and the amount of current passing through the current path are determined. The structure provided with the gate electrode to control is mentioned. Examples of the organic transistor having such a configuration include a field effect organic transistor and a static induction organic transistor.

  A field effect organic transistor usually has a source electrode and a drain electrode, and a current path between these electrodes, and an active layer containing the compound of the present invention or the polymer compound of the present invention, and the amount of current passing through the current path. An organic transistor having a gate electrode to be controlled and an insulating layer disposed between the active layer and the gate electrode. In particular, an organic transistor having a structure in which a source electrode and a drain electrode are provided in contact with an active layer and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween is preferable.

  The static induction organic transistor usually has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the compound of the present invention or the polymer compound of the present invention, and the amount of current passing through the current path. And an organic transistor having a gate electrode provided in an active layer. In particular, an organic transistor having a configuration in which a source electrode, a drain electrode, and the gate electrode are provided in contact with the active layer is preferable.

  The gate electrode of the electrostatic induction organic transistor may have a structure in which a current path flowing from the source electrode to the drain electrode can be formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. An example of such a gate electrode is a comb-type electrode.

FIG. 1 is a schematic cross-sectional view showing a first configuration example of an organic transistor (field effect organic transistor) of the present invention.
As shown in FIG. 1, the organic transistor 100 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the main surface of the substrate 1 so as to be separated from the substrate 1 at a predetermined interval, and a source The active layer 2 formed on the substrate 1 so as to cover the electrode 5 and the drain electrode 6, the insulating layer 3 formed on the active layer 2, and the source electrode 5 and the drain electrode 6 on the insulating layer 3 layer. And a gate electrode 4 formed on the insulating layer 3 so as to straddle the source electrode 5 and the drain electrode 6 when viewed from the thickness direction of the substrate 1. .

FIG. 2 is a schematic cross-sectional view showing a second configuration example of the organic transistor (field effect organic transistor) of the present invention.
The organic 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 and the source electrode 5 so as to cover the source electrode 5, and a source A drain electrode 6 formed on the active layer 2 so as to be separated from the electrode 5 at a predetermined interval, an insulating layer 3 formed on the active layer 2 and the drain electrode 6, and the source electrode 5 and the drain electrode 6. A gate electrode 4 is formed on the insulating layer 3 so as to straddle the source electrode 5 and the drain electrode 6 when viewed from the thickness direction of the substrate 1 so as to cover the insulating layer 3 on the region in between.

FIG. 3 is a schematic cross-sectional view showing a third configuration example of the organic transistor (field effect organic transistor) of the present invention.
The organic transistor 120 shown in FIG. 3 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 a gate electrode 4 A predetermined region on the insulating layer 3 is formed so as to cover a part of the region of the insulating layer 3 formed in the lower part and to straddle the source electrode 5 and the drain electrode 6 when viewed from the thickness direction of the substrate 1. A source electrode 5 and a drain electrode 6 formed so as to be spaced apart from each other, and a part of the source electrode 5 and the drain electrode 6 are covered and formed on the insulating layer 3 so as to straddle the source electrode 5 and the drain electrode 6. Active layer 2.

FIG. 4 is a schematic cross-sectional view showing a fourth configuration example of the organic transistor (field effect organic transistor) of the present invention.
The organic transistor 130 shown in FIG. 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, a substrate 1 and an insulating layer 3 formed on the gate electrode 4 so as to cover the gate electrode 4, a substrate The source electrode 5 formed on the insulating layer 3 so as to cover a part of the region of the insulating layer 3 so as to straddle the gate electrode 4 when viewed from the thickness direction of 1, and a part of the source electrode 5 are covered. Thus, the active layer 2 formed on the insulating layer 3, the drain electrode formed so as to cover a part of the active layer 2 and a part of the insulating layer 3 and to be separated from the source electrode 5 at a predetermined interval 6.

FIG. 5 is a schematic cross-sectional view showing a fifth configuration example of the organic transistor (static induction organic transistor) of the present invention.
An organic transistor 140 shown in FIG. 5 is separated from the substrate 1, the source electrode 5 formed on the substrate 1, the active layer 2 formed on the source electrode 5, and the active layer 2 at a predetermined interval. The gate electrode 4 having a plurality of comb teeth formed as described above, and the active layer 2a covering the active layer 2 and the gate electrode 4 so as to integrally cover all of the gate electrode 4 (the material constituting the active layer 2a is , Which may be the same as or different from the active layer 2), and a drain electrode integrally formed on the active layer 2 a so as to overlap the gate electrode 4 when viewed from the thickness direction of the substrate 1. 6.

FIG. 6 is a schematic cross-sectional view showing a sixth configuration example of the organic transistor (field effect organic transistor) of the present invention.
An organic transistor 150 shown in FIG. 6 includes a substrate 1, an active layer 2 formed on the substrate 1, and a source electrode 5 and a drain electrode 6 formed on the active layer 2 so as to be spaced apart at a predetermined interval. The insulating layer 3 formed on the active layer 2 across the source electrode 5 and the drain electrode 6 so as to cover a part of the source electrode 5 and the drain electrode 6, and the source when viewed from the thickness direction of the substrate 1. And a gate electrode 4 formed on the insulating layer 3 so as to straddle the electrode 5 and the drain electrode 6.

FIG. 7 is a schematic cross-sectional view showing a seventh configuration example of the organic transistor (field effect organic transistor) of the present invention.
The organic transistor 160 shown in FIG. 7 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 a thickness of the substrate 1. The active layer 2 formed so as to cover the region on the gate electrode 4 when viewed from the direction, and the gate electrode 4 so as to cover a part of the active layer 2 and viewed from the thickness direction of the substrate 1. The source electrode 5 formed on the active layer 2 across a part of the active layer 2 and the source electrode 5 so as to cover a part of the active layer 2 and the gate electrode 4 when viewed from the thickness direction of the substrate 1 5 and a drain electrode 6 formed on the active layer 2 so as to be separated from each other by a predetermined interval.

FIG. 8 is a schematic cross-sectional view showing an eighth configuration example of the organic transistor (field effect organic transistor) of the present invention.
An organic transistor 170 shown in FIG. 8 includes a gate electrode 4, an insulating layer 3 formed on the gate electrode 4, an active layer 2 formed on the insulating layer 3, and a predetermined interval on the active layer 2. It has the source electrode 5 and the drain electrode 6 which were formed so that it might space apart. In this case, the gate electrode 4 serves as a substrate.

FIG. 9 is a schematic cross-sectional view showing a ninth configuration example of the organic transistor (field effect organic transistor) of the present invention.
An organic transistor 180 shown in FIG. 9 includes a gate electrode 4, an insulating layer 3 formed on the gate electrode 4, and a part of the source electrode 5 formed on the insulating layer 3 so as to be separated at a predetermined interval. And the active layer 2 formed on the insulating layer 3 so as to straddle part of the drain electrode 6.

  In the above-described organic transistor of the present invention, the active layer 2 and / or the active layer 2a is constituted by a film containing the compound of the present invention or the polymer compound of the present invention, and between the source electrode 5 and the drain electrode 6. Functions as a current path (channel). The gate electrode 4 controls the amount of current passing through the channel by applying a voltage.

  The field effect organic transistor having the above-described configuration can be manufactured by a known method, for example, a manufacturing method described in JP-A-5-110069. The electrostatic induction organic transistor can be manufactured by a known method such as a manufacturing method described in JP-A-2004-006476.

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

The material of the insulating layer 3 may be any material having high electrical insulation, and SiO _x , SiN _x , Ta ₂ O ₅ , polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass, photoresist, and the like can be used. Since the operating voltage can be lowered, it is preferable to use a material having a high dielectric constant.

  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. The active layer 2 may be formed after the modification.

  In the case of a field effect transistor, the charge generally passes near the interface between the insulating layer 3 and the active layer 2. Accordingly, the state of this interface greatly affects the field effect mobility of the transistor. Therefore, as a method for improving the interface state and improving the properties, control of the interface with a silane coupling agent has been proposed (for example, Surface Chemistry, 2007, Vol. 28, No. 5, p. 242-248). reference.).

Examples of silane coupling agents include alkylchlorosilanes (octyltrichlorosilane (OTS), octadecyltrichlorosilane (ODTS), phenylethyltrichlorosilane, etc.), alkylalkoxysilanes, fluorinated alkylchlorosilanes, and fluorinated alkylalkoxysilanes. And silylamine compounds such as hexamethyldisilazane (HMDS). Further, the surface of the insulating layer may be subjected to ozone UV treatment or O ₂ plasma treatment before being treated with the surface treatment agent.

  By such treatment, the surface energy of the silicon oxide film or the like used as the insulating layer 3 can be controlled. Further, since the orientation of the film constituting the active layer 2 on the insulating layer 3 is improved by the surface treatment, higher field effect mobility can be obtained.

  Materials for the gate electrode 4 include gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum, low resistance polysilicon, low resistance amorphous silicon, and other metals, tin oxide, indium oxide, and indium tin oxide. A material such as (ITO) can be used.

  These materials may be used alone or in combination of two or more. Note that a highly doped silicon substrate may be used as the gate electrode 4. The highly doped silicon substrate has not only the performance as the gate electrode 4 but also the performance as the substrate. When the gate electrode 4 having such performance as a substrate is used, the substrate 1 may be omitted.

  The source electrode 5 and the drain electrode 6 are preferably made of a low-resistance material, and particularly preferably made of gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum or the like. These materials may be used alone or in combination of two or more.

  In the organic transistor, a layer composed of another compound may be interposed between the source electrode 5 and the drain electrode 6 and the active layer 2. Examples of such layers include low molecular compounds having electron transport properties, low molecular compounds having hole transport properties, alkali metals, alkaline earth metals, rare earth metals, complexes of these metals with organic compounds, iodine, bromine, Halogens such as chlorine and iodine chloride, sulfur oxide compounds such as sulfuric acid, sulfuric anhydride, sulfur dioxide and sulfate, nitric oxide compounds such as nitric acid, nitrogen dioxide and nitrate, halogenated compounds such as perchloric acid and hypochlorous acid, Examples thereof include layers made of aromatic thiol compounds such as alkyl thiol compounds, aromatic thiols, and fluorinated alkyl aromatic thiols.

  In addition, after manufacturing the organic transistor as described above, it is preferable to form a protective film on the organic transistor in order to protect the element. Thereby, an organic transistor is interrupted | blocked from air | atmosphere and the fall of the characteristic of an organic transistor can be suppressed. Further, when a display device to be driven is formed on an organic transistor, the protective film can also reduce the influence on the organic transistor in the formation process.

Examples of the method for forming the protective film include a method of covering the organic transistor with a UV curable resin, a thermosetting resin, an inorganic SiON _x film, or the like. In order to effectively block the atmosphere, it is preferable to form a protective film after the organic transistor is manufactured without exposing the organic transistor to the atmosphere (for example, in a dry nitrogen gas atmosphere or in a vacuum).

  A field effect transistor, which is a kind of organic transistor thus configured, can be applied as a liquid crystal display of an active matrix driving system, a switching element for driving a pixel of an organic electroluminescence display, or the like. The field effect transistor of the present embodiment described above contains the compound of the present invention or the polymer compound of the present invention as an active layer, and thereby includes an active layer excellent in charge mobility. The field effect mobility is high. Therefore, it is useful for manufacturing a display having a faster response speed.

  Examples are given below to illustrate the present invention in more detail. The present invention is not limited to these examples.

(Measurement conditions, etc.)
The nuclear magnetic resonance (NMR) spectrum was measured using the product name JMN-270 (270 MHz at 1H measurement) manufactured by JEOL (JEOL Ltd.) or the product name JMNLA-600 (150 MHz at 13C measurement) manufactured by the same company. . Chemical shifts are expressed in parts per million (ppm). Tetramethylsilane (TMS) was used as an 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, four, respectively. Represents a quartet, a multiplet, and a broad line.

Cyclic voltammetry (hereinafter referred to as “CV”) was measured using an apparatus manufactured by BAS, using a Pt electrode manufactured by BAS as a working electrode, a Pt line as a counter electrode, and an Ag line as a reference electrode. The sweep rate during this measurement was 100 mV / second, and the scanning potential region was −2.8 V to 1.6 V. The reduction potential and the oxidation potential are measured by dissolving the compound to be measured in methylene chloride at a concentration of 1 × 10 ⁻³ mol / L and tetrabutylammonium hexafluorophosphate as a supporting electrolyte at a concentration of 0.1 mol / L. Performed using the dissolved solution.

Synthesis example 1
<Synthesis of Compound A>
In a screw test tube, 2.00 g (8.81 mmol) of 4-bromophthalic anhydride, 50 mL of dimethylformamide, and 1.13 g (8.81 mmol) of 2-ethylhexylamine were added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, water was added to the reaction solution, the organic layer was extracted using ethyl acetate, and the organic layer was dried using magnesium sulfate. The dried organic layer was concentrated under reduced pressure using an evaporator, and purified by silica gel column chromatography using a solvent in which hexane and ethyl acetate were mixed so that the volume ratio of hexane to ethyl acetate was 10, as a developing solvent, 2.24 g of pale yellow oily compound A represented by the following formula was obtained. The yield of compound A was 75%.

The analysis result of the obtained compound A is as follows.
TLC R _f = 0.4 (hexane / ethyl acetate = 10/1 (volume ratio)).
¹ H NMR (400 MHz, CDCl ₃ ): δ 7.95 (d, 1 H, J = 1.8 Hz), 7.83 (dd, 1 H, J = 7.8, 1.8 Hz), 7.69 (d, 1H, J = 7.8 Hz), 3.56 (d, 2H, J = 6.9 Hz), 1.81 (m, 1H), 1.28 (m, 8H), 0.88 (m, 6H) .

Synthesis example 2
<Synthesis of Compound B>
In a screw test tube, 1.00 g (2.95 mmol) of compound A, 1.44 g (14.7 mmol) of trimethylsilylacetylene, 56 mg (0.295 mmol) of copper iodide, dichlorobis (triphenylphosphine) palladium (II ), 207 mg (0.30 mmol), tetrahydrofuran (5 mL) and triethylamine (5 mL) were added, and the air in the screw test tube was replaced with nitrogen gas, and the mixture was refluxed for 12 hours. The reaction solution was concentrated under reduced pressure using an evaporator and purified by silica gel column chromatography using a solvent in which an equal amount of hexane and chloroform was mixed as a developing solvent. 02 g was obtained. The yield of compound B was 97%.

The analysis result of the obtained compound B is as follows.
TLC R _f = 0.3 (hexane / chloroform = 1/1).
¹ H NMR (400 MHz, CDCl ₃ ): δ 7.87 (s, 1H), 7.75 (d, 1H, J = 7.8 Hz), 7.73 (d, 1H, J = 7.8 Hz), 3 .65 (d, 2H, J = 5.6 Hz), 1.81 (m, 1H), 1.29 (m, 8H), 0.88 (m, 6H), 0.26 (s, 9H).

Synthesis Example 3 <Synthesis of Compound C>
In an eggplant-shaped flask, 400 mg (1.12 mmol) of Compound B, 4 mL of tetrahydrofuran, 1 mL of methanol, and 309 mg (2.24 mmol) of potassium carbonate were added and stirred for 1 hour. Thereafter, the reaction solution was filtered through Celite, concentrated under reduced pressure using an evaporator, and then silica gel column chromatography using a solvent in which hexane and ethyl acetate were mixed so that the volume ratio of hexane to ethyl acetate was 10, as a developing solvent. Purified by chromatography, 210 mg of pale yellow oily compound C represented by the following formula was obtained. The yield of compound C was 66%.

The analysis result of the obtained compound C is as follows.
TLC R _f = 0.5 (hexane / ethyl acetate = 10/1).
¹ H NMR (400 MHz, CDCl ₃ ): δ 7.90 (s, 1H), 7.78 (s, 2H), 3.56 (d, 2H, J = 7.8 Hz), 1.81 (m, 1H) ), 1.29 (m, 8H), 0.88 (m, 6H).

Synthesis example 4
<Synthesis of Compound D>
In a screw test tube, 89 mg (0.30 mmol) of 4,7-dibromo-2,1,3-benzothiadiazole, 5 mg (0.03 mmol) of copper iodide, tetrakis (triphenylphosphine) palladium (0) 39 mg (0.030 mmol), 189 mg (0.674 mmol) of Compound C, 6 mL of tetrahydrofuran and 0.6 mL of diisopropylethylamine were added, and the air in the screw-mouth test tube was replaced with nitrogen gas, and the mixture was refluxed for 12 hours. The reaction solution was concentrated under reduced pressure using an evaporator, purified by silica gel column chromatography using chloroform as a developing solvent to obtain a crude product, and then recrystallization gave a yellow solid compound D represented by the following formula. 189 mg was obtained. The yield of compound D was 89%. In recrystallization, crystals were obtained by a two-layer method using chloroform and acetone, and then washed with hexane and acetone.

The analysis result of the obtained compound D is as follows.
TLC R _f = 0.2 (chloroform).
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.09 (d, 2H, J = 1.4 Hz), 7.97 (dd, 2H, J = 8.2, 1.4 Hz), 7.87 (d, 2H, J = 8.2 Hz), 7.86 (s, 2H), 3.59 (d, 4H, J = 8.7 Hz), 1.84 (m, 2H), 1.29 (m, 16H) 0.90 (m, 12H).

Example 1 <Synthesis of Compound E>
In a screw test tube, 40 mg (0.057 mmol) of Compound D, 2,4-bis (methylthio) -1,3,4,4-dithiadiphosphetane-2,4-disulfide (represented by the following formula) Compound Z) (65 mg, 0.229 mmol) and toluene (4 mL) were added, and the air in the screw cap test tube was replaced with nitrogen gas, followed by refluxing for 6 hours. The reaction solution was concentrated under reduced pressure using an evaporator, and purified by silica gel column chromatography using a mixed solvent of hexane and chloroform in an equal amount as a developing solvent to obtain a crude product. Then, chloroform was used for the moving bed. 20 mg of a red solid compound E represented by the following formula was obtained by GPC. The yield of compound E was 46%.

The analysis result of the obtained compound E is as follows.
TLC R _f = 0.5 (hexane / chloroform = 1/1).
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.23 (s, 2H), 8.04 (d, 2H, J = 8.2 Hz), 7.98 (d, 2H, J = 8.2 Hz), 7 .97 (s, 2H), 4.50 (d, 4H, J = 8.0 Hz), 2.30 (m, 2H), 1.40 (m, 16H), 0.96 (m, 12H).

Synthesis example 5
<Synthesis of Compound F>
In a test tube, 300 mg (0.403 mmol) of 5,5′-bis (tributylstannyl) -2,2′-bithiophene, 299 mg (0.965 mmol) of 4-bromo-N-hexylphthalimide, tetrakis (triphenyl) Phosphine) palladium (0) (46 mg, 0.040 mmol) and toluene (5 mL) were added and reacted at 180 ° C. for 5 minutes under microwave irradiation. The reaction solution was concentrated under reduced pressure using an evaporator and purified by alumina column chromatography to obtain a crude product. As a developing solvent for alumina column chromatography, hexane was first used, and then chloroform was used. Thereafter, Compound F as a yellow solid represented by the following formula was isolated from the crude product by gel permeation chromatography. The yield of compound F was 186 mg, and the yield was 74%.

The analysis result of the obtained compound F is as follows.
TLC R _f = 0.2 (hexane / chloroform = 1/1).
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.04 (d, 2H, J = 1.8 Hz), 7.78 (dd, 2H, J = 7.9, 1.8 Hz), 7.83 (d, 2H, J = 7.8 Hz), 7.43 (d, 2H, J = 7.4 Hz), 7.27 (d, 2H, J = 7.4 Hz), 3.68 (t, 4H, J = 8) .2 Hz), 1.68 (p, 4H, J = 8.2 Hz), 1.31 (m, 12H), 0.88 (t, 6H, J = 6.9 Hz).

Example 2 <Synthesis of Compound G>
50 mg (0.080 mmol) of Compound F, 91 mg (0.32 mmol) of Compound Z, and 5 mL of toluene were placed in the screw cap test tube, and the air in the screw cap test tube was replaced with nitrogen gas and refluxed for 12 hours. The reaction solution was concentrated under reduced pressure using an evaporator, and the solid crude product was washed with dichloromethane and then ether to obtain 54 mg of a black solid compound G represented by the following formula. The yield of compound G was 98%.

The analysis result of the obtained compound G is as follows.
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.03 (s, 2H), 7.85 (s, 4H), 7.47 (d, 2H, J = 3.7 Hz), 7.28 (d, 2H) , J = 3.7 Hz), 4.41 (t, 4H, J = 7.8 Hz), 1.73 (m, 4H), 1.35 (m, 12H), 0.89 (m, 6H).

Synthesis Example 6
<Synthesis of Compound H>
In a test tube, 300 mg (0.403 mmol) of 5,5′-bis (tributylstannyl) -2,2′-bithiophene, 327 mg (0.967 mmol) of compound A, tetrakis (triphenylphosphine) palladium (0) 46 mg (0.040 mmol) and 5 mL of toluene were added and reacted at 180 ° C. for 5 minutes under microwave irradiation. The reaction solution was concentrated under reduced pressure using an evaporator, and the resulting solid was washed with dichloromethane and then with ether to isolate a black solid compound H represented by the following formula. The yield of compound H was 225 mg, and the yield was 82%.

The analysis result of the obtained compound H is as follows.
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.04 (d, 2H, J = 1.4 Hz), 7.89 (dd, 2H, J = 7.8, 1.4 Hz), 7.83 (d, 2H, J = 7.8 Hz), 7.43 (d, 2H, J = 3.8 Hz), 7.27 (d, 2H, J = 3.8 Hz), 3.53 (t, 4H, J = 7) .3 Hz), 1.84 (m, 2H), 1.32 (m, 16H), 0.91 (m, 12H).

Example 3
<Synthesis of Compound I>
100 mg (0.146 mmol) of Compound H, 166 mg (0.584 mmol) of Compound Z, and 5 mL of toluene were placed in the screw cap test tube, and the air in the screw cap test tube was replaced with nitrogen gas and refluxed for 12 hours. The reaction solution was concentrated under reduced pressure using an evaporator, and the solid crude product was washed with dichloromethane and then ether to obtain 95 mg of black solid Compound I represented by the following formula. The yield of Compound I was 88%.

The analysis results of the obtained compound I are as follows.
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.01 (s, 2H), 7.83 (s, 4H), 7.46 (d, 2H, J = 4.1 Hz), 7.27 (d, 2H) , J = 4.1 Hz), 4.38 (m, 4H), 2.19 (m, 2H), 1.32 (m, 16H), 0.87 (m, 12H).

Synthesis Example 7 <Synthesis of Compound J>
In a test tube, 100 mg (0.152 mmol) of 4,7-bis (5- (tributylstannyl) thiophen-2-yl) benzo [c] [1,2,5] thiadiazole and 128 mg (0. 381 mmol), 18 mg (0.016 mmol) of tetrakis (triphenylphosphine) palladium (0) and 5 mL of toluene were added and reacted at 180 ° C. for 5 minutes under microwave irradiation. The reaction solution was concentrated under reduced pressure using an evaporator, washed with ether to obtain a crude product, and then a red solid compound J represented by the following formula was isolated by gel permeation chromatography. The yield of Compound J was 90 mg, and the yield was 70%.

The analysis results of the obtained compound J are as follows.
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.15 (d, 2H, J = 5.5 Hz), 8.15 (s, 2H), 8.00 (d, 2H, J = 7.8 Hz), 7 .96 (s, 2H), 7.85 (d, 2H, J = 7.8 Hz), 7.59 (d, 2H, J = 5.5 Hz), 3.60 (d, 4H, J = 7. 8 Hz), 1.85 (m, 2H), 1.30 (m, 16H), 0.91 (m, 12H).

Example 4
<Synthesis of Compound K>
50 mg (0.061 mmol) of compound J, 68 mg (0.24 mmol) of compound Z, and 5 mL of toluene were placed in the screw cap test tube, and the air in the screw cap test tube was replaced with nitrogen gas and refluxed for 12 hours. The reaction solution was concentrated under reduced pressure using an evaporator, and the solid crude product was washed with dichloromethane and then with ether to obtain 33 mg of black solid compound K. The yield of compound K was 62%.

The analysis result of the obtained compound K is as follows.
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.11 (d, 2H, J = 4.1 Hz), 8.15 (d, 2H, J = 1.4 Hz), 7.91 (dd, 2H, J = 7.8, 1.4 Hz), 7.90 (s, 2H), 7.82 (d, 2H, J = 7.8 Hz), 7.59 (d, 2H, J = 4.1 Hz), 4. 38 (m, 4H), 2.20 (m, 2H), 1.32 (m, 16H), 0.89 (m, 12H).

Example 5
CV measurement was performed using Compound E. As a result, the reduction potential E _1/2 of Compound E was −1.08V. It was -3.72 eV when LUMO of the compound E was computed from the reduction potential.

Example 6
CV was measured using Compound I. As a result, the reduction potential E1 _{/ 2} of Compound I was −1.11V. The LUMO of compound I was calculated from the reduction potential and found to be -3.69 eV.

Example 7
CV was measured using Compound K. As a result, the reduction potential E1 _{/ 2} of Compound K was −1.14V. It was -3.66eV when LUMO of the compound K was computed from the reduction potential.

DESCRIPTION OF SYMBOLS 1 Substrate 2, 2a Active layer 3 Insulating layer 4 Gate electrode 5 Source electrode 6 Drain electrode 100, 110, 120, 130, 140, 150, 160, 170, 180 Organic transistor

Claims (10)

A compound containing at least two structures represented by the following formula (1).

(In Formula (1), Z ¹ and Z ² are each independently an oxygen atom, a sulfur atom, a selenium atom, a group represented by ═C (R ¹ ) (R ² ), or ═N (R ³ ). Represents at least one of Z ¹ and Z ² is a sulfur atom or a selenium atom, R ¹ , R ² and R ³ each independently represents a cyano group or —C (═O); R ⁴ represents a group represented by R ^4. R ⁴ has a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An aryl group which may be substituted or a heterocyclic group which may have a substituent, when two R ^{4 s} are present, they may be the same or different, and E ¹ represents an oxygen atom, sulfur atom, a selenium atom, -N ^{(R 5)} - group or a ^-C represented by ^{(R 6) = C (R} 7) - is represented by .R ^5, R ⁶ and R ⁷ represents a group each independently represent a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an alkoxy group which may have a substituent, R ⁶ and R ⁷ are each an alkylthio group optionally having a substituent, an aryl group optionally having a substituent, a heterocyclic group optionally having a substituent, a halogen atom, or a cyano group. They may be bonded to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which each is bonded.Ring A ¹ has an aromatic carbocyclic ring or a substituent which may have a substituent. Represents a heterocyclic ring which may be The compound of Claim 1 represented by following formula (2).

(In formula (2), Z ¹ , Z ² , E ¹ and ring A ¹ represent the same meaning as described above. Two Z ^{1 s} may be the same or different. Two Z ^{2 s.} May be the same or different, and two E ¹ may be the same or different, and two rings A ¹ may be the same or different. An arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, a group represented by —C≡C—, or —C (R ⁸ ) ═C (R ⁹ R ⁸ and R ⁹ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent. , An alkylthio group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent Represents a halogen atom or a cyano group, n represents an integer of 0 or more, and when there are a plurality of B, they may be the same or different, and when there are a plurality of R ⁸ and R ⁹ , They may be the same or different.) The high molecular compound containing the structural unit represented by following formula (3).

(In Formula (3), Z ¹ and Z ² are each independently an oxygen atom, a sulfur atom, a selenium atom, a group represented by ═C (R ¹ ) (R ² ), or ═N (R ³ ). Represents at least one of Z ¹ and Z ² is a sulfur atom or a selenium atom, R ¹ , R ² and R ³ each independently represents a cyano group or —C (═O); R ⁴ represents a group represented by R ^4. R ⁴ has a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. If even also have an aryl group or a substituted group represents an aromatic heterocyclic group .R ⁴ there are two, they may .E ¹ be different even if the same is oxygen atom , A sulfur atom, a selenium atom, a group represented by —N (R ⁵ ) — or a group represented by —C (R ⁶ ) ═C (R ⁷ ) — R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, R ⁶ and R ⁷ each represents an alkylthio group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom or a cyano group. May be bonded to each other to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which each is bonded.Ring A ¹ represents an aromatic carbocyclic ring or a substituent which may have a substituent. It represents a heterocyclic ring that may have.) The compound or polymer compound according to any one of claims 1 to 3, wherein Z ¹ and Z ² are sulfur atoms. E ¹ is, -N ^{(R 5)} - is a group represented by The compound or a polymer compound according to any one of claims 1 to 4. Ring A ¹ is a thiophene ring, a benzene ring, a pyridine ring or a naphthalene ring, a compound or a polymer compound according to any one of claims 1 to 5.   The organic-semiconductor material containing the compound or high molecular compound of any one of Claims 1-6.   The organic-semiconductor element which has an organic layer containing the organic-semiconductor material of Claim 7.   An organic solar cell provided with a pair of electrodes and the layer containing the organic-semiconductor material of Claim 7 provided between this pair of electrodes.   The organic transistor which has a source electrode, a drain electrode, a gate electrode, and an active layer, and contains the organic-semiconductor material of Claim 7 in this active layer.

Images